Pesticide-inactivating heterocyclic derivatives having sulfur-containing substituents

Abstract

Disclosed are compounds of formula (I), wherein the substituents are as defined in claim 1. Furthermore, the invention relates to agrochemical compositions comprising compounds of formula (I), the preparation of these compositions, and the use of the compounds or compositions 10 in agriculture or horticulture for combating, preventing or controlling animal pests, including arthropods and in particular insects, molluscs, nematodes or representatives of the order Acarina.

Description

[0001] The present invention relates to pesticidally active, in particular insecticidal, heterocyclic derivatives containing a sulphur substituent, processes for their preparation, compositions containing those compounds, and their use for controlling animal pests, including arthropods and in particular insects or representatives of the order Acarina.

[0002] Heterocyclic benzoannulated dihydropyrrolone and phthalimide derivatives with sulfur-containing substituents have been described in the literature, for example, in J. Org. Chem. [Journal of Organic Chemistry] 2003, 62, 8240 and Bull. Chem. Soc. Chim. Belg. [Bulletin of the Belgian Chemical Society] 1997, 106, 151. However, none of these references describe pesticidal effects. Structurally diverse pesticidally active heterocyclic derivatives with sulfur-containing substituents have been described, for example, in WO 2012 / 012086848, WO 2013 / 018928, and WO 2019 / 131575.

[0003] It has now been found, surprisingly, that certain novel pesticidally active derivatives having sulphur-containing substituents have advantageous properties as pesticides.

[0004] The present invention therefore provides compounds of formula I,

[0005]

[0006] in

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

[0008] R2 is C1-C6 haloalkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C1-C6 haloalkoxy, C1-C4 haloalkylsulfonyloxy;

[0009] Q is a group selected from the group consisting of: formula Qa and Qb

[0010]

[0011] wherein the arrow indicates the point of attachment to the nitrogen atom of the bicyclic ring;

[0012] and wherein A represents CH or N;

[0013] X is S, SO or SO2;

[0014] R1 is C1-C4 alkyl, or C3-C6 cycloalkyl-C1-C4 alkyl;

[0015] Q1 is hydrogen, halogen, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted by cyano, C1-C6 cyanoalkyl, C1-C6 cyanoalkoxy, C1-C6 haloalkoxy, -N(R4)2, -N(R4)C(=O)R5, -N(R4)CON(R4)2, (oxazolidin-2-one)-3-yl, or 2-pyridyloxy; or

[0016] Q1 is a five- to six-membered aromatic ring system, which is attached to the ring comprising the substituent A via a ring carbon atom, which ring system is unsubstituted or mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl and C1-C4 alkylsulfonyl; and the ring system may contain 1, 2 or 3 ring heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, wherein the ring system may not contain more than one ring oxygen atom and not more than one ring sulfur atom; or

[0017] Q1 is a five-membered aromatic ring system, which is attached to the ring comprising the substituent A via a ring nitrogen atom, the ring system being unsubstituted or mono- or polysubstituted by substituents selected from the group consisting of halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl and C1-C4 alkylsulfonyl; and the ring system comprises 1, 2 or 3 ring heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, wherein the ring system comprises at least one ring nitrogen atom and may not comprise more than one ring oxygen atom and does not comprise more than one ring sulfur atom;

[0018] R3 is hydrogen, halogen or C1-C4 alkyl;

[0019] Each R4 is independently hydrogen, C1-C4 alkyl or C3-C6 cycloalkyl; and

[0020] R5 is C1-C6 alkyl, C1-C6 haloalkyl or C3-C6 cycloalkyl.

[0021] The present invention also provides agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of the compound of formula I.

[0022] Compounds of formula I with at least one basic center can form acid addition salts, for example, with strong inorganic acids (such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrohalic acids), strong organic carboxylic acids (such as unsubstituted or, for example, halogen-substituted C1-C4-alkanecarboxylic acids, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example 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, halogen-substituted C1-C4-alkanesulfonic acids or arylsulfonic acids, for example methanesulfonic acid or p-toluenesulfonic acid). Compounds of formula I having at least one acidic group can, for example, form salts with bases, such as mineral salts, for example alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts; or with ammonia or organic amines (for example morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, for example ethylamine, diethylamine, triethylamine or dimethylpropylamine, or mono-, di- or trihydroxy-lower alkylamines, for example monoethanolamine, diethanolamine or triethanolamine).

[0023] In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form, such as N-oxides, or in salt form (eg in the form of agronomically usable salts).

[0024] N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen-containing heteroaromatic compounds. They are described, for example, by A. Albini and S. Pietra in 1991 in the book "Heterocyclic N-oxides", published by CRC Press, Boca Raton.

[0025] The compounds of formula I according to the invention also include hydrates which may be formed during salt formation.

[0026] When substituents are indicated as being further substituted, this means that they carry one or more identical or different substituents, for example one to four substituents. Typically, there are no more than three such optional substituents at the same time. Preferably, there are no more than two such substituents (that is, the group is substituted by one or two indicated substituents) at the same time. When additional substituents are larger groups such as cycloalkyl or phenyl, it is most preferred that there is only one such optional substituent. When a group is indicated as being substituted by, for example, an alkyl group, this includes those groups that are a part of other groups, for example the alkyl group in an alkylthio group.

[0027] As used herein, the term "C1-C n“Alkyl” refers to a saturated straight or branched chain hydrocarbon group having 1 to n carbon atoms, attached via any carbon atom, such as any of the following: 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.

[0028] As used herein, the term "C1-C n “Haloalkyl” refers to straight-chain or branched saturated alkyl groups (as mentioned above) having 1 to n carbon atoms, attached via any 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., for example, any of the following: chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl The term "Ci-C2-fluoroalkyl" shall mean a C1-C2-alkyl group containing 1, 2, 3, 4, or 5 fluorine atoms, such as difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, or pentafluoroethyl.

[0029] As used herein, the term "C1-C n"Alkoxy" refers to a straight-chain or branched saturated alkyl group having 1 to n carbon atoms (as mentioned above) attached via an oxygen atom, i.e., for example, any of the following: methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy.

[0030] As used herein, the term "C1-C n "Haloalkoxy" refers to the C1-C n Alkoxy groups, which are partially or fully substituted by fluorine, chlorine, bromine and / or iodine, i.e., for example, any 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.

[0031] As used herein, the term "C1-C n "Alkylsulfanyl" refers to a linear or branched saturated alkyl group having 1 to n carbon atoms (as mentioned above) attached via a sulfur atom, i.e., for example, any of the following: methylthio, ethylthio, n-propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio or 1,1-dimethylethylthio.

[0032] As used herein, the term "C1-C n“Alkylsulfinyl” refers to a straight-chain or branched saturated alkyl group having 1 to n carbon atoms (as mentioned above) attached via the sulfur atom of the sulfinyl group, i.e., for example, any of the following: methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, 1-methylethyl-sulfinyl, n-butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl, 1,1-dimethyl-ethylsulfinyl, n-pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methyl-butylsulfinyl, 1,1-dimethylpropylsulfinyl, 1,2-dimethylpropylsulfinyl, 2,2-dimethylpropylsulfinyl or 1-ethylpropylsulfinyl.

[0033] As used herein, the term "C1-C n "Alkylsulfonyl" refers to a straight-chain or branched saturated alkyl group having 1 to n carbon atoms (as mentioned above) attached via the sulfur atom of the sulfonyl group, i.e., for example, any of the following: methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl or tert-butylsulfonyl.

[0034] As used herein, the term "C1-C n "Haloalkylsulfanyl" refers to the C1-C n Alkylthio groups, which are partially or fully substituted by fluorine, chlorine, bromine and / or iodine, i.e., for example, 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 1-(fluoromethyl)-2-fluoroethylthio, 1-(chloromethyl)-2-chloroethylthio, 1-(bromomethyl)-2-bromoethylthio, 4-fluorobutylthio, 4-chlorobutylthio, or 4-bromobutylthio.

[0035] The term "C1-C n "Haloalkylsulfinyl" and "C1-C n "Haloalkylsulfonyl" refers to the above groups, but wherein the sulfur is in oxidation state 1 or 2, respectively.

[0036] As used herein, the term "C1-Cn "Cyanoalkyl" refers to a straight-chain or branched saturated alkyl group having 1 to n carbon atoms (as mentioned above) substituted by a cyano group, for example, cyanomethylene, cyanoethylene, 1,1-dimethylcyanomethyl, cyanomethyl, cyanoethyl and 1-dimethylcyanomethyl.

[0037] As used herein, in terms such as "C3-C n The suffix "-C1-C n Alkyl" (wherein n is an integer from 1 to 6) refers to a C3-C n A cycloalkyl-substituted straight-chain or branched saturated alkyl group. n Cycloalkyl-C1-C n An example of an alkyl group is, for example, cyclopropylmethyl.

[0038] As used herein, the term "C3-C6 cycloalkyl" refers to a 3-6 membered cycloalkyl group such as cyclopropane, cyclobutane, cyclopropane, cyclopentane and cyclohexane.

[0039] Halogen is typically fluorine, chlorine, bromine or iodine. This also applies accordingly to halogen in combination with other meanings, such as haloalkyl.

[0040] In the context of the present invention, "mono- or polysubstituted" in the definition of the Q1 substituent typically means, depending on the chemical structure of the substituent, mono- to pentasubstituted, more preferably mono-, di- or trisubstituted.

[0041] In the context of the present invention, the phrases “Q1 is a five- to six-membered aromatic ring system, which is linked to the ring comprising the substituent A via a ring carbon atom…”, and the phrases “Q1 is a five-membered aromatic ring system, which is linked to the ring comprising the substituent A via a ring nitrogen atom…”, as the case may be, refer to the manner of attachment of specific embodiments of the substituent Q1 to the group Q represented by formula Qa or formula Qb, as the case may be.

[0042] In the context of the present invention, examples of “Q1 is a five- to six-membered aromatic ring system, which is linked to the ring containing the substituent A via a ring carbon atom, ...; and which may contain 1, 2 or 3 ring heteroatoms...” are, but are not limited to, phenyl, pyrazolyl, triazolyl, pyridinyl and pyrimidinyl; preferably, phenyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, pyrimidin-2-yl, pyrimidin-4-yl, and pyrimidin-5-yl.

[0043] In the context of the present invention, examples of “Q1 is a five-membered aromatic ring system, which is linked to the ring containing the substituent A via a ring nitrogen atom, ...; and the ring system contains 1, 2 or 3 ring heteroatoms...” are, but are not limited to, pyrazolyl, pyrrolyl, imidazolyl and triazolyl; preferably, pyrrol-1-yl, pyrazol-1-yl, triazol-2-yl, 1,2,4-triazol-1-yl, triazol-1-yl, and imidazol-1-yl.

[0044] As listed below, certain embodiments according to the present invention are provided.

[0045] Example 1 provides a compound of formula I as defined above, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.

[0046] Embodiment 2 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein Q is Qa and preferred values ​​for G1, G2, R2, A, X, R1, Q1, R3, R4 and R5 in any combination thereof are as follows:

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

[0048] It is also preferred that when G1 and G2 are both N;

[0049] It is also preferred that when G1 and G2 are both CH;

[0050] Most preferably, G1 is CH and G2 is N;

[0051] Preferably, R2 is C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C4 haloalkylsulfonyl or C1-C4 haloalkylsulfonyloxy;

[0052] More preferably, R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3 or CF3;

[0053] Most preferably, R2 is CF2CF3 or CF3;

[0054] Preferably, A is N or CH;

[0055] Most preferably, A is N;

[0056] Preferably, X is S or SO2;

[0057] Most preferably, X is SO2;

[0058] Preferably, R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl;

[0059] More preferably, R1 is ethyl or cyclopropylmethyl;

[0060] Most preferably, R1 is ethyl;

[0061] Preferably, Q1 is hydrogen, halogen, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted by cyano, C1-C6 cyanoalkyl, C1-C6 haloalkoxy, -N(R4)2, -N(R4)COR5, -N(R4)CON(R4)2, (oxazolidin-2-one)-3-yl or 2-pyridyloxy;

[0062] It is also preferred that when Q1 is a five- to six-membered aromatic ring system (connected to the ring comprising the substituent A via a ring carbon atom), said ring system is unsubstituted or monosubstituted with a substituent selected from the group consisting of halogen and C1-C4 haloalkyl; and said ring system may contain 1 or 2 ring nitrogen atoms;

[0063] It is also preferred that when Q1 is a five-membered aromatic ring system (connected to the ring comprising substituent A via a ring nitrogen atom), said ring system is unsubstituted or monosubstituted with a substituent selected from the group consisting of halogen and C1-C4 haloalkyl; and said ring system comprises 2 or 3 ring nitrogen atoms.

[0064] More preferably, Q1 is hydrogen, halogen, trifluoromethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoroethoxy, (oxazolidin-2-one)-3-yl, 2-pyridyloxy, N-attached pyrazolyl which may be monosubstituted by chloro or trifluoromethyl, N-attached triazolyl, C-attached pyrimidinyl, -N(R4)2, -N(R4)COR5, or -N(R4)CON(R4)2, in each of which R4 is independently hydrogen or methyl and R5 is methyl, ethyl or cyclopropyl;

[0065] Most preferably, Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(H)CONH(CH3), -N(CH3)CONH(CH3), (oxazolidin-2-one)-3-yl, 2-pyridyloxy, pyrazol-1-yl, 3-chloro-pyrazol-1-yl, 3-trifluoromethyl-pyrazol-1-yl, 1,2,4-triazol-1-yl or pyrimidin-2-yl;

[0066] Preferably, each R4 is independently hydrogen or C1-C4 alkyl;

[0067] Most preferably, each R4 is independently hydrogen or methyl;

[0068] Preferably, R5 is C1-C6 alkyl or C3-C6 cycloalkyl;

[0069] More preferably, R5 is methyl, ethyl or cyclopropyl;

[0070] Most preferably, R5 is methyl;

[0071] Preferably, R3 is hydrogen or C1-C4 alkyl;

[0072] More preferably, R3 is hydrogen or methyl; and

[0073] Most preferably, R3 is hydrogen.

[0074] Embodiment 3 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, wherein Q is Qb and preferred values ​​for G1, G2, R2, R1, X, Q1, A, R4, R5 and R3 in any combination thereof are as follows:

[0075] Preferably, G1 is N and G2 is CH, or G1 is CH and G2 is N;

[0076] It is also preferred that when G1 and G2 are both N;

[0077] It is also preferred that when G1 and G2 are both CH;

[0078] Most preferably, G1 is CH and G2 is N;

[0079] Preferably, R2 is C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C4 haloalkylsulfonyl or C1-C4 haloalkylsulfonyloxy;

[0080] More preferably, R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3 or CF3;

[0081] Most preferably, R2 is CF2CF3 or CF3;

[0082] Preferably, A is N or CH;

[0083] Most preferably, A is N;

[0084] Preferably, X is S or SO2;

[0085] Most preferably, X is SO2;

[0086] Preferably, R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl;

[0087] More preferably, R1 is ethyl or cyclopropylmethyl;

[0088] Most preferably, R1 is ethyl;

[0089] Preferably, Q1 is hydrogen, halogen, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted by cyano, C1-C6 cyanoalkyl, C1-C6 haloalkoxy, -N(R4)2, -N(R4)COR5, -N(R4)CON(R4)2, (oxazolidin-2-one)-3-yl or 2-pyridyloxy;

[0090] It is also preferred that when Q1 is a five- to six-membered aromatic ring system (connected to the ring comprising the substituent A via a ring carbon atom), said ring system is unsubstituted or monosubstituted with a substituent selected from the group consisting of halogen and C1-C4 haloalkyl; and said ring system may contain 1 or 2 ring nitrogen atoms;

[0091] It is also preferred that when Q1 is a five-membered aromatic ring system (connected to the ring comprising substituent A via a ring nitrogen atom), said ring system is unsubstituted or monosubstituted with a substituent selected from the group consisting of halogen and C1-C4 haloalkyl; and said ring system comprises 2 or 3 ring nitrogen atoms.

[0092] More preferably, Q1 is hydrogen, halogen, trifluoromethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoroethoxy, (oxazolidin-2-one)-3-yl, 2-pyridyloxy, N-attached pyrazolyl which may be monosubstituted by chloro or trifluoromethyl, N-attached triazolyl, C-attached pyrimidinyl, -N(R4)2, -N(R4)COR5, or -N(R4)CON(R4)2, in each of which R4 is independently hydrogen or methyl and R5 is methyl, ethyl or cyclopropyl;

[0093] Most preferably, Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(H)CONH(CH3), -N(CH3)CONH(CH3), (oxazolidin-2-one)-3-yl, 2-pyridyloxy, pyrazol-1-yl, 3-chloro-pyrazol-1-yl, 3-trifluoromethyl-pyrazol-1-yl, 1,2,4-triazol-1-yl or pyrimidin-2-yl;

[0094] Preferably, each R4 is independently hydrogen or C1-C4 alkyl;

[0095] Most preferably, each R4 is independently hydrogen or methyl;

[0096] Preferably, R5 is C1-C6 alkyl or C3-C6 cycloalkyl;

[0097] More preferably, R5 is methyl, ethyl or cyclopropyl;

[0098] Most preferably, R5 is methyl;

[0099] Preferably, R3 is hydrogen or C1-C4 alkyl;

[0100] More preferably, R3 is hydrogen or methyl; and

[0101] Most preferably, R3 is hydrogen.

[0102] As described below, further embodiments according to the present invention are provided.

[0103] A preferred group of compounds having formula I is represented by compounds having formula I-A1

[0104]

[0105] wherein A, R1, R2, R3, X, Q1, R4 and R5 are as defined above under Formula I.

[0106] In a preferred group of compounds having formula I-A1, A is CH or N; R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkoxy, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; R3 is hydrogen or C1-C4 alkyl; X is S or SO2; Q1 is hydrogen, halogen, C1-C2 haloalkyl, C1-C2 haloalkoxy, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted by cyano, C1-C6 cyanoalkyl, C1-C6 haloalkoxy, -N(R4)2, -N(R4)COR5, -N(R4)CON(R4)2, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; wherein each R4 is independently hydrogen or C1-C4 alkyl; and R5 is C1-C6 alkyl or C3-C6 cycloalkyl.

[0107] In another preferred group of compounds having formula I-A1, A is CH or N; R1 is ethyl or cyclopropylmethyl; R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3 or CF3; R3 is hydrogen or methyl; X is S or SO2; and Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(H)CONH(CH3), -N(CH3)CONH(CH3), (oxazolidin-2-one)-3-yl, or 2-pyridyloxy.

[0108] In another further preferred group of compounds having formula I-A1, Q1 is a five- to six-membered aromatic ring system (attached to the ring containing substituent A via a ring carbon atom), said ring system being unsubstituted or monosubstituted with a substituent selected from the group consisting of halogen and C1-C4 haloalkyl; and said ring system may contain 1 or 2 ring nitrogen atoms. In this embodiment, more preferably, Q1 is a C-attached pyrimidinyl.

[0109] Also preferred compounds of formula I-A1 are those wherein Q is a five-membered aromatic ring system (connected to the ring containing substituent A via a ring nitrogen atom), the ring system being unsubstituted or monosubstituted with a substituent selected from the group consisting of halogen and C1-C4 haloalkyl; and the ring system comprising 2 or 3 ring nitrogen atoms. In this embodiment, more preferably, Q is N-attached pyrazolyl which may be monosubstituted with chloro or trifluoromethyl; or Q is N-attached triazolyl.

[0110] In the above-mentioned compounds of formula I-A1 and all preferred embodiments of compounds of formula I-A1, unless otherwise stated, A, R1, R2, R3, X, Q1, R4 and R5 are as defined above under formula I; preferably, A is CH or N, more preferably, A is N; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3 or CF3; most preferably, R2 is CF2CF3 or CF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R3 is hydrogen; preferably, Q1 is hydrogen, halogen, trifluoromethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoroethoxy, (oxazolidin-2-one)-3-yl, 2-pyridyloxy, N-linked pyrazolyl which may be monosubstituted with chloro or trifluoromethyl. More preferably, Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3) , -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(H)CONH(CH3), -N(CH3)CONH(CH3), (oxazolidin-2-one)-3-yl, 2-pyridyloxy, pyrazol-1-yl, 3-chloro-pyrazol-1-yl, 3-trifluoromethyl-pyrazol-1-yl, 1,2,4-triazol-1-yl or pyrimidin-2-yl.

[0111] A further preferred group of compounds according to this embodiment are compounds of formula (I-A1-1), which are compounds of formula (I-A1), wherein preferably, A is N; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is SO2CF3, -OCF3, CF2CF3 or CF3; most preferably, R2 is CF2CF3 or CF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R3 is hydrogen; preferably, Q Q1 is hydrogen, halogen, trifluoromethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, 2-pyridyloxy, N-attached pyrazolyl which may be monosubstituted by chloro or trifluoromethyl, or -N(R4)COR5, wherein R4 is hydrogen and R5 is methyl or ethyl; more preferably, Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -N(CH3)COCH3, 2-pyridyloxy, 3-chloro-pyrazol-1-yl or 3-trifluoromethyl-pyrazol-1-yl.

[0112] Another preferred group of compounds having formula I is represented by compounds having formula I-A2

[0113]

[0114] wherein A, R1, R2, R3, X, Q1, R4 and R5 are as defined above under Formula I.

[0115] In a preferred group of compounds having formula I-A2, A is CH or N; R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkoxy, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; R3 is hydrogen or C1-C4 alkyl; X is S or SO2; Q1 is hydrogen, halogen, C1-C2 haloalkyl, C1-C2 haloalkoxy, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted by cyano, C1-C6 cyanoalkyl, C1-C6 haloalkoxy, -N(R4)2, -N(R4)COR5, -N(R4)CON(R4)2, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; wherein each R4 is independently hydrogen or C1-C4 alkyl; and R5 is C1-C6 alkyl or C3-C6 cycloalkyl.

[0116] In another preferred group of compounds having formula I-A2, A is CH or N; R1 is ethyl or cyclopropylmethyl; R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3 or CF3; R3 is hydrogen or methyl; X is S or SO2; and Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(H)CONH(CH3), -N(CH3)CONH(CH3), (oxazolidin-2-one)-3-yl, or 2-pyridyloxy.

[0117] In another further preferred group of compounds having formula I-A2, Q1 is a five- to six-membered aromatic ring system (attached to the ring comprising substituent A via a ring carbon atom), said ring system being unsubstituted or monosubstituted with a substituent selected from the group consisting of halogen and C1-C4 haloalkyl; and said ring system may comprise 1 or 2 ring nitrogen atoms. In this embodiment, more preferably, Q1 is a C-attached pyrimidinyl.

[0118] Also preferred compounds of formula I-A2 are those wherein Q is a five-membered aromatic ring system (connected to the ring containing substituent A via a ring nitrogen atom), the ring system being unsubstituted or monosubstituted with a substituent selected from the group consisting of halogen and C1-C4 haloalkyl; and the ring system comprising 2 or 3 ring nitrogen atoms. In this embodiment, more preferably, Q is N-attached pyrazolyl which may be monosubstituted with chloro or trifluoromethyl; or Q is N-attached triazolyl.

[0119] In the above-mentioned compounds of formula I-A2 and all preferred embodiments of compounds of formula I-A2, unless otherwise stated, A, R1, R2, R3, X, Q1, R4 and R5 are as defined above under formula I; preferably, A is CH or N, more preferably, A is N; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3 or CF3; most preferably, R2 is CF2CF3 or CF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R3 is hydrogen; preferably, Q1 is hydrogen, halogen, trifluoromethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoroethoxy, (oxazolidin-2-one)-3-yl, 2-pyridyloxy, N-linked pyrazolyl which may be monosubstituted with chloro or trifluoromethyl. More preferably, Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3) , -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(H)CONH(CH3), -N(CH3)CONH(CH3), (oxazolidin-2-one)-3-yl, 2-pyridyloxy, pyrazol-1-yl, 3-chloro-pyrazol-1-yl, 3-trifluoromethyl-pyrazol-1-yl, 1,2,4-triazol-1-yl or pyrimidin-2-yl.

[0120] A further preferred group of compounds according to this embodiment are compounds of formula (I-A2-1), which are compounds of formula (I-A2), wherein preferably, A is N; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is SO2CF3, -OCF3, CF2CF3 or CF3; most preferably, R2 is CF2CF3 or CF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R3 is hydrogen; preferably, Q1 is hydrogen, cyclopropyl, N-linked triazolyl, C-linked pyrimidinyl, -N(R4)2, -N(R4)COR5, or -N(R4)CON(R4)2, in each of which R4 is independently hydrogen or methyl and R5 is methyl, ethyl or cyclopropyl; more preferably, Q1 is hydrogen, cyclopropyl, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(CH3)CONH(CH3), 1,2,4-triazol-1-yl or pyrimidin-2-yl.

[0121] Another preferred group of compounds having formula I is represented by compounds having formula I-B1

[0122]

[0123] wherein A, R1, R2, R3, X, Q1, R4 and R5 are as defined above under Formula I.

[0124] In a preferred group of compounds having formula I-B1, A is CH or N; R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkoxy, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; R3 is hydrogen or C1-C4 alkyl; X is S or SO2; Q1 is hydrogen, halogen, C1-C2 haloalkyl, C1-C2 haloalkoxy, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted by cyano, C1-C6 cyanoalkyl, C1-C6 haloalkoxy, -N(R4)2, -N(R4)COR5, -N(R4)CON(R4)2, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; wherein each R4 is independently hydrogen or C1-C4 alkyl; and R5 is C1-C6 alkyl or C3-C6 cycloalkyl.

[0125] In another preferred group of compounds having formula I-B1, A is CH or N; R1 is ethyl or cyclopropylmethyl; R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3 or CF3; R3 is hydrogen or methyl; X is S or SO2; and Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(H)CONH(CH3), -N(CH3)CONH(CH3), (oxazolidin-2-one)-3-yl, or 2-pyridyloxy.

[0126] In another further preferred group of compounds of formula I-B1, Q1 is a five- to six-membered aromatic ring system (attached to the ring comprising substituent A via a ring carbon atom), said ring system being unsubstituted or monosubstituted with a substituent selected from the group consisting of halogen and C1-C4 haloalkyl; and said ring system may comprise 1 or 2 ring nitrogen atoms. In this embodiment, more preferably, Q1 is a C-attached pyrimidinyl.

[0127] Also preferred compounds of formula I-B1 are those wherein Q is a five-membered aromatic ring system (connected to the ring containing substituent A via a ring nitrogen atom), the ring system being unsubstituted or monosubstituted with a substituent selected from the group consisting of halogen and C1-C4 haloalkyl; and the ring system comprising 2 or 3 ring nitrogen atoms. In this embodiment, more preferably, Q is N-attached pyrazolyl which may be monosubstituted with chloro or trifluoromethyl; or Q is N-attached triazolyl.

[0128] In the above-mentioned compounds of formula I-B1 and all preferred embodiments of compounds of formula I-B1, unless otherwise stated, A, R1, R2, R3, X, Q1, R4 and R5 are as defined above under formula I; preferably, A is CH or N, more preferably, A is N; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3 or CF3; most preferably, R2 is CF2CF3 or CF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R3 is hydrogen; preferably, Q1 is hydrogen, halogen, trifluoromethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoroethoxy, (oxazolidin-2-one)-3-yl, 2-pyridyloxy, N-linked pyrazolyl which may be monosubstituted with chloro or trifluoromethyl. More preferably, Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3) , -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(H)CONH(CH3), -N(CH3)CONH(CH3), (oxazolidin-2-one)-3-yl, 2-pyridyloxy, pyrazol-1-yl, 3-chloro-pyrazol-1-yl, 3-trifluoromethyl-pyrazol-1-yl, 1,2,4-triazol-1-yl or pyrimidin-2-yl.

[0129] A further preferred group of compounds according to this embodiment are compounds of formula (I-B1-1), which are compounds of formula (I-B1), wherein preferably, A is N; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is SO2CF3, -OCF3, CF2CF3 or CF3; most preferably, R2 is CF2CF3 or CF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R3 is hydrogen; preferably, Q Q1 is hydrogen, halogen, trifluoromethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, 2-pyridyloxy, N-attached pyrazolyl which may be monosubstituted by chloro or trifluoromethyl, or -N(R4)COR5, wherein R4 is hydrogen and R5 is methyl or ethyl; more preferably, Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -N(CH3)COCH3, 2-pyridyloxy, 3-chloro-pyrazol-1-yl or 3-trifluoromethyl-pyrazol-1-yl.

[0130] Another preferred group of compounds according to this embodiment are compounds of formula (I-B1-2), which are compounds of formula (I-B1), wherein preferably, A is N; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is SO2CF3, -OCF3, CF2CF3 or CF3; most preferably, R2 is CF2CF3 or CF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R3 is hydrogen; preferably, Q1 is hydrogen, halogen, trifluoromethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, 2-pyridyloxy, N-attached pyrazolyl which may be monosubstituted by chloro or trifluoromethyl, or -N(R4)COR5, wherein R4 is hydrogen and R5 is methyl or ethyl; more preferably, Q1 is hydrogen, 1-cyanocyclopropyl or 1-cyano-1-methyl-ethyl.

[0131] Another preferred group of compounds having formula I is represented by compounds having formula I-B2

[0132]

[0133] wherein A, R1, R2, R3, X, Q1, R4 and R5 are as defined above under Formula I.

[0134] In a preferred group of compounds having formula I-B2, A is CH or N; R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkoxy, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; R3 is hydrogen or C1-C4 alkyl; X is S or SO2; Q1 is hydrogen, halogen, C1-C2 haloalkyl, C1-C2 haloalkoxy, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted by cyano, C1-C6 cyanoalkyl, C1-C6 haloalkoxy, -N(R4)2, -N(R4)COR5, -N(R4)CON(R4)2, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; wherein each R4 is independently hydrogen or C1-C4 alkyl; and R5 is C1-C6 alkyl or C3-C6 cycloalkyl.

[0135] In another preferred group of compounds having formula I-B2, A is CH or N; R1 is ethyl or cyclopropylmethyl; R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3 or CF3; R3 is hydrogen or methyl; X is S or SO2; and Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(H)CONH(CH3), -N(CH3)CONH(CH3), (oxazolidin-2-one)-3-yl, or 2-pyridyloxy.

[0136] In another further preferred group of compounds having formula I-B2, Q1 is a five- to six-membered aromatic ring system (attached to the ring comprising substituent A via a ring carbon atom), said ring system being unsubstituted or monosubstituted with a substituent selected from the group consisting of halogen and C1-C4 haloalkyl; and said ring system may comprise 1 or 2 ring nitrogen atoms. In this embodiment, more preferably, Q1 is a C-attached pyrimidinyl.

[0137] Also preferred compounds of formula I-B2 are those wherein Q is a five-membered aromatic ring system (connected to the ring containing substituent A via a ring nitrogen atom), the ring system being unsubstituted or monosubstituted with a substituent selected from the group consisting of halogen and C1-C4 haloalkyl; and the ring system comprising 2 or 3 ring nitrogen atoms. In this embodiment, more preferably, Q is N-attached pyrazolyl which may be monosubstituted with chloro or trifluoromethyl; or Q is N-attached triazolyl.

[0138] In the above-mentioned compounds of formula I-B2 and all preferred embodiments of compounds of formula I-B2, unless otherwise stated, A, R1, R2, R 3、 X, Q 1、R4 and R5 are as defined above under Formula I; preferably, A is CH or N, more preferably, A is N; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3 or CF3; most preferably, R2 is CF2CF3 or CF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R3 is hydrogen; preferably, Q1 is hydrogen, halogen, trifluoromethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoroethoxy, (oxazolidin-2-one)-3-yl, 2-pyridyloxy, N-attached pyrazolyl which may be monosubstituted by chloro or trifluoromethyl, N-attached triazolyl, C-attached pyrimidinyl, -N(R4)2, -N(R 4) COR5, or -N(R4)CON(R4)2, in each of which R4 is independently hydrogen or methyl and R5 is methyl, ethyl or cyclopropyl; more preferably, Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(H)CONH(CH3), -N(CH3)CONH(CH3), (oxazolidin-2-one)-3-yl, 2-pyridyloxy, pyrazol-1-yl, 3-chloro-pyrazol-1-yl, 3-trifluoromethyl-pyrazol-1-yl, 1,2,4-triazol-1-yl or pyrimidin-2-yl.

[0139] A further preferred group of compounds according to this embodiment are compounds of formula (I-B2-1), which are compounds of formula (I-B2), wherein preferably, A is N; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is SO2CF3, -OCF3, CF2CF3 or CF3; most preferably, R2 is CF2CF3 or CF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R3 is hydrogen; preferably, Q1 is hydrogen, cyclopropyl, N-linked triazolyl, C-linked pyrimidinyl, -N(R4)2, -N(R4)COR5, or -N(R4)CON(R4)2, in each of which R4 is independently hydrogen or methyl and R5 is methyl, ethyl or cyclopropyl; more preferably, Q1 is hydrogen, cyclopropyl, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(CH3)CONH(CH3), 1,2,4-triazol-1-yl or pyrimidin-2-yl.

[0140] Another preferred group of compounds having formula I is represented by compounds having formula I-C1

[0141]

[0142] wherein A, R1, R2, R3, X, Q1, R4 and R5 are as defined above under Formula I.

[0143] In a preferred group of compounds having formula I-C1, A is CH or N; R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkoxy, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; R3 is hydrogen or C1-C4 alkyl; X is S or SO2; Q1 is hydrogen, halogen, C1-C2 haloalkyl, C1-C2 haloalkoxy, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted by cyano, C1-C6 cyanoalkyl, C1-C6 haloalkoxy, -N(R4)2, -N(R4)COR5, -N(R4)CON(R4)2, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; wherein each R4 is independently hydrogen or C1-C4 alkyl; and R5 is C1-C6 alkyl or C3-C6 cycloalkyl.

[0144] In another preferred group of compounds having formula I-C1, A is CH or N; R1 is ethyl or cyclopropylmethyl; R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3 or CF3; R3 is hydrogen or methyl; X is S or SO2; and Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(H)CONH(CH3), -N(CH3)CONH(CH3), (oxazolidin-2-one)-3-yl, or 2-pyridyloxy.

[0145] In another further preferred group of compounds of formula I-C1, Q1 is a five- to six-membered aromatic ring system (attached to the ring comprising substituent A via a ring carbon atom), said ring system being unsubstituted or monosubstituted with a substituent selected from the group consisting of halogen and C1-C4 haloalkyl; and said ring system may comprise 1 or 2 ring nitrogen atoms. In this embodiment, more preferably, Q1 is a C-attached pyrimidinyl.

[0146] Also preferred compounds of formula I-C1 are those wherein Q is a five-membered aromatic ring system (attached to the ring containing substituent A via a ring nitrogen atom), said ring system being unsubstituted or monosubstituted with a substituent selected from the group consisting of halogen and C1-C4 haloalkyl; and said ring system comprising 2 or 3 ring nitrogen atoms. In this embodiment, more preferably, Q is N-attached pyrazolyl which may be monosubstituted with chloro or trifluoromethyl; or Q is N-attached triazolyl.

[0147] In the above-mentioned compounds of formula I-C1 and all preferred embodiments of compounds of formula I-C1, unless otherwise stated, A, R1, R2, R3, X, Q1, R4 and R5 are as defined above under formula I; preferably, A is CH or N, more preferably, A is N; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3 or CF3; most preferably, R2 is CF2CF3 or CF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R3 is hydrogen; preferably, Q1 is hydrogen, halogen, trifluoromethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoroethoxy, (oxazolidin-2-one)-3-yl, 2-pyridyloxy, N-linked pyrazolyl which may be monosubstituted with chloro or trifluoromethyl. More preferably, Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3) , -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(H)CONH(CH3), -N(CH3)CONH(CH3), (oxazolidin-2-one)-3-yl, 2-pyridyloxy, pyrazol-1-yl, 3-chloro-pyrazol-1-yl, 3-trifluoromethyl-pyrazol-1-yl, 1,2,4-triazol-1-yl or pyrimidin-2-yl.

[0148] A further preferred group of compounds according to this embodiment are compounds of formula (I-C1-1), which are compounds of formula (I-C1), wherein preferably, A is N; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is SO2CF3, -OCF3, CF2CF3 or CF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R3 is hydrogen; preferably, Q1 is hydrogen, halogen, trifluoromethane, or thiocyanate; Methyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, 2-pyridyloxy, N-attached pyrazolyl which may be monosubstituted by chloro or trifluoromethyl, or -N(R4)COR5, wherein R4 is hydrogen and R5 is methyl or ethyl; more preferably, Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -N(CH3)COCH3, 2-pyridyloxy, 3-chloro-pyrazol-1-yl or 3-trifluoromethyl-pyrazol-1-yl.

[0149] Another preferred group of compounds according to this embodiment are compounds of formula (I-C1-2), which are compounds of formula (I-C1), wherein preferably, A is N; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is SO2CF3, -OCF3, CF2CF3 or CF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R3 is hydrogen; preferably, Q1 is hydrogen, halogen, trifluoromethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, 2-pyridyloxy, N-linked pyrazolyl which may be monosubstituted by chloro or trifluoromethyl, or -N(R4)COR5, wherein R4 is hydrogen and R5 is methyl or ethyl; more preferably, Q1 is hydrogen or 1-cyanocyclopropyl.

[0150] Another preferred group of compounds having formula I is represented by compounds having formula I-C2

[0151]

[0152] wherein A, R1, R2, R3, X, Q1, R4 and R5 are as defined above under Formula I.

[0153] In a preferred group of compounds having formula I-C2, A is CH or N; R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkoxy, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; R3 is hydrogen or C1-C4 alkyl; X is S or SO2; Q1 is hydrogen, halogen, C1-C2 haloalkyl, C1-C2 haloalkoxy, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted by cyano, C1-C6 cyanoalkyl, C1-C6 haloalkoxy, -N(R4)2, -N(R4)COR5, -N(R4)CON(R4)2, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; wherein each R4 is independently hydrogen or C1-C4 alkyl; and R5 is C1-C6 alkyl or C3-C6 cycloalkyl.

[0154] In another preferred group of compounds having formula I-C2, A is CH or N; R1 is ethyl or cyclopropylmethyl; R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3 or CF3; R3 is hydrogen or methyl; X is S or SO2; and Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(H)CONH(CH3), -N(CH3)CONH(CH3), (oxazolidin-2-one)-3-yl, or 2-pyridyloxy.

[0155] In another further preferred group of compounds having formula I-C2, Q1 is a five- to six-membered aromatic ring system (attached to the ring comprising substituent A via a ring carbon atom), said ring system being unsubstituted or monosubstituted with a substituent selected from the group consisting of halogen and C1-C4 haloalkyl; and said ring system may comprise 1 or 2 ring nitrogen atoms. In this embodiment, more preferably, Q1 is a C-attached pyrimidinyl.

[0156] Also preferred compounds of formula I-C2 are those wherein Q is a five-membered aromatic ring system (connected to the ring containing substituent A via a ring nitrogen atom), said ring system being unsubstituted or monosubstituted with a substituent selected from the group consisting of halogen and C1-C4 haloalkyl; and said ring system comprising 2 or 3 ring nitrogen atoms. In this embodiment, more preferably, Q is N-attached pyrazolyl which may be monosubstituted with chloro or trifluoromethyl; or Q is N-attached triazolyl.

[0157] In the above-mentioned compounds of formula I-C2 and all preferred embodiments of compounds of formula I-C2, unless otherwise stated, A, R1, R2, R3, X, Q1, R4 and R5 are as defined above under formula I; preferably, A is CH or N, more preferably, A is N; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3 or CF3; most preferably, R2 is CF2CF3 or CF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R3 is hydrogen; preferably, Q1 is hydrogen, halogen, trifluoromethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoroethoxy, (oxazolidin-2-one)-3-yl, 2-pyridyloxy, N-linked pyrazolyl which may be monosubstituted by chloro or trifluoromethyl. More preferably, Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3) , -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(H)CONH(CH3), -N(CH3)CONH(CH3), (oxazolidin-2-one)-3-yl, 2-pyridyloxy, pyrazol-1-yl, 3-chloro-pyrazol-1-yl, 3-trifluoromethyl-pyrazol-1-yl, 1,2,4-triazol-1-yl or pyrimidin-2-yl.

[0158] A further preferred group of compounds according to this embodiment are compounds of formula (I-C2-1), which are compounds of formula (I-C2), wherein preferably, A is N; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is SO2CF3, -OCF3, CF2CF3 or CF3; most preferably, R2 is CF2CF3 or CF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R3 is hydrogen; preferably, Q1 is hydrogen, cyclopropyl, N-linked triazolyl, C-linked pyrimidinyl, -N(R4)2, -N(R4)COR5, or -N(R4)CON(R4)2, in each of which R4 is independently hydrogen or methyl and R5 is methyl, ethyl or cyclopropyl; more preferably, Q1 is hydrogen, cyclopropyl, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(CH3)CONH(CH3), 1,2,4-triazol-1-yl or pyrimidin-2-yl.

[0159] Another preferred group of compounds having formula I is represented by compounds having formula I-D1

[0160]

[0161] wherein A, R1, R2, R3, X, Q1, R4 and R5 are as defined above under Formula I.

[0162] In a preferred group of compounds having formula I-D1, A is CH or N; R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkoxy, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; R3 is hydrogen or C1-C4 alkyl; X is S or SO2; Q1 is hydrogen, halogen, C1-C2 haloalkyl, C1-C2 haloalkoxy, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted by cyano, C1-C6 cyanoalkyl, C1-C6 haloalkoxy, -N(R4)2, -N(R4)COR5, -N(R4)CON(R4)2, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; wherein each R4 is independently hydrogen or C1-C4 alkyl; and R5 is C1-C6 alkyl or C3-C6 cycloalkyl.

[0163] In another preferred group of compounds having formula I-D1, A is CH or N; R1 is ethyl or cyclopropylmethyl; R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3 or CF3; R3 is hydrogen or methyl; X is S or SO2; and Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(H)CONH(CH3), -N(CH3)CONH(CH3), (oxazolidin-2-one)-3-yl, or 2-pyridyloxy.

[0164] In another further preferred group of compounds having formula I-D1, Q1 is a five- to six-membered aromatic ring system (attached to the ring comprising substituent A via a ring carbon atom), said ring system being unsubstituted or monosubstituted with a substituent selected from the group consisting of halogen and C1-C4 haloalkyl; and said ring system may comprise 1 or 2 ring nitrogen atoms. In this embodiment, more preferably, Q1 is a C-attached pyrimidinyl.

[0165] Also preferred compounds of formula I-D1 are those wherein Q1 is a five-membered aromatic ring system (attached to the ring comprising substituent A via a ring nitrogen atom), said ring system being unsubstituted or monosubstituted with a substituent selected from the group consisting of halogen and C1-C4 haloalkyl; and said ring system comprising 2 or 3 ring nitrogen atoms. In this embodiment, more preferably, Q1 is an N-attached pyrazolyl group which may be monosubstituted with chloro or trifluoromethyl; or Q1 is an N-attached triazolyl group.

[0166] In the above-mentioned compounds of formula I-D1 and all preferred embodiments of compounds of formula I-D1, unless otherwise stated, A, R1, R2, R3, X, Q1, R4 and R5 are as defined above under formula I; preferably, A is CH or N, more preferably, A is N; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3 or CF3; most preferably, R2 is CF2CF3 or CF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R3 is hydrogen; preferably, Q1 is hydrogen, halogen, trifluoromethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoroethoxy, (oxazolidin-2-one)-3-yl, 2-pyridyloxy, N-linked pyrazolyl which may be monosubstituted with chloro or trifluoromethyl. More preferably, Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3) , -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(H)CONH(CH3), -N(CH3)CONH(CH3), (oxazolidin-2-one)-3-yl, 2-pyridyloxy, pyrazol-1-yl, 3-chloro-pyrazol-1-yl, 3-trifluoromethyl-pyrazol-1-yl, 1,2,4-triazol-1-yl or pyrimidin-2-yl.

[0167] A further preferred group of compounds according to this embodiment are compounds of formula (I-D1-1), which are compounds of formula (I-D1), wherein preferably, A is N; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is SO2CF3, -OCF3, CF2CF3 or CF3; most preferably, R2 is CF2CF3 or CF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R3 is hydrogen; preferably, Q Q1 is hydrogen, halogen, trifluoromethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, 2-pyridyloxy, N-attached pyrazolyl which may be monosubstituted by chloro or trifluoromethyl, or -N(R4)COR5, wherein R4 is hydrogen and R5 is methyl or ethyl; more preferably, Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -N(CH3)COCH3, 2-pyridyloxy, 3-chloro-pyrazol-1-yl or 3-trifluoromethyl-pyrazol-1-yl.

[0168] Another preferred group of compounds according to this embodiment are compounds of formula (I-D1-2), which are compounds of formula (I-D1), wherein preferably, A is N; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is SO2CF3, -OCF3, CF2CF3 or CF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R3 is hydrogen; preferably, Q1 is hydrogen, halogen, trifluoromethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, 2-pyridyloxy, N-linked pyrazolyl which may be monosubstituted by chloro or trifluoromethyl, or -N(R4)COR5, wherein R4 is hydrogen and R5 is methyl or ethyl; more preferably, Q1 is hydrogen or 1-cyanocyclopropyl.

[0169] Another preferred group of compounds having formula I is represented by compounds having formula I-D2

[0170]

[0171] wherein A, R1, R2, R3, X, Q1, R4 and R5 are as defined above under Formula I.

[0172] In a preferred group of compounds having formula I-D2, A is CH or N; R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkoxy, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; R3 is hydrogen or C1-C4 alkyl; X is S or SO2; Q1 is hydrogen, halogen, C1-C2 haloalkyl, C1-C2 haloalkoxy, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted by cyano, C1-C6 cyanoalkyl, C1-C6 haloalkoxy, -N(R4)2, -N(R4)COR5, -N(R4)CON(R4)2, (oxazolidin-2-one)-3-yl or 2-pyridyloxy; wherein each R4 is independently hydrogen or C1-C4 alkyl; and R5 is C1-C6 alkyl or C3-C6 cycloalkyl.

[0173] In another preferred group of compounds having formula I-D2, A is CH or N; R1 is ethyl or cyclopropylmethyl; R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3 or CF3; R3 is hydrogen or methyl; X is S or SO2; and Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(H)CONH(CH3), -N(CH3)CONH(CH3), (oxazolidin-2-one)-3-yl, or 2-pyridyloxy.

[0174] In another further preferred group of compounds having formula I-D2, Q1 is a five- to six-membered aromatic ring system (attached to the ring comprising substituent A via a ring carbon atom), said ring system being unsubstituted or monosubstituted with a substituent selected from the group consisting of halogen and C1-C4 haloalkyl; and said ring system may comprise 1 or 2 ring nitrogen atoms. In this embodiment, more preferably, Q1 is a C-attached pyrimidinyl.

[0175] Also preferred compounds of formula I-D2 are those wherein Q is a five-membered aromatic ring system (attached to the ring comprising substituent A via a ring nitrogen atom), said ring system being unsubstituted or monosubstituted with a substituent selected from the group consisting of halogen and C1-C4 haloalkyl; and said ring system comprising 2 or 3 ring nitrogen atoms. In this embodiment, more preferably, Q is N-attached pyrazolyl which may be monosubstituted with chloro or trifluoromethyl; or Q is N-attached triazolyl.

[0176] In the above-mentioned compounds of formula I-D2 and all preferred embodiments of compounds of formula I-D2, unless otherwise stated, A, R1, R2, R3, X, Q1, R4 and R5 are as defined above under formula I; preferably, A is CH or N, more preferably, A is N; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3 or CF3; most preferably, R2 is CF2CF3 or CF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R3 is hydrogen; preferably, Q1 is hydrogen, halogen, trifluoromethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoroethoxy, (oxazolidin-2-one)-3-yl, 2-pyridyloxy, N-linked pyrazolyl which may be monosubstituted by chloro or trifluoromethyl. More preferably, Q1 is hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3) , -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(H)CONH(CH3), -N(CH3)CONH(CH3), (oxazolidin-2-one)-3-yl, 2-pyridyloxy, pyrazol-1-yl, 3-chloro-pyrazol-1-yl, 3-trifluoromethyl-pyrazol-1-yl, 1,2,4-triazol-1-yl or pyrimidin-2-yl.

[0177] A further preferred group of compounds according to this embodiment are compounds of formula (I-D2-1), which are compounds of formula (I-D2), wherein preferably, A is N; preferably, R1 is ethyl or cyclopropylmethyl; most preferably, R1 is ethyl; preferably, R2 is SO2CF3, -OCF3, CF2CF3 or CF3; most preferably, R2 is CF2CF3 or CF3; preferably, X is S or SO2; most preferably, X is SO2; preferably, R3 is hydrogen; preferably, Q1 is hydrogen, cyclopropyl, N-linked triazolyl, C-linked pyrimidinyl, -N(R4)2, -N(R4)COR5, or -N(R4)CON(R4)2, in each of which R4 is independently hydrogen or methyl and R5 is methyl, ethyl or cyclopropyl; more preferably, Q1 is hydrogen, cyclopropyl, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(CH3)CONH(CH3), 1,2,4-triazol-1-yl or pyrimidin-2-yl.

[0178] An outstanding group of compounds according to the invention are those having the formula IE

[0179]

[0180] in

[0181] G1 and G2 are independently CH or N;

[0182] R2 is C1-C6 haloalkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C1-C6 haloalkoxy, preferably CF3, CF2CF3, SCF3, SOCF3, SO2CF3 or OCF3;

[0183] Q is a group selected from the group consisting of: Formula Qa1 and Qb1

[0184]

[0185] wherein the arrow indicates the point of attachment to the nitrogen atom of the bicyclic ring;

[0186] And among them

[0187] X is S, SO, or SO2, preferably S or SO2, even more preferably SO2;

[0188] R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl, preferably ethyl or cyclopropylmethyl;

[0189] Q1 is hydrogen, halogen, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted by cyano, C1-C6 cyanoalkyl, -N(R4)2, -N(R4)C(=O)R5, -N(R4)CON(R4)2, or 2-pyridyloxy; preferably, Q1 is hydrogen, chlorine, bromine, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(CH3)CONH(CH3), or 2-pyridyloxy; or

[0190] Q1 is unsubstituted pyrimidinyl, preferably pyrimidin-2-yl; or

[0191] Q1 is unsubstituted N-linked triazolyl, preferably 1,2,4-triazol-1-yl; or

[0192] Q1 is an N-attached pyrazolyl group which may be monosubstituted by chloro or trifluoromethyl; preferably, Q1 is 3-chloro-pyrazol-1-yl or 3-trifluoromethyl-pyrazol-1-yl;

[0193] Each R4 is independently hydrogen or C1-C4 alkyl, preferably hydrogen or methyl; and

[0194] R5 is C1-C6 alkyl or C3-C6 cycloalkyl, preferably methyl or cyclopropyl.

[0195] A further outstanding group of compounds according to this embodiment are compounds of formula (I-E1), which are compounds of formula (IE), wherein

[0196] G1 and G2 are independently CH or N;

[0197] R2 is C1-C6 haloalkyl, C1-C4 haloalkylsulfonyl or C1-C6 haloalkoxy, preferably CF3, CF2CF3, SO2CF3 or OCF3;

[0198] Q is a group selected from the group consisting of: formula Qa1 and Qb1, wherein

[0199] X is SO2;

[0200] R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl, preferably ethyl or cyclopropylmethyl;

[0201] Q1 is hydrogen, halogen, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted by cyano, C1-C6 cyanoalkyl, -N(R4)2, -N(R4)C(=O)R5, -N(R4)CON(R4)2, or 2-pyridyloxy; preferably, Q1 is hydrogen, chlorine, bromine, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(CH3)CONH(CH3), or 2-pyridyloxy; or

[0202] Q1 is unsubstituted pyrimidinyl, preferably pyrimidin-2-yl; or

[0203] Q1 is unsubstituted N-linked triazolyl, preferably 1,2,4-triazol-1-yl; or

[0204] Q1 is N-linked pyrazolyl, which is monosubstituted by chloro or trifluoromethyl; preferably, Q1 is 3-chloro-pyrazol-1-yl or 3-trifluoromethyl-pyrazol-1-yl;

[0205] Each R4 is independently hydrogen or C1-C4 alkyl, preferably hydrogen or methyl; and

[0206] R5 is C1-C6 alkyl or C3-C6 cycloalkyl, preferably methyl or cyclopropyl.

[0207] A further outstanding group of compounds according to this embodiment are compounds of formula (I-E2), which are compounds of formula (IE), wherein

[0208] G1 and G2 are independently CH or N;

[0209] R2 is CF3, SO2CF3 or OCF3;

[0210] Q is a group selected from the group consisting of: formula Qa1 and Qb1, wherein

[0211] X is SO2;

[0212] R1 is ethyl or cyclopropylmethyl; and

[0213] Q1 is hydrogen, chloro, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(CH3)CONH(CH3), 2-pyridyloxy, pyrimidin-2-yl, 1,2,4-triazol-1-yl, 3-chloro-pyrazol-1-yl or 3-trifluoromethyl-pyrazol-1-yl.

[0214] Another outstanding group of compounds according to the invention are those having the formula IF

[0215]

[0216] in

[0217] G1 and G2 are independently CH or N;

[0218] R2 is C1-C6 haloalkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C1-C6 haloalkoxy, preferably CF3, CF2CF3, SCF3, SOCF3, SO2CF3 or OCF3;

[0219] Q is a group selected from the group consisting of: formula Qa2 and Qb2

[0220]

[0221] wherein the arrow indicates the point of attachment to the nitrogen atom of the bicyclic ring;

[0222] And among them

[0223] Q1 is hydrogen, halogen, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted by cyano, C1-C6 cyanoalkyl, -N(R4)2, -N(R4)C(=O)R5, -N(R4)CON(R4)2, or 2-pyridyloxy; preferably, Q1 is hydrogen, chlorine, bromine, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(CH3)CONH(CH3), or 2-pyridyloxy; or

[0224] Q1 is unsubstituted pyrimidinyl, preferably pyrimidin-2-yl; or

[0225] Q1 is unsubstituted N-linked triazolyl, preferably 1,2,4-triazol-1-yl; or

[0226] Q1 is an N-attached pyrazolyl group which may be monosubstituted by chloro or trifluoromethyl; preferably, Q1 is 3-chloro-pyrazol-1-yl or 3-trifluoromethyl-pyrazol-1-yl;

[0227] Each R4 is independently hydrogen or C1-C4 alkyl, preferably hydrogen or methyl; and

[0228] R5 is C1-C6 alkyl or C3-C6 cycloalkyl, preferably methyl or cyclopropyl.

[0229] A further outstanding group of compounds according to this embodiment are compounds of formula (I-F1), which are compounds of formula (IF), wherein

[0230] G1 and G2 are independently CH or N;

[0231] R2 is C1-C6 haloalkyl, C1-C4 haloalkylsulfonyl or C1-C6 haloalkoxy, preferably CF3, CF2CF3, SO2CF3 or OCF3;

[0232] Q is a group selected from the group consisting of: formula Qa2 and Qb2, wherein

[0233] Q1 is hydrogen, halogen, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted by cyano, C1-C6 cyanoalkyl, -N(R4)2, -N(R4)C(=O)R5, -N(R4)CON(R4)2, or 2-pyridyloxy; preferably, Q1 is hydrogen, chlorine, bromine, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(CH3)CONH(CH3), or 2-pyridyloxy; or

[0234] Q1 is unsubstituted pyrimidinyl, preferably pyrimidin-2-yl; or

[0235] Q1 is unsubstituted N-linked triazolyl, preferably 1,2,4-triazol-1-yl; or

[0236] Q1 is N-linked pyrazolyl, which is monosubstituted by chloro or trifluoromethyl; preferably, Q1 is 3-chloro-pyrazol-1-yl or 3-trifluoromethyl-pyrazol-1-yl;

[0237] Each R4 is independently hydrogen or C1-C4 alkyl, preferably hydrogen or methyl; and

[0238] R5 is C1-C6 alkyl or C3-C6 cycloalkyl, preferably methyl or cyclopropyl.

[0239] A further outstanding group of compounds according to this embodiment are compounds of formula (I-F2), which are compounds of formula (IF), wherein

[0240] G1 and G2 are independently CH or N;

[0241] R2 is CF3, SO2CF3 or OCF3;

[0242] Q is a group selected from the group consisting of: formula Qa2 and Qb2, wherein

[0243] Q1 is hydrogen, chloro, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(CH3)CONH(CH3), 2-pyridyloxy, pyrimidin-2-yl, 1,2,4-triazol-1-yl, 3-chloro-pyrazol-1-yl or 3-trifluoromethyl-pyrazol-1-yl.

[0244] A further outstanding group of compounds according to this embodiment are compounds of formula (I-F3), which are compounds of formula (IF), wherein

[0245] G1 is CH;

[0246] G2 is N;

[0247] R2 is C1-C6 haloalkyl, C1-C4 haloalkylsulfonyl or C1-C6 haloalkoxy, preferably CF3, CF2CF3, SO2CF3 or OCF3;

[0248] Q is a group selected from the group consisting of: formula Qa2 and Qb2, wherein

[0249] Q1 is hydrogen, halogen, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted by cyano, C1-C6 cyanoalkyl, -N(R4)2, -N(R4)C(=O)R5, -N(R4)CON(R4)2, or 2-pyridyloxy; preferably, Q1 is hydrogen, chlorine, bromine, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(CH3)CONH(CH3), or 2-pyridyloxy; or

[0250] Q1 is unsubstituted pyrimidinyl, preferably pyrimidin-2-yl; or

[0251] Q1 is unsubstituted N-linked triazolyl, preferably 1,2,4-triazol-1-yl; or

[0252] Q1 is N-linked pyrazolyl, which is monosubstituted by chloro or trifluoromethyl; preferably, Q1 is 3-chloro-pyrazol-1-yl or 3-trifluoromethyl-pyrazol-1-yl;

[0253] Each R4 is independently hydrogen or C1-C4 alkyl, preferably hydrogen or methyl; and

[0254] R5 is C1-C6 alkyl or C3-C6 cycloalkyl, preferably methyl or cyclopropyl.

[0255] Another outstanding group of compounds according to this embodiment are compounds of formula (I-F4), which are compounds of formula (IF), wherein

[0256] G1 is CH;

[0257] G2 is N;

[0258] R2 is C1-C6 haloalkyl, C1-C4 haloalkylsulfonyl or C1-C6 haloalkoxy, preferably CF3, CF2CF3, SO2CF3 or OCF3;

[0259] Q is a group selected from the group consisting of: formula Qa2 and Qb2, wherein

[0260] Q1 is hydrogen, halogen, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted by cyano, C1-C6 cyanoalkyl, -N(R4)C(=O)R5, 2-pyridyloxy, or N-attached pyrazolyl monosubstituted by chloro or trifluoromethyl, and when Q is Qa2, preferably hydrogen, bromo, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, -N(CH3)COCH3, 2-pyridyloxy, 3-chloro-pyrazol-1-yl or 3-trifluoromethyl-pyrazol-1-yl; or

[0261] Q1 is hydrogen, halogen, C3-C6 cycloalkyl, -N(R4)2, -N(R4)C(=O)R5, -N(R4)CON(R4)2, unsubstituted pyrimidinyl, or unsubstituted N-attached triazolyl, and when Q is Qb2, preferably hydrogen, chlorine, cyclopropyl, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(CH3)CONH(CH3), pyrimidin-2-yl or 1,2,4-triazol-1-yl;

[0262] Each R4 is independently hydrogen or C1-C4 alkyl, preferably hydrogen or methyl; and

[0263] R5 is C1-C6 alkyl or C3-C6 cycloalkyl, preferably methyl or cyclopropyl.

[0264] A further outstanding group of compounds according to this embodiment are compounds of formula (I-F5), which are compounds of formula (I-F4), wherein

[0265] R2 is C1-C6 haloalkyl, preferably CF3 or CF2CF3.

[0266] A further outstanding group of compounds according to this embodiment are compounds of formula (I-F6), which are compounds of formula (I-F3), wherein

[0267] G1 is N; and G2 is CH.

[0268] A further outstanding group of compounds according to this embodiment are compounds of formula (I-F7), which are compounds of formula (I-F4), wherein

[0269] G1 is N; and G2 is CH.

[0270] A further outstanding group of compounds according to this embodiment are compounds of formula (I-F8), which are compounds of formula (I-F4), wherein

[0271] G1 is N;

[0272] G2 is CH;

[0273] R2 is C1-C6 haloalkyl, preferably CF3 or CF2CF3; and

[0274] Q is Qa2, where

[0275] Q1 is hydrogen, C3-C6 cycloalkyl monosubstituted by cyano, or C1-C6 cyanoalkyl, preferably hydrogen, 1-cyanocyclopropyl or 1-cyano-1-methyl-ethyl.

[0276] A further outstanding group of compounds according to this embodiment are compounds of formula (I-F9), which are compounds of formula (I-F3), wherein

[0277] G1 is CH; and G2 is CH.

[0278] A further outstanding group of compounds according to this embodiment are compounds of formula (I-F10), which are compounds of formula (I-F4), wherein

[0279] G1 is CH; and G2 is CH.

[0280] A further outstanding group of compounds according to this embodiment are compounds of formula (I-F11), which are compounds of formula (I-F4), wherein

[0281] G1 is CH;

[0282] G2 is CH;

[0283] R2 is C1-C6 haloalkyl, C1-C4 haloalkylsulfonyl or C1-C6 haloalkoxy, preferably CF3, CF2CF3, SO2CF3 or OCF3; and

[0284] Q is Qa2, where

[0285] Q1 is hydrogen or C3-C6 cycloalkyl monosubstituted by cyano, preferably hydrogen or 1-cyanocyclopropyl.

[0286] The compounds according to the present invention may have any number of benefits, including, in particular, favorable levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (e.g., higher biological activity, favorable activity spectrum, increased safety, improved physico-chemical properties, or increased biodegradability or environmental profile). In particular, it has now been unexpectedly discovered that certain compounds of formula (I) can exhibit favorable safety profiles relative to non-target arthropods, particularly pollinators such as honey bees, solitary bees, and bumblebees. Most particularly, relative to the Italian honey bee (Apis mellifera).

[0287] In another aspect, the present invention provides a composition comprising an insecticidal, acaricidal, nematicidal or molluscicidal effective amount of a composition having formula (I-A1), (I-A1-1), (I-A2), (I-A2-1), (I-B1), (I-B1-1), (I-B1-2), (I-B2), (I-B2-1), (I-C1), (I-C1-1), (I-C1-2), (I-C2), (I-C2-1) , (I-D1), (I-D1-1), (I-D1-2), (I-D2), (I-D2-1), (1-E), (1-E1), (1-E2), (1-F), and (1-F1) to (1-F11) as defined in any one of the embodiments of the compound of formula (I), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and optionally an adjuvant or diluent.

[0288] In another aspect, the present invention provides a method for combating and controlling insects, acarids, nematodes or molluscs, the method comprising applying to the pest, the locus of the pest, or a plant susceptible to attack by the pest an insecticidal, acaricidal, nematicidal or molluscicidal effective amount of a compound as described in formula (I-A1), (I-A1-1), (I-A2), (I-A2-1), (I-B1), (I-B1-1), (I-B1-2), (I-B2), (I-B2-1), (I-C1), (I-C1-1), (I-C1-2), (I-C2-1), (I-C2-2), (I-C2-3), (I-C2-4), (I-C2-5), (I-C2-6), (I-C2-7), (I-C2-8), (I-C2-9), (I-C2-10), (I-C2-11), (I-C2-12), (I-C2-13), (I-C2-14), (I-C2-15), (I-C2-16), (I-C2-17), (I-C2-18), (I-C2-21), (I-C2-22), (I-C2-19), (I-C2-23), (I-C2-24), (I-C2-25), (I-C2-26), (I-C2-27), (I-C2-28), (I-C2-39), (I-C2-40), (I-C2-51), (I-C2- A compound of formula (I) as defined in any one of the embodiments of the compound of (I-C1-2), (I-C2), (I-C2-1), (I-D1), (I-D1-1), (I-D1-2), (I-D2), (I-D2-1), (1-E), (1-E1), (1-E2), (1-F), and (1-F1) to (1-F11) (as above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, or a composition as defined above.

[0289] In yet another aspect, the present invention provides a method for protecting plant propagation material from attack by insects, acarids, nematodes or molluscs, said method comprising treating said propagation material or the locus where said propagation material is planted with a composition as defined above.

[0290] The process for preparing compounds of formula I according to the present invention is carried out by methods known to those skilled in the art. Compounds of formula I-a3 (wherein X is SO2, and A, R1, R2, R3, G1, G2, and Q1 are as defined above under formula I) can be prepared by oxidizing compounds of formula I-a2 (wherein X is SO, and A, R1, R2, R3, G1, G2, and Q1 are as defined above under formula I). ​​The reaction can be carried out with reagents such as peracids (such as peracetic acid or chloroperbenzoic acid), or hydroperoxides (such as, for example, hydrogen peroxide or tert-butyl hydroperoxide), or inorganic oxidants (such as monoperoxodisulfate or potassium permanganate). In a similar manner, compounds of formula I-a2 (wherein X is SO, and A, R1, R2, R3, G1, G2, and Q1 are as defined above under Formula I) can be prepared by oxidizing compounds of formula I-a1 (wherein X is S, and A, R1, R2, R3, G1, G2, and Q1 are as defined above under Formula I) under similar conditions described above. 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 up to the boiling point of the solvent system. The conversion of compounds of formula I-a1 to compounds of formula I-a2 and I-a3 is shown in Scheme 1.

[0291] Option 1:

[0292]

[0293] Compounds of formula I-aa3 (Scheme 2) wherein X is SO2 and A, R1, R2, R3, G1, G2 and Q1 are as defined above under Formula I can be prepared by analogous procedures as described in Scheme 1 for the synthesis of compounds of formula I-a3.

[0294] Option 2:

[0295]

[0296] Compounds of formula I, wherein R1, G1, G2 and Q are as defined above under formula I, can be prepared by reacting a compound of formula VII, wherein R2, G1 and G2 are as defined above under formula I, and a compound of formula VIII, wherein Q is as defined above under formula I and wherein LG3 is a halogen (or a pseudohalogen leaving group, such as triflate), in the presence of a base, such as sodium carbonate, potassium carbonate or cesium carbonate, or sodium hydride, in a suitable solvent, such as, for example, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide or acetonitrile, at a temperature between 0°C and 150°C, optionally under microwave irradiation. Alternatively, compounds of formula I (wherein R2, G1, G2 and Q are as defined above under formula I) can be prepared by heating in the presence of 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, such as copper(I) iodide), optionally in the presence of a ligand (such as a diamine ligand (such as N,N′-dimethylethylenediamine or trans-cyclohexanediamine) or dibenzylideneacetone (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 (such as palladium(II) acetate, bis(dibenzylideneacetone)palladium(0) (Pd(dba)2) or tris(dibenzylideneacetone)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)]methanesulfonate palladium(II) or BrettPhos Pd G3 [(2-di-cyclohexylphosphino-3,6-dimethoxy-2′,4′,6′-triisopropyl-1,1′-biphenyl)-2-(2′-amino-1,1′-biphenyl)] methanesulfonate palladium (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 of formula VII (wherein R2, G1, and G2 are as defined above in formula I) and a compound of formula VIII (wherein Q is as defined above in formula I and wherein LG3 is a halogen (or a pseudohalogen leaving group such as a triflate, preferably bromine or iodine) are reacted to prepare. The above reaction can be carried out in the presence of a solvent such as toluene, dimethylformamide DMF, N-methylpyrrolidine NMP, dimethyl sulfoxide DMSO, dioxane, tetrahydrofuran THF) and is described in the literature.

[0297] Option 3:

[0298]

[0299] For example, WO 2012031004, WO 2009042907 and Synthetic Communications, 41: 67-72, 2011.

[0300] Alternatively, compounds of formula I (wherein R2, G1, G2 and Q are as defined above under formula I) can be prepared by reacting a compound of formula VI (wherein R2, G1 and G2 are as defined above under formula I and LG2 is a leaving group (e.g. Br, Cl or I, preferably bromine) and R is C1-C6 alkyl, benzyl or phenyl) and a compound of formula IX (wherein Q is 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 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. Such reactions proceed by nucleophilic substitution and subsequent cyclization and are also reported in the literature, for example described in WO 2009042907.

[0301] Alternatively, compounds of formula I (wherein R2, G1, G2 and Q are as defined above under formula I) can be prepared by cyclizing compounds of formula X (wherein R2, G1, G2 and Q are as defined in formula I), for example in the presence of phosphorus oxychloride, optionally in the presence of a solvent or diluent such as toluene or xylene, at temperatures between 0°C and 180°C, preferably between 20°C and 120°C.

[0302] Option 4:

[0303]

[0304] Compounds of formula I, wherein R2, G1, G2 and Q are as defined above under formula I, can also be cyclized to compounds of formula Xa, wherein R2, G1, G2 and Q are as defined above under formula I and wherein X0 is halogen, preferably chlorine, or X0 is X by cyclization 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-dimethyl-formamide, N,N-dimethylacetamide, acetonitrile, ethyl acetate or toluene, at a temperature between 0°C and 50°C. 01 or X 02 ) to prepare. Certain bases (such as pyridine and triethylamine) can be successfully used as bases and solvents.

[0305] Compounds of formula Xa (wherein R2, G1, G2 and Q are as defined above under formula I and wherein X0 is halogen, preferably chlorine, or X0 is X 01 or X 02 ) can be prepared by activating a compound of formula X (wherein R2, G1, G2 and Q are as defined above under formula I) by methods known to those skilled in the art and described, for example, in Tetrahedron, 2005, 61(46), 10827-10852. Preference is given to forming an activated species Xa, where R2, G1, G2 and Q are as defined above under formula I and where X0 is halogen, preferably chlorine. For example, compound Xa (wherein X0 is halogen, preferably chlorine) is formed by treating X with, for example, oxalyl chloride (COCl) 2 or thionyl chloride SOCl 2 in an inert solvent, such as dichloromethane CH2Cl2 or tetrahydrofuran THF, in the presence of a catalytic amount of N,N-dimethylformamide DMF, at a temperature between 20°C and 100°C, preferably 25°C. Alternatively, treatment of a compound of formula X with, for example, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide EDC or dicyclohexylcarbodiimide DCC at a temperature between 50° C. and 180° C., optionally in the presence of a base such as triethylamine, in an inert solvent such as pyridine or tetrahydrofuran (THF) will yield an activated species Xa (wherein X0 is X 01 or X 02 ).

[0306] Compounds of formula VII, wherein R2, G1 and G2 are as defined above in formula I, can be prepared by reacting a compound of 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 C1-C6 alkyl, benzyl or phenyl, with ammonia or an ammonia surrogate (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.

[0307] Compounds of formula X, wherein R2, G1, G2 and Q are as defined above under formula I, can be prepared by nucleophilic substitution reaction of a compound of formula VI, wherein R2, G1 and G2 are as defined above under formula I and LG2 is a leaving group (e.g., Br, Cl or I, preferably bromine) and R is C1-C6 alkyl, benzyl or phenyl) with an amino compound of formula IX, wherein Q is as defined above under formula I, followed by in situ hydrolysis of an intermediate ester of formula XVII, wherein R2, G1, G2 and Q are as defined above under formula I, and wherein R is C1-C6 alkyl, benzyl or phenyl.

[0308]

[0309] The unhydrolyzed ester compound of formula XVII generated in situ can be isolated and can also be converted via saponification in the presence of a suitable base (e.g., NaOH, LiOH, Ba(OH)2) to form a carboxylic acid of formula X. The conversion of the compound of formula VI to the compound of formula X can be carried out in the presence of a base (e.g., sodium hydride, KOtBu, butyllithium, lithium diisopropylamide, etc.) and in the presence of a solvent (e.g., dioxane, DMF, DMA, DMSO, THF) at a temperature between -30°C and 150°C. The compound of 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 C1-C6 alkyl, benzyl or phenyl) can be prepared by free radical-initiated benzyl halogenation of a compound of formula V (wherein R2, G1 and G2 are as defined above in formula I and R is C1-C6 alkyl, benzyl or phenyl). Such reactions are well known to those skilled in the art and can be carried out in the presence of an electrophilic halogenating agent such as Br2, NBS, Cl2, NIS, etc., and in the presence of a free radical initiator such as AIBN (azobisisobutyronitrile), benzoyl peroxide, or under photochemical conditions and at a temperature ranging from 20°C to the boiling point of the solvent, and in the presence of a solvent such as toluene, xylene, acetonitrile, hexane, dichloroethane or carbon tetrachloride. Such reactions are known under the name Wohl-Ziegler bromination and are reported in the literature, for example, in Synthesis, 2015, 47, 1280-1290 and J.Am.Chem.Soc., 1963, 85(3), pp. 354-355.

[0310] Compounds of formula V, 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 a Suzuki reaction, which involves, for example, reacting a compound of formula IV, wherein R2, G1 and G2 are as defined above in formula I, LG1 is a halogen Br, Cl, I, preferably Cl, and R is C1-C6 alkyl, benzyl or phenyl, with trimethylboroxine or potassium methyltrifluoroborate and other methylboronic acid equivalents. The reaction can be catalyzed by a palladium-based catalyst such as tetrakis(triphenylphosphine)palladium(0), (1,1'bis(diphenylphosphino)ferrocene)dichloro-palladium-dichloromethane (1:1 complex) or chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-diphenyl)[2-(2'-amino-1,1'-diphenyl)]palladium(II) (XPhos palladacycle 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, dioxane, acetonitrile, N,N-dimethylformamide, a mixture of 1,2-dimethoxyethane and water or a mixture of dioxane / water or a mixture of toluene / water, 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.

[0311] Compounds of formula IV (wherein R2, G1 and G2 are as defined above in formula I, LG1 is halogen (Br, Cl, I, preferably Cl) and R is C1-C6 alkyl, benzyl or phenyl) can be prepared by reacting a compound of formula III (wherein R2, G1 and G2 are as defined above in formula I, LG1 is halogen Br, Cl, I, preferably Cl) and ROH (wherein R is 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 under the name Fischer esterification and are reported in the literature, for example, in J. Org. Chem., 2006, 71, 3332-3334, Chem. Commun., 1997, 351-352 and Synthesis, 2008, 3407-3410. Such esterification reactions can also be carried out by reacting a compound of formula III with TMSCHN2 to form a compound of formula IV (wherein R2, G1 and G2 are as defined above in formula I, LG1 is a halogen Br, Cl, I, preferably Cl and R is methyl) and are reported in Angew. Chem. Int. Ed., 2007, 46, 7075.

[0312] Compounds of formula III (wherein R2, G1 and G2 are as defined above in formula I, LG1 is halogen Br, Cl, I, preferably Cl) can be prepared by metallization of compounds of formula II (wherein R2, G1 and G2 are as defined above in formula I, LG1 is halogen Br, Cl, I, preferably Cl) with a suitable base and subsequently reacted with carbon dioxide. The metallization reaction can be carried out using a base (e.g., an organolithium compound such as lithium tetramethylpiperidinium, lithium diisopropylamide, sec-BuLi, etc.) at a temperature ranging from -78 to 40° C. in the presence of a solvent (e.g., THF, DMPU, dioxane, 2-Me-THF). Such reactions are reported in the literature, for example, in Tetrahedron, 2004, 60(51), 11869-11874.

[0313] Alternatively, a compound of formula IV (wherein R2, G1 and G2 are as defined above in formula I, LG1 is halogen, such as Br, Cl or I (preferably Cl) and R is C1-C6 alkyl, benzyl or phenyl)

[0314] Option 3a:

[0315]

[0316] Can be prepared by reacting a compound of 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 (such as tert-butyl nitrite t-BuONO, isoamyl nitrite, or sodium nitrite) 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 (Scheme 3a). This transformation is preferably carried out in an inert solvent (such as acetonitrile, or a halogenated solvent like 1,2-dichloroethane, or water) at a temperature between 0°C and 150°C, preferably at a temperature ranging from room temperature to the boiling point of the reaction mixture.

[0317] Compounds of 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 of formula IV-b (wherein R2, G1 and G2 are as defined above in formula I and LG4 is halogen, preferably Br, Cl or I) by methods found, for example, in WO 2016 / 020286, which involve carbonylation reactions, wherein the compound of formula (IV-b) is reacted with carbon monoxide CO (usually 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.

[0318] Compounds of 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 of 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 at room temperature to 100°C.

[0319] Compounds of formula VI-a

[0320]

[0321] in

[0322] R2 and G1 are as defined above under Formula I, and wherein LG2 is a leaving group (e.g., Br, Cl, or I) and R1 is C1-C6 alkyl, benzyl, or phenyl) is novel, specifically developed for use in preparing compounds of Formula I according to the present invention, and therefore represents another object of the present invention. The substituent preferences and preferred embodiments for compounds of Formula I are also valid for compounds of Formula VI-a. Preferably, LG2 is bromo or chloro; even more preferably, LG2 is bromo. Preferably, R1 is C1-C6 alkyl; even more preferably, R1 is methyl or ethyl.

[0323] Alternatively, compounds of Formula I (wherein G1, G2, R2 and Q are as defined above under Formula I) can be prepared according to Scheme 5.

[0324] Option 5:

[0325]

[0326] In Scheme 5, compounds of formula I (wherein G1, G2, R2 and Q are as defined above under formula I) can be prepared from compounds of formula X (wherein G1, G2, R2 and Q are as defined above under formula I) by the methods described above in Scheme 4 (Scheme 6). Compounds of formula X can be prepared by reacting compounds of formula XII (wherein G1, G2, R2 are as defined above in formula I) with compounds of formula IX (wherein Q is as defined above in formula I) under reductive amination conditions (Scheme 6). The reaction can be carried out in the presence of a reducing agent (e.g., sodium cyanoborohydride, sodium triacetoxyborohydride, etc.), and optionally in the presence of an acid (e.g., trifluoroacetic acid, formic acid, acetic acid, etc.), and at a temperature ranging from 0°C to the boiling point of the solvent. The reaction can be carried out in the presence of an inert solvent (e.g., ethanol, methanol, dioxane or tetrahydrofuran). Such reactions involving the two-step conversion of compounds of formula XII to compounds of formula I have been described in the literature, for example in Bioorganic & Medicinal Chemistry Letters 26 (2016) 5947-5950.

[0327] Compounds of formula XII, wherein G1, G2 and R2 are as defined above in formula I, can be prepared from compounds of formula XI, wherein G1, G2 and R2 are as defined above in formula I, LG2 is chlorine, bromine or iodine, preferably bromine and R is C1-C6 alkyl, benzyl or phenyl, by hydrolysis. The reaction can be carried out under alkaline conditions using a metal hydroxide, for example aqueous sodium hydroxide in the presence of a solvent such as dioxane, tetrahydrofuran or water and at a temperature ranging from 20 to 150° C., as reported in Synlett 1992, (6), 531-533, or under acidic aqueous conditions, for example acetic acid, hydrochloric acid or sulfuric acid in the presence of a solvent such as water, dioxane, a halogenated solvent such as dichloroethane, as reported in Tetrahedron 62 (2006) 9589-9602. Compounds of formula XI (wherein G1, G2 and R2 are as defined above in formula I, LG2 is chloro, bromo or iodo, preferably bromo and R is C1-C6 alkyl, benzyl or phenyl) can be prepared from compounds of 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 analogous to those described in Scheme 3 for converting compounds of formula V to compounds of formula VI.

[0328] Option 6:

[0329]

[0330] Alternatively, compounds of formula I (wherein G1, G2, R2 and Q are as defined above under formula I) can be prepared from compounds of formula XV (wherein G1, G2, R2 and Q are as defined above under formula I) by selective reduction of the carbonyl function (Scheme 7).

[0331] Option 7:

[0332]

[0333] The reaction can be carried out in the presence of a reducing agent (e.g., NaBH , LiAlH , palladium on carbon) in the presence of hydrogen, or in the presence of a combination of two reducing agents (e.g., NaBH , then triethylsilane). Such reactions have been described in, for example, US 20100160303 A1. Compounds with formula XV (wherein G 1, G 2, R 2 and Q are as defined above under formula I) can be prepared by hydrolysis reactions and subsequent cyclization reactions for converting compounds with formula X into compounds with formula I as described in scheme 4, by compounds with formula XIV (wherein G 1, G 2, R 2 and Q are as defined above under formula I). Compounds of formula XIV, wherein G1, G2, R2 and Q are as defined above under formula I and R is C1-C6 alkyl, benzyl or phenyl, can be prepared by reacting compounds of formula XIII, wherein R2, G1, G2 are as defined above under formula I and R is C1-C6 alkyl, benzyl or phenyl, with compounds of formula IX, wherein Q is as defined above under formula I, by an amidation reaction also as described in Scheme 4. Compounds of formula XIII, wherein R2, G1 and G2 are as described above under formula I and R is C1-C6 alkyl, benzyl or phenyl, can be prepared by benzyl oxidation of compounds of formula V, wherein R2, G1, G2 are as defined above under formula I and R is C1-C6 alkyl, benzyl or phenyl. The reaction can be carried out in the presence of an oxidant (such as KMNO4, nBu4MnO4, K2S2O8) in the presence of oxygen, or under photochemical conditions in the presence of oxygen and at a temperature ranging from 20°C to the boiling point of the solvent. The reaction is carried out in the presence of an inert solvent (such as acetonitrile, ethyl acetate, DMSO, dichloroethane). Such reactions are known in the literature, for example Synthesis [Synthesis], 2017, 49, 4007-4016, Synthesis [Synthesis], 2006, 1757-1759 and IOSR Journal of Applied Chemistry [Application Chemistry Magazine], 2014, 7, 16-27.

[0334] Alternatively, compounds of formula I (wherein R2, G1, G2 and Q are as defined above in formula I) can be prepared by cyclization of compounds of formula XVII (wherein R2, G1, G2 and Q are as defined above in formula I and R is C1-C6 alkyl, benzyl or phenyl) (Scheme 8):

[0335] Option 8:

[0336]

[0337] The reaction can be carried out in the presence of a base (such as potassium tert-butoxide, lithium diisopropylamide, sodium hydride, etc.) and at a temperature ranging from -20°C to the boiling point of the solvent, and in the presence of an inert solvent (such as tetrahydrofuran, dioxane, DMF). Such reactions are reported in Synlett [Synthesis Express] 2006 (4): 591-594. Compounds of formula XVII (wherein R2, G1, G2 and Q are as defined above in formula I and R is C1-C6 alkyl, benzyl or phenyl) can be prepared by reacting compounds of formula XVI (wherein R2, G1 and G2 are as defined above in formula I and R is C1-C6 alkyl, benzyl or phenyl) with compounds of formula IX (wherein Q is as defined above in formula I) under Mitsunobu conditions. Such reactions are well known to those skilled in the art and can be carried out in the presence of a phosphine reagent (such as triphenylphosphine, tributylphosphine or polymer-supported triphenylphosphine, etc.), in the presence of an azodicarboxylate reagent (such as diethyl azodicarboxylate, diisopropyl azodicarboxylate), at a temperature ranging from 0°C to 100°C, and in the presence of an inert solvent (such as acetonitrile, dichloromethane, tetrahydrofuran, toluene). Such reactions are reported, for example, in Synthesis, 1981 (1), 1-28. Compounds of 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 a compound of 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. The reaction can be carried out at a temperature ranging from 0° C. to 150° C. and in the presence of an inert solvent (e.g., tetrahydrofuran, dioxane) using a reducing agent, for example, a metal hydride (e.g., lithium aluminum hydride, DIBAL-H), or a borane (e.g., diborane, borane tetrahydrofuran, etc.). Such reactions have been reported in Tetrahedron Letters, 1982, 23, 2475-2478.

[0338] Compounds having formula XVII-a

[0339]

[0340] in

[0341] R2, G1, G2 and Q are as defined above under Formula I, and R ais hydrogen, C1-C6 alkyl, benzyl or phenyl) is novel and has been specifically developed for the preparation of compounds of formula I according to the present invention and therefore represents another object of the present invention. The preferences and preferred embodiments of the substituents of the compounds of formula I are also valid for the compounds of formula XVII-a. Preferably, Ra is hydrogen or C1-C6 alkyl; even more preferably, Ra is hydrogen, methyl or ethyl.

[0342] Compounds of formula IX, wherein Q is as defined above in formula I, can be prepared by deprotection of the tert-butyl group of compounds of formula XIX, wherein Q is as defined above in formula I (Scheme 9).

[0343] Option 9:

[0344]

[0345] The reaction can be carried out in the presence of an acid catalyst (such as trifluoroacetic acid, hydrochloric acid or sulfuric acid). A compound of formula IX (wherein Q is as defined above in formula I) can be prepared by reacting a compound of formula XVIII (wherein Q is as defined above in formula I) with an organic azide in the presence of a suitable base t-BuOH and in the presence of a coupling agent, 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 solvent. The reaction can be carried out in the presence of a coupling agent (such as T3P), or as described in Scheme 6, by activating the carboxylic acid with SOCl2 or oxalyl chloride or other coupling agents to convert the compound of formula X into a compound of formula Xa. Examples of organic azides include TMSN3, sodium azide or tosyl azide and suitable solvents can be toluene, xylene, THF or acetonitrile. Examples of suitable Lewis acids can include Zn(OTf)2, Sc(OTf)2, or Cu(OTf)2, etc. Compounds of formula XIX can also be prepared by reacting a compound of formula XVIII with diphenylphosphoryl azide in the presence of an organic base (e.g., triethylamine, diisopropylethylamine, etc.), in the presence of tert-butyl alcohol and an inert solvent (e.g., a halogenated solvent (e.g., dichloromethane, dichloroethane) or a cyclic ether (e.g., tetrahydrofuran, etc.), and at a temperature ranging from 50° C. to the boiling point of the solvent. Such reactions for converting carboxylic acids into amines are well known to those skilled in the art under the name Curtius reaction and are reported in Org. Lett., 2005, 7, 4107-4110; Journal of Medicinal Chemistry, 49(12), 3614-3627; 2006, J. Am. Chem. Soc., 1972, 94(17), pp. 6203-6205. Compounds of formula IX (wherein Q is as defined above in formula I) can also be prepared from compounds of formula XX (wherein Q is as defined above in formula I) by a Hofmann rearrangement reaction. The reaction can be carried out in the presence of a base (e.g., a metal hydroxide such as aqueous sodium hydroxide or potassium hydroxide, or an organic base such as DBU (1,8-diazabicyclo(5.4.0)undec-7-ene)) and in the presence of an electrophilic halogenating agent such as chlorine, bromine, or N-bromo-succinimide, and at a temperature ranging from 20°C to the boiling point of the solvent. This type of reaction is known by the name Hofmann rearrangement and is reported in the literature, for example, in Chem. Ber. 1881, 14, 2725.Compounds of formula XX (wherein Q is as defined above in formula I) can be prepared by reacting compounds of formula XVIII with ammonia (e.g., NH4OH, NH3, or other ammonia surrogates) in the presence of a formic acid activator as described in Scheme 4.

[0346] A subgroup of compounds having formula IX (wherein Q is defined as Qa, wherein X is SO2, A is N and R1, R3 and Q1 are as defined in formula I) can be defined as compounds having formula IX-1 (Scheme 9a).

[0347] Option 9a :

[0348]

[0349] Compounds of formula IX-1 can be prepared by an amination reaction involving, for example, reacting a compound of formula IX-1a (wherein R1, R3 and Q1 are as defined in formula I, and LG4 is a halogen, preferably F, Br or Cl) with ammonia or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or hydrobromide salt, or any other equivalent salt). The source of nitrogen can be ammonia (NH3) itself or an ammonia equivalent, such as, for example, ammonium hydroxide NH4OH, ammonium chloride NH4Cl, ammonium acetate NH4OAc, ammonium carbonate (NH4)2CO3 and other NH3 substitutes. This conversion is optionally carried out under microwave irradiation at a temperature between 0° C. and 150° C. (preferably at a temperature ranging from room temperature to the boiling point of the reaction mixture), optionally in the presence of a base, preferably in a suitable solvent (or diluent) such as alcohols, amides, esters, ethers, nitriles and water, particularly preferably methanol, ethanol, 2,2,2-trifluoroethanol, propanol, isopropanol, N,N-dimethylformamide, N,N-dimethylacetamide, dioxane, tetrahydrofuran, dimethoxyethane, acetonitrile, ethyl acetate, water or a mixture thereof.

[0350] Compounds of formula IX-1a (wherein R1, R3 and Q1 are as defined in formula I and LG4 is halogen, preferably F, Br or Cl) can be prepared by oxidizing compounds of formula IX-1b (wherein R1, R3 and Q1 are as defined in formula I and LG4 is halogen, preferably F, Br or Cl) under the conditions described above.

[0351] Compounds of formula IX-1b (wherein R1, R3 and Q1 are as defined in formula I and LG4 is halogen, preferably F, Br or Cl) can be prepared by reacting compounds of formula IX-1c (wherein R3 and Q1 are as defined in formula I and LG4 is halogen, preferably F, Br or Cl) with nitrites (such as tert-butyl nitrite, t-BuONO, isoamyl nitrite or sodium nitrite) under Sandmeyer-type reaction conditions in the presence of a hydrohalic acid and a disulfide R1S-SR1 or alternatively a thiol R1SH (wherein R1 is as defined above in formula I). ​​This transformation is preferably carried out in an inert solvent (such as acetonitrile, or a halogenated solvent like 1,2-dichloroethane) at temperatures between 0°C and 150°C, preferably at temperatures ranging from room temperature to the boiling point of the reaction mixture, optionally in the presence of a copper salt.

[0352] Compounds having formula IX-a

[0353]

[0354] in

[0355] R1 and X are as defined above under Formula I, and Q 1a The substituents of formula I and IX-a are novel and have been developed specifically for the preparation of compounds of formula I according to the invention and therefore represent a further object of the present invention. The substituent preferences and preferred embodiments of the compounds of formula I are also valid for the compounds of formula IX-a.

[0356] A subset of compounds having Formula I, wherein G1, G2, and R2 are as defined above in Formula I and wherein Q is defined as Qb, wherein A, Q1, R3, X, and R1 are as defined in Formula I, can be defined as compounds having Formula I-Qb (Scheme 10).

[0357] Plan 10

[0358]

[0359] (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.

[0360] (b) Stiller reaction: Pd catalyst (e.g. Pd(PPh3)4 or Pd(PPh3)Cl2), solvent (e.g. toluene), 25-180°C.

[0361] (c) C-N bond formation: optional base (e.g., K2CO3 or Cs2CO3), optionally in the presence of a 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.

[0362] In the specific case of Scheme 10, when Q1 is an optionally substituted triazole connected to the ring comprising the group A via a ring nitrogen atom, then a compound of formula I-Qb wherein X is SO or SO2 can be prepared from a compound of formula XXIb wherein G1, G2, A, R3, R1 and R2 are as defined above in formula I and wherein X is SO or SO2, and wherein Xb is a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an arylsulfonate or alkylsulfonic acid leaving group such as triflate) by reacting with an optionally Substituted triazoles Q1-H containing a suitable NH functionality (XXIIaa) wherein Q1 is an N-linked triazole group are prepared by reacting in a solvent such as an alcohol (e.g., methanol, ethanol, isopropanol or a higher boiling linear or branched alcohol), pyridine or acetic acid, optionally in the presence of an additional base such as potassium carbonate K2CO3 or cesium carbonate Cs2CO3, optionally in the presence of a copper catalyst such as copper(I) iodide, at a temperature between 30°C and 180°C, optionally under microwave irradiation (CN bond formation).

[0363] In the specific case of Scheme 10, when Q1 is -N(R4)COR5 or -N(R4)CON(R4)2 (wherein R4 and R5 are as defined in Formula I), then compounds of formula I-Qb (wherein X is SO or SO2) can be prepared from compounds of formula XXIb (wherein A, R1, R2, G1, G2 and R3 are as defined in Formula I, and wherein X is SO or SO2, and wherein Xb is a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an aryl sulfonate or alkyl sulfonate (such as triflate)) by reaction with a reagent Q1-H(XXIIaa) (equivalent to HN(R4)COR5 or HN(R4)CON(R4)2, wherein R4 and R5 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-methylpyrrolidine NMP, dimethyl sulfoxide DMSO, dioxane, tetrahydrofuran THF, etc.), optionally in the presence of a catalyst (such as palladium (II) acetate, bis (dibenzylideneacetone) palladium (0) (Pd (dba) 2) or tris (dibenzylideneacetone) dipalladium (0) (Pd2 (dba) 3), optionally in the form of a chloroform adduct), or in the presence of 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)] methanesulfonate palladium (II) or BrettPhos Pd G3[(2-di-cyclohexylphosphino-3,6-dimethoxy-2′,4′,6′-triisopropyl-1,1′-diphenyl)-2-(2′-amino-1,1′-biphenyl)]methanesulfonatepalladium(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.

[0364] In the specific case of Scheme 10, when Q1 is -N(R4)2 (wherein R4 is as defined in Formula I), then compounds of formula I-Qb (wherein X is SO or SO2) can be prepared from compounds of formula XXIb (wherein A, R1, R2, G1, G2 and R3 are as defined in Formula I, and wherein X is SO or SO2, and wherein Xb is a leaving group such as, for example, chloro, bromo or iodo (preferably chloro or bromo), or an aryl sulfonate or alkyl sulfonate (such as trifluoromethanesulfonate)) by reaction with a reagent Q1-H(XXIIaa) (equivalent to HN(R4)2, wherein R4 is as defined in Formula I), or a salt thereof such as a hydrohalide salt, preferably a hydrochloride or hydrobromide salt, or a trifluoroacetate salt, or any other equivalent salt (CN bond formation). Such a reaction is usually carried out in an inert solvent (such as alcohol, amide, ester, ether, nitrile and water, particularly preferably methanol, ethanol, 2,2,2-trifluoroethanol, propanol, isopropanol, N,N-dimethylformamide, N,N-dimethylacetamide, dioxane, tetrahydrofuran, dimethoxyethane, acetonitrile, ethyl acetate, toluene, water or a mixture thereof) at a temperature between 0° C. and 150° C., optionally under microwave irradiation or under pressure using an autoclave, optionally in the presence of a copper catalyst (such as copper powder, copper (I) iodide or copper sulfate (optionally in the form of a hydrate) or a mixture thereof), optionally in the presence of a ligand (such as a diamine ligand (for example, N,N′-dimethylethylenediamine or trans-cyclohexyldiamine) or dibenzylideneacetone (dba) or 1,10-phenanthroline), and optionally in the presence of a base (such as potassium phosphate).

[0365] The reagents HN(R4)2, HN(R4)COR5, or HN(R4)CON(R4)2 (wherein R4 and R5 are as defined in Formula I) are known, commercially available, or can be prepared by methods known to those skilled in the art.

[0366] Alternatively, compounds of formula I-Qb, wherein X is SO or SO2, can be prepared by a Suzuki reaction involving, for example, reacting a compound of formula XXIb, wherein A, R1, R2, G1, G2 and R3 are as defined in formula I, and wherein X is SO or SO2, and wherein Xb is a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an arylsulfonate or alkylsulfonate such as triflate, with a compound of formula (XXII), wherein Q1 is as defined in formula I, and wherein 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 b1The reaction can be catalyzed by a palladium-based catalyst (e.g., tetrakis(triphenylphosphine)palladium(0), (1,1'-bis(diphenylphosphino)ferrocene)dichloro-palladium-dichloromethane (1:1 complex) or chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-diphenyl)[2-(2'-amino-1,1'-diphenyl)]palladium(II) (XPhos palladacycle complex)) in the presence of a base (e.g., sodium carbonate, tripotassium phosphate or cesium fluoride) in a solvent or solvent mixture (e.g., dioxane, acetonitrile, N,N-dimethylformamide, a mixture of 1,2-dimethoxyethane and water or a mixture of dioxane / water or a mixture of toluene / water), preferably under an inert atmosphere. The reaction temperature may preferably be in the range of from room temperature to the boiling point of the reaction mixture, or the reaction may be carried out under microwave irradiation. Such Suzuki reactions are well known to those skilled in the art and have been reviewed in, for example, J. Organomet. Chem. 576, 1999, 147-168.

[0367] Alternatively, a compound of formula I-Qb wherein X is SO or SO2 may be prepared by reacting a compound of formula (XXIIa) wherein Q1 is as defined above and wherein Y b2 The present invention relates to a compound of formula XXIb (wherein A, R1, R2, G1, G2 and R3 are as defined in formula I, and wherein X is SO or SO2, and wherein Xb is a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an arylsulfonate or alkylsulfonate (such as trifluoromethanesulfonate). Such a Stirler reaction is generally carried out in the presence of a palladium catalyst such as tetrakis(triphenylphosphine)palladium(0) or bis(triphenylphosphine)palladium(II) dichloride, in an inert solvent such as N,N-dimethylformamide, acetonitrile, toluene or dioxane, optionally in the presence of an additive such as cesium fluoride or lithium chloride, and optionally in the presence of an additional catalyst such as copper(I) iodide. Such Stiehler couplings are also familiar 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.

[0368] When Q1 is a five-membered aromatic ring system (linked to the ring comprising the group A via a ring nitrogen atom), then a compound of formula I-Qb wherein X is SO or SO2 can be prepared from a compound of formula XXIb wherein A, R1, R2, G1, G2 and R3 are as defined in formula I, and wherein X is SO or SO2, and wherein Xb is a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an aryl sulfonate or alkyl sulfonate such as triflate, by reacting with a heterocycle Q1-H comprising a suitable NH functionality (XXII aa) (wherein Q1 is as defined above), in the presence of a base (such as potassium carbonate K2CO3 or cesium carbonate Cs2CO3), optionally in the presence of a copper catalyst (such as copper (I) iodide), with or without additives (such as L-proline, N,N'-dimethylcyclohexane-1,2-diamine or N,N'-dimethyl-ethylenediamine), in an inert solvent (such as N-methylpyrrolidone NMP or N,N-dimethylformamide DMF), at a temperature between 30 ° C and 150 ° C, optionally under microwave irradiation to prepare.

[0369] Oxidation of a compound of formula XXIb (wherein A, R1, R2, G1, G2 and R3 are as defined in formula I, and wherein X is S, and wherein Xb is a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an arylsulfonate or alkylsulfonate (such as trifluoromethanesulfonate)) with a suitable oxidizing agent to a compound of formula XXIb (wherein X is SO or SO2) can be achieved under the conditions already described above.

[0370] A large number of compounds of formula (XXII), (XXIIa) and (XXIIaa) are commercially available or can be prepared by one skilled in the art.

[0371] Alternatively, compounds of formula I-Qb, wherein X is SO or SO2, can be prepared from compounds of formula XXIIb, wherein X is S (sulfide), by involving the same chemical process as described above but by changing the order of the steps (i.e., by running the sequence XXIb (X is S) to I-Qb (X is S) via Suzuki reaction, Stiller reaction, or CN bond formation, followed by an oxidation step to form I-Qb (X is SO or SO2)).

[0372] A subgroup of compounds of Formula I (wherein G1, G2, and R2 are as defined above and wherein Q is defined as Qa, wherein A, Q1, R3, X, and R1 are as defined in Formula I) can be defined as compounds of Formula I-Qa (Scheme 11). The chemical process for obtaining compounds of Formula I-Qb from compounds of Formula XXIIb as previously described in Scheme 10 can be similarly applied to prepare compounds of Formula I-Qa from compounds of Formula XXIa (Scheme 11), wherein all previously mentioned substituent definitions remain valid.

[0373] Option 11:

[0374]

[0375] (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.

[0376] (b) Stiller reaction: Pd catalyst (e.g., Pd(PPh3)4 or Pd(PPh3)Cl2), solvent (e.g., toluene), 25-180°C.

[0377] (c) C-N bond formation: optional base (e.g., K2CO3 or Cs2CO3), optionally in the presence of a 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.

[0378] The reactants may be reacted in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxide, and carbocyclic amines. Examples that may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0379] The reactants can be reacted 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 of these. If the reaction is carried out in the presence of a base, the base used in excess (e.g., triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline) can also serve as a solvent or diluent.

[0380] These reactions are advantageously carried out in a temperature range of from about -80°C to about +140°C, preferably from about -30°C to about +100°C, in many cases in a range between ambient temperature and about +80°C.

[0381] A compound of formula I can be converted into another compound of formula I in a manner known per se by replacing one or more substituents of the starting compound of formula I with (another) further substituent according to the invention in a conventional manner and by subsequent modification of the compound by reactions known to those skilled in the art (such as oxidation, alkylation, reduction, acylation and other methods).

[0382] Depending on the reaction conditions and starting materials chosen as appropriate in the respective case, it is possible, for example, to replace only one substituent with another substituent according to the invention in one reaction step or to replace several substituents with other substituents according to the invention in one and the same reaction step.

[0383] Salts of compounds of formula I can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula I are obtained by treatment with a suitable acid or a suitable ion exchanger reagent, and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.

[0384] Salts of compounds of the formula I can be converted in a customary manner into the free compounds I, acid addition salts (for example by treatment with suitable basic compounds or with suitable ion exchange reagents) and salts with bases (for example by treatment with suitable acids or with suitable ion exchange reagents).

[0385] Salts of compounds of the formula I can be converted in a manner known per se into other salts, acid addition salts of compounds of the formula I, for example into other acid addition salts, for example by treating salts of inorganic acids (such as hydrochlorides) with suitable metal salts of the acid (such as sodium, barium or silver salts, for example with silver acetate) in a suitable solvent in which the inorganic salt formed (such as silver chloride) is insoluble and therefore precipitates from the reaction mixture.

[0386] Depending on the procedure or reaction conditions, those compounds of the formula I which have salt-forming properties can be obtained in free form or in the form of salts.

[0387] Depending on the number of asymmetric carbon atoms present in the molecule, the absolute and relative configuration and / or on the configuration of non-aromatic double bonds present in the molecule, the compounds of the formula I and, where appropriate, their tautomers (in each case in free form or in salt form) may be present in the form of one of the possible isomers or as a mixture of these, for example in the form of pure isomers, such as enantiomers and / or diastereomers, or as isomer mixtures, such as enantiomeric mixtures, for example racemates, diastereomeric mixtures or racemic mixtures; the present invention relates to the pure isomers and also to all possible isomer mixtures, and this is to be understood in each case above and below, even when stereochemical details are not explicitly mentioned in each case.

[0388] Diastereomeric mixtures or racemic mixtures of compounds of formula I in free form or in salt form, the acquisition of which may depend on the starting materials and procedures chosen, can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example, by fractional crystallization, distillation and / or chromatography.

[0389] Enantiomeric mixtures obtainable in an analogous manner (e.g. racemates) can be resolved into the optical enantiomers by known methods, for example by recrystallization from optically active solvents; by chromatography on chiral adsorbents, for example high performance liquid chromatography (HPLC) on acetylcellulose; by cleavage with specific immobilized enzymes with the aid of suitable microorganisms; by forming inclusion compounds, for example using chiral crown ethers, in which only one enantiomer is complexed; or by conversion into diastereomeric salts, for example by reacting the basic end product racemate with an optically active acid (e.g. a carboxylic acid, for example camphoric acid, tartaric acid or malic acid, or a sulfonic acid, for example camphorsulfonic acid) and separating the diastereomeric mixtures obtainable in this way, for example on the basis of their different solubilities, by fractional crystallization to give the diastereoisomers, from which the desired enantiomer can be freed by the action of suitable reagents, for example basic reagents.

[0390] Pure diastereomers or enantiomers can be obtained according to the invention not only by separation of the appropriate isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the method according to the invention with starting materials having the appropriate stereochemistry.

[0391] N-oxides can be prepared by reacting a compound of formula I with a suitable oxidizing agent (e.g. H O / urea adduct) in the presence of an anhydride (e.g. trifluoroacetic anhydride). Such oxidations are known from the literature, for example from J. Med. Chem., 32 (12), 2561-73, 1989 or WO 2000 / 15615.

[0392] If the individual components have different biological activities, it is advantageous to isolate or synthesize the biologically more effective isomers, such as enantiomers or diastereomers or isomer mixtures, such as enantiomeric mixtures or diastereomeric mixtures, in each case.

[0393] If appropriate, the compounds of formula I and, where appropriate, their tautomers (in each case in free form or in salt form) can also be obtained in the form of hydrates and / or include other solvents, such as those which can be used for crystallization of compounds present in solid form.

[0394] The compounds of formula I according to the following tables A-1 to L-12 can be prepared according to the methods described above. The following examples are intended to illustrate the present invention and show preferred compounds of formula I in the form of compounds of formulae I-1 to I-9.

[0395] The following tables show specific compounds of the present invention. In these tables, CH2cPr means CH2-cyclopropyl.

[0396] Table A-1 provides 16 compounds A-1.001 to A-1.016 of formula I-1, wherein G1 is N, G2 is N, X is S, R1 is CH2CH3, A is N and Q1 is as defined in Table B.

[0397]

[0398] For example, A-1.009 is

[0399]

[0400] Table B: Definition of substituents for Q1:

[0401]

[0402]

[0403] Table A-2 provides 16 compounds A-2.001 to A-2.016 of formula I-1, wherein G1 is N, G2 is N, X is S, R1 is CH2CH3, A is CH and Q1 is as defined in Table B.

[0404] Table A-3 provides 16 compounds A-3.001 to A-3.016 of formula I-1, wherein G1 is N, G2 is N, X is S, R1 is CH2cPr, A is N and Q1 is as defined in Table B.

[0405] Table A-4 provides 16 compounds A-4.001 to A-4.016 of formula I-1, wherein G1 is N, G2 is N, X is S, R1 is CH2cPr, A is CH and Q1 is as defined in Table B.

[0406] Table A-5 provides 16 compounds A-5.001 to A-5.016 of formula I-1, wherein G1 is N, G2 is N, X is SO, R1 is CH2CH3, A is N and Q1 is as defined in Table B.

[0407] Table A-6 provides 16 compounds A-6.001 to A-6.016 of formula I-1, wherein G1 is N, G2 is N, X is SO, R1 is CH2CH3, A is CH and Q1 is as defined in Table B.

[0408] Table A-7 provides 16 compounds A-7.001 to A-7.016 of formula I-1, wherein G1 is N, G2 is N, X is SO, R1 is CH2cPr, A is N and Q1 is as defined in Table B.

[0409] Table A-8 provides 16 compounds A-8.001 to A-8.016 of formula I-1, wherein G1 is N, G2 is N, X is SO, R1 is CH2cPr, A is CH and Q1 is as defined in Table B.

[0410] Table A-9 provides 16 compounds A-9.001 to A-9.016 of formula I-1, wherein G1 is N, G2 is N, X is SO2, R1 is CH2CH3, A is N and Q1 is as defined in Table B.

[0411] Table A-10 provides 16 compounds A-10.001 to A-10.016 of formula I-1, wherein G1 is N, G2 is N, X is SO2, R1 is CH2CH3, A is CH and Q1 is as defined in Table B.

[0412] Table A-11 provides 16 compounds A-11.001 to A-11.016 of formula I-1, wherein G1 is N, G2 is N, X is SO2, R1 is CH2cPr, A is N and Q1 is as defined in Table B.

[0413] Table A-12 provides 16 compounds A-12.001 to A-12.016 of formula I-1, wherein G1 is N, G2 is N, X is SO2, R1 is CH2cPr, A is CH and Q1 is as defined in Table B.

[0414] Table A-13 provides 16 compounds A-13.001 to A-13.016 of formula I-1, wherein G1 is N, G2 is CH, X is S, R1 is CH2CH3, A is N and Q1 is as defined in Table B.

[0415] Table A-14 provides 16 compounds A-14.001 to A-14.016 of formula I-1, wherein G1 is N, G2 is CH, X is S, R1 is CH2CH3, A is CH and Q1 is as defined in Table B.

[0416] Table A-15 provides 16 compounds A-15.001 to A-15.016 of formula I-1, wherein G1 is N, G2 is CH, X is S, R1 is CH2cPr, A is N and Q1 is as defined in Table B.

[0417] Table A-16 provides 16 compounds A-16.001 to A-16.016 of formula I-1, wherein G1 is N, G2 is CH, X is S, R1 is CH2cPr, A is CH and Q1 is as defined in Table B.

[0418] Table A-17 provides 16 compounds A-17.001 to A-17.016 of formula I-1, wherein G1 is N, G2 is CH, X is SO, R1 is CH2CH3, A is N and Q1 is as defined in Table B.

[0419] Table A-18 provides 16 compounds A-18.001 to A-18.016 of formula I-1, wherein G1 is N, G2 is CH, X is SO, R1 is CH2CH3, A is CH and Q1 is as defined in Table B.

[0420] Table A-19 provides 16 compounds A-19.001 to A-19.016 of formula I-1, wherein G1 is N, G2 is CH, X is SO, R1 is CH2cPr, A is N and Q1 is as defined in Table B.

[0421] Table A-20 provides 16 compounds A-20.001 to A-20.016 of formula I-1, wherein G1 is N, G2 is CH, X is SO, R1 is CH2cPr, A is CH and Q1 is as defined in Table B.

[0422] Table A-21 provides 16 compounds A-21.001 to A-21.016 of formula I-1, wherein G1 is N, G2 is CH, X is SO2, R1 is CH2CH3, A is N and Q1 is as defined in Table B.

[0423] Table A-22 provides 16 compounds A-22.001 to A-22.016 of formula I-1, wherein G1 is N, G2 is CH, X is SO2, R1 is CH2CH3, A is CH and Q1 is as defined in Table B.

[0424] Table A-23 provides 16 compounds A-23.001 to A-23.016 of formula I-1, wherein G1 is N, G2 is CH, X is SO2, R1 is CH2cPr, A is N and Q1 is as defined in Table B.

[0425] Table A-24 provides 16 compounds A-24.001 to A-24.016 of formula I-1, wherein G1 is N, G2 is CH, X is SO2, R1 is CH2cPr, A is CH and Q1 is as defined in Table B.

[0426] Table A-25 provides 16 compounds A-25.001 to A-25.016 of formula I-1, wherein G1 is CH, G2 is N, X is S, R1 is CH2CH3, A is N and Q1 is as defined in Table B.

[0427] Table A-26 provides 16 compounds A-26.001 to A-26.016 of formula I-1, wherein G1 is CH, G2 is N, X is S, R1 is CH2CH3, A is CH and Q1 is as defined in Table B.

[0428] Table A-27 provides 16 compounds A-27.001 to A-27.016 of formula I-1, wherein G1 is CH, G2 is N, X is S, R1 is CH2cPr, A is N, and Q1 is as defined in Table B.

[0429] Table A-28 provides 16 compounds A-28.001 to A-28.016 of formula I-1, wherein G1 is CH, G2 is N, X is S, R1 is CH2cPr, A is CH and Q1 is as defined in Table B.

[0430] Table A-29 provides 16 compounds A-29.001 to A-29.016 of formula I-1, wherein G1 is CH, G2 is N, X is SO, R1 is CH2CH3, A is N, and Q1 is as defined in Table B.

[0431] Table A-30 provides 16 compounds A-30.001 to A-30.016 of formula I-1, wherein G1 is CH, G2 is N, X is SO, R1 is CH2CH3, A is CH and Q1 is as defined in Table B.

[0432] Table A-31 provides 16 compounds A-31.001 to A-31.016 of formula I-1, wherein G1 is CH, G2 is N, X is SO, R1 is CH2cPr, A is N and Q1 is as defined in Table B.

[0433] Table A-32 provides 16 compounds A-32.001 to A-32.016 of formula I-1, wherein G1 is CH, G2 is N, X is SO, R1 is CH2cPr, A is CH and Q1 is as defined in Table B.

[0434] Table A-33 provides 16 compounds A-33.001 to A-33.016 of formula I-1, wherein G1 is CH, G2 is N, X is SO2, R1 is CH2CH3, A is N and Q1 is as defined in Table B.

[0435] Table A-34 provides 16 compounds A-34.001 to A-34.016 of formula I-1, wherein G1 is CH, G2 is N, X is SO2, R1 is CH2CH3, A is CH and Q1 is as defined in Table B.

[0436] Table A-35 provides 16 compounds A-35.001 to A-35.016 of formula I-1, wherein G1 is CH, G2 is N, X is SO2, R1 is CH2cPr, A is N and Q1 is as defined in Table B.

[0437] Table A-36 provides 16 compounds A-36.001 to A-36.016 of formula I-1, wherein G1 is CH, G2 is N, X is SO2, R1 is CH2cPr, A is CH and Q1 is as defined in Table B.

[0438] Table A-37 provides 16 compounds A-37.001 to A-37.016 of formula I-1, wherein G1 is CH, G2 is CH, X is S, R1 is CH2CH3, A is N, and Q1 is as defined in Table B.

[0439] Table A-38 provides 16 compounds A-38.001 to A-38.016 of formula I-1, wherein G1 is CH, G2 is CH, X is S, R1 is CH2CH3, A is CH and Q1 is as defined in Table B.

[0440] Table A-39 provides 16 compounds A-39.001 to A-39.016 of formula I-1, wherein G1 is CH, G2 is CH, X is S, R1 is CH2cPr, A is N, and Q1 is as defined in Table B.

[0441] Table A-40 provides 16 compounds A-40.001 to A-40.016 of formula I-1, wherein G1 is CH, G2 is CH, X is S, R1 is CH2cPr, A is CH and Q1 is as defined in Table B.

[0442] Table A-41 provides 16 compounds A-41.001 to A-41.016 of formula I-1, wherein G1 is CH, G2 is CH, X is SO, R1 is CH2CH3, A is N, and Q1 is as defined in Table B.

[0443] Table A-42 provides 16 compounds A-42.001 to A-42.016 of formula I-1, wherein G1 is CH, G2 is CH, X is SO, R1 is CH2CH3, A is CH and Q1 is as defined in Table B.

[0444] Table A-43 provides 16 compounds A-43.001 to A-43.016 of formula I-1, wherein G1 is CH, G2 is CH, X is SO, R1 is CH2cPr, A is N, and Q1 is as defined in Table B.

[0445] Table A-44 provides 16 compounds A-44.001 to A-44.016 of formula I-1, wherein G1 is CH, G2 is CH, X is SO, R1 is CH2cPr, A is CH and Q1 is as defined in Table B.

[0446] Table A-45 provides 16 compounds A-45.001 to A-45.016 of formula I-1, wherein G1 is CH, G2 is CH, X is SO2, R1 is CH2CH3, A is N and Q1 is as defined in Table B.

[0447] Table A-46 provides 16 compounds A-46.001 to A-46.016 of formula I-1, wherein G1 is CH, G2 is CH, X is SO2, R1 is CH2CH3, A is CH and Q1 is as defined in Table B.

[0448] Table A-47 provides 16 compounds A-47.001 to A-47.016 of formula I-1, wherein G1 is CH, G2 is CH, X is SO2, R1 is CH2cPr, A is N and Q1 is as defined in Table B.

[0449] Table A-48 provides 16 compounds A-48.001 to A-48.016 of formula I-1, wherein G1 is CH, G2 is CH, X is SO2, R1 is CH2cPr, A is CH and Q1 is as defined in Table B.

[0450] The following tables illustrate specific compounds of the present invention.

[0451]

[0452] Table C-1 provides 16 compounds C-1.001 to C-1.016 of formula I-2, wherein R2 is OSO2CF3, X is S, R1 is CH2CH3 and Q1 is as defined in Table B.

[0453] Table C-2 provides 16 compounds C-2.001 to C-2.016 of formula I-2, wherein R2 is OSO2CF3, X is S, R1 is CH2cPr and Q1 is as defined in Table B.

[0454] Table C-3 provides 16 compounds C-3.001 to C-3.016 of formula I-2, wherein R2 is OSO2CF3, X is SO, R1 is CH2CH3 and Q1 is as defined in Table B.

[0455] Table C-4 provides 16 compounds C-4.001 to C-4.016 of formula I-2, wherein R2 is OSO2CF3, X is SO, R1 is CH2cPr and Q1 is as defined in Table B.

[0456] Table C-5 provides 16 compounds C-5.001 to C-5.016 of formula I-2, wherein R2 is OSO2CF3, X is SO2, R1 is CH2CH3 and Q1 is as defined in Table B.

[0457] Table C-6 provides 16 compounds C-6.001 to C-6.016 of formula I-2, wherein R2 is OSO2CF3, X is SO2, R1 is CH2cPr and Q1 is as defined in Table B.

[0458] Table C-7 provides 16 compounds C-7.001 to C-7.016 of formula I-2, wherein R2 is SO2CF3, X is S, R1 is CH2CH3 and Q1 is as defined in Table B.

[0459] Table C-8 provides 16 compounds C-8.001 to C-8.016 of formula I-2, wherein R2 is SO2CF3, X is S, R1 is CH2cPr and Q1 is as defined in Table B.

[0460] Table C-9 provides 16 compounds C-9.001 to C-9.016 of formula I-2, wherein R2 is SO2CF3, X is SO, R1 is CH2CH3 and Q1 is as defined in Table B.

[0461] Table C-10 provides 16 compounds C-10.001 to C-10.016 of formula I-2, wherein R2 is SO2CF3, X is SO, R1 is CH2cPr and Q1 is as defined in Table B.

[0462] Table C-11 provides 16 compounds C-11.001 to C-11.016 of formula I-2, wherein R2 is SO2CF3, X is SO2, R1 is CH2CH3 and Q1 is as defined in Table B.

[0463] Table C-12 provides 16 compounds C-12.001 to C-12.016 of formula I-2, wherein R2 is SO2CF3, X is SO2, R1 is CH2cPr and Q1 is as defined in Table B.

[0464] Table C-13 provides 16 compounds C-13.001 to C-13.016 of formula I-2, wherein R2 is OCF3, X is S, R1 is CH2CH3 and Q1 is as defined in Table B.

[0465] Table C-14 provides 16 compounds C-14.001 to C-14.016 of formula I-2, wherein R2 is OCF3, X is S, R1 is CH2cPr and Q1 is as defined in Table B.

[0466] Table C-15 provides 16 compounds C-15.001 to C-15.016 of formula I-2, wherein R2 is OCF3, X is SO, R1 is CH2CH3 and Q1 is as defined in Table B.

[0467] Table C-16 provides 16 compounds C-16.001 to C-16.016 of formula I-2, wherein R2 is OCF3, X is SO, R1 is CH2cPr and Q1 is as defined in Table B.

[0468] Table C-17 provides 16 compounds C-17.001 to C-17.016 of formula I-2, wherein R2 is OCF3, X is SO2, R1 is CH2CH3 and Q1 is as defined in Table B.

[0469] Table C-18 provides 16 compounds C-18.001 to C-18.016 of formula I-2, wherein R2 is OCF3, X is SO2, R1 is CH2cPr and Q1 is as defined in Table B.

[0470] The following tables illustrate specific compounds of the present invention.

[0471]

[0472] Table D-1 provides 16 compounds D-1.001 to D-1.016 of formula I-3, wherein X is S, R1 is CH2CH3, A is N and Q1 is as defined in Table B.

[0473] Table D-2 provides 16 compounds D-2.001 to D-2.016 of formula I-3, wherein X is S, R1 is CH2CH3, A is CH and Q1 is as defined in Table B.

[0474] Table D-3 provides 16 compounds D-3.001 to D-3.016 of formula I-3, wherein X is S, R1 is CH2cPr, A is N, and Q1 is as defined in Table B.

[0475] Table D-4 provides 16 compounds D-4.001 to D-4.016 of formula I-3, wherein X is S, R1 is CH2cPr, A is CH and Q1 is as defined in Table B.

[0476] Table D-5 provides 16 compounds D-5.001 to D-5.016 of formula I-3, wherein X is SO, R1 is CH2CH3, A is N, and Q1 is as defined in Table B.

[0477] Table D-6 provides 16 compounds D-6.001 to D-6.016 of formula I-3, wherein X is SO, R1 is CH2CH3, A is CH and Q1 is as defined in Table B.

[0478] Table D-7 provides 16 compounds D-7.001 to D-7.016 of formula I-3, wherein X is SO, R1 is CH2cPr, A is N, and Q1 is as defined in Table B.

[0479] Table D-8 provides 16 compounds D-8.001 to D-8.016 of formula I-3, wherein X is SO, R1 is CH2cPr, A is CH and Q1 is as defined in Table B.

[0480] Table D-9 provides 16 compounds D-9.001 to D-9.016 of formula I-3, wherein X is SO2, R1 is CH2CH3, A is N and Q1 is as defined in Table B.

[0481] Table D-10 provides 16 compounds D-10.001 to D-10.016 of formula I-3, wherein X is SO2, R1 is CH2CH3, A is CH and Q1 is as defined in Table B.

[0482] Table D-11 provides 16 compounds D-11.001 to D-11.016 of formula I-3, wherein X is SO2, R1 is CH2cPr, A is N and Q1 is as defined in Table B.

[0483] Table D-12 provides 16 compounds D-12.001 to D-12.016 of formula I-3, wherein X is SO2, R1 is CH2cPr, A is CH and Q1 is as defined in Table B.

[0484]

[0485] Table E-1 provides 16 compounds E-1.001 to E-1.016 of formula I-4, wherein X is S, R1 is CH2CH3, A is N and Q1 is as defined in Table B.

[0486] Table E-2 provides 16 compounds E-2.001 to E-2.016 of formula I-4, wherein X is S, R1 is CH2CH3, A is CH and Q1 is as defined in Table B.

[0487] Table E-3 provides 16 compounds E-3.001 to E-3.016 of formula I-4, wherein X is S, R1 is CH2cPr, A is N, and Q1 is as defined in Table B.

[0488] Table E-4 provides 16 compounds E-4.001 to E-4.016 of formula I-4, wherein X is S, R1 is CH2cPr, A is CH and Q1 is as defined in Table B.

[0489] Table E-5 provides 16 compounds E-5.001 to E-5.016 of formula I-4, wherein X is SO, R1 is CH2CH3, A is N, and Q1 is as defined in Table B.

[0490] Table E-6 provides 16 compounds E-6.001 to E-6.016 of formula I-4, wherein X is SO, R1 is CH2CH3, A is CH and Q1 is as defined in Table B.

[0491] Table E-7 provides 16 compounds E-7.001 to E-7.016 of formula I-4, wherein X is SO, R1 is CH2cPr, A is N, and Q1 is as defined in Table B.

[0492] Table E-8 provides 16 compounds E-8.001 to E-8.016 of formula I-4, wherein X is SO, R1 is CH2cPr, A is CH and Q1 is as defined in Table B.

[0493] Table E-9 provides 16 compounds E-9.001 to E-9.016 of formula I-4, wherein X is SO2, R1 is CH2CH3, A is N and Q1 is as defined in Table B.

[0494] Table E-10 provides 16 compounds E-10.001 to E-10.016 of formula I-4, wherein X is SO2, R1 is CH2CH3, A is CH and Q1 is as defined in Table B.

[0495] Table E-11 provides 16 compounds E-11.001 to E-11.016 of formula I-4, wherein X is SO2, R1 is CH2cPr, A is N and Q1 is as defined in Table B.

[0496] Table E-12 provides 16 compounds E-12.001 to E-12.016 of formula I-4, wherein X is SO2, R1 is CH2cPr, A is CH and Q1 is as defined in Table B.

[0497] The following tables illustrate specific compounds of the present invention.

[0498]

[0499] Table G-1 provides 16 compounds G-1.001 to G-1.016 of formula I-5, wherein G1 is N, G2 is N, X is S, R1 is CH2CH3 and Q1 is as defined in Table B.

[0500] Table-G2 provides 16 compounds G-2.001 to G-2.016 of formula I-5, wherein G1 is N, G2 is N, X is S, R1 is CH2cPr and Q1 is as defined in Table B.

[0501] Table-G3 provides 16 compounds G-3.001 to G-3.016 of formula I-5, wherein G1 is N, G2 is N, X is SO, R1 is CH2CH3 and Q1 is as defined in Table B.

[0502] Table-G4 provides 16 compounds G-4.001 to G-4.016 of formula I-5, wherein G1 is N, G2 is N, X is SO, R1 is CH2cPr and Q1 is as defined in Table B.

[0503] Table-G5 provides 16 compounds G-5.001 to G-5.016 of formula I-5, wherein G1 is N, G2 is N, X is SO2, R1 is CH2CH3 and Q1 is as defined in Table B.

[0504] Table-G6 provides 16 compounds G-6.001 to G-6.016 of formula I-5, wherein G1 is N, G2 is N, X is SO2, R1 is CH2cPr and Q1 is as defined in Table B.

[0505] Table-G7 provides 16 compounds G-7.001 to G-7.016 of formula I-5, wherein G1 is N, G2 is CH, X is S, R1 is CH2CH3 and Q1 is as defined in Table B.

[0506] Table-G8 provides 16 compounds G-8.001 to G-8.016 of formula I-5, wherein G1 is N, G2 is CH, X is S, R1 is CH2cPr and Q1 is as defined in Table B.

[0507] Table-G9 provides 16 compounds G-9.001 to G-9.016 of formula I-5, wherein G1 is N, G2 is CH, X is SO, R1 is CH2CH3 and Q1 is as defined in Table B.

[0508] Table-G10 provides 16 compounds G-10.001 to G-10.016 of formula I-5, wherein G1 is N, G2 is CH, X is SO, R1 is CH2cPr and Q1 is as defined in Table B.

[0509] Table-G11 provides 16 compounds G-11.001 to G-11.016 of formula I-5, wherein G1 is N, G2 is CH, X is SO2, R1 is CH2CH3 and Q1 is as defined in Table B.

[0510] Table-G12 provides 16 compounds G-12.001 to G-12.016 of formula I-5, wherein G1 is N, G2 is CH, X is SO2, R1 is CH2cPr and Q1 is as defined in Table B.

[0511] Table-G13 provides 16 compounds G-13.001 to G-13.016 of formula I-5, wherein G1 is CH, G2 is N, X is S, R1 is CH2CH3 and Q1 is as defined in Table B.

[0512] Table-G14 provides 16 compounds G-14.001 to G-14.016 of formula I-5, wherein G1 is CH, G2 is N, X is S, R1 is CH2cPr and Q1 is as defined in Table B.

[0513] Table-G15 provides 16 compounds G-15.001 to G-15.016 of formula I-5, wherein G1 is CH, G2 is N, X is SO, R1 is CH2CH3 and Q1 is as defined in Table B.

[0514] Table-G16 provides 16 compounds G-16.001 to G-16.016 of formula I-5, wherein G1 is CH, G2 is N, X is SO, R1 is CH2cPr and Q1 is as defined in Table B.

[0515] Table-G17 provides 16 compounds G-17.001 to G-17.016 of formula I-5, wherein G1 is CH, G2 is N, X is SO2, R1 is CH2CH3 and Q1 is as defined in Table B.

[0516] Table-G18 provides 16 compounds G-18.001 to G-18.016 of formula I-5, wherein G1 is CH, G2 is N, X is SO2, R1 is CH2cPr and Q1 is as defined in Table B.

[0517] Table-G19 provides 16 compounds G-19.001 to G-19.016 of formula I-5, wherein G1 is CH, G2 is CH, X is S, R1 is CH2CH3 and Q1 is as defined in Table B.

[0518] Table-G20 provides 16 compounds G-20.001 to G-20.016 of formula I-5, wherein G1 is CH, G2 is CH, X is S, R1 is CH2cPr and Q1 is as defined in Table B.

[0519] Table-G21 provides 16 compounds G-21.001 to G-21.016 of formula I-5, wherein G1 is CH, G2 is CH, X is SO, R1 is CH2CH3 and Q1 is as defined in Table B.

[0520] Table-G22 provides 16 compounds G-22.001 to G-22.016 of formula I-5, wherein G1 is CH, G2 is CH, X is SO, R1 is CH2cPr and Q1 is as defined in Table B.

[0521] Table-G23 provides 16 compounds G-23.001 to G-23.016 of formula I-5, wherein G1 is CH, G2 is CH, X is SO2, R1 is CH2CH3 and Q1 is as defined in Table B.

[0522] Table-G24 provides 16 compounds G-24.001 to G-24.016 of formula I-5, wherein G1 is CH, G2 is CH, X is SO2, R1 is CH2cPr and Q1 is as defined in Table B.

[0523] The following tables illustrate specific compounds of the present invention.

[0524]

[0525] Table I-1 provides 10 compounds I-1.001 to I-1.010 of Formula I, wherein G1 is N, G2 is N, X is S, R1 is CH2CH3, A is N and Q1 is as defined in Table H.

[0526] Table H: Definition of substituents for Q1:

[0527]

[0528]

[0529] Table I-2 provides 10 compounds I-2.001 to I-2.010 of formula I-6, wherein G1 is N, G2 is N, X is S, R1 is CH2CH3, A is CH and Q1 is as defined in Table H.

[0530] Table I-3 provides 10 compounds I-3.001 to I-3.010 of formula I-6, wherein G1 is N, G2 is N, X is S, R1 is CH2cPr, A is N and Q1 is as defined in Table H.

[0531] Table I-4 provides 10 compounds I-4.001 to I-4.010 of formula I-6, wherein G1 is N, G2 is N, X is S, R1 is CH2cPr, A is CH and Q1 is as defined in Table H.

[0532] Table I-5 provides 10 compounds I-5.001 to I-5.010 of formula I-6, wherein G1 is N, G2 is N, X is SO, R1 is CH2CH3, A is N and Q1 is as defined in Table H.

[0533] Table I-6 provides 10 compounds I-6.001 to I-6.010 of formula I-6, wherein G1 is N, G2 is N, X is SO, R1 is CH2CH3, A is CH and Q1 is as defined in Table H.

[0534] Table I-7 provides 10 compounds I-7.001 to I-7.010 of formula I-6, wherein G1 is N, G2 is N, X is SO, R1 is CH2cPr, A is N and Q1 is as defined in Table H.

[0535] Table I-8 provides 10 compounds I-8.001 to I-8.010 of formula I-6, wherein G1 is N, G2 is N, X is SO, R1 is CH2cPr, A is CH and Q1 is as defined in Table H.

[0536] Table I-9 provides 10 compounds I-9.001 to I-9.010 of formula I-6, wherein G1 is N, G2 is N, X is SO2, R1 is CH2CH3, A is N and Q1 is as defined in Table H.

[0537] Table I-10 provides 10 compounds I-10.001 to I-10.010 of formula I-6, wherein G1 is N, G2 is N, X is SO2, R1 is CH2CH3, A is CH and Q1 is as defined in Table H.

[0538] Table I-11 provides 10 compounds I-11.001 to I-11.010 of formula I-6, wherein G1 is N, G2 is N, X is SO2, R1 is CH2cPr, A is N and Q1 is as defined in Table H.

[0539] Table I-12 provides 10 compounds I-12.001 to I-12.010 of formula I-6, wherein G1 is N, G2 is N, X is SO2, R1 is CH2cPr, A is CH and Q1 is as defined in Table H.

[0540] Table I-13 provides 10 compounds I-13.001 to I-13.010 of formula I-6, wherein G1 is N, G2 is CH, X is S, R1 is CH2CH3, A is N and Q1 is as defined in Table H.

[0541] Table I-14 provides 10 compounds I-14.001 to I-14.010 of formula I-6, wherein G1 is N, G2 is CH, X is S, R1 is CH2CH3, A is CH and Q1 is as defined in Table H.

[0542] Table I-15 provides 10 compounds I-15.001 to I-15.010 of formula I-6, wherein G1 is N, G2 is CH, X is S, R1 is CH2cPr, A is N and Q1 is as defined in Table H.

[0543] Table I-16 provides 10 compounds of formula I-6 (I-16.001 to I-16.010), wherein G1 is N, G2 is CH, X is S, R1 is CH2cPr, A is CH, and Q1 is as defined in Table H.

[0544] Table I-17 provides 10 compounds I-17.001 to I-17.010 of formula I-6, wherein G1 is N, G2 is CH, X is SO, R1 is CH2CH3, A is N and Q1 is as defined in Table H.

[0545] Table I-18 provides 10 compounds I-18.001 to I-18.010 of formula I-6, wherein G1 is N, G2 is CH, X is SO, R1 is CH2CH3, A is CH and Q1 is as defined in Table H.

[0546] Table I-19 provides 10 compounds of formula I-6 (I-19.001 to I-19.010), wherein G1 is N, G2 is CH, X is SO, R1 is CH2cPr, A is N, and Q1 is as defined in Table H.

[0547] Table 1-20 provides 10 compounds of formula I-6 (I-20.001 to I-20.010), wherein G1 is N, G2 is CH, X is SO, R1 is CH2cPr, A is CH and Q1 is as defined in Table H.

[0548] Table I-21 provides 10 compounds I-21.001 to I-21.010 of formula I-6, wherein G1 is N, G2 is CH, X is SO2, R1 is CH2CH3, A is N and Q1 is as defined in Table H.

[0549] Table I-22 provides 10 compounds I-22.001 to I-22.010 of formula I-6, wherein G1 is N, G2 is CH, X is SO2, R1 is CH2CH3, A is CH and Q1 is as defined in Table H.

[0550] Table I-23 provides 10 compounds I-23.001 to I-23.010 of formula I-6, wherein G1 is N, G2 is CH, X is SO2, R1 is CH2cPr, A is N and Q1 is as defined in Table H.

[0551] Table 1-24 provides 10 compounds of formula I-6 (I-24.001 to I-24.010), wherein G1 is N, G2 is CH, X is SO2, R1 is CH2cPr, A is CH and Q1 is as defined in Table H.

[0552] Table 1-25 provides 10 compounds of formula I-6 (I-25.001 to I-25.010), wherein G1 is CH, G2 is N, X is S, R1 is CH2CH3, A is N, and Q1 is as defined in Table H.

[0553] Table 1-26 provides 10 compounds of formula I-6 (I-26.001 to I-26.010), wherein G1 is CH, G2 is N, X is S, R1 is CH2CH3, A is CH, and Q1 is as defined in Table H.

[0554] Table 1-27 provides 10 compounds of formula I-6 (I-27.001 to I-27.010), wherein G1 is CH, G2 is N, X is S, R1 is CH2cPr, A is N, and Q1 is as defined in Table H.

[0555] Table 1-28 provides 10 compounds of formula I-6 (I-28.001 to I-28.010), wherein G1 is CH, G2 is N, X is S, R1 is CH2cPr, A is CH, and Q1 is as defined in Table H.

[0556] Table 1-29 provides 10 compounds of formula I-6 (I-29.001 to I-29.010), wherein G1 is CH, G2 is N, X is SO, R1 is CH2CH3, A is N, and Q1 is as defined in Table H.

[0557] Table 1-30 provides 10 compounds of formula I-6 (I-30.001 to I-30.010), wherein G1 is CH, G2 is N, X is SO, R1 is CH2CH3, A is CH, and Q1 is as defined in Table H.

[0558] Table I-31 provides 10 compounds of formula I-6 (I-31.001 to I-31.010), wherein G1 is CH, G2 is N, X is SO, R1 is CH2cPr, A is N, and Q1 is as defined in Table H.

[0559] Table 1-32 provides 10 compounds of formula I-6 (I-32.001 to I-32.010), wherein G1 is CH, G2 is N, X is SO, R1 is CH2cPr, A is CH, and Q1 is as defined in Table H.

[0560] Table I-33 provides 10 compounds I-33.001 to I-33.010 of formula I-6, wherein G1 is CH, G2 is N, X is SO2, R1 is CH2CH3, A is N and Q1 is as defined in Table H.

[0561] Table 1-34 provides 10 compounds of formula I-6 (I-34.001 to I-34.010), wherein G1 is CH, G2 is N, X is SO2, R1 is CH2CH3, A is CH and Q1 is as defined in Table H.

[0562] Table 1-35 provides 10 compounds of formula I-6 (I-35.001 to I-35.010), wherein G1 is CH, G2 is N, X is SO2, R1 is CH2cPr, A is N, and Q1 is as defined in Table H.

[0563] Table 1-36 provides 10 compounds of formula I-6 (I-36.001 to I-36.010), wherein G1 is CH, G2 is N, X is SO2, R1 is CH2cPr, A is CH and Q1 is as defined in Table H.

[0564] Table 1-37 provides 10 compounds of formula I-6 (I-37.001 to I-37.010), wherein G1 is CH, G2 is CH, X is S, R1 is CH2CH3, A is N, and Q1 is as defined in Table H.

[0565] Table 1-38 provides 10 compounds of formula I-6 (I-38.001 to I-38.010), wherein G1 is CH, G2 is CH, X is S, R1 is CH2CH3, A is CH, and Q1 is as defined in Table H.

[0566] Table 1-39 provides 10 compounds of formula I-6 (I-39.001 to I-39.010), wherein G1 is CH, G2 is CH, X is S, R1 is CH2cPr, A is N, and Q1 is as defined in Table H.

[0567] Table 1-40 provides 10 compounds of formula I-6 (I-40.001 to I-40.010), wherein G1 is CH, G2 is CH, X is S, R1 is CH2cPr, A is CH, and Q1 is as defined in Table H.

[0568] Table I-41 provides 10 compounds of formula I-6 (I-41.001 to I-41.010), wherein G1 is CH, G2 is CH, X is SO, R1 is CH2CH3, A is N, and Q1 is as defined in Table H.

[0569] Table 1-42 provides 10 compounds of formula I-6 (I-42.001 to I-42.010), wherein G1 is CH, G2 is CH, X is SO, R1 is CH2CH3, A is CH, and Q1 is as defined in Table H.

[0570] Table 1-43 provides 10 compounds of formula I-6 (I-43.001 to I-43.010), wherein G1 is CH, G2 is CH, X is SO, R1 is CH2cPr, A is N, and Q1 is as defined in Table H.

[0571] Table 1-44 provides 10 compounds of formula I-6 (I-44.001 to I-44.010), wherein G1 is CH, G2 is CH, X is SO, R1 is CH2cPr, A is CH, and Q1 is as defined in Table H.

[0572] Table I-45 provides 10 compounds I-45.001 to I-45.010 of formula I-6, wherein G1 is CH, G2 is CH, X is SO2, R1 is CH2CH3, A is N and Q1 is as defined in Table H.

[0573] Table 1-46 provides 10 compounds of formula I-6 (I-46.001 to I-46.010), wherein G1 is CH, G2 is CH, X is SO2, R1 is CH2CH3, A is CH, and Q1 is as defined in Table H.

[0574] Table 1-47 provides 10 compounds of formula I-6 (I-47.001 to I-47.010), wherein G1 is CH, G2 is CH, X is SO2, R1 is CH2cPr, A is N, and Q1 is as defined in Table H.

[0575] Table 1-48 provides 10 compounds of formula I-6 (I-48.001 to I-48.010), wherein G1 is CH, G2 is CH, X is SO2, R1 is CH2cPr, A is CH, and Q1 is as defined in Table H.

[0576] The following tables illustrate specific compounds of the present invention.

[0577]

[0578] Table J-1 provides 10 compounds J-1.001 to J-1.010 of formula I-7, wherein R2 is SO2CF3, X is S, R1 is CH2CH3 and Q1 is as defined in Table H.

[0579] Table J-2 provides 10 compounds J-2.001 to J-2.010 of formula I-7, wherein R2 is SO2CF3, X is S, R1 is CH2cPr and Q1 is as defined in Table H.

[0580] Table J-3 provides 10 compounds J-3.001 to J-3.010 of formula I-7, wherein R2 is SO2CF3, X is SO, R1 is CH2CH3 and Q1 is as defined in Table H.

[0581] Table J-4 provides 10 compounds J-4.001 to J-4.010 of formula I-7, wherein R2 is SO2CF3, X is SO, R1 is CH2cPr and Q1 is as defined in Table H.

[0582] Table J-5 provides 10 compounds J-5.001 to J-5.010 of formula I-7, wherein R2 is SO2CF3, X is SO2, R1 is CH2CH3 and Q1 is as defined in Table H.

[0583] Table J-6 provides 10 compounds J-6.001 to J-6.010 of formula I-7, wherein R2 is SO2CF3, X is SO2, R1 is CH2cPr and Q1 is as defined in Table H.

[0584] Table J-7 provides 10 compounds J-7.001 to J-7.010 of formula I-7, wherein R2 is OSO2CF3, X is S, R1 is CH2CH3 and Q1 is as defined in Table H.

[0585] Table J-8 provides 10 compounds J-8.001 to J-8.010 of formula I-7, wherein R2 is OSO2CF3, X is S, R1 is CH2cPr and Q1 is as defined in Table H.

[0586] Table J-9 provides 10 compounds J-9.001 to J-9.010 of formula I-7, wherein R2 is OSO2CF3, X is SO, R1 is CH2CH3 and Q1 is as defined in Table H.

[0587] Table J-10 provides 10 compounds J-10.001 to J-10.010 of formula I-7, wherein R2 is OSO2CF3, X is SO, R1 is CH2cPr and Q1 is as defined in Table H.

[0588] Table J-11 provides 10 compounds J-11.001 to J-11.010 of formula I-7, wherein R2 is OSO2CF3, X is SO2, R1 is CH2CH3 and Q1 is as defined in Table H.

[0589] Table J-12 provides 10 compounds J-12.001 to J-12.010 of formula I-7, wherein R2 is OSO2CF3, X is SO2, R1 is CH2cPr and Q1 is as defined in Table H.

[0590] Table J-13 provides 10 compounds J-13.001 to J-13.010 of formula I-7, wherein R2 is OCF3, X is S, R1 is CH2CH3 and Q1 is as defined in Table H.

[0591] Table J-14 provides 10 compounds J-14.001 to J-14.010 of formula I-7, wherein R2 is OCF3, X is S, R1 is CH2cPr and Q1 is as defined in Table H.

[0592] Table J-15 provides 10 compounds J-15.001 to J-15.010 of formula I-7, wherein R2 is OCF3, X is SO, R1 is CH2CH3 and Q1 is as defined in Table H.

[0593] Table J-16 provides 10 compounds J-16.001 to J-16.010 of formula I-7, wherein R2 is OCF3, X is SO, R1 is CH2cPr and Q1 is as defined in Table H.

[0594] Table J-17 provides 10 compounds J-17.001 to J-17.010 of formula I-7, wherein R2 is OCF3, X is SO2, R1 is CH2CH3 and Q1 is as defined in Table H.

[0595] Table J-18 provides 10 compounds J-18.001 to J-18.010 of formula I-7, wherein R2 is OCF3, X is SO2, R1 is CH2cPr and Q1 is as defined in Table H.

[0596] The following tables illustrate specific compounds of the present invention.

[0597]

[0598] Table K-1 provides 10 compounds K-1.001 to K-1.010 of formula I-8, wherein X is S, R1 is CH2CH3, A is N and Q1 is as defined in Table H.

[0599] Table K-2 provides 10 compounds K-2.001 to K-2.010 of formula I-8, wherein X is S, R1 is CH2CH3, A is CH and Q1 is as defined in Table H.

[0600] Table K-3 provides 10 compounds K-3.001 to K-3.010 of formula I-8, wherein X is S, R1 is CH2cPr, A is N and Q1 is as defined in Table H.

[0601] Table K-4 provides 10 compounds K-4.001 to K-4.010 of formula I-8, wherein X is S, R1 is CH2cPr, A is CH and Q1 is as defined in Table H.

[0602] Table K-5 provides 10 compounds K-5.001 to K-5.010 of formula I-8, wherein X is SO, R1 is CH2CH3, A is N and Q1 is as defined in Table H.

[0603] Table K-6 provides 10 compounds K-6.001 to K-6.010 of formula I-8, wherein X is SO, R1 is CH2CH3, A is CH and Q1 is as defined in Table H.

[0604] Table K-7 provides 10 compounds K-7.001 to K-7.010 of formula I-8, wherein X is SO, R1 is CH2cPr, A is N and Q1 is as defined in Table H.

[0605] Table K-8 provides 10 compounds K-8.001 to K-8.010 of formula I-8, wherein X is SO, R1 is CH2cPr, A is CH and Q1 is as defined in Table H.

[0606] Table K-9 provides 10 compounds K-9.001 to K-9.010 of formula I-8, wherein X is SO2, R1 is CH2CH3, A is N and Q1 is as defined in Table H.

[0607] Table K-10 provides 10 compounds K-10.001 to K-10.010 of formula I-8, wherein X is SO2, R1 is CH2CH3, A is CH and Q1 is as defined in Table H.

[0608] Table K-11 provides 10 compounds K-11.001 to K-11.010 of formula I-8, wherein X is SO2, R1 is CH2cPr, A is N and Q1 is as defined in Table H.

[0609] Table K-12 provides 10 compounds K-12.001 to K-12.010 of formula I-8, wherein X is SO2, R1 is CH2cPr, A is CH and Q1 is as defined in Table H.

[0610] The following tables illustrate specific compounds of the present invention.

[0611]

[0612] Table L-1 provides 10 compounds L-1.001 to L-1.010 of formula I-9, wherein X is S, R1 is CH2CH3, A is N and Q1 is as defined in Table H.

[0613] Table L-2 provides 10 compounds L-2.001 to L-2.010 of formula I-9, wherein X is S, R1 is CH2CH3, A is CH and Q1 is as defined in Table H.

[0614] Table L-3 provides 10 compounds L-3.001 to L-3.010 of formula I-9, wherein X is S, R1 is CH2cPr, A is N and Q1 is as defined in Table H.

[0615] Table L-4 provides 10 compounds L-4.001 to L-4.010 of formula I-9, wherein X is S, R1 is CH2cPr, A is CH and Q1 is as defined in Table H.

[0616] Table L-5 provides 10 compounds L-5.001 to L-5.010 of formula I-9, wherein X is SO, R1 is CH2CH3, A is N and Q1 is as defined in Table H.

[0617] Table L-6 provides 10 compounds L-6.001 to L-6.010 of formula I-9, wherein X is SO, R1 is CH2CH3, A is CH and Q1 is as defined in Table H.

[0618] Table L-7 provides 10 compounds L-7.001 to L-7.010 of formula I-9, wherein X is SO, R1 is CH2cPr, A is N and Q1 is as defined in Table H.

[0619] Table L-8 provides 10 compounds L-8.001 to L-8.010 of formula I-9, wherein X is SO, R1 is CH2cPr, A is CH and Q1 is as defined in Table H.

[0620] Table L-9 provides 10 compounds L-9.001 to L-9.010 of formula I-9, wherein X is SO2, R1 is CH2CH3, A is N and Q1 is as defined in Table H.

[0621] Table L-10 provides 10 compounds L-10.001 to L-10.010 of formula I-9, wherein X is SO2, R1 is CH2CH3, A is CH and Q1 is as defined in Table H.

[0622] Table L-11 provides 10 compounds L-11.001 to L-11.010 of formula I-9, wherein X is SO2, R1 is CH2cPr, A is N and Q1 is as defined in Table H.

[0623] Table L-12 provides 10 compounds L-12.001 to L-12.010 of formula I-9, wherein X is SO2, R1 is CH2cPr, A is CH and Q1 is as defined in Table H.

[0624] The compounds of formula I according to the invention are active ingredients of preventive and / or therapeutic value in the field of pest control. Even at low application rates, they have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish, and plants. The active ingredients according to the invention act against all or individual developmental stages of normally sensitive but also resistant animal pests, such as insects or representatives of the order Acarina. The insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i.e., destruction of the pests occurs immediately or only after a certain period of time (e.g., during molting); or indirectly, for example, by reducing egg laying and / or hatching rates, corresponding to a good activity of at least 50% to 60% destruction (mortality).

[0625] Examples of the animal pests mentioned above are:

[0626] from the order Acarina, e.g.

[0627] Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp., Eotetranychus spp., Eriophyes spp.), Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp.), Steneotarsonemus spp., Tarsonemus spp., and Tetranychus spp.;

[0628] From the order Phthirus, e.g.

[0629] Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp., and Phylloxera spp.;

[0630] From the order Coleoptera, e.g.

[0631] 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., Diabrotica spp.), Argentine beetle (Diloboderus abderus), herbivorous ladybird species (Epilachna spp.), Eremnus species, Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa ​​decemLineata, Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Maladera castanea, American leaf beetle species (Megascelis spp.), rapeseed beetle (Melighetes aeneus), Melolontha spp., Myochrousarmatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp.), Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp.), Somaticus spp., Sphenophorus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp., and Trogoderma spp.;

[0632] From the order Diptera, e.g.

[0633] Aedes spp., Anopheles spp., Antherigonas occata., Bactrocea oleae, Bibio hortulanus, Bradysia spp., Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyza tripunctata, Glossina spp.), Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis spp., Riveria quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp.) and Tipula spp.;

[0634] From the order Hemiptera, e.g.

[0635] Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Amblypelta nitida, Bathycoeliathalassina, Blissus spp., Cimex spp., Clavigrallatomentosicollis, Creontiades spp., Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp., Euschistus spp., Eurydema pulchrum, Eurygaster spp.), Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp., Margarodes spp., Murgantia histrionic, Neomegalotomus spp., Nesidiocoris tenuis, Nezara spp., Nysius simulans, Oebalus insularis, Piesma spp., Piezodorus spp., Rhodnius spp.), cocoa stink bug (Sahlbergella singularis), chestnut stink bug (Scaptocoris castanea), black stink bug species (Scotinophara spp.), Thyanta species, Triatoma species (Triatoma spp.), cassava web stink bug (Vatiga illudens);

[0636] Acyrthosium pisum, Adalges species, Agallina ensigera, Agonascena targionii, Aleurodicus spp., Aleurocanthus spp., Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarascabiguttula, Amritodus atkinsoni, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli), Bemisia spp., Brachycaudus spp., Brevicoryne brassicae, Cacopsylla spp., Cavariella aegopodii Scop., Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp., Cofanaspectra, Cryptomyzus spp., Cicadulina spp., Coccus hesperidum, Dalbulus maidis, Dialeurodes spp., Diaphorina citri), Diuraphis noxia, Dysaphis spp., Empoasca spp., Eriosoma larigerum, Erythroneura spp.), Gascardia species, Glycaspis brimblecombei, Hyadaphis pseudobrassicae, Hyalopterus spp., Hyperomyzus pallidus, Idioscopus clypealis, Jacobiasca lybica, Laodelphax spp., Lecanium corni, Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp., Mahanarva spp., Metcalfapruinosa, Metopolophium dirhodum, Myndus crudus), Myzus spp., Neotoxoptera sp., Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter, Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Peregrinus maidis, Perkinsiella spp., Phorodon humuli, Phylloxera spp., Planococcus spp.), Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psyllas spp., Pulvinaria aethiopica, Quadraspidiotus spp.), Quesadagigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Sogatella furcifera, Spissistilus festinus, Tarophagus proserpina, Toxoptera spp., Trialeurodes spp., Tridiscus sporoboli, Trionymus spp., Trioza erytreae, Unaspis citri, Zygina flammigera, Zyginidia scutellaris;

[0637] from the order Hymenoptera, e.g.

[0638] Acromyrmex species, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprions spp., Pogonomyrmex spp., Slenopsis invicta, Solenopsis spp., and Vespa spp.;

[0639] From the order Isoptera, e.g.

[0640] Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Tropical fire ants (Solenopsis geminate)

[0641] From the order Lepidoptera, for example,

[0642] Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp., Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseolafusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp.), Chrysoteuchiatopiaria, Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp., Crocidolomia binotalis, Cryptophlebialeucotreta, Cydalima perspectalis, Cydia spp., Diaphania perspectalis, Diatraea spp.), Sudan bollworm (Diparopsis castanea), Earias spp., sweet potato stem borer (Eldana saccharina), Ephestia spp., Epinotia spp., Saltmarsh moth (Estigmene acrea), Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella, Euproctis spp.), Euxoa spp., Feltia jaculiferia, Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp., Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostegebifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp.), Mamestra brassicae, Manduca sexta, Mythimna spp., Noctua spp., Operophtera spp., Orniodes indica, Ostrinia nubilalis (European corn borer), Pammene spp., Pandemis spp., Panolis flammea, Papaipema nebris, Pectinophora gossypiela (red bell moth), Perileucoptera coffeella (coffee leaf miner), Pseudaletia unipuncta (one-star armyworm), Phthorimaea operculella (potato moth), Pieris rapae (rabbit butterfly), Pieris spp., Plutella xylostella), Prays spp., Pseudoplusia spp., Rachiplusia nu, Richia albicosta, Scirpophaga spp., Sesamia spp., Sparganothis spp.), Spodoptera spp., Sylepta derogate, Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tuta absoluta, and Yponomeuta spp.;

[0643] From the order Mallophaga, for example,

[0644] Damalina spp. and Trichodectes spp.;

[0645] From the order Orthoptera, for example,

[0646] Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscus spp., and Schistocerca spp.;

[0647] From the order Psocoptera, for example,

[0648] Liposcelis spp.;

[0649] From the order Siphonaptera, for example,

[0650] Ceratophyllus spp., Ctenocephalides spp., and Xenopsylla cheopis;

[0651] From the order Thysanoptera, for example,

[0652] Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp.

[0653] From the order of the Thysanura, for example, Lepisma saccharina.

[0654] The active ingredients according to the invention can be used for controlling, i.e. suppressing or destroying pests of the aforementioned type, which occur in particular on plants, especially on useful and ornamental plants in agriculture, horticulture and forestry, or on organs of these plants, such as fruits, flowers, leaves, stems, tubers or roots, and in some cases even plant organs formed at a later point in time still remain protected against these pests.

[0655] Suitable target crops are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beets, such as sugar beets or fodder beets; fruits, such as pome, stone or soft fruit, such as apples, pears, plums, peaches, apricots, cherries or berries, such as strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soybeans; oilseed crops, such as rapeseed, mustard, poppy, olives, sunflower, coconut, castor, cocoa or peanuts; Cucurbit crops, such as pumpkin, cucumber, or melon; 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 avocado, cinnamon, or camphor; and also tobacco, nuts, coffee, eggplant, sugarcane, tea, pepper, grapevines, hops, plantago, and latex plants.

[0656] The compositions and / or methods of the present invention may also be used on any ornamental and / or vegetable crop, including flowers, shrubs, broadleaf trees, and evergreen plants.

[0657] For example, the present invention can be used with any of the following ornamental plant species: Ageratum, Alonso spp., Anemone, Amur sunflower, Anthemis, Antirrhinum, Aster, Begonia (e.g., Rieger begonia, Begonia spp., Begonia tubéreux), Bougainvillea, Brachycome spp., Brassica (ornamental plants), Calceolaria, Capsicum, Catharanthus roseus, Canna, Cornflower, Chrysanthemum, Cineraria (Cinnamon), Coreopsis, Crassula coccinea, Cuphea ignea, Dahlia, Delphinium, Dicentra, Dorotheantus spp.), Lisianthus, Forsythia, Fuchsia, Geranium gnaphalium, Gerbera, Globe amaranth, Heliotrope, Sunflower, Hibiscus, Hydrangea, Hydrangea, Rhododendron, Impatiens (African balsam), Iresines spp., Kalanchoe, Lantana, March flower, Lion's ear, Lilium, Japanese lily, Physalis, Monarda, Monarda, Tagetes, Dianthus (carnation), Canna, Oxalis, Daisy, Pelargonium (Pelargonium pelargonium, Pelargonium pelargonium), Viola (pansy), Petunia, Phlox, Plectranthus spp.), poinsettia, creeper (Parthenocissus quinquefolia, Parthenocissus quinquefolia), primrose, ranunculus, azalea, Rosa (rose), rudbeckia, African violet, salvia, Scaevola aemola, Schizanthus wisetonensis, sedum, nightshade, Solanum spp., marigold, tobacco, verbena, zinnia, and other bedding plants.

[0658] For example, the present invention can be used with any of the following vegetable species: Allium species (garlic, onion, A. oschaninii, leek, shallot, scallion), fennel, celery (Apium graveolus), asparagus, beets, Brassica species (cabbage, Chinese cabbage, turnip), peppers, chickpeas, endive, chicory species (chicory, endive), watermelon (Citrillus lanatus), Cucumber species (cucumber, melon), Cucurbita species (zucchini, Indian pumpkin), Cyanara spp. (artichoke, cardoon), wild carrot, fennel, Hypericum species, lettuce, Lycopersicon species (tomato, cherry tomato), mint species, basil, parsley, Phaseolus species (bean, pea), peas, radish, edible rhubarb, Rosemary species, sage species, black salsify (Scorzonera hispanica), eggplant, spinach, new Valerian species (V. eriocarpa), and broad beans.

[0659] Preferred ornamental plant species include African violet, begonia, dahlia, gerbera, hydrangea, verbena, rose, kalanchoe, poinsettia, aster, cornflower, coreopsis, delphinium, monarda, phlox, rudbeckia, sedum, petunia, violet, impatiens, geranium, chrysanthemum, ranunculus, fuchsia, salvia, hydrangea, rosemary, sage, St. John's wort, mint, sweet pepper, tomato, and cucumber.

[0660] The active ingredients according to the invention are particularly suitable for controlling the bean aphid (Aphis craccivora), cucumber leaf beetle (Diabrotica balteata), tobacco budworm (Heliothis virescens), peach aphid (Myzus persicae), diamondback moth (Plutella xylostella) and sea armyworm (Spodoptera littoralis) on cotton, vegetables, corn, rice and soybean crops. The active ingredients according to the invention are also particularly suitable for controlling the cabbage looper (preferably on vegetables), codling moth (preferably on apples), green leafhopper (preferably on vegetables, vineyards), potato leaf beetle (preferably on potatoes) and striped stem borer (preferably on rice).

[0661] The active ingredients according to the invention are particularly suitable for controlling bean aphids, cucumber leaf beetles, tobacco budworms, green peach aphids, diamondback moths and sea worms on cotton, vegetables, corn, rice and soybean crops. The active ingredients according to the invention are also particularly suitable for controlling cabbage loopers (preferably on vegetables), codling moths (preferably on apples), green leafhoppers (preferably on vegetables, vineyards), potato leaf beetles (preferably on potatoes) and striped stem borers (preferably on rice).

[0662] In another aspect, the present invention may also relate to a method for controlling damage to plants and parts thereof by plant-parasitic nematodes (endoparasitic, semi-endoparasitic and ectoparasitic nematodes), in particular the following plant-parasitic nematodes, such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other species of root knot nematodes; cyst-forming nematodes, Globodera rostochiensis and other species of Globodera; cereal cyst nematodes, soybean cyst nematodes, Heterodera avenae, soybean cyst nematodes, Heterodera exigua and Heterodera schachtii. schachtii), Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus, and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus, and other Bursaphelenchus species; Ring nematodes, nematodes), Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stemand bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci, and other Ditylenchus species; Awl nematodes, Dolichodorus species;Spiral nematodes, Heliocotylenchus multicinctus, and other species of the genus Helicotylenchus; Sheath and sheathoid nematodes, species of the genera Hemicycliophora, and species of the genera Hemicriconemoides; Hirshmanniella species; Lancenematodes, species of the genus Hoploaimus; False rootknot nematodes, species of the genus Nacobbus; Needle nematodes, Longidoruse longatus, and other species of the genus Longidorus; Pin nematodes, species of the genus Pratylenchus; Lesion nematodes. nematodes), Pratylenchus negletus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi, and other Pratylenchus species; Burrowing nematodes, Radopholus similis, and other Radopholus species; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis, and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus) and other species of the genera Trichodorus and Paratrichodorus;Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant-parasitic nematode species, such as Subanguinas spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp.

[0663] The compounds of the present invention also have activity against mollusks. Examples include, for example, the Ampullariidae; the Arion genus (A. ater, A. circumscriptus, A. hortensis, A. rufus); the Bradybaenidae (Bradybaenidae); fruticum); Cepaea (C. hortensis, C. nemoralis); Ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H. obvia); Helicidae (Helicigona arbustorum); Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. Tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.

[0664] The term "crops" is to be understood as also including crop plants which have been transformed by the use of recombinant DNA techniques such that they are able to synthesize one or more selectively acting toxins, such as are known, for example, from toxigenic bacteria, in particular those of the genus Bacillus.

[0665] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, such as those from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as delta-endotoxins (e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C), or vegetative insecticidal proteins (Vips) (e.g., Vip1, Vip2, Vip3, or Vip3A); or insecticidal proteins of nematode-parasitic bacteria, such as Photorhabdus species or Xenorhabdus species, such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, spider toxins, wasp toxins, and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomyces toxins; plant lectins, such as pea lectin, barley lectin, and lectin. Lectin or snowdrop agglutinin; lectins; protease inhibitors, such as trypsin inhibitor, serine protease inhibitor, potato storage protein (patatin), cysteine ​​protease inhibitor, papain inhibitor; ribosome inactivating protein (RIP), such as ricin, maize-RIP, abrin, luffain, saporin or bryophyllin; steroid metabolizing enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitor, HMG-COA-reductase; ion channel blockers, such as sodium channel or calcium channel blockers; juvenile hormone esterase; diuretic hormone receptor; stilbene synthase; bibenzyl synthase; chitinase and glucanase.

[0666] In the context of the present invention, δ-endotoxins (e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C) or vegetative insecticidal proteins (Vips) (e.g., Vip1, Vip2, Vip3, or Vip3A) are understood to include, but are not limited to, mixed toxins, truncated toxins, and modified toxins. Mixed toxins are recombinantly produced by combining different domains of those proteins (see, e.g., WO 02 / 15701). Truncated toxins, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of a naturally occurring toxin are replaced. In such amino acid replacements, it is preferred that a non-naturally occurring protease recognition sequence be inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see WO 03 / 018810).

[0667] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed in, for example, EP-A-0 374 753, WO 93 / 07278, WO 95 / 34656, EP-A-0 427 529, EP-A-451 878 and WO 03 / 052073.

[0668] Methods for producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP-A-0367474, EP-A-0401979 and WO 90 / 13651.

[0669] The toxins contained in the transgenic plants render the plants tolerant to harmful insects. Such insects can be found in any insect taxonomic group, but are particularly common among beetles (Coleoptera), two-winged insects (Diptera), and moths (Lepidoptera).

[0670] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known and some are commercially available. Examples of such plants are: (Zea mays variety expressing Cry1Ab toxin); YieldGard (maize variety expressing Cry3Bb1 toxin); YieldGard (Zea mays varieties expressing Cry1Ab and Cry3Bb1 toxins); (Zea mays variety expressing Cry9C toxin); Herculex (a maize variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) that confers tolerance to the herbicide glufosinate-ammonium); NuCOTN (cotton variety expressing Cry1Ac toxin); Bollgard (cotton variety expressing Cry1Ac toxin); Bollgard (cotton varieties expressing Cry1Ac and Cry2Ab toxins); (cotton variety expressing Vip3A and Cry1Ab toxins); (potato variety expressing Cry3A toxin); GT Advantage (GA21 glyphosate tolerance trait), CB Advantage (Bt11 corn borer (CB) trait) and

[0671] Further examples of such genetically modified crops are:

[0672] 1. Bt11 maize, from Syngenta Seeds SAS, Cheminde l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. This genetically modified maize is resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia serrata) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenically expresses the PAT enzyme to confer tolerance to the herbicide glufosinate ammonium.

[0673] 2. Bt176 maize, from Syngenta Seeds SAS, Cheminde l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. This genetically modified maize is resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia serrata) by transgenic expression of the Cry1Ab toxin. Bt176 maize also transgenicly expresses the PAT enzyme to confer tolerance to the herbicide glufosinate ammonium.

[0674] 3. MIR604 maize, from Syngenta Seeds SAS, Cheminde l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. This maize plant is rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055, modified by insertion of a cathepsin-G protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03 / 018810.

[0675] 4. MON 863 maize, from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses the Cry3Bb1 toxin and confers resistance to certain coleopteran insects.

[0676] 5. IPC 531 cotton, from Monsanto Europe AB, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0677] 6.1507 maize, from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Genetically modified maize expressing the protein Cry1F for resistance to certain lepidopteran insects and the protein PAT for tolerance to the herbicide glufosinate-ammonium.

[0678] 7. NK603×MON 810 maize, from Monsanto Europe, 270-272 Boulevard Tervuren, B-1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. This is a conventionally bred hybrid maize variety, constructed by crossing the genetically modified varieties NK603 and MON 810. NK603×MON 810 maize transgenically expresses the protein CP4 EPSPS obtained from the Agrobacterium strain CP4, rendering it herbicide tolerant. (contains glyphosate), and also Cry1Ab toxin from Bacillus thuringiensis subsp. kurstakia, which confers resistance to certain lepidopteran insects, including the European corn borer.

[0679] Transgenic crops of insect-resistant plants are also described in the BATS (Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) report 2003 ( http: / / bats.ch )middle.

[0680] 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 acting antipathogenic substances, such as so-called "pathogenesis-related proteins" (PRPs, see, for example, EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesizing such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 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 publications mentioned above.

[0681] Crops can also be modified to increase resistance to fungal (eg, Fusarium, Anthracnose, or Phytophthora), bacterial (eg, Pseudomonas), or viral (eg, Potato Leaf Roll Virus, Tomato Spotted Wilt Virus, Cucumber Mosaic Virus) pathogens.

[0682] Crops also include those with increased resistance to nematodes, such as Heterodera glycines.

[0683] Crops with tolerance to abiotic stress include those with increased tolerance to drought, high salinity, high temperature, cold, frost or light radiation, for example, through expression of NF-YB or other proteins known in the art.

[0684] Antipathogenic substances that can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers of sodium channels and calcium channels, for example viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; so-called "pathogenesis-related proteins" (PRPs, see, for example, EP-A-0392225); antipathogenic substances produced by microorganisms, such as peptide antibiotics or heterocyclic antibiotics involved in plant pathogen defense (see, for example, WO 95 / 33818) or protein or polypeptide factors (so-called "plant disease resistance genes", as described in WO 03 / 000906).

[0685] Other areas of use of the compositions according to the invention are the protection of stored goods and storage rooms and the protection of raw materials such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, in particular the protection of humans, domestic animals and productive livestock from pests of the types mentioned.

[0686] The present invention also provides a method for controlling pests (such as mosquitoes and other disease vectors; see also http: / / www.who.int / malaria / vector_control / irs / en / ). In one embodiment, the method for controlling pests comprises applying the composition of the present invention to the target pests, their locus, or a surface or substrate by painting, rolling, spraying, coating, or dipping. By way of example, IRS (indoor residual spraying) application to surfaces (such as walls, ceilings, or floor surfaces) is contemplated by the methods of the present invention. In another embodiment, application of such compositions to substrates such as nonwoven or fabric materials in the form of (or for use in the manufacture of) netting, coverings, bedding, curtains, and tents is contemplated.

[0687] In one embodiment, the method for controlling this type of harmful organism comprises applying the composition of the present invention of pest-killing effective dose to target harmful organism, their place or surface or substrate, so that on this surface or substrate, effective pest-killing activity of retention is provided.Such application can be carried out by brushing, rolling, spraying, coating or dipping pest-killing composition of the present invention.By way of example, the IRS application of surface (such as wall, ceiling or floor surface) has been considered by method of the present invention, so that effective pest-killing activity of retention is provided on this surface.In another embodiment, it has been considered to use this type of composition for the residual control of the harmful organism on substrate, and this substrate is the fabric material of the form (or can be used in the manufacture of these articles) such as being in netting, covering, bedding, curtain and tent.

[0688] The substrate to be treated (including nonwovens, fabrics or nettings) can be made of natural fibers such as cotton, raffia, jute, flax, sisal, burlap or wool, or synthetic fibers such as polyamide, polyester, polypropylene, polyacrylonitrile or the like. Polyester is particularly suitable. Methods for textile treatment are known, for example WO 2008 / 151984, WO 2003 / 034823, US 5631072, WO 2005 / 64072, WO 2006 / 128870, EP 1724392, WO 2005113886 or WO 2007 / 090739.

[0689] A further area of ​​use of the compositions according to the invention is in the field of tree injection / trunk treatment of all ornamental trees as well as all kinds of fruit and nut trees.

[0690] In the field of tree injection / trunk treatment, the compounds according to the invention are particularly suitable for combating wood-boring insects from the orders Lepidoptera and from the orders Coleoptera mentioned above, in particular against the wood-boring insects listed in the following Tables A and B:

[0691] Table A. Examples of economically important exotic wood-boring insects.

[0692]

[0693]

[0694] Table B. Examples of economically important native wood-boring insects.

[0695]

[0696]

[0697]

[0698]

[0699] The present invention can also be used to control any insect pest that may be present in turfgrass, including, for example, beetles, caterpillars, fire ants, ground pearls, millipedes, woodlice, mites, mole crickets, scale insects, mealybugs, cicadas, southern wheat stink bugs, and white grubs. The present invention can be used to control insect pests at all stages of their life cycle, including eggs, larvae, nymphs, and adults.

[0700] In particular, the present invention can be used to control insect pests that feed on the roots of turfgrasses, including grubs (such as Cyclocephala spp. (e.g., marked beetles, C. lurida), Rhizotrogus spp. (e.g., European beetles, European root beetles (R. majalis)), Cotinus spp. (e.g., Green June beetles, C. nitida), Popillia spp. (e.g., Japanese beetles, P. japonica), Phyllophaga spp. (e.g., May / June beetles), Ataenius spp. (e.g., Black turfgrass ataenius, A. spretulus), Maladera spp. (e.g., Asiatic garden beetles, A. spp.), and other insect pests. beetle, M. castanea, and Tomarus genera), ground pearls (Margarodes spp.), mole crickets (tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana), and leatherjackets (European crane fly, Tipula spp.).

[0701] The present invention can also be used to control insect pests of turfgrass in thatched homes, including armyworms (such as the fall armyworm Spodoptera frugiperda, and the common armyworm Pseudaletia unipuncta), cutworms, weevils (Sphenophorus spp., such as S. venatus verstitus and S. parvulus), and grass borers (such as Crambus spp. and the tropical grass borer, Herpetogramma phaeopteralis).

[0702] The present invention can also be used to control insect pests in turfgrasses that live above ground and feed on turfgrass leaves, including wheat stink bugs (such as the southern wheat stink bug, Blissus insularis), Bermudagrass mite (Eriophyes cynodoniensis), Grass mealybug (Antonina graminis), Propsapia bicincta, leafhoppers, cutworms (Noctuidae), and Schizaphis graminis.

[0703] The present invention can also be used to control other pests in turfgrass, such as introduced fire ants (Solenopsis invicta) that create nests in lawns.

[0704] In the hygiene sector, the compositions according to the invention are effective against ectoparasites such as hard ticks, soft ticks, scabies, autumn mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.

[0705] Examples of such parasites are:

[0706] From the order of the Liceae: Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.

[0707] From the order Trichophagus: Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., and Felicola spp.

[0708] From the order Diptera and the suborders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp. spp.), Philipomyia species, Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.), Hippobosca spp., Lipoptena spp., and Melophagus spp.

[0709] From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.

[0710] From the order of the Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.

[0711] From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattelagermanica and Supella spp.

[0712] Subclass Acaria (family Acarida) and orders Meta-stigmata and Meso-stigmata, for example, Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyommas spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp. spp.), Sternostoma spp., and Varroa spp.

[0713] From the orders Actinedida (Prostigmata) and Acaridida (Astigmata), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp. spp.), Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcooptes spp., Notoedress spp., Knemidocoptes spp., Cytodites spp., and Laminosioptes spp.

[0714] The compositions according to the invention are also suitable for protecting materials in the case of, for example, wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and construction from infestation by insects.

[0715] The compositions according to the invention can be used, for example, to combat the following pests: beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale), Minthes rugicollis, Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec., and Dinoderus minutus, as well as Hymenoptera, such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, and Urocerus augu, and termites, such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes spp. indicola), Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, and Coptotermes formosanus, as well as borers such as Silverfish (Lepisma saccharina).

[0716] The compounds according to the invention can be used as pesticides in unmodified form, but they are usually formulated into compositions in various ways using formulation adjuvants such as carriers, solvents and surfactants. These formulations can be in different physical forms, for example, in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, mobile oils, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or water-miscible organic solvents as carriers), impregnated polymer films or in other known forms, for example, from 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. Dilution can be performed with, for example, water, liquid fertilizers, micronutrients, biological organisms, oils or solvents.

[0717] These formulations can be prepared, for example, by mixing the active ingredient with a formulation adjuvant to obtain a composition in the form of a finely divided solid, granules, solution, dispersion or emulsion. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of plant or animal origin, modified oils of plant or animal origin, organic solvents, water, surface-active substances or combinations thereof.

[0718] These active ingredients can also be contained in very fine microcapsules. Microcapsules contain active ingredients in porous carriers. This allows the active ingredients to be released (e.g., slowly released) into the environment in controlled amounts. Microcapsules typically have a diameter of from 0.1 to 500 microns. The amount of active ingredient they contain is approximately from 25% to 95% of the capsule weight by weight. These active ingredients can be in the form of a holistic solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulated membrane can include, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymer, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane, or chemically modified polymers and starch xanthate, or other polymers known to those skilled in the art. Alternatively, very fine microcapsules can be formed, in which the active ingredient is contained in the form of finely dispersed particles in a solid matrix of a base material, but these microcapsules themselves are not wrapped.

[0719] Formulation auxiliaries suitable for preparing the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol rosinate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl Formamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol, alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, α-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, acetic acid glyceryl, diacetic acid glyceryl, triacetic acid glyceryl, decaglycerol Hexadecane, Hexanediol, Isoamyl Acetate, Isobornyl Acetate, Isooctane, Isophorone, Cumene, Isopropyl Myristate, Lactic Acid, Lauramine, Mesityl Oxide, Methoxypropanol, Methyl Isoamyl Ketone, Methyl Isobutyl Ketone, Methyl Laurate, Methyl Caprylate, Methyl Oleate, Methylene Chloride, m-Xylene, n-Hexane, n-Octylamine, Octadecanoic Acid, Octylamine Acetate, Oleic Acid, Oleylamine, o-Xylene, Phenol, Polyethylene Glycol, Propionic Acid, Propyl Lactate , propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, 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 higher molecular weight alcohols such as amyl alcohol, tetrahydrofuranol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc.

[0720] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour, soy flour, pumice, wood flour, ground walnut shells, lignin, and similar substances.

[0721] Many surface-active substances can be used advantageously in both solid and liquid formulations, especially those which can be diluted with a carrier before use. Surface-active substances can be anionic, cationic, nonionic or polymeric and they can act as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide addition products, such as ethoxylated nonylphenol; alcohol / alkylene oxide addition products, such as ethoxylated tridecanol; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; salts of dialkylsulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary ammoniums, such as dodecyltrimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and dialkyl phosphates; as well as other substances, such as described in: McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Company (MC Publishing Company). Corp., Ridgewood New Jersey (1981).

[0722] Other adjuvants that can be used in pesticidal formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, substances and buffers that neutralize or change the pH, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze agents, microbicides, and liquid and solid fertilizers.

[0723] The composition according to the invention may comprise an additive comprising an oil of plant or animal origin, a mineral oil, an alkyl ester of such an oil or a mixture of such an oil and an oil derivative. The amount of the oil additive in the composition according to the invention is generally from 0.01% to 10% based on the mixture to be applied. For example, the oil additive may be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oil or an oil of plant origin, such as rapeseed oil, olive oil or sunflower oil; emulsified vegetable oils; alkyl esters of oils of plant origin, such as methyl derivatives; or oils of animal origin, such as fish oil or tallow. Preferred oil additives include C8-C 22 Alkyl esters of fatty acids, especially C 12 -C 18Methyl derivatives of fatty acids, such as the methyl esters of lauric acid, palmitic acid, and oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th edition, Southern Illinois University, 2010.

[0724] These compositions according to the invention generally comprise from 0.1% to 99% by weight, in particular from 0.1% to 95% by weight, of a compound according to the invention and from 1% to 99.9% by weight of formulation adjuvants, which preferably include from 0 to 25% by weight of surface-active substances. While commercial products may preferably be formulated as concentrates, the end user will generally use dilute formulations.

[0725] The application rate varies within wide limits and depends on the nature of the soil, the application method, the crop plants, the harmful organisms to be controlled, the prevailing climatic conditions, and other factors dictated by the application method, the time of application, and the target crop. In general, the compound can be applied at a rate of from 1 to 2000 l / ha, in particular from 10 to 1000 l / ha.

[0726] A preferred formulation may have the following composition (wt %):

[0727] Emulsifiable concentrates :

[0728] Active ingredient: 1% to 95%, preferably 60% to 90%

[0729] Surfactant: 1% to 30%, preferably 5% to 20%

[0730] Liquid carrier: 1% to 80%, preferably 1% to 35%

[0731] Dust agent :

[0732] Active ingredient: 0.1% to 10%, preferably 0.1% to 5%

[0733] Solid carrier: 99.9% to 90%, preferably 99.9% to 99%

[0734] Suspension concentrates :

[0735] Active ingredient: 5% to 75%, preferably 10% to 50%

[0736] Water: 94% to 24%, preferably 88% to 30%

[0737] Surfactant: 1% to 40%, preferably 2% to 30%

[0738] wettable powder :

[0739] Active ingredient: 0.5% to 90%, preferably 1% to 80%

[0740] Surfactant: 0.5% to 20%, preferably 1% to 15%

[0741] Solid carrier: 5% to 95%, preferably 15% to 90%

[0742] Granules :

[0743] Active ingredient: 0.1% to 30%, preferably 0.1% to 15%

[0744] Solid carrier: 99.5% to 70%, preferably 97% to 85%

[0745] The following examples further illustrate (but do not limit) the present invention.

[0746] <![CDATA[ wettable powder ]]> a) b) c) Active ingredient 25％ 50％ 75％ Sodium lignin sulfonate 5％ 5％ - Sodium lauryl sulfate 3％ - 5％ Sodium diisobutylnaphthalenesulfonate - 6％ 10％ Phenol polyglycol ether (7-8 mol of ethylene oxide) - 2％ - Highly dispersed silicic acid 5％ 10％ 10％ Kaolin 62％ 27％ -

[0747] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a wettable powder which can be diluted with water to give a suspension of the desired concentration.

[0748] <![CDATA[ Powder for dry seed treatment ]]> a) b) c) Active ingredient 25％ 50％ 75％ Light mineral oil 5％ 5％ 5％ Highly dispersed silicic acid 5％ 5％ - Kaolin 65％ 40％ - talc - 20％

[0749] The combination is thoroughly mixed with adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a dust that can be used directly for seed treatment.

[0750]

[0751]

[0752] Emulsions of any desired dilution which can be used in plant protection can be obtained from these concentrates by dilution with water.

[0753] <![CDATA[ Dust agent ]]> a) b) c) Active ingredient 5％ 6％ 4％ talc 95％ - - Kaolin - 94％ - Mineral fillers - - 96％

[0754] Ready-to-use dusts are obtained by mixing the combination with a carrier and grinding the mixture in a suitable grinder. Such dusts can also be used for dry seed dressing of seeds.

[0755] <![CDATA[ Extruder pellets ]]> Active ingredient 15％ Sodium lignin sulfonate 2％ Carboxymethyl cellulose 1％ Kaolin 82％

[0756] The combination is mixed and ground with the adjuvants, and the mixture is moistened with water.

[0757] The mixture is extruded and then dried in a stream of air.

[0758] <![CDATA[ Coated granules ]]> Active ingredient 8％ Polyethylene glycol (molecular weight 200) 3％ Kaolin 89％

[0759] This finely ground combination is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

[0760] Suspension concentrates

[0761]

[0762]

[0763] The finely ground combination is intimately mixed with adjuvants to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation materials can be treated and protected against microbial infestation by spraying, pouring or immersion.

[0764] Flowable concentrate for seed treatment

[0765] Active ingredient 40％ Propylene glycol 5％ Copolymer butanol PO / EO 2％ Tristyrylphenol with 10-20 moles of EO 2％ 1,2-Benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5％ Monoazo-pigment calcium salt 5％ Silicone oil (75% aqueous emulsion) 0.2％ water 45.3％

[0766] The finely ground combination is intimately mixed with adjuvants to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation materials can be treated and protected against microbial infestation by spraying, pouring or immersion.

[0767] Extended-release capsule suspension

[0768] 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of a defoamer, and 51.6 parts of water until the desired particle size is reached. To this emulsion, 2.8 parts of a mixture of 1,6-hexanediamine in 5.3 parts of water are added. The mixture is stirred until polymerization is complete. The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% active ingredient. The diameter of the medium capsules is 8-15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for this purpose.

[0769] Formulation types include emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (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 concentrates (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume concentrates (UL), finished products (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG), or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0770] Preparation example:

[0771] "Mp" means melting point in ° C. Free radical means methyl group. 1 H NMR measurements were recorded on a Brucker 400 MHz spectrometer and chemical shifts are given in ppm relative to a TMS standard. Spectra were measured in deuterated solvents as indicated. The compounds were characterized using any of the following LCMS methods. Characteristic LCMS values ​​obtained for each compound are the retention time ("Rt", reported in minutes) and the measured molecular ion (M+H). + .

[0772] LCMS method:

[0773] Method 1:

[0774] Spectra were recorded on a mass spectrometer from Agilent Technologies (6410 triple quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative ion, MS2 scan, capillary: 4.00 kV, fragmentor voltage: 100 V, desolvation temperature: 350°C, gas flow: 11 L / min, nebulizer gas: 45 psi, mass range: 110 to 1000 Da) and a 1200 series HPLC from Agilent: quaternary pump, heated column compartment 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 0% B, 100% A; 0.9-1.8 min 100% B; flow rate (mL / min) 1.8.

[0775] Method 2:

[0776] Spectra were recorded on a mass spectrometer from Waters (SQD single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative, full scan, capillary: 3.00 kV, cone range: 41 V, source temperature: 150°C, desolvation temperature: 500°C, cone gas flow: 50 L / Hr, desolvation gas flow: 1000 L / Hr, mass range: 110 to 800 Da) and a Class H UPLC from Waters: binary pump, heated column compartment and diode array detector. Column: Waters UPLC HSS T3 C18, 1.8 μm, 30×2.1 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; 0.-0.2 min 10%-50% B; 0.2-0.7 min 50%-100% B; flow rate (mL / min) 0.8.

[0777] Method 3:

[0778] Spectra were recorded on a mass spectrometer from Waters (SQD single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative, full scan, capillary: 3.00 kV, cone range: 41 V, source temperature: 150°C, desolvation temperature: 500°C, cone gas flow: 50 L / Hr, desolvation gas flow: 1000 L / Hr, mass range: 110 to 800 Da) and a Class H UPLC from Waters: binary pump, heated column compartment, and diode array detector. Column: Waters UPLC HSS T3 C18, 1.8 μm, 30×2.1 mm, temperature: 40° C., DAD wavelength range (nm): 210 to 400, solvent gradient: A = water + 5% acetonitrile + 0.1% HCOOH, B = acetonitrile + 0.05% HCOOH, gradient: 0 min 10% B; 0.-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.

[0779] Method 4:

[0780] Spectra were recorded on a mass spectrometer (ZQ single quadrupole mass spectrometer) from Waters equipped with an electrospray source (polarity: positive or negative, capillary: 3.00 kV, cone range: 30-60 V, extractor: 2.00 V, source temperature: 150° C., desolvation temperature: 350° C., cone gas flow: 0 L / Hr, desolvation gas flow: 650 L / Hr; mass range: 100 Da to 900 Da) and an Acquity UPLC from Waters: binary pump, heated column compartment, and diode array detector). Solvent degasser, binary pump, heated column compartment, and diode array detector. Column: Waters UPLCHSS T3, 1.8 μm, 30×2.1 mm, temperature: 60° C., DAD wavelength range (nm): 210 to 500, solvent gradient: A=water+5% MeOH+0.05% HCOOH, B=acetonitrile+0.05% HCOOH: gradient: 0 min 0% B, 100% A; 1.2-1.5 min 100% B; flow rate (ml / min) 0.85.

[0781] Example P1: 2-(3-Ethylsulfonyl-2-pyridinyl)-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridine-1- Preparation of ketone (Compound P1)

[0782]

[0783] Step A1: 5-chloro-2-(trifluoromethyl)pyridine-4-carboxylic acid (Intermediate I1) and 2,2,6,6-tetramethylpiperidin-1- Preparation of 5-chloro-2-(trifluoromethyl)pyridine-4-carboxylate (Intermediate I2)

[0784]

[0785] 2.0M butyllithium solution (165mL, 330mmol, 4.00 equivalents) in tetrahydrofuran is added dropwise to -78 DEG C of cooling solutions of 2,2,6,6-tetramethylpiperidine (35.0g, 248mmol, 3.00 equivalents) in tetrahydrofuran (500mL). After the addition is complete, the reaction mixture is stirred at -50 DEG C for 30min and cooled to -78 DEG C again, followed by the addition of a solution of 5-chloro-2-(trifluoromethyl)pyridine (15.0g, 82.6mmol) in tetrahydrofuran (100mL). The reaction mixture is stirred at -78 DEG C for 30min and then added to a saturated solution of CO in tetrahydrofuran cooled at -78 DEG C via a cannula. Once the addition is complete, the reaction mixture is warmed to room temperature and quenched by adding a saturated aqueous ammonium chloride solution (200mL). The aqueous phase was extracted twice with ethyl acetate (200 mL), and the combined organic phases were dried over sodium sulfate, filtered, and concentrated under reduced pressure to give 2,2,6,6-tetramethylpiperidin-1-ium 5-chloro-2-(trifluoromethyl)pyridine-4-carboxylate (intermediate I2). The aqueous phase was acidified to pH 3 by adding 2M aqueous hydrochloric acid solution and extracted twice with a 90 / 10 mixture of dichloromethane / methanol (200 mL). The combined organic phases were dried over sodium sulfate, filtered, and concentrated under reduced pressure to give 5-chloro-2-(trifluoromethyl)pyridine-4-carboxylic acid (intermediate I1). Both crude materials were used in the next step without further purification. LCMS (method 2): retention time 0.67 min, m / z 226 / 228 [M+H] + . 1 H NMR (400 MHz, DMSO-d6) δ / ppm: 8.18 (s, 1H), 8.98 (s, 1H) (5-chloro-2-(trifluoromethyl)pyridine-4-carboxylic acid I1).

[0786] Step A2: Preparation of ethyl 5-chloro-2-(trifluoromethyl)pyridine-4-carboxylate (Intermediate I3)

[0787]

[0788] A mixture of 5-chloro-2-(trifluoromethyl)pyridine-4-carboxylic acid (intermediate I1 prepared as described above) (1.00 g, 4.43 mmol) and concentrated sulfuric acid (1.00 mL) in ethanol (30 mL) was heated under reflux overnight. After cooling to room temperature, the reaction mixture was concentrated and the residue was diluted with ice water (50 mL). The aqueous phase was extracted twice with ethyl acetate (2*30 mL), the combined organic phases were washed with brine (30 mL), dried over sodium sulfate, filtered and concentrated. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired compound as a yellow liquid. LCMS (method 2): retention time 1.10 min, m / z 254 / 256 [M+H]+ . 1 H NMR (400MHz, CDCl3) δ / ppm: 1.45 (t, J = 7.12Hz, 3H), 4.49 (q, J = 7.12Hz, 2H), 8.04 (s, 1H), 8.82 (s, 1H).

[0789] Step A3: Preparation of ethyl 5-methyl-2-(trifluoromethyl)pyridine-4-carboxylate (Intermediate I4)

[0790]

[0791] Potassium phosphate (4.5g, 21.3mmol, 3.0 equivalents) and tricyclohexylphosphine (0.2g, 0.71mmol, 0.10 equivalents) are added to a mixture of 5-chloro-2-(trifluoromethyl)pyridine-4-carboxylic acid ethyl ester (intermediate I3 prepared as described above) (1.8g, 7.1mmol) and methyl-boric acid (1.3g, 21.3mmol, 3.0 equivalents) in toluene (50mL) and water (5.0mL). The mixture is purged with nitrogen for 10min, and then palladium acetate (0.08g, 0.035mmol, 0.05 equivalents) is added. Purge is continued for 10min and the reaction mixture is heated at 100°C for 2 hours. After cooling to room temperature, the mixture is diluted with water (50mL) and ethyl acetate (50mL) and filtered through diatomaceous earth (washed with ethyl acetate). The phases are separated, the aqueous phase is extracted with ethyl acetate, and the combined organic phases are dried over sodium sulfate, filtered and concentrated. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired compound as a pale yellow liquid. LCMS (Method 2): retention time 1.08 min, m / z 234 [M+H] + . 1 H NMR (400MHz, CDCl3) δ / ppm: 1.44 (t, J = 7.16Hz, 3H), 2.66 (s, 3H), 4.44 (q, J = 7.16Hz, 2H), 8.08 (s, 1H), 8.68 (s, 1H).

[0792] Step A4: Preparation of ethyl 5-(bromomethyl)-2-(trifluoromethyl)pyridine-4-carboxylate (Intermediate I5)

[0793]

[0794] N-Bromosuccinimide (1.40 g, 7.80 mmol, 1.40 equiv) and benzoyl peroxide (0.42 g, 1.70 mmol, 0.30 equiv) were added to a solution of ethyl 5-methyl-2-(trifluoromethyl)pyridine-4-carboxylate (intermediate I4 prepared as described above) (1.30 g, 5.60 mmol) in tetrachloromethane (45 mL). The reaction mixture was heated at 70 ° C overnight. After cooling to room temperature, the reaction mixture was diluted with ice water (20 mL) and the aqueous phase was extracted twice with ethyl acetate (10 mL). The combined organic phases were dried over sodium sulfate, filtered and concentrated. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired product. LCMS (method 2): retention time 1.12 min, m / z 312 / 314 [M+H] + . 1 H NMR (400MHz, CDCl3) δ / ppm: 1.44 (t, J = 7.15Hz, 3H), 4.50 (q, J = 7.15Hz, 2H), 4.94 (s, 2H), 7.27 (s, 1H), 8.14 (s, 1H), 8.85 (s, 1H).

[0795] Step B1: Preparation of 3-ethylsulfonylpyridin-2-amine (Intermediate I6)

[0796]

[0797] A mixture of 3-ethylsulfonyl-2-fluoro-pyridine (CAS 2092522-98-8, prepared according to patent JP2018076354) (0.6 g, 3.0 mmol) in a 7.0 M ammonia solution (6.0 mL) in methanol in an autoclave vessel was heated at 70 ° C for 4 hours. After cooling to room temperature, the autoclave was placed under normal pressure again, and the reaction mixture was concentrated under vacuum. The crude material was directly purified by flash chromatography on silica gel (methanol in dichloromethane) to obtain the desired compound. LCMS (method 1): retention time 0.33 min, m / z 187 [M + H] + . 1 H NMR (400MHz, CDCl3) δ / ppm: 1.11 (t, J=7.34Hz, 3H), 3.30 (q, J=7.34Hz, 2H), 6.66-6 .81(m,3H),7.86(dd,J1=7.76,J2=1.90Hz,1H),8.27(dd,J1=4.71,J2=1.90Hz,1H).

[0798] Step C1: 5-[[(3-ethylsulfonyl-2-pyridinyl)amino]methyl]-2-(trifluoromethyl)pyridine-4-carboxylic acid Ethyl ester (Intermediate I7) and 5-[[(3-ethylsulfonyl-2-pyridinyl)amino]methyl]-2-(trifluoromethyl)pyridine-4-carboxylic acid Preparation of (Intermediate I8)

[0799]

[0800] Sodium hydride (60% quality, 64 mg, 1.61 mmol, 1.50 equivalents) is added to a 0 ° C cooling solution of 3-ethylsulfonylpyridine-2-amine (intermediate I6 prepared as described above) (200 mg, 1.07 mmol) in N, N-dimethylformamide (10 mL). After stirring for 15 min, a solution of ethyl 5-(bromomethyl)-2-(trifluoromethyl)pyridine-4-carboxylate (intermediate I5 prepared as described above) (352 mg, 1.13 mmol, 1.05 equivalents) in N, N-dimethylformamide (0.5 mL) is added and the ice bath is removed. After stirring at room temperature for 1 hour, the reaction mixture is quenched by adding ice water (10 mL). The aqueous phase is first extracted twice with ethyl acetate (2 × 5 mL) and then extracted once with a 90 / 10 dichloromethane / methanol mixture. The combined ethyl acetate extracts are dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired compound 17. The dichloromethane / methanol extracts were dried over sodium sulfate, filtered, and concentrated to give crude 5-[[(3-ethylsulfonyl-2-pyridinyl)amino]methyl]-2-(trifluoromethyl)picolinic acid (Intermediate 18), which was used in Step C3 without further purification.

[0801] Step C2: 5-[[(3-ethylsulfonyl-2-pyridinyl)amino]methyl]-2-(trifluoromethyl)pyridine-4-carboxylic acid Preparation of (Intermediate I8)

[0802]

[0803] Barium hydroxide (octahydrate) (91 mg, 0.29 mmol, 2.0 equiv) was added to a suspension of ethyl 5-[[(3-ethylsulfonyl-2-pyridinyl)amino]methyl]-2-(trifluoromethyl)pyridine-4-carboxylate (Intermediate I7 ​​prepared as described above) (60 mg, 0.143 mmol) in methanol (2.4 mL) at 0°C. After stirring at room temperature for 2 h, the reaction mixture was diluted with methanol (5.0 mL), filtered and concentrated under reduced pressure. The crude material was used in the next step without further purification. LCMS (Method 1): retention time 1.31 min, m / z 390 [M+H] + .

[0804] Step C3: 2-(3-ethylsulfonyl-2-pyridinyl)-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridine-1- Preparation of ketone (Compound P1)

[0805]

[0806] Phosphorus oxychloride (0.16 mL, 2.0 equiv) was added to a solution of 5-[[(3-ethylsulfonyl-2-pyridinyl)amino]methyl]-2-(trifluoromethyl)pyridine-4-carboxylic acid (Intermediate I8 prepared as described above) (330 mg, 0.85 mmol) in pyridine (2 mL) at 0°C. After stirring at 0°C for 1 h, the reaction mixture was concentrated, the crude material was diluted with water (20 mL), and the aqueous phase was extracted twice with ethyl acetate (10 mL). The combined organic phases were dried over sodium sulfate, filtered, and concentrated. The crude material was purified by flash chromatography on silica gel (methanol in dichloromethane) to give the desired compound. LCMS (Method 2): retention time 0.91 min, m / z 372 [M+H] + . 1 H NMR (400MHz, CDCl3) δ / ppm: 1.39 (t, J = 7.34Hz, 3H), 3.52 (q, J = 7.34Hz, 2H), 5.20 (br s,2H),7.65(dd,J1=7.95Hz,J2=4.77Hz,1H),8.21(s,1H),8.47(dd,J1=7.95Hz,J2=1.83Hz,1H)8.85(dd,J1=4.77Hz,J2=1.83Hz,1H),9.05(s,1H).

[0807] Example P2: 2-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridine-2- Preparation of [3-pyridyl]-2-methyl-propionitrile (Compound P2)

[0808]

[0809] Step A1: Preparation of methyl 5-chloro-2-(trifluoromethyl)pyridine-4-carboxylate (Intermediate I9)

[0810]

[0811] A solution of trimethylsilyldiazomethane (2.0 M in hexanes) (80 mL, 160 mmol, 2.0 equiv) was added dropwise to a solution of 5-chloro-2-(trifluoromethyl)pyridine-4-carboxylic acid (intermediate I1 prepared as described in step A1 of Example P1) (18 g, 80 mmol) in methanol (200 mL) and toluene (200 mL) cooled at 0°C. After stirring at 0°C for 1 hour, the reaction mixture was evaporated to dryness and the crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired product as a yellow liquid. LCMS (Method 2): retention time 1.04 min, m / z 240 / 242 [M+H] + . 1 H NMR (400MHz, CDCl3) δ / ppm: 4.03 (s, 3H) 8.07 (s, 1H) 8.83 (s, 1H).

[0812] Step A2: Preparation of methyl 5-methyl-2-(trifluoromethyl)pyridine-4-carboxylate (Intermediate I10)

[0813]

[0814] Following the procedure described in Example P1, Step A3, by reaction of intermediate I9 (prepared as described above). LCMS (Method 2): retention time 1.01 min, m / z 220 [M+H] + .

[0815] Step A3: Preparation of methyl 5-(bromomethyl)-2-(trifluoromethyl)pyridine-4-carboxylate (Intermediate I11)

[0816]

[0817] Following the procedure described in Example P1, Step A4, by reaction of intermediate I10 (prepared as described above). LCMS (Method 2): retention time 1.06 min, m / z 298 / 300 [M+H] + . 1 H NMR (400MHz, CDCl3) δ / ppm: 4.04 (s, 3H), 4.95 (s, 2H), 8.15 (s, 1H), 8.87 (s, 1H).

[0818] Step B1: tert-Butyl N-[5-(1-cyano-1-methyl-ethyl)-3-ethylsulfanyl-2-pyridinyl]carbamate Preparation of both (Intermediate I12) and 2-(6-amino-5-ethylsulfanyl-3-pyridyl)-2-methyl-propionitrile (Intermediate I13) Preparation

[0819]

[0820] Diphenylphosphoryl azide (0.88 mL, 4.0 mmol, 1.0 equivalent) is added to a mixture of 5- (1- cyano -1- methyl - ethyl) -3- ethylsulfanyl -pyridine -2- carboxylic acid (CAS 2225113-81-3, prepared according to WO2018077565) (1.0 g, 4.0 mmol) and trimethylamine (0.56 mL, 4.0 mmol, 1.0 equivalent) in toluene (5.0 mL). After stirring at room temperature for 30 min, tert-butyl alcohol (0.76 mL, 8.0 mmol, 2.0 equivalents) is added and the reaction mixture is heated at 90 ° C. After stirring for 4 hours, the reaction mixture is cooled to room temperature and diluted with water (50 mL) and saturated sodium bicarbonate aqueous solution (10 mL). The aqueous phase is extracted twice with ethyl acetate (20 mL), the combined organic layer is washed with brine (50 mL), dried over sodium sulfate, filtered and concentrated. The crude material was purified to give the desired compound 112, along with some intermediate 113. 1H NMR (400 MHz, CDCl3) δ / ppm: 1.26 (t, J = 7.34 Hz, 3H), 1.71 (s, 6H), 2.82 (q, J = 7.34 Hz, 2H) 5.18 (br s, 2H) 7.68 (d, J = 2.51 Hz, 1H) 8.11 (d, J = 2.51 Hz, 1H), for compound I13.

[0821] Step B2: Preparation of 2-(6-amino-5-ethylsulfanyl-3-pyridyl)-2-methyl-propionitrile (Intermediate I13)

[0822]

[0823] 2,2,2-Trifluoroacetic acid (2.34 mL, 31.1 mmol, 10 equiv) was added dropwise to a solution of tert-butyl N-[5-(1-cyano-1-methyl-ethyl)-3-ethylsulfanyl-2-pyridinyl]carbamate (intermediate I12 prepared as described above) (1.00 g, 3.11 mmol) in dichloromethane (2.00 mL) at 0°C. After stirring at room temperature for 5 hours, the reaction mixture was poured onto water (50 mL) and the pH was brought to 9 by adding saturated sodium bicarbonate solution. The aqueous phase was extracted twice with dichloromethane (25 mL) and the combined organic phases were dried over sodium sulfate, filtered and concentrated. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired compound. LCMS (Method 2): retention time 0.64 min, m / z 222 [M+H] + .

[0824] Similarly, 1-(6-amino-5-ethylsulfanyl-3-pyridyl)cyclopropanecarbonitrile can be obtained from 5-(1-cyanocyclopropyl)-3-ethylsulfanyl-pyridine-2-carboxylic acid (CAS 2225113-77-7; WO 18077565) by treatment with diphenylphosphoryl azide and 2,2,2-trifluoroacetic acid. LCMS (Method 2): Retention time 0.27 min, m / z 220 [M+H] + . 1 H NMR (400MHz, CDCl3) δ / ppm: 1.26 (t, J = 7.4Hz, 3H), 1.31 (m, 2H), 1.66 (m, 2H), 2.81 (q, J = 7.4Hz, 2H), 5.18 (br s, 2H), 7.56 (d, J = 2.3Hz, 1H), 7.97 (d, J = 2.3Hz, 1H).

[0825] Similarly, 3-ethylsulfanyl-5-(2-pyridyloxy)pyridin-2-amine can be obtained from 3-ethylsulfanyl-5-(2-pyridyloxy)pyridine-2-carboxylic acid (Compound IP-6; preparation is given below) by treatment with diphenylphosphoryl azide and 2,2,2-trifluoroacetic acid. LCMS (Method 3): Retention time 0.83 min, m / z 248 [M+H] + . 1 H NMR (400MHz, CDCl3) δ / ppm: 1.34 (t, J = 7.3Hz, 3H), 2.89 (q, J = 7.3Hz, 2H), 6.99 (d, J = 8.2Hz, 1H), 7.08 (m, 1H), 7.30 (br s,2H),7.71-7.78(m,2H),7.81(d,1H),8.13(dd,J=4.9,1.7Hz,1H).

[0826] Step B3: Preparation of 2-(6-amino-5-ethylsulfonyl-3-pyridinyl)-2-methyl-propionitrile (Intermediate I14)

[0827]

[0828] 3-Chloroperbenzoic acid (8.06 g, 32.7 mmol) was added to a solution of 2-(6-amino-5-ethylsulfanyl-3-pyridyl)-2-methyl-propionitrile (intermediate I13 prepared as described above) (3.45 g, 15.6 mmol) in dichloromethane (100 mL) at 0°C. After stirring at 0°C for 30 min, the reaction mixture was quenched by the addition of 2M sodium hydroxide solution and the aqueous phase was extracted twice with dichloromethane. The combined organic layers were washed with saturated sodium thiosulfate solution, brine, dried over sodium sulfate and filtered, and concentrated under reduced pressure after controlling for the presence of any remaining peroxide with a starch test. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired product. LCMS (Method 2): retention time 0.85 min, m / z 254 [M+H] + . 1 H NMR (400MHz, CDCl3) δ / ppm: 1.31 (t, J = 7.52Hz, 3H), 1.74 (s, 6H). 3.19 (q, J=7.52Hz, 2H), 5.92 (br s, 2H), 7.98 (d, J=2.51Hz, 1H), 8.46 (d, J=2.51Hz, 1H).

[0829] Similarly, 1-(6-amino-5-ethylsulfonyl-3-pyridyl)cyclopropanecarbonitrile can be obtained from 1-(6-amino-5-ethylsulfanyl-3-pyridyl)cyclopropanecarbonitrile. LCMS (Method 3): retention time 0.73 min, m / z 252 [M+H]+ . 1 HNMR(400MHz, CDCl3)δ / ppm:1.32(t,J=7.4Hz,3H),1.35(m,2H),1.75(m,2H),3.18(q,J=7.4Hz,2H),5.89(br s, 2H), 7.83 (d, J = 2.5Hz, 1H), 8.36 (d, J = 2.5Hz, 1H).

[0830] Data for 3-ethylsulfonyl-5-(2-pyridyloxy)pyridin-2-amine:

[0831] LCMS (Method 3): retention time 0.92 min, m / z 280 [M+H] + . 1 H NMR (400MHz, CDCl3) δ / ppm: 1.34 (t, J = 7.4Hz, 3H), 3.24 (q, J = 7.4Hz, 2H), 5.77 (br s,2H),6.99(d,J=8.3Hz,1H),7.04(m,1H),7.74(m,1H),7.87(d,J=2.7Hz,1H),8.12(dd,J=5.0,1.2Hz,1H),8.24(d,J=2.7Hz,1H).

[0832] Step C1: 5-[[[5-(1-Cyano-1-methyl-ethyl)-3-ethylsulfonyl-2-pyridinyl]amino]methyl]- Preparation of methyl 2-(trifluoromethyl)pyridine-4-carboxylate (Intermediate I15)

[0833]

[0834] Following the procedure described in Step C1 of Example P1, by reaction of intermediate I11 (prepared as described above in Step A3) and intermediate I14 (prepared as described above in Step B3). LCMS (Method 2): retention time 1.13 min, m / z 471 [M+H] + .

[0835] Step C2: 5-[[[5-(1-Cyano-1-methyl-ethyl)-3-ethylsulfonyl-2-pyridinyl]amino]methyl]- Preparation of 2-(trifluoromethyl)pyridine-4-carboxylic acid (Intermediate I16)

[0836]

[0837] Following the procedure described in Example P1, Step C2, by reaction of intermediate I15 (prepared as described above). LCMS (Method 2): Retention time 1.02 min, m / z 457 [M+H] + .

[0838] Step C3: 2-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridine-2- Preparation of [3-pyridyl]-2-methyl-propionitrile (Compound P2)

[0839]

[0840] Following the procedure described in step C3 of Example P1, by reaction of intermediate I16 (prepared as described above). LCMS (Method 2): retention time 1.00 min, m / z 439 [M+H] + . 1 H NMR (400MHz, CDCl3) δ / ppm: 1.41 (t, J = 7.48Hz, 3H), 1.88 (s, 6H), 3.56 (q, J = 7.48Hz, 2H), 5.20 (br s, 2H), 8.21 (s, 1H), 8.46 (d, J = 2.57Hz, 1H), 9.00 (d, J = 2.57Hz, 1H), 9.07 (s, 1H).

[0841] Example P3: N-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridine-2- Preparation of 3-pyridyl]-N-methyl-acetamide (Compound P3)

[0842]

[0843] Step A1: Preparation of 2,5-dibromo-3-ethylsulfanyl-pyridine (Intermediate I17)

[0844]

[0845] In 90min, a solution of 2,5-dibromopyridin-3-amine (CAS 90902-84-4) (8g, 31.8mmol) in 1,2-dichloroethane (200mL) was slowly added to a solution of diethyl sulfide (7.82mL, 63.6mmol, 2.00 equivalents) and tert-butyl nitrite (5.67mL, 47.7mmol, 1.50 equivalents) in 1,2-dichloroethane (60mL) and dichloromethane (40mL) heated at 40°C. After the addition was complete, the reaction mixture was stirred at 40°C for 1 hour. After cooling to room temperature, the reaction mixture was diluted with water (100mL), and the aqueous phase was extracted twice with dichloromethane (100mL). The combined organic phases were dried over sodium sulfate, filtered and concentrated. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to obtain the desired product. LCMS (method 2): retention time 1.16 min, m / z 296 / 298 / 300 [M+H] + . 1 H NMR (400MHz, CDCl3) δ / ppm: 1.44 (t, J = 7.48Hz, 3H), 2.98 (q, J = 7.48Hz, 2H), 7.52 (s, 1H), 8.19 (s, 1H).

[0846] Step A2: Preparation of 2,5-dibromo-3-ethylsulfonyl-pyridine (Intermediate I18)

[0847]

[0848] Following the procedure described in step B3 of example P2, intermediate I17 (prepared as described above) was reacted. LCMS (method 2): retention time 0.92 min, m / z 328 / 330 / 332 [M+H] + .

[0849] Step A3: Preparation of 5-bromo-3-ethylsulfonyl-pyridin-2-amine (Intermediate I19)

[0850]

[0851] Following the procedure described in step B1 of example P1, intermediate I17 (prepared as described above) was reacted. LCMS (method 2): retention time 0.82 min, m / z 265 / 267 [M+H] + . 1 H NMR (400 MHz, DMSO-d6) δ / ppm: 1.15 (t, J = 7.34 Hz, 3H), 3.33 (q, 2H, hidden under the H2O peak exchanged in DMSO), 5.75 (s, 1H) 6.95 (br s, 2H) 7.93 (d, J = 2.32 Hz, 1H) 8.37 (d, J = 2.45 Hz, 1H).

[0852] Step B1: 5-[[(5-Bromo-3-ethylsulfonyl-2-pyridinyl)amino]methyl]-2-(trifluoromethyl)pyridine-4-yl Preparation of methyl formate (intermediate I20)

[0853]

[0854] Following the procedure described in Step C1 of Example P1, by reaction of Intermediate I11 (prepared as described in Step A3 of Example P2) and Intermediate I19 (prepared in Step A3 above). LCMS (Method 2): Retention time 1.20 min, m / z 482 / 484 [M+H] + .

[0855] Step B2: 5-[[(5-Bromo-3-ethylsulfonyl-2-pyridinyl)amino]methyl]-2-(trifluoromethyl)pyridine-4-yl Preparation of formic acid (intermediate I21)

[0856]

[0857] Following the procedure described in step C2 of Example P1, by reaction of intermediate I20 (prepared as described above). LCMS (Method 2): retention time 1.07 min, m / z 468 / 470 [M+H] + .

[0858] Step B3: 2-(5-bromo-3-ethylsulfonyl-2-pyridinyl)-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridinyl Preparation of pyridin-1-one (Compound P7)

[0859]

[0860] Following the procedure described in step C3 of Example P1, by reaction of intermediate I21 (prepared as described above). LCMS (Method 2): retention time 1.07 min, m / z 450 / 452 [M+H] + . 1 H NMR (400MHz, CDCl3) δ / ppm: 1.41 (t, J = 7.42Hz, 3H), 3.55 (q, J = 7.42Hz, 2H), 5.17 (br s, 2H), 8.20 (s, 1H), 8.56 (d, J = 2.32Hz, 1H), 8.87 (d, J = 2.32Hz, 1H), 9.06 (s, 1H).

[0861] Step B4: N-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridine-2-yl]- Preparation of 3-pyridyl]-N-methyl-acetamide (Compound P3)

[0862]

[0863] In a microwave vial, cesium carbonate (213 mg, 0.65 mmol, 1.40 equivalents) and Xantphos (38 mg, 0.065 mmol, 0.14 equivalents) are added to a solution of 2-(5-bromo-3-ethylsulfonyl-2-pyridyl)-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-1-one (210 mg, 0.47 mmol) (intermediate I22 prepared as described above) in dioxane (10 mL). After degassing with nitrogen for 5 min, tris(dibenzylideneacetone)dipalladium (8.5 mg, 0.01 mmol, 0.02 equivalents) is added and the mixture is degassed for another 5 min, followed by addition of N-methylacetamide (0.108 mL, 1.40 mmol, 3.00 equivalents). The vial is sealed and transferred to a microwave and heated at 160 ° C under microwave radiation for 1 hour. After cooling, the mixture was diluted with water (10 mL) and ethyl acetate (10 mL) and filtered through celite. The organic phase was dried over sodium sulfate, filtered and concentrated. The crude material was purified by flash chromatography on silica gel (methanol in dichloromethane) to give the desired compound. LCMS (Method 2): retention time 0.92 min, m / z 443 [M+H] + .

[0864] Example P6: 1-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridine-2- Preparation of 2-pyridyl-1,3-dimethyl-urea (P6)

[0865]

[0866] Step A1: Preparation of 6-chloro-3-ethylsulfonyl-pyridin-2-amine (Intermediate I22)

[0867]

[0868] 2-Bromo-6-chloro-3-ethylsulfonyl-pyridine (CAS 2118896-18-5, WO 2017134066A1) (4.0 g, 14 mmol) and ammonia in dioxane (50 mL, 30 mmol, 0.5 mol / L) were added to a miniclave container and heated at 100 ° C for 5 h. The reaction mixture was poured into water (50 mL) and extracted with ethyl acetate (3 × 50 mL). The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude product was purified by combiflash (50% ethyl acetate / cyclohexane) to give 6-chloro-3-ethylsulfonyl-pyridin-2-amine. LCMS (Method 2): retention time 0.85 min, m / z 221 / 223 [M + H] + .

[0869] 1 H NMR (400MHz, CDCl3) δ / ppm: 1.31 (t, 3H) 3.16 (q, 2H) 5.99 (br s, 2H) 6.79 (d, 1H) 7.89 (d, 1H).

[0870] Step B1: 5-[[(6-chloro-3-ethylsulfonyl-2-pyridinyl)amino]methyl]-2-(trifluoromethyl)pyridine-4-yl Preparation of methyl formate (intermediate I23)

[0871]

[0872] Following the procedure described in Step C1 of Example P1, by reaction of intermediate I11 (prepared as described in Step A3 of Example P2) and intermediate I22 (prepared in Step A1 above). LCMS (Method 2): retention time 1.14 min, m / z 438 / 440 [M+H] + .

[0873] Step B2: 5-[[(6-chloro-3-ethylsulfonyl-2-pyridinyl)amino]methyl]-2-(trifluoromethyl)pyridine-4-yl Preparation of formic acid (intermediate I24)

[0874]

[0875] Following the procedure described in step C2 of Example P1, by reaction of intermediate I23 (prepared as described above). LCMS (Method 2): retention time 1.06 min, m / z 424 / 426 [M+H] + .

[0876] Step B3: 2-(6-chloro-3-ethylsulfonyl-2-pyridinyl)-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridinyl Preparation of pyridin-1-one (intermediate I25)

[0877]

[0878] Following the procedure described in Example P1, Step C3, by reaction of intermediate I24 (prepared as described above). LCMS (Method 2): Retention time 1.03 min, m / z 406 / 408 [M+H] + .

[0879] Step B4: 2-[3-Ethylsulfonyl-6-(methylamino)-2-pyridinyl]-6-(trifluoromethyl)-3H-pyrrolo[3-(2-(4-(2-methylamino)-2-pyridinyl)-1-(2-(4-methylamino)-2-pyridinyl)]-1-(2-(4-methylamino)-2-pyridinyl)-1-(2-(4-methylamino)-2-pyrid Preparation of [3,4-c]pyridin-1-one (Compound P4)

[0880]

[0881] 2-(6-chloro-3-ethylsulfonyl-2-pyridinyl)-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-1-one (80 mg, 0.1971 mmol) and methylamine (2.0 mL, 2 mol / mL) were added to a 25 mL round-bottom flask and the reaction mixture was left to stir at room temperature for 2 h. Additional methylamine (1 mL, 2 mol / mL) was added to the above reaction mixture and the reaction mixture was stirred for another 2 h. The reaction mixture was then concentrated under vacuum and the residue was purified by column chromatography (1%-3% MeOH / dichloromethane) to give 2-[3-ethylsulfonyl-6-(methylamino)-2-pyridinyl]-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-1-one. LCMS (method 1): retention time 1.24 min, m / z 401 [M+H] + . 1 H NMR (400MHz, CDCl3) δ / ppm 1.24-1.38 (m, 3H) 3.01 (d, J = 5.01Hz, 3H) 3.39 (m, J = 6.85Hz, 2H) 5.10 (br s, 2H) 5.23 (m, 1H) 6.53 (d, J = 8.80Hz, 1H) 8.04 (br d,J=8.93Hz,1H)8.19(s,1H)9.01(s,1H).

[0882] Step B5: N-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridine-2-yl]- Preparation of phenyl]-2-pyridyl]-N-methyl-carbamate (I26)

[0883]

[0884] To a solution of 5-ethylsulfonyl-N-methyl-6-[3-methyl-6-(trifluoromethyl)imidazo[4,5-c]pyridin-2-yl]pyridin-2-amine (75 mg, 0.18 mmol) in acetonitrile (1.0 mL) was added anhydrous pyridine (0.14 mL, 0.18 mmol) and phenyl chloroformate (31 mg, 0.18 mmol) at 0° C. The reaction mixture was stirred at room temperature overnight and then additional pyridine (0.14 mL, 0.18 mmol) and phenyl chloroformate (31 mg, 0.18 mmol) were added and the reaction mixture was heated at 50° C. overnight. Additional equivalents of pyridine (0.14 mL, 0.18 mmol) and phenyl chloroformate (31 mg, 0.18 mmol) were added and the reaction mixture was heated at 80° C. for 3 h. The reaction mixture was concentrated under vacuum and directly adsorbed onto silica gel and purified using silica gel flash chromatography (30%-40% ethyl acetate in cyclohexane) to give N-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-2-yl]-2-pyridinyl]-N-methyl-carbamic acid phenyl ester (I26). LCMS (Method 2): Retention time 1.14 min, 521 [M+H] + .

[0885] Step B6: 1-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridine-2-yl]- Preparation of 2-pyridyl-1,3-dimethyl-urea (P6)

[0886]

[0887] A solution of N-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-2-yl]-2-pyridinyl]-N-methyl-carbamic acid phenyl ester (80 mg, 0.15 mmol) in anhydrous methylamine (3 mL, 0.006 mmol, 2 mmol / L) was heated at 100 ° C under microwave irradiation for 1 h. The reaction mixture was then concentrated under vacuum, directly adsorbed onto silica gel and purified using silica gel flash chromatography (gradient: 2%-5% MeOH / dichloromethane) to give 1-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-2-yl]-2-pyridinyl]-1,3-dimethyl-urea (P6). LCMS (Method 2): retention time 0.93 min, 458 [M+H] + . 1H NMR (400MHz, CDCl3) δ / ppm: 1.31-1.40 (m, 3H), 2.90 (d, J = 4.65Hz, 3H), 3.40 (q, J = 7.34Hz, 2H ),3.52(s,3H),5.12(s,2H),7.30-7.35(m,1H),8.23(s,1H),8.35(d,J=8.93Hz,1H),8.66(br s,1H),9.07(s,1H).

[0888] Example P23: 2-(3-Ethylsulfonyl-2-pyridyl)-6-(trifluoromethylsulfonyl)isoindolin-1-one ( Preparation of Compound P23

[0889]

[0890] Step 1: Preparation of 2-bromo-4-(trifluoromethylsulfanyl)aniline (Intermediate I-1)

[0891]

[0892] To a solution of 4-(trifluoromethylsulfanyl)aniline (0.50 g, 2.6 mmol) in N,N-dimethylformamide (2 mL) was added a solution of N-bromosuccinimide (0.42 g, 2.3 mmol) in N,N-dimethylformamide (2 mL) at 10°C. The reaction mixture was stirred at room temperature for 2 hours. It was then diluted with water and extracted three times with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired product (0.55 g). LCMS (Method 1): retention time 1.56 min, m / z 271.8 [M+H] + . 1 H NMR (400MHz, CDCl3) δppm: 6.76 (d, 1H), 7.36-7.41 (m, 1H), 7.71 (d, 1H).

[0893] Step 2: Preparation of methyl 2-amino-5-(trifluoromethylsulfanyl)benzoate (Intermediate I-2)

[0894]

[0895] An autoclave was charged with 2-bromo-4-(trifluoromethylsulfanyl)aniline (Intermediate I-1 prepared as described above, 4.0 g, 15 mmol), trimethylamine (4.1 mL, 29 mmol), 1,1'-bis(diphenylphosphino)ferrocene-dichloropalladium(ii) dichloromethane complex (2.5 g, 2.9 mmol), followed by methanol (40 mL) and N,N-dimethylformamide (20 mL). The reactor was closed and flushed three times with carbon monoxide. The reaction mixture was then heated to 80°C and stirred under a 10 bar carbon monoxide atmosphere for 6 hours. After cooling to room temperature, the reaction mixture was diluted with brine and extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired product (2.0 g). LCMS (Method 2): retention time 1.13 min, m / z 252 [M+H] + . 1 H NMR (400MHz, CDCl3) δppm: 3.91 (s, 3H), 6.65-6.71 (m, 1H), 7.49 (dd, J = 8.56, 2.20Hz, 1H), 8.17 (m, 1H).

[0896] Step 3: Preparation of methyl 2-bromo-5-(trifluoromethylsulfanyl)benzoate (Intermediate I-3)

[0897]

[0898] At 0 ℃, to 2-amino-5-(trifluoromethylsulfanyl) methyl benzoate (intermediate I-2 prepared as described above, 6.5g, 26mmol) in hydrobromic acid (48% in water, 65mL) solution of sodium nitrite (3.6g, 52mmol) in water (20mL) is added dropwise. The reaction mixture was stirred at 0 ℃ for 30 minutes, then copper bromide (I) (6.6g, 46mmol) was added. At 0 ℃, the reaction mixture was stirred for another 30 minutes, and then at room temperature stirred overnight. The reaction mixture was diluted with water and extracted with ethyl acetate three times. The organic layer merged was dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to obtain the desired product (5.9g). 1 HNMR (400MHz, CDCl3) δppm: 3.97 (s, 3H), 7.61 (dd, J = 8.38, 2.26Hz, 1H), 7.75 (d, J = 8.31Hz, 1H), 8.08 (d, J = 2.20Hz, 1H).

[0899] Step 4: Preparation of methyl 2-methyl-5-(trifluoromethylsulfanyl)benzoate (Intermediate I-4)

[0900]

[0901] A flask was charged with methyl 2-bromo-5-(trifluoromethylsulfanyl)benzoate (intermediate I-3 prepared as described above, 6.3 g, 20 mmol), methylboronic acid (3.7 g, 60 mmol), tripotassium phosphate (13 g, 60 mmol), tricyclohexylphosphine (0.56 g, 2.0 mmol), then toluene (76 mL) and water (13 mL). The flask was purged with nitrogen for 10 minutes, then palladium (II) acetate (0.22 g, 1.0 mmol) was added and the purging continued for an additional 10 minutes. The reaction mixture was heated to 95° C. and stirred for 16 hours. The reaction mixture was quenched with water and extracted three times with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired product (3.9 g, 16 mmol). 1 H NMR (400MHz, CDCl3) δppm: 2.65 (s, 3H), 3.93 (s, 3H), 7.27 (s, 1H), 7.32 (s, 1H), 7.68 (d, J = 7.90Hz, 1H), 8.18-8.24 (m, 1H).

[0902] Step 5: Preparation of methyl 2-methyl-5-(trifluoromethylsulfonyl)benzoate (Intermediate I-5)

[0903]

[0904] To a solution of methyl 2-methyl-5-(trifluoromethylsulfanyl)benzoate (Intermediate I-4 prepared as described above, 3.9 g, 16 mmol) in dichloromethane (78 mL) was added 3-chloroperbenzoic acid (19 g, 78 mmol) at 0°C. The reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was quenched with 2M sodium hydroxide solution at 0°C and extracted twice with dichloromethane. The combined organic layers were washed with water and brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (100% cyclohexane) to give the desired product (2.7 g). 1 H NMR (400MHz, CDCl3) δppm: 2.78 (s, 3H), 3.97 (s, 3H), 7.58 (d, J = 8.07Hz, 1H), 8.04 (dd, J = 8.13, 2.02Hz, 1H), 8.57 (d, J = 1.96Hz, 1H).

[0905] Step 6: Preparation of methyl 2-(bromomethyl)-5-(trifluoromethylsulfonyl)benzoate (Intermediate I-6)

[0906]

[0907] To a solution of methyl 2-methyl-5-(trifluoromethylsulfonyl)benzoate (intermediate I-5, 2.7 g, 9.6 mmol prepared as described above) in tetrachloromethane (77 mL) was added N-bromosuccinimide (2.4 g, 13 mmol) and benzoyl peroxide (0.83 g, 2.4 mmol) at room temperature. The reaction mixture was heated to 60° C. and stirred for 16 hours. After cooling to room temperature, the reaction mixture was diluted with ice-cold water and extracted three times with dichloromethane. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired product (1.0 g). 1 H NMR (400MHz, CDCl3) δppm: 4.02 (s, 3H), 5.03 (s, 3H), 7.83 (d, J = 8.19Hz, 1H), 8.15 (dd, J = 8.19, 1.96Hz, 1H), 8.62 (d, J = 1.96Hz, 1H).

[0908] Step 7: Preparation of tert-butyl N-(3-ethylsulfonyl-2-pyridyl)carbamate (Intermediate I-7)

[0909]

[0910] To a solution of 3-ethylsulfonylpyridin-2-amine (0.60 g, 3.2 mmol) in N,N-dimethylformamide (6 mL) was added sodium hydride (60%, 0.23 g, 5.8 mmol) at 0°C. The reaction mixture was stirred at this temperature for 30 minutes. To this mixture was added a solution of tert-butoxycarbonyl tert-butyl carbonate (0.84 g, 3.9 mmol) in N,N-dimethylformamide (3 mL) at 0°C. The reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was diluted with a saturated aqueous ammonium chloride solution and extracted three times with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (dichloromethane in ethyl acetate) to give the desired product (0.50 g). LCMS (Method 2): retention time 0.91 min, m / z 231 [M-56] + . 1 H NMR (400MHz, CDCl3) δppm: 1.31 (t, 3H), 1.57 (s, 9H), 3.20 (q, 2H), 7.17 (dd, 1H), 8.16 (dd, 1H), 8.72 (dd, 1H), 8.96 (br s, 1H).

[0911] Step 8: 2-[[tert-Butoxycarbonyl-(3-ethylsulfonyl-2-pyridinyl)amino]methyl]-5-(trifluoromethyl) Preparation of methyl (2-(2-sulfonyl)benzoate (Intermediate I-8)

[0912]

[0913] To a solution of tert-butyl N-(3-ethylsulfonyl-2-pyridyl)carbamate (Intermediate I-7 prepared as described above, 0.40 g, 1.4 mmol) in N,N-dimethylformamide (8 mL) was added sodium hydride (60%, 73 mg, 1.8 mmol) at 0°C. The reaction mixture was stirred at this temperature for 30 minutes. To this mixture was added a solution of methyl 2-(bromomethyl)-5-(trifluoromethyl-sulfonyl)benzoate (Intermediate I-6 prepared as described above, 0.66 g, 1.8 mmol) in N,N-dimethylformamide (2 mL) at 0°C. The reaction mixture was stirred at 10°C for 1 hour. The reaction mixture was diluted with water and extracted three times with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to yield the desired product (0.35 g). LCMS (method 1): retention time 1.59 min, m / z 510 [M-56] + . 1 H NMR (400MHz, CDCl3) δppm: 1.28 (s, 9H), 1.38 (t, 3H), 3.50 (q, 2H), 3.94 (s, 3H), 5.02 (br d, 1H), 5.76 (m, 1H), 7.47 (br d,1H),8.18(dd,1H),8.38(m,1H),8.49(br d,1H),8.58(m,1H),8.67(dd,1H).

[0914] Step 9: 2-[[(3-ethylsulfonyl-2-pyridinyl)amino]methyl]-5-(trifluoromethylsulfonyl)benzoic acid Preparation of methyl ester (intermediate I-9)

[0915]

[0916] To a solution of methyl 2-[[tert-butoxycarbonyl-(3-ethylsulfonyl-2-pyridinyl)amino]methyl]-5-(trifluoromethylsulfonyl)benzoate (Intermediate I-8 prepared as described above, 0.32 g, 0.56 mmol) in dichloromethane (4 mL) was added trifluoroacetic acid (0.17 mL, 5.6 mmol). The reaction mixture was stirred at room temperature for 5 hours. It was then concentrated under reduced pressure and co-evaporated with toluene to give the crude desired product, which was used without further purification. LCMS (Method 1): retention time 1.57 min, m / z 467 [M+H] + .

[0917] Step 10: 2-[[(3-ethylsulfonyl-2-pyridinyl)amino]methyl]-5-(trifluoromethylsulfonyl)benzoic acid Preparation of (Intermediate I-10)

[0918]

[0919] To a solution of crude methyl 2-[[(3-ethylsulfonyl-2-pyridinyl)amino]methyl]-5-(trifluoromethyl-sulfonyl)benzoate (Intermediate I-9 prepared as described above, 0.25 g, 0.54 mmol) in methanol (5 mL) and water (2.5 mL) was added dihydroxybarium octahydrate (0.34 g, 1.1 mmol). The reaction mixture was stirred at room temperature for 3 hours. It was then acidified with 2N hydrochloric acid and extracted three times with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure to give the crude desired product, which was used without further purification. LCMS (Method 1): retention time 1.39 min, m / z 453 [M+H] + .

[0920] Step 11: 2-(3-ethylsulfonyl-2-pyridyl)-6-(trifluoromethylsulfonyl)isoindolin-1-one (compound Preparation of compound P23

[0921]

[0922] To a solution of crude 2-[[(3-ethylsulfonyl-2-pyridinyl)amino]methyl]-5-(trifluoromethylsulfonyl)benzoic acid (Intermediate I-10 prepared as described above, 0.25 g, 0.54 mmol) in pyridine (3 mL) was added phosphorus oxychloride (0.11 mL, 1.1 mmol, 2.0 equiv) at 0°C. The reaction mixture was stirred at this temperature for 1 hour. It was then acidified with 2N hydrochloric acid and extracted three times with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired product (0.10 g) as a solid, mp 202°C-204°C. LCMS (Method 2): retention time 0.99 min, m / z 435 [M+H] + . 1 H NMR (400MHz, CDCl3) δppm: 1.39 (t, 3H), 3.55 (q, 2H), 5.19 (br s,2H),7.64(dd,1H),7.88(d,1H),8.31(dd,1H),8.47(dd,1H),8.61(s,1H),8.84(dd,1H).

[0923] Example P25: 1-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethoxy)isoindolin-2-yl]-3-pyridine Preparation of [4-[ ...(4-amino-3-cyclopropanecarbonitrile)]] (Compound P25)

[0924]

[0925] Step 1: Preparation of methyl 2-amino-5-(trifluoromethoxy)benzoate (Intermediate II-1)

[0926]

[0927] To a solution of 2-amino-5-(trifluoromethoxy)benzoic acid (5.0 g, 23 mmol) in N,N-dimethylformamide (50 mL) was added potassium carbonate (6.3 g, 45 mmol) and iodomethane (1.4 mL, 23 mmol) at room temperature. The reaction mixture was stirred at room temperature overnight. It was then quenched with water and extracted three times with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired product (4.0 g). LCMS (method 2): retention time 1.08 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).

[0928] Step 2: Preparation of methyl 2-bromo-5-(trifluoromethoxy)benzoate (Intermediate II-2)

[0929]

[0930] At 0 ℃, to 2-amino-5-(trifluoromethoxy) benzoic acid methyl ester (intermediate II-1 prepared as described above, 7.3g, 31mmol) in the solution of hydrobromic acid (48% in water, 73mL), dropwise add a solution of sodium nitrite (4.3g, 62mmol) in water (22mL).Reaction mixture was stirred at 0 ℃ for 30 minutes, then copper bromide (I) (8.0g, 56mmol) was added.At 0 ℃, reaction mixture was stirred for 30 minutes again, and then at room temperature stirred 5 hours.Reaction mixture was diluted with water and extracted with ethyl acetate three times.The organic layer merged is dried over sodium sulfate, filtered and concentrated under reduced pressure.Roughage is obtained desired product (5.3g) by flash chromatography on silica gel (ethyl acetate in cyclohexane) purifying. 1 HNMR (400MHz, CDCl3) δppm: 3.96 (s, 3H), 7.22 (m, 1H), 7.66-7.73 (m, 2H).

[0931] Step 3: Preparation of methyl 2-methyl-5-(trifluoromethoxy)benzoate (Intermediate II-3)

[0932]

[0933] In a flask, 2-bromo-5-(trifluoromethoxy)benzoic acid methyl ester (intermediate II-2 prepared as described above, 5.3g, 18mmol), methylboric acid (3.3g, 53mmol), tripotassium phosphate (11g, 53mmol), tricyclohexylphosphine (0.50g, 1.8mmol) were loaded, followed by toluene (64mL) and water (11mL). The flask was purged with nitrogen for 10 minutes, then palladium acetate (II) (0.20g, 0.89mmol) was added and the purging continued for an additional 10 minutes. The reaction mixture was heated to 100°C and stirred for 3 hours. The reaction mixture was quenched with water and extracted three times with ethyl acetate. The combined organic layer was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (100% cyclohexane) to obtain the desired product (2.0g). 1 HNMR (400MHz, CDCl3) δppm: 2.61 (s, 3H), 3.92 (s, 3H), 7.29 (m, 2H), 7.78 (s, 1H).

[0934] Step 4: Preparation of methyl 2-(bromomethyl)-5-(trifluoromethoxy)benzoate (Intermediate II-4)

[0935]

[0936] To a solution of methyl 2-methyl-5-(trifluoromethoxy)benzoate (intermediate II-3 prepared as described above, 1.9 g, 8.1 mmol) in tetrachloromethane (65 mL) was added N-bromosuccinimide (2.0 g, 11 mmol) and benzoyl peroxide (0.70 g, 2.0 mmol) at room temperature. 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 and extracted three times with dichloromethane. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired product (1.6 g). 1 H NMR (400MHz, CDCl3) δppm: 3.97 (s, 3H), 4.95 (s, 2H), 7.53 (m, 1H), 7.83 (d, 1H), 8.10 (m, 1H).

[0937] Step 5: 2-[[[5-(1-cyanocyclopropyl)-3-ethylsulfonyl-2-pyridinyl]amino]methyl]-5-(trifluoromethyl)- Preparation of methyl methoxybenzoate (Intermediate II-5)

[0938]

[0939] To a solution of 1-(6-amino-5-ethylsulfonyl-3-pyridyl)cyclopropanecarbonitrile (0.35 g, 1.4 mmol) in N,N-dimethylformamide (5 mL) was added sodium hydride (60%, 84 mg, 2.1 mmol) at 0°C. The reaction mixture was stirred at this temperature for 30 minutes. To this mixture was added a solution of methyl 2-(bromomethyl)-5-(trifluoromethoxy)benzoate (Intermediate II-4 prepared as described above, 0.61 g, 2.0 mmol) in N,N-dimethylformamide (3.5 mL) at 0°C. The reaction mixture was stirred at 10°C for 1 hour. The reaction mixture was diluted with water and extracted three times with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to yield the desired product (0.25 g). LCMS (Method 1): retention time 1.59 min, m / z 484 [M+H] + .

[0940] Step 6: 2-[[[5-(1-cyanocyclopropyl)-3-ethylsulfonyl-2-pyridinyl]amino]methyl]-5-(trifluoromethyl)- Preparation of methoxy)benzoic acid (Intermediate II-6)

[0941]

[0942] To a solution of methyl 2-[[[5-(1-cyanocyclopropyl)-3-ethylsulfonyl-2-pyridinyl]amino]methyl]-5-(trifluoromethoxy)benzoate (Intermediate II-5 prepared as described above, 0.25 g, 0.52 mmol) in methanol (5 mL) and water (2.5 mL) was added dihydroxybarium octahydrate (0.33 g, 1.0 mmol). The reaction mixture was stirred at room temperature for 3 hours. It was then acidified with 2N hydrochloric acid and extracted three times with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure to give the crude desired product, which was used without further purification. LCMS (Method 1): retention time 1.48 min, m / z 470 [M+H] + .

[0943] Step 7: 1-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethoxy)isoindolin-2-yl]-3-pyridine Preparation of [4-[ ...(4-amino-3-cyclopropanecarbonitrile)]] (Compound P25)

[0944]

[0945] To a solution of crude 2-[[[5-(1-cyanocyclopropyl)-3-ethylsulfonyl-2-pyridinyl]amino]methyl]-5-(trifluoromethoxy)benzoic acid (Intermediate II-6 prepared as described above, 0.22 g, 0.47 mmol) in pyridine (3 mL) was added phosphorus oxychloride (0.088 mL, 0.94 mmol) at 0°C. The reaction mixture was stirred at this temperature for 1 hour. It was then acidified with 2N hydrochloric acid and extracted three times with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give the desired product (70 mg) as a solid, mp 149°C-151°C. LCMS (Method 1): retention time 1.53 min, m / z 452 [M+H] + . 1 H NMR(400MHz, CDCl3)δppm:1.39(t,3H),1.59-1.64(m,2H),1.92-2.03(m,2H),3.56(q ,2H),5.02(s,2H),7.51(m,1H),7.59(m,1H),7.77(s,1H),8.20(d,1H),8.84(d,1H).

[0946] Table P: Examples of compounds of formula I

[0947]

[0948]

[0949]

[0950]

[0951]

[0952] Intermediate preparation:

[0953] Example IP1: Preparation of methyl 2-(bromomethyl)-5-(trifluoromethyl)pyridine-3-carboxylate (Intermediate IP-3)

[0954]

[0955] Step 1: Preparation of methyl 2-chloro-5-(trifluoromethyl)pyridine-3-carboxylate (Intermediate IP-1)

[0956]

[0957] To a solution of 2-chloro-5-(trifluoromethyl)pyridine-3-carboxylic acid (CAS 505084-59-3; 7.00 g, 31.0 mmol) in N,N-dimethylformamide (70 mL) was added cesium carbonate (12.1 g, 37.2 mmol). The reaction mixture was stirred at room temperature for 5 minutes, then iodomethane (2.90 mL, 46.6 mmol) was added. Stirring was continued at room temperature for 1 hour. The reaction mixture was diluted with ice water and extracted three times with ethyl acetate. The combined organic layers were washed with ice water and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure to give the desired product (7.00 g), which was used without further purification. LCMS (Method 3): m / z 240 / 242 [M+H] + , retention time Rt = 1.00min. 1 H NMR (400MHz, CDCl3) δppm 4.01 (s, 3H), 8.41 (d, 1H), 8.78 (d, 1H).

[0958] Step 2: Preparation of methyl 2-methyl-5-(trifluoromethyl)pyridine-3-carboxylate (Intermediate IP-2)

[0959]

[0960] In reactor, methylboric acid (7.73g, 125mmol), tripotassium phosphate (26.6g, 125mmol), tricyclohexylphosphine (1.17g, 4.17mmol) are loaded, then toluene (100mL) and water (13mL) are loaded. Flask is purged with nitrogen for 15 minutes. In reaction mixture, 2-chloro-5-(trifluoromethyl) pyridine-3-methyl formate (intermediate IP-1 prepared as described above, 10.0g, 41.7mmol) and palladium acetate (II) (0.469g, 2.09mmol) are added. First reaction mixture is heated to 100 ℃ and stirred for 2 hours, then stirred at 90 ℃ and spent the night. After cooling to room temperature, mixture is diluted with water and ethyl acetate, and filtered through diatomaceous earth pad. These layers are separated, and organic layer is dried over sodium sulfate, filtered and concentrated under reduced pressure, to obtain desired product (5.00g), which is used without further purification. LCMS (Method 3): m / z 220 [M+H] + , retention time Rt = 0.93min. 1 H NMR (400MHz, CDCl3) δppm 2.92 (s, 3H), 3.97 (s, 3H), 8.44 (d, 1H), 8.87 (m, 1H).

[0961] Step 3: Preparation of methyl 2-(bromomethyl)-5-(trifluoromethyl)pyridine-3-carboxylate (Intermediate IP-3)

[0962]

[0963] To a solution of methyl 2-methyl-5-(trifluoromethyl)pyridine-3-carboxylate (intermediate IP-2 prepared as described above, 3.50 g, 16.0 mmol) in tetrachloromethane (80 mL) was added N-bromo-succinimide (4.00 g, 22.0 mmol) and benzoyl peroxide (70%, 1.40 g, 4.00 mmol). The reaction mixture was heated to 70° C. and stirred for 3 hours. After cooling to room temperature, it was diluted with ice water and extracted three times with dichloromethane. The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (gradient of ethyl acetate in cyclohexane) to give the desired product (1.40 g). LCMS (Method 3): m / z 298 / 300 [M+H] + , retention time Rt = 1.01min. 1 H NMR (400MHz, CDCl3) δppm: 4.03 (s, 3H), 5.08 (s, 2H), 8.53 (d, J = 2.01Hz, 1H), 8.96 (m, 1H).

[0964] Example IP2: Preparation of 3-ethylsulfanyl-5-(2-pyridyloxy)pyridine-2-carboxylic acid (Intermediate IP-6)

[0965]

[0966] Step 1: Preparation of 3-ethylsulfanyl-5-hydroxy-pyridine-2-carboxylic acid methyl ester (IP-4)

[0967]

[0968] To a solution of 5-bromo-3-ethylsulfanyl-pyridine-2-carboxylic acid methyl ester (prepared as described in WO 2016 / 026848) (10.0 g, 36.21 mmol) in acetonitrile (72 ml) was added cesium carbonate (25.96 g, 79.67 mmol) and (E)-benzaldehyde oxime (5.7 g, 47.08 mmol), and the suspension was heated to 80 ° C overnight. The solvent was evaporated in vacuo and the residue was dissolved with ethyl acetate and water. The separated aqueous layer was acidified with an aqueous solution of 1M hydrochloric acid and extracted with ethyl acetate (3x) and once with dichloromethane. The combined organic phases were dried over sodium sulfate, filtered and concentrated. The residue was purified by flash chromatography on silica gel (0%-10% methanol gradient in dichloromethane) to give 3-ethylsulfanyl-5-hydroxy-pyridine-2-carboxylic acid methyl ester. LCMS (Method 4): m / z 214 [M+H] + ; Retention time: 0.68min.

[0969] Step 2: Preparation of methyl 3-ethylsulfanyl-5-(2-pyridyloxy)pyridine-2-carboxylate (IP-5)

[0970]

[0971] A mixture of 3-ethylsulfanyl-5-hydroxy-pyridine-2-carboxylic acid methyl ester (Compound IP-4 prepared as described above; 2.00 g, 9.4 mmol), potassium carbonate (2.6 g, 19 mmol), 2-iodopyridine (1.5 mL, 14.0 mmol), and copper iodide (0.187 g, 0.94 mmol) in N,N-dimethylformamide (20 mL) was stirred at 110° C. for 6 hours. The reaction mixture was neutralized with a 2M aqueous solution of hydrochloric acid (50 mL), diluted with water (50 mL), and extracted with ethyl acetate (3×50 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo to give 3-ethylsulfanyl-5-(2-pyridyloxy)pyridine-2-carboxylic acid methyl ester. This material was used in the next step without further purification. LCMS (Method 1): m / z 291 [M+H] + ; Retention time: 1.37min. 1 H NMR(400MHz, CDCl3)δ / ppm:1.38(t,3H),2.87(q,2H),3.98(s,3H),7.03(d,1H),7. 10(m,1H),7.52(d,J=2.3Hz,1H),7.77(m,1H),8.16(m,1H),8.29(d,J=2.3Hz,1H).

[0972] Step 3: Preparation of 3-ethylsulfanyl-5-(2-pyridyloxy)pyridine-2-carboxylic acid (IP-6)

[0973]

[0974] To a solution of methyl 3-ethylsulfanyl-5-(2-pyridyloxy)pyridine-2-carboxylate (Compound IP-5 prepared as described above; 0.900 g, 3.10 mmol) in tetrahydrofuran (10 mL) was added lithium hydroxide monohydrate (0.0951 g, 4.65 mmol) and water (2 mL). The reaction mixture was stirred at room temperature for 2 hours, then acidified with a 2M aqueous solution of hydrochloric acid (25 mL) and extracted with ethyl acetate (3×25 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo to give 3-ethylsulfanyl-5-(2-pyridyloxy)pyridine-2-carboxylic acid as a solid. LCMS (Method 1): m / z 277 [M+H] + ; Retention time: 1.26min.

[0975] By adding other insecticides, acaricides and / or fungicidal active ingredients, the activity of the composition according to the present invention can be significantly widened and adapted to prevailing conditions. Mixtures of compounds of Formula I with other insecticides, acaricides and / or fungicidal active ingredients can also have other unexpected advantages, which can also be described as synergistic in a wider sense. For example, better tolerance of plants, reduced phytotoxicity, insects can be controlled at their different developmental stages, or better behavior during their production (e.g., during grinding or mixing, during their storage or during their use).

[0976] Suitable active ingredients to be added here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.

[0977] The following mixtures of a compound of formula I with an active ingredient are preferred (the abbreviation "TX" means "a compound selected from the group consisting of the compounds described in Tables A-1 to A-48, Tables C1 to C18, Tables D1 to D12, Tables E1 to E12, Tables G1 to G24, Tables I1 to I48, Tables J1 to J18, Tables K1 to K12 and Tables L-1 to L-12 and Table P according to the invention"):

[0978] Auxiliary agent, the auxiliary agent is selected from the group consisting of: petroleum (alias) (628) + TX,

[0979] Auxiliary agent, the auxiliary agent is selected from the group consisting of: petroleum (alias) (628) + TX,

[0980] Acaricide, the acaricide is selected from the group consisting of: 1,1-bis(4-chlorophenyl)-2-ethoxyethanol (IUPAC name) (910) + TX, 2,4-dichlorophenylbenzenesulfonate (IUPAC / Chemical Abstracts name) (1059) + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide (IUPAC name) (1295) + TX, 4-chlorophenylphenylsulfone (IUPAC name) (981) + TX, abamectin (1) + TX, acequinoxaline (3) + TX, acetofennig [CCN] + TX, flumethrin (9) + TX, aldicarb (16) + TX, aldicarb (863) + TX, α-cypermethrin (202) + TX, cypermethrin (870) + TX, sulfamethoxam [CCN] + TX, aminothioate (872) + TX, amitriptyline (875) + TX, amitriptyline hydrogen oxalate (875) + TX, amitraz (24) + TX, cypermethrin (881) + TX, arsenic trioxide (882) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azinphos-methyl (44) + TX, azinphos-methyl (45) + TX, azobenzene (IUPAC name) (888) + TX, azacyclotin (46) + TX, azothoate (889) + TX, benomyl (62) + TX, benoxafos (alias) [CCN] + TX, benzoximate (71) + TX, benzyl benzoate (IUPAC name) [CCN] + TX, bifenazate (74) + TX, flumethrin (76) + TX, binacarb (907) + TX, bromethrin (alias) + TX, bromocyclene (918) + TX, bromophos (920) + TX, ethyl bromophos (921) + TX, bromopropylate (94) + TX, buprofezin (99) + TX, butanone (103) + TX, butanone sulfone (104) + TX, butylpyridaben (alias) + TX, lime sulfur mixture (calcium polysulfide)(IUPAC name)(111)+TX、campheechlor)(941)+TX、carbanolate(943)+TX、carbaryl(115)+TX、carbofuran(118)+TX、carbothion(947)+TX、CGA 50'439(research code)(125)+TX、chinomethionat(126)+TX、chlorbenside(959)+TX、chlordimeform(964)+TX、Chlorpheniramine hydrochloride (964) + TX, chlorfenapyr (130) + TX, chlorfenapyr (968) + TX, chlorfenson (970) + TX, chlorfensulfide (971) + TX, chlorfenphos (131) + TX, chlorobenzilate (975) + TX, chloromebuform (977) + TX, chloromethiuron (978) + TX, chloropropylate (983) + TX, chlorpyrifos (145) + TX, methyl chlorpyrifos (146) + TX, chlorthiophos (994) + TX, cinerin I (696) + TX, cinerin II (696) + TX, cinerins (696) + TX, clofentazine (158) + TX, closantel (other name) [CCN] + TX, coumaphos (174) + TX, crotamiton (other name) [CCN] + TX, crotoxyphos (1010) + TX, thiophene (1013) + TX, cyanthoate (1020) + TX, fluazifop (CAS Reg. No. 400882-07-7) + TX, cyhalothrin (196)+TX、Cyclohexan(199)+TX、Cypermethrin(201)+TX、DCPM(1032)+TX、DDT(219)+TX、Demephion(1037)+TX、Demephion-O(1037)+TX、Demephion-S(1037)+TX、Demeton(1038)+TX、Methyldemeton(224)+TX、Demeton-O(1038)+TX、Methyldemeton-O(224)+TX、Demeton-S(1038)+TX、Methyldemeton-S(224)+TX、Demeton-S-methylsulfon(1039)+TX TX, diflubenzuron (226) + TX, chlorpyrifos (1042) + TX, diazinon (227) + TX, sulfonamide (230) + TX, dichlorvos (236) + TX, dicliphos (alias) + TX, chlorpyrifos (242) + TX, dicrotophos (243) + TX, pendimethalin (1071) + TX, dimefox (1081) + TX, dimethoate (262) + TX, dinacti (alias) (653) + TX, dinex (1089) + TX, dinex-diclexine (1089) + TX,Dinobuton (269) + TX, dinocap (270) + TX, dinocap-4 [CCN] + TX, dinocap-6 [CCN] + TX, dinitropropionate (1090) + TX, dinopenton (1092) + TX, dinosulfon (1097) + TX, dinoterbon (1098) + TX, dioxathionate (1102) + TX, diphenylsulfone (IUPAC name) (1103) + TX, disulfiram (alias) [CCN] + TX, ethophos (278) + TX, DNOC (282) + TX, phenoxyacetic acid ( dofenapyn (1113) + TX, doramectin (alias) [CCN] + TX, endosulfan (294) + TX, endothion (1121) + TX, EPN (297) + TX, eprinomectin (alias) [CCN] + TX, ethion (309) + TX, ethoate-methyl (1134) + TX, etoxazole (320) + TX, etrimfos (1142) + TX, fenazaflor (1147) + TX, fenazaquin (328) + TX, fenbutatin oxide)(330)+TX, fenothiocarb(337)+TX, cypermethrin(342)+TX, fenpyrad(alias)+TX, fenpyroximate(345)+TX, fenson(1157)+TX, fentrifanil(1161)+TX, cypermethrin(349)+TX, fipronil(354)+TX, fluacrypyrim(360)+TX 、Fluzolan (1166) + TX、flubenzimine (1167) + TX、flufenuron (366) + TX、flucythrinate (367) + TX、fluenetil (1169) + TX、flufenuron (370) + TX、flumethrin (372) + TX、fluorbenside (1174) + TX、fluvalinate (1184) + TX、FMC 1137 (research code) (1185) + TX、anthraquinone (405) + TX、anthraquinone hydrochloride (405) + TX、formothion (1192) + TX、formparanate (1193) + TX、γ-HCH (430) + TX、Glyodin (1205) + TX, halfenprox (424) + TX, heptenophos (432) + TX, hexadecyl cyclopropanecarboxylate (IUPAC / Chemical Abstracts name) (1216) + TX, hexathiazolin (441) + TX, iodomethane (IUPAC name) (542) + TX, isocarbophos (alias) (473) + TX, isopropyl O-(methoxyaminothiophosphoryl) salicylate (IUPAC name) (473) + TX, ivermectin (alias) [CCN] + TX, jasmolin I (696) + TX, jasmolin II (696) + TX, jodfenphos (1248) + TX, lindane (43 0)+TX, lufenuron (490)+TX, malathion (492)+TX, malonoben (1254)+TX, mecarbam (502)+TX, mephosfolan (1261)+TX, methylthiophene (alias) [CCN]+TX, methacrifos (1266)+TX, methylamidophos (527)+TX, methidathion (529)+TX, methiocarb (530)+TX, methomyl (531)+TX, methyl bromide (537)+TX, metolcarb (550)+TX, metolcarb (556)+TX, mexacarbate (1290)+TX, milbemycin (557)+TX, milbemycin oxime)(alias)[CCN]+TX、mipafox(1293)+TX、monocrotophos(561)+TX、morphothion(1300)+TX、moxidectin(alias)[CCN]+TX、naled(567)+TX、NC-184(compound code)+TX、NC-512(compound code)+TX、nifluridide(1309)+TX、nikkomycin(alias)[CCN]+TX、nitrilac arb)(1313)+TX, nitrilacarb 1:1 zinc chloride complex (1313)+TX, NNI-0101(compound code)+TX, NNI-0250(compound code)+TX, omethoate(594)+TX, oxamyl (602)+TX, oxydeprofos(1324)+TX, oxydisulfoton(1325)+TX, pp'-DDT(219)+TX, parathion(615)+TX,Permethrin (626) + TX, petroleum oil (alias) (628) + TX, fenthion (1330) + TX, fenthion (631) + TX, phorate (636) + TX, phosalone (637) + TX, phosfolan (1338) + TX, phosmet (638) + TX, phosphamidon (639) + TX, phoxim (642) + TX, methylpirimiphos (652) + TX, polychloroterpenes (traditional name) (1347) + TX, polynactins (alias) (653) + TX, prochloraz (1350) + TX, profenofos (66 2)+TX, promacyl (1354)+TX, propargyl (671)+TX, propetamphos (673)+TX, propoxur (678)+TX, prothidathion (1360)+TX, prothoate (1362)+TX, pyrethrin I (696)+TX, pyrethrin II (696)+TX, pyrethrins (696)+TX, pyridaphenthion (699)+TX, pyridaphenthion (701)+TX, pyrimidifen )(706)+TX, pyrimithiophos (1370)+TX, quinalphos (711)+TX, quintiofos (1381)+TX, R-1492 (research code) (1382)+TX, RA-17 (research code) (1383)+TX, rotenone (722)+TX, schradan (1389)+TX, sebufos (alias)+TX, selamectin (alias) [CCN]+TX, SI-0009 (compound code)+TX, sophamide (1402)+TX, quaternary ketone Mite (738) + TX, spiromesifen (739) + TX, SSI-121 (research code) (1404) + TX, Sulfiram (alias) [CCN] + TX, sulfluramid (750) + TX, sulfotep (753) + TX, sulfur (754) + TX, SZI-121 (research code) (757) + TX, τ-fluvalinate (398) + TX, tebufenpyrad (763) + TX, TEPP (1417) + TX, terbufen (terbam) (alias) + TX, stirofos (777) + TX, tetradifon (786) + TX,Tetranactin (alias) (653) + TX, tetrasul (1425) + TX, thiafenox (alias) + TX, thiocarboxime (1431) + TX, thiofanox (800) + TX, thiometon (801) + TX, thuringiensin (alias) [CCN] + TX, thiafenox (t riamiphos) (1441) + TX, triarathene (1443) + TX, triazophos (820) + TX, triazuron (alias) + TX, trichlorfon (824) + TX, trifenofos (1455) + TX, trinactin (alias) (653) + TX, aphidox (847) + TX, vaniliprole [CCN] and YI-5302 (compound code) + TX,

[0981] an algaecide selected from the group consisting of bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endoxan (295) + TX, fentin (347) + TX, slaked lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX,

[0982] An anthelmintic selected from the group consisting of abamectin (1) + TX, clefonate (1011) + TX, doramectin (alias) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alias) [CCN] + TX, ivermectin (alias) [CCN] + TX, milbemycin oxime (alias) [CCN] + TX, moxidectin (alias) [CCN] + TX, piperazine [CCN] + TX, selamectin (alias) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,

[0983] Avicide selected from the group consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX,

[0984] Bactericide, the bactericide is selected from the group consisting of: 1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodesine (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, mercury + Fen (alias) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, chlorpheniramine (766) + TX, and thimerosal (alias) [CCN] + TX,

[0985] Biological agent, the biological agent is selected from the group consisting of: GV of cotton brown banded moth (alias) (12) + TX, Radiation-forming soil bacteria (alias) (13) + TX, Amblyseius spp. (alias) (19) + TX, Spodoptera exigua NPV (alias) (28) + TX, Anagrus atomus (alias) (29) + TX, Aphelinus abdominalis (alias) (33) + TX, Aphidius colemani (alias) (34) + TX, Aphidoletes aphidimyza (alias) (35) + TX, Spodoptera exigua NPV (alias) (38) + TX, Bacillus firmus (alias) (48) + TX, Bacillus sphaericus (alias) Neide)(scientific name)(49)+TX、Bacillus thuringiensisBerliner)(scientific name)(51)+TX、Bacillus thuringiensissubsp.aizawai)(scientific name)(51)+TX、Bacillus thuringiensissubsp.israelensis)(scientific name)(51)+TX、Bacillus thuringiensissubsp.japonensis)(scientific name)(51)+TX、Bacillus thuringiensissubsp.kurstaki)(scientific name)(51)+TX、Bacillus thuringiensissubsp.tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alias) (53) + TX, Beauveria brongniartii (alias) (54) + TX, Chrysoperla carnea (alias) (151) + TX, Cryptolaemus montrouzieri (alias) (178) + TX, Codling moth GV (alias) (191) + TX, Dacnusa sibirica (alias) (212) + TX, Diglyphus isaea (alias) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus) (alias) (300) + TX, Spodoptera exigua NPV (alias) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alias) (433) + TX, Hippodamia convergens (alias) (442) + TX, Leptomastix dactylopii (alias) (488) + TX, Macrolophus caliginosus (alias) (491) + TX, Spodoptera exigua 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, Neodiprion sertifer NPV and Neodiprion sertifer (Neodiprion sertifer) NPV.lecontei)NPV (alias) (575) + TX, Paecilomyces species (alias) (596) + TX, Paecilomyces fumosoroseus (alias) (613) + TX, Phytoseiulus persimilis (alias) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosisvirus (scientific name) (741) + TX, Steinernema bibionis (alias) (742) + TX, Steinernema carpocapsae (alias) (742) + TX, Steinernema glaseri (alias) (742) + TX, Steinernema riobrave) (alias) (742) + TX, Steinernema riobravis (alias) (742) + TX, Steinernema capterisci (alias) (742) + TX, Steinernema spp. (alias) (742) + TX, Trichogramma spp. (alias) (826) + TX, Typhlodromus occidentalis (alias) (844) and Verticillium lecanii (alias) (848) + TX,.

[0986] Soil disinfectant selected from the group consisting of iodomethane (IUPAC name) (542) and bromomethane (537) + TX,

[0987] A chemical sterilant selected from the group consisting of: apholanate [CCN] + TX, bis(aziridine) methylaminophosphine sulfide (bisazir) (alias) [CCN] + TX, busulfan (alias) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alias) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholanate [CCN] + TX, methyl thiote ... apholate) [CCN] + TX, morzid [CCN] + TX, penfluron (alias) [CCN] + TX, tepa [CCN] + TX, thiohempa (alias) [CCN] + TX, thiohexamethylenetepa (alias) [CCN] + TX, trotamide (alias) [CCN] and urethaneimide (alias) [CCN] + TX,

[0988] Insect pheromone, the insect pheromone is selected from the group consisting of: (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol (IUPAC name) (222) + TX, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, (E,Z)-tetradec-4,10-dien-1-yl acetate (IUPAC name) (779) + TX, (Z)-dodec-7-en-1-yl acetate (IUPAC name) (285) + TX, (Z)-hexadecan-11-enal (IUPAC name) (436) + TX, (Z)-hexadecan-11-en-1-yl acetate (IUPAC name) (437) +TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438) +TX, (Z)-eicos-13-en-10-one (IUPAC name) (448) +TX, (Z)-tetradec-7-en-1-al (IUPAC name) (782) +TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783) +TX, (Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784) +TX, (7E,9Z)-dodec-7,9-dien-1-yl acetate (IUPAC name) (283) +TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate (IUPAC name) (780) +TX, (9Z,12E)-tetradec-9,12-Dien-1-yl acetate (IUPAC name) (781) + TX, 14-methyloctadec-1-ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol and 4-methylnonan-5-one (IUPAC name) (544) + TX, alpha-multistriatin (alias) [CCN] + TX, western pine beetle gathering pheromone (brevicomin) (alias) [CCN] + TX, codlelure (alias) [CCN] + TX, codlemon mone)(alias)(167)+TX、cuelure)(alias)(179)+TX、disparlure)(277)+TX、1-dodecane-8-en-1-yl acetate(IUPAC name)(286)+TX、1-dodecane-9-en-1-yl acetate(IUPAC name)(287)+TX、10-10-dien-1-yl acetate(IUPAC name)(284)+TX、dominicalure(alias)[CCN]+TX、ethyl 4-methyloctanoate(IUPAC name) C name) (317) + TX, eugenol (alias) [CCN] + TX, southern pine beetle gathering pheromone (frontalin) (alias) [CCN] + TX, gossyplure (alias) (420) + TX, grandlure (421) + TX, grandlure I (alias) (421) + TX, grandlure II (alias) (421) + TX, grandlure III (alias) (421) + TX, grandlure IV (alias) (421) + TX, hexalure )[CCN]+TX、ipsdienol(alias)[CCN]+TX、ipsenol(alias)[CCN]+TX、japonilure(alias)(481)+TX、lineatin(alias)[CCN]+TX、litlure(alias)[CCN]+TX、looplure(alias)[CCN]+TX、medlure[CCN]+TX、megatomoic acid(alias)[CCN]+TX、methyl eugenol(alias)(540)+TX、muscalure(563)+TX、octadeca-2,13-dien-1-yl acetate(IUPAC name)(588)+TX、octadeca-3,13-Dien-1-yl acetate (IUPAC name) (589) + TX, orfralure (alias) [CCN] + TX, oryctalure (alias) (317) + TX, ostramone (alias) [CCN] + TX, siglure [CCN] + TX, sordidin (alias) (736) + TX, sulcatol )(Other name)[CCN]+TX, tetradec-11-en-1-yl acetate (IUPAC name) (785)+TX, Mediterranean fruit fly attractant (839)+TX, Mediterranean fruit fly attractant A (Other name) (839)+TX, Mediterranean fruit fly attractant B1 (Other name) (839)+TX, Mediterranean fruit fly attractant B2 (Other name) (839)+TX, Mediterranean fruit fly attractant C (Other name) (839) and trunc-call (Other name)[CCN]+TX,

[0989] An insect repellent selected from the group consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, DEET [CCN] + TX, dimethyl carbate) [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexylurea [CCN] + TX, methoquin-butyl (1276) + TX, methyl neodecylamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,

[0990] An insecticide selected from the group consisting of: 1-dichloro-1-nitroethane (IUPAC / Chemical Abstracts name) (1058) + TX, 1,1-dichloro-2,2-di(4-ethylphenyl)ethane (IUPAC name) (1056) + TX, 1,2-dichloropropane (IUPAC / Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane with 1,3-dichloropropene (IUPAC name) (1063) + TX, 1-bromo-2-chloroethane (IUPAC / Chemical Abstracts name) (916) + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate (IUPAC name) (1451) + TX, 2, 2-Dichlorovinyl 2-ethylsulfinylethyl methyl phosphate (IUPAC name) (1066) + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate (IUPAC / Chemical Abstracts name) (1109) + TX, 2-(2-butoxyethoxy)ethyl thiocyanate (IUPAC / Chemical Abstracts name) (935) + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate (IUPAC / Chemical Abstracts name) (1084) + TX, 2-(4-chloro-3,5-xylyloxy)ethanol (IUPAC name) (986) + TX, 2-chlorovinyl diethyl phosphate (IUPAC name) C name) (984) + TX, 2-imidazolidinone (IUPAC name) (1225) + TX, 2-isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate (IUPAC name) (1284) + TX, 2-thiocyanatoethyl laurate (IUPAC name) (1433) + TX, 3-bromo-1-chloroprop-1-ene (IUPAC name) (917) + TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate (IUPAC name) (1283) + TX, 4-methyl(prop-2-ynyl)amino-3,5-ditolyl methylcarbamate ( IUPAC name) (1285) + TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate (IUPAC name) (1085) + TX, avermectin (1) + TX, acephate (2) + TX, acetamiprid (4) + TX, domesticaphos (alias) [CCN] + TX, acetamiprid [CCN] + TX, flumethrin (9) + TX, acrylonitrile (IUPAC name) (861) + TX, chlorpyrifos (15) + TX, aldicarb (16) + TX, aldicarb (863) + TX, chloronaphthalene (864) + TX, allethrin (17) + TX, aloamicin (alias) [CCN] + TX, chlorpyrifos (866) + TX,α-Cypermethrin (202) + TX, α-ecdysone (alias) [CCN] + TX, aluminum phosphide (640) + TX, cypermethrin (870) + TX, thioamide (872) + TX, cypermethrin (873) + TX, cypermethrin (875) + TX, cypermethrin hydrogen oxalate (875) + TX, amitraz (24) + TX, neonicotinoid (877) + TX, ethidathion (883) + TX, AVI 382 (compound code) + TX, AZ 60541 (compound code) + TX, azadirachtin (alias) (41) + TX, methyl pyriphos (42) + TX, azinphos-ethyl (44) + TX, azinphos-methyl (45) + TX, azophos (889) + TX, Bacillus thuringiensis delta endotoxins (alias) (52) + TX, barium hexafluorosilicate (alias) [CCN] + TX, barium polysulfide (IUPAC / Chemical Abstracts name) (892) + TX, cypermethrin [CCN] + TX, Bayer 22 / 190 (research code) (893) + TX, Bayer 22408 (research code) (894) + TX, Benthiocarb (58) + TX, Benfuracarb (60) + TX, Dimethoprim (66) + TX, β-cyfluthrin (194) + TX, β-cypermethrin (203) + TX, Bifenthrin (76) + TX, Bio-allethrin (78) + TX, Bio-allethrin S-cyclopentenyl isomer (alias) (79) + T X, bioethanomethrin [CCN] + TX, biopermethrin (908) + TX, pyrethrin (80) + TX, bis(2-chloroethyl) ether (IUPAC name) (909) + TX, bistrifluan (83) + TX, borax (86) + TX, bromethrin (alias) + TX, bromopheniramine (914) + TX, bromomethoxazole (918) + TX, bromo-DDT (alias) [CCN] + TX, bromophos (920) + TX, bromophos-ethyl (921) + TX, oxathiocarb (924) + TX, thiamethoxam (99) + TX, cypermethrin (926) + TX, demethylated butylpyrimidinphos (butathiofos) (927) + TX, butanone carbendazim (103) + TX, butyl ester phosphine (932) + TX, butanone carbendazim (104) + TX, butylpyridaben (alias) + TX, cadusofos (109) + TX, calcium arsenate [CCN ]+TX, calcium cyanide (444)+TX, calcium polysulfide (IUPAC name) (111)+TX, toxaphene (941)+TX, chlormethoxam (943)+TX, carbaryl (115)+TX, chlorpyrifos (118)+TX, carbon disulfide (IUPAC / Chemical Abstracts name) (945)+TX, carbon tetrachloride (IUPAC name) (946)+TX, trithion (947)+TX, chlorpyrifos (119)+TX,Cartap (123) + TX, Cartap hydrochloride (123) + TX, Veratridine (alias) (725) + TX, Borneol (960) + TX, Chlordane (128) + TX, Chlordecone (963) + TX, Chlordimeform (964) + TX, Chlordimeform hydrochloride (964) + TX, Chlorpheniramine (129) + TX, Chlorfenapyr (130) + TX, Chlorfenapyr (131) + T X、Chlorfluazuron (132) + TX、Chloromethylphos (136) + TX、Chloroform [CCN] + TX、Chloropicrin (141) + TX、Chlornithine oxime phos (989) + TX、Chlorprazophos (990) + TX、Chlorpyrifos (145) + TX、Chlorpyrifos-methyl (146) + TX、Chlorpyrifos (994) + TX、Chlorfenapyr (150) + TX, cypermethrin I (696) + TX, cypermethrin II (696) + TX, cypermethrins (696) + TX, cis-resmethrin (alias) + TX, cis-resmethrin (80) + TX, cypermethrin (alias) + TX, cypermethrin (999) + TX, closantel (alias) [CCN] + TX, clothianidin (165) + TX, copper acetylarensite [CCN] + TX, copper arsenate [CCN] + TX, copper oleate [CCN] + TX, coumaphos (174) + TX, cypermethrin (1006) + TX, crotamiton (alias) [CCN] + TX, baclofos (1010) + TX, clofosinate (1011) + TX, cryolite (alias) (177) + TX, CS 708 (research code) (1012) + TX, benzonitrile phosphonium (1019) + TX, cypermethrin (184) + TX, cypermethrin (1020) + TX, cypermethrin [CCN] + TX, cypermethrin (188) + TX, flucythrin (193) + TX, cyhalothrin (196) + TX, cypermethrin (201) + TX, cypermethrin (206) + TX, cyproconazole (209) + TX, cypermethrin (alias) [CCN] + TX, d-limonene (alias) [CCN] + TX, d-tetramethrin (alias) (788) + TX, DAEP ( 1031)+TX, Dazomethane (216)+TX, DDT (219)+TX, decarbofuran (1034)+TX, cypermethrin (223)+TX, tanafur (1037)+TX, tanafur-O (1037)+TX, tanafur-S (1037)+TX, tebuconazole (1038)+TX, tebuconazole-methyl (224)+TX, tebuconazole-O (1038)+TX, tebuconazole-O-methyl (224)+TX, tebuconazole-S (1038)+TX, tebuconazole-S-methyl (224)+TX,Demeton-S-methylsulphon (1039) + TX, diafenthiuron (226) + TX, dimpropyridaz + TX, chloromet (1042) + TX, diamidophos (1044) + TX, diazinon (227) + TX, isochlorophos (1050) + TX, chloranthate (1051) + TX, dichlorvos (236) + TX, dicliphos ( alias) + TX, dicresyl (alias) [CCN] + TX, dicrotophos (243) + TX, dicynilide (244) + TX, dieldrin (1070) + TX, diethyl 5-methylpyrazol-3-yl phosphate (IUPAC name) (1076) + TX, diflubenzuron (250) + TX, diprophylline (dilor) (alias) [CCN] + TX, tetrafluthrin [CCN] + TX, methylfluanilide Phosphorus (1081) + TX, Dimethoate (1085) + TX, Dimethoate (262) + TX, Permethrin (1083) + TX, Methylchlor (265) + TX, Dimethoate (1086) + TX, Dimethoate (1089) + TX, Dimethoate (1089) + TX, Propanol (1093) + TX, Pentosan (1094) + TX, Danosan (1095) + TX, Dinotefuran (2 71)+TX, fenpropimorph (1099)+TX, vegetable phosphorus (1100)+TX, dioxocarb (1101)+TX, dimethoate (1102)+TX, disulfophos (278)+TX, dithiocarb (1108)+TX, DNOC (282)+TX, doramectin (alias) [CCN]+TX, DSP (1115)+TX, ecdysone (alias) [CCN]+TX, EI 1642 (research code) (1118) + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, EMPC (1120) + TX, fenthrin (292) + TX, endosulfan (294) + TX, fenthion (1121) + TX, endrin (1122) + TX, EPBP (1123) + TX, EPN (297) + TX, fenthion (1124) + TX, eprinomectin (alias) [CCN ]+TX, cypermethrin (302)+TX, Oxfordshire etaphos (alias) [CCN]+TX, ethiofencarb (308)+TX, ethiofen (309)+TX, ethiprole (310)+TX, methyl thiosulfate (1134)+TX, ethoprophos (312)+TX, ethyl formate (IUPAC name) [CCN]+TX, ethyl-DDD (alias) (1056)+TX, ethylene dibromide (316)+TX,Ethylene dichloride (chemical name) (1136) + TX, ethylene oxide [CCN] + TX, ethofenprox (319) + TX, ethophos (1142) + TX, EXD (1143) + TX, thiamethoxam (323) + TX, fenamiphos (326) + TX, cypermethrin (1147) + TX, cypermethrin (1148) + TX, fenthiocarb (1149) + TX, fenfluramide (1150) + TX, fenthiocarb (335) + TX, fenthiocarb (336) + TX, fenoxacrim (1153) + TX, fenoxycarb (340) + TX, cypermethrin (1155) + TX, cypermethrin (342) + TX, fenpyrad )(Other names)+TX, fenthion (1158)+TX, fenthion (346)+TX, fenthion-ethyl [CCN]+TX, cypermethrin (349)+TX, flubendiamide (354)+TX, flonicamid (358)+TX, flubendiamide (CAS registration number: 272451-65-7)+TX, flucofuron (1168)+TX, flufenoxuron (366)+TX, flucythrin (367)+TX, flufluanid (1169)+TX, flufenoxuron [CCN]+TX, flufenoxuron (370)+TX, trifluthrin (1171)+TX, flufenoxuron (372)+TX, fluvalinate (1184)+TX, FMC 1137 (research code) (1185) + TX, diflubenzuron (1191) + TX, fluazifop (405) + TX, fluazifop hydrochloride (405) + TX, anthiophos (1192) + TX, formparanate (1193) + TX, butylfenthion (1194) + TX, forspiramate (1195) + TX, thiathion (408) + TX, butylthiophos (1196) + TX, furathiocarb (412) + TX, pyrethroid (1200) + TX, γ-cyhalothrin (197) + TX, γ-HCH (430) + TX, biguanide salt (422) + TX, biguanide acetate (422) + TX, GY-81 (research code) code) (423) + TX, benzyl methoxyfen (424) + TX, chlorfenapyr (425) + TX, HCH (430) + TX, HEOD (1070) + TX, febuda (1211) + TX, heptenophos (432) + TX, cypermethrin [CCN] + TX, hexaflumuron (439) + TX, HHDN (864) + TX, hydrazone (443) + TX, hydrocyanic acid (444) + TX, methoprene (445) + TX, hyquincarb (1223) + TX, imidacloprid (458) + TX, cypermethrin (460) + TX, indoxacarb (465) + TX, iodomethane (IUPAC name) (542) + TX,IPSP (1229) + TX, chlorfenvinphos (1231) + TX, carbofuran (1232) + TX, isocarbophos (alias) (473) + TX, isoaldrin (1235) + TX, isofenphos (1236) + TX, transplanting agent (1237) + TX, isoprocarb (472) + TX, O-(methoxyaminothiophosphoryl) salicylic acid isopropyl ester (IUPAC name) (473) + TX, blastifungin (474) + TX, isothioate (1244) + TX, oxazophos (480) + TX, ivermectin (alias) [CCN] + TX, jasmonate I (696) + TX, jasmonate II (696) + TX, iodonium sulfate (1248) + TX, juvenile hormone I (alias) [CCN] + TX, juvenile hormone II (alias) [CCN] + TX, juvenile hormone III (alias) [CCN] + TX, chlorpentyl (1249) + TX, methoprene (484) + TX, λ-cyhalothrin (198) + TX, lead arsenate [CCN] + TX, lepidomycin (CCN) + TX, parabromophos (1250) + TX, lindane (430) + TX, lirimfos (1251) + TX, lufenuron (490) + TX, thiazophos (1253) + TX, m-isopropylphenyl methylcarbamate (IUPAC name) (1014) + TX, magnesium phosphide (IUPAC name) (640) + TX, horse Lathion (492) + TX, tebuconazole (1254) + TX, azidophos (1255) + TX, mefenphos (502) + TX, tetramethylphos (1258) + TX, mefenphos (1260) + TX, diamphos (1261) + TX, mercurous chloride (513) + TX, mesulfenfos (1263) + TX, metaflumizone (CCN) + TX, metamizole (519) + TX, metamizole potassium (alias) (519) + TX, metamizole sodium (519) + TX, cypermethrin (1266) + TX, methamidophos (527) + TX, methanesulfonyl fluoride (IUPAC / Chemical Abstracts name) (1268) + TX, methidathion (529) + TX )+TX, methiocarb (530)+TX, chlorpyrifos (1273)+TX, methomyl (531)+TX, methoprene (532)+TX, mequindox (1276)+TX, methoxythrin (alias) (533)+TX, methoxychlor (534)+TX, anisyl (535)+TX, methyl bromide (537)+TX, methyl isothiocyanate (543)+TX, methyl chloroform (alias) [CCN]+TX, dichloromethane [CCN]+TX, metofluthrin [CCN]+TX, metoclopramide (550)+TX, oxadiazine (1288)+TX, mefenphos (556)+TX, zikwei (1290)+TX, mitoxantrone (557)+TX,Milbemycin (alias) [CCN] + TX, propylaminophosphine (1293) + TX, mirex (1294) + TX, monocrotophos (561) + TX, thiophos (1300) + TX, moxidectin (alias) [CCN] + TX, naphthylphos (alias) [CCN] + TX, dibromophos (567) + TX, naphthalene (IUPAC / Chemical Abstracts name) (1303) + TX, NC-170 (research code) (1306) + TX, NC-184 (compound code) + TX, nicotine (578) + TX, nicotine sulfate (5 78) + TX, fluazifop (1309) + TX, nitenpyram (579) + TX, nithiazine (1311) + TX, pentocyanamide (1313) + TX, pentocyanamide 1:1 zinc chloride complex (1313) + TX, NNI-0101 (compound code) + TX, NNI-0250 (compound code) + TX, nornicotine (traditional name) (1319) + TX, flubendiamide (585) + TX, novifluanidone (586) + TX, O-5-dichloro-4-iodophenyl O-ethylethylsulfonate Phosphonothioate (IUPAC name) (1057) + TX, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-ylphosphonothioate (IUPAC name) (1074) + TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-ylphosphonothioate (IUPAC name) (1075) + TX, O,O,O',O'-tetrapropyl dithiopyrophosphate (IUPAC name) (1424) + TX, oleic acid (IUPAC name) (593) + TX, omethoate (594) + TX, Linwei (602) + TX, sulfone-methyl (609) + TX, isosulfonylphos (1324) + TX, sulfone-methylphos (1325) + TX, pp'-DDT (219) + TX, p-dichlorobenzene [CCN] + TX, parathion (615) + TX, parathion-methyl (616) + TX, flubendiamide (alias) [CCN] + TX, pentachlorophenol (623) + TX, pentachlorophenyl laurate (IUPAC name) (623) + TX, permethrin (626) + TX, petroleum oil (alias) (628) + TX, PH 60-38 (research code) (1328) + TX, fenthion (1330) + TX, phenothrin (630) + TX, fenthion (631) + TX, phorate (636) + TX, phosalone (637) + TX, thiophanate (1338) + TX, phosmet (638) + TX, parachlorothion (1339) + TX, phosphamidon (639) + TX, phosphine (IUPAC name) (640) + TX, phoxim (642) + TX, phoxim-methyl (1340) + TX, pirimetaphos (1344) + TX,Pirimicarb (651) + TX, Pirimicarb-ethyl (1345) + TX, Pirimicarb-methyl (652) + TX, Polychlorodicyclopentadiene isomers (IUPAC name) (1346) + TX, Polychloroterpenes (traditional name) (1347) + TX, Potassium arsenite [CCN] + TX, Potassium thiocyanate [CCN] + TX, Promethrin (655) + TX, Precocin I (alias) [CCN] + TX, Precocin II (alias) [CCN] + TX, Precocin III (alias) [CCN] +TX, primidophos (1349) +TX, profenofos (662) +TX, profluthrin [CCN] +TX, cypermethrin (1354) +TX, cypermethrin (1355) +TX, propanofos (1356) +TX, chlorpyrifos (673) +TX, propoxur (678) +TX, ethidium azide (1360) +TX, prothiophos (686) +TX, thiophos (1362) +TX, protrifenbute [C CN]+TX, pymetrozine (688)+TX, pyraclofos (689)+TX, pyrimidinephos (693)+TX, pyresmethrin (1367)+TX, pyrethrin I (696)+TX, pyrethrin II (696)+TX, pyrethrins (696)+TX, pyrethrin (699)+TX, pyridalyl (700)+TX, pyridafenphos (701)+TX, pyrimidinephos (706)+TX, pyrimidinephos (1370)+TX, pyrimidinephos Ether (708) + TX, quassia extract (Quassia) (Other name) [CCN] + TX, quinalphos (711) + TX, quinalphos-methyl (1376) + TX, quinalphos (1380) + TX, quintiofos (1381) + TX, R-1492 (research code) (1382) + TX, rafoxanide (Other name) [CCN] + TX, resmethrin (719) + TX, rotenone (722) + TX, RU 15525 (research code) (723) + TX, RU 25475 (research code) (1386) + TX, ryania (alias) (1387) + TX, ryanodine (traditional name) (1387) + TX, sabafos (alias) (725) + TX, octamethrin (1389) + TX, cadastre (alias) + TX, selamectin (alias) [CCN] + TX, SI-0009 (compound code) + TX, SI-0205 (compound code) + TX, SI-0404 (compound code) + TX, SI-0405 (compound code) + TX, flusilate (728) + TX, SN 72129 (research code) (1397) + TX, sodium arsenite [CCN] + TX,Sodium cyanide (444) + TX, sodium fluoride (IUPAC / Chemical Abstracts name) (1399) + TX, sodium hexafluorosilicate (1400) + TX, sodium pentachlorophenol (623) + TX, sodium selenate (IUPAC name) (1401) + TX, sodium thiocyanate [CCN] + TX, threonylthion (1402) + TX, spinosad (737) + TX, spiromesifen (739) + TX, spirotetramat (CCN) + TX, sulcofuron (746) + TX, sulcofuron-sodium (746) + TX, sulfluramid (750) + TX, thiophanate (753) + TX, sulfonyl fluoride (756) + TX 、Sulfoprofen (1408) + TX、Tar (alias) (758) + TX、τ-fluvalinate (398) + TX、thiabendazim (1412) + TX、TDE (1414) + TX、tebufenoxam (762) + TX、tebufenpyrad (763) + TX、butylpyrimidinphos (764) + TX、flubenzuron (768) + TX、tefluthrin (769) + TX、tebuconazole (770) +...

Claims

1. A compound having formula (I) in G1 and G2 are independently CH or N; R2 is C1-C6 haloalkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl or C1-C6 haloalkoxy, C1-C4 haloalkylsulfonyloxy; Q is a group selected from the group consisting of: Formula Qa and Qb wherein the arrow indicates the point of attachment to the nitrogen atom of the bicyclic ring; and wherein A represents CH or N; X is S, SO or SO2; R1 is C1-C4 alkyl, or C3-C6 cycloalkyl-C1-C4 alkyl; Q1 is hydrogen, halogen, trifluoromethyl, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoroethoxy, (oxazolidin-2-one)-3-yl, 2-pyridyloxy, N-attached pyrazolyl which may be monosubstituted with chloro or trifluoromethyl, N-attached triazolyl, C-attached pyrimidinyl, -N(R4)2, -N(R4)COR5, or -N(R4)CON(R4)2; R3 is hydrogen, halogen or C1-C4 alkyl; Each R4 is independently hydrogen or methyl; and R5 is methyl, ethyl or cyclopropyl; or An agrochemically acceptable salt of a compound of formula I.

2. The compound of claim 1 having formula I, which is represented by a compound having formula I-A1 wherein A, R1, R2, R3, X, Q1, R4, and R5 are as defined in claim 1 under formula I.

3. The compound of claim 1 having formula I, which is represented by a compound having formula I-A2 wherein A, R1, R2, R3, X, Q1, R4, and R5 are as defined in claim 1 under formula I.

4. The compound of claim 1 having formula I, which is represented by a compound having formula I-B1 wherein A, R1, R2, R3, X, Q1, R4, and R5 are as defined in claim 1 under formula I.

5. The compound of claim 1 having formula I, which is represented by a compound having formula I-B2 wherein A, R1, R2, R3, X, Q1, R4, and R5 are as defined in claim 1 under formula I.

6. The compound of claim 1 having formula I, which is represented by a compound having formula I-C1 wherein A, R1, R2, R3, X, Q1, R4, and R5 are as defined in claim 1 under formula I.

7. The compound of claim 1 having formula I, which is represented by a compound having formula I-C2 wherein A, R1, R2, R3, X, Q1, R4, and R5 are as defined in claim 1 under formula I.

8. The compound of claim 1 having formula I, which is represented by a compound having formula I-D1 wherein A, R1, R2, R3, X, Q1, R4, and R5 are as defined in claim 1 under formula I.

9. The compound of claim 1 having formula I, which is represented by a compound having formula I-D2 wherein A, R1, R2, R3, X, Q1, R4, and R5 are as defined in claim 1 under formula I.

10. A compound of formula I according to any one of claims 1 to 9, wherein A is CH or N; R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl; R2 is C1-C2 haloalkyl, C1-C2 haloalkylsulfanyl, C1-C2 haloalkylsulfinyl or C1-C2 haloalkylsulfonyl; R3 is hydrogen or C1-C4 alkyl; and X is S or SO2.

11. A compound of formula I according to any one of claims 1 to 9, wherein A is CH or N; R1 is ethyl or cyclopropylmethyl; R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3 or CF3; R3 is hydrogen or methyl; and X is S or SO2.

12. A compound of formula I according to any one of claims 1 to 9, wherein A is CH or N; R1 is ethyl; R2 is -OSO2CF3, SO2CF3, -OCF3, CF2CF3 or CF3; R3 is hydrogen or methyl; and X is S or SO2.

13. A compound of formula I according to any one of claims 1 to 9, wherein Q1 is hydrogen, bromine, trifluoromethyl, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, 2,2,2-trifluoroethoxy, -NH(CH3), -N(CH3)COCH3, -N(CH3)COCH2CH3, -N(CH3)CO(cyclopropyl), -N(H)CONH(CH3), -N(CH3)CONH(CH3), (oxazolidin-2-one)-3-yl, 2-pyridyloxy, pyrazol-1-yl, 3-chloro-pyrazol-1-yl, 3-trifluoromethyl-pyrazol-1-yl, 1,2,4-triazol-1-yl or pyrimidin-2-yl.

14. The compound of claim 1 having formula I, selected from the group consisting of: 2-(3-ethylsulfonyl-2-pyridinyl)-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-1-one (Compound P1); 2-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-2-yl]-3-pyridinyl]-2-methyl-propionitrile (Compound P2); N-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-2-yl]-3-pyridinyl]-N-methyl-acetamide (Compound P3); 2-[3-ethylsulfonyl-6-(methylamino)-2-pyridinyl]-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-1-one (Compound P4); 2-[3-ethylsulfonyl-6-(1,2,4-triazol-1-yl)-2-pyridinyl]-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-1-one (Compound P5); 1-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-2-yl]-2-pyridinyl]-1,3-dimethyl-urea (Compound P6); 2-(5-bromo-3-ethylsulfonyl-2-pyridinyl)-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-1-one (Compound P7); 1-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-2-yl]-3-pyridinyl]cyclopropanecarbonitrile (Compound P8); 2-[3-ethylsulfonyl-5-[3-(trifluoromethyl)pyrazol-1-yl]-2-pyridinyl]-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-1-one (Compound P9); 2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridinyl]-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-1-one (Compound P10); 1-[5-ethylsulfonyl-6-[5-oxo-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-6-yl]-3-pyridinyl]cyclopropanecarbonitrile (Compound P11); 2-[3-ethylsulfonyl-5-(2-pyridyloxy)-2-pyridyl]-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-1-one (Compound P12); 2-[5-(3-chloropyrazol-1-yl)-3-ethylsulfonyl-2-pyridinyl]-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-1-one (Compound P13); 2-(5-cyclopropyl-3-ethylsulfonyl-2-pyridinyl)-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-1-one (Compound P14); 2-(6-cyclopropyl-3-ethylsulfonyl-2-pyridinyl)-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-1-one (Compound P15); 2-(3-ethylsulfonyl-6-pyrimidin-2-yl-2-pyridinyl)-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-1-one (Compound P16); 3-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-2-yl]-2-pyridinyl]oxazolidin-2-one (Compound P17); N-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-2-yl]-2-pyridinyl]-N-methyl-cyclopropanecarboxamide (Compound P18); N-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-2-yl]-2-pyridinyl]-N-methyl-propionamide (Compound P19); N-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-2-yl]-2-pyridinyl]-N-methyl-acetamide (Compound P20); 2-(3-ethylsulfonyl-2-pyridinyl)-6-(trifluoromethyl)isoindolin-1-one (Compound P21); 6-(3-ethylsulfonyl-2-pyridinyl)-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-5-one (Compound P22); 2-(3-ethylsulfonyl-2-pyridinyl)-6-(trifluoromethylsulfonyl)isoindolin-1-one (Compound P23); 2-(3-ethylsulfonyl-2-pyridinyl)-6-(trifluoromethoxy)isoindolin-1-one (Compound P24); 1-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethoxy)isoindolin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (Compound P25); 1-[5-ethylsulfonyl-6-[1-oxo-6-(trifluoromethyl)isoindolin-2-yl]-3-pyridyl]cyclopropanecarbonitrile (Compound P26); 2-[5-ethylsulfonyl-6-[5-oxo-3-(trifluoromethyl)-7H-pyrrolo[3,4-b]pyridin-6-yl]-3-pyridinyl]-2-methyl-propionitrile (Compound P27); and 1-[5-(Cyclopropylmethylsulfonyl)-6-[1-oxo-6-(trifluoromethyl)-3H-pyrrolo[3,4-c]pyridin-2-yl]-3-pyridinyl]cyclopropanecarbonitrile (Compound P28).

15. A composition comprising an insecticidal, acaricidal, nematicidal or molluscicidal effective amount of a compound of formula (I) as defined in any one of claims 1 to 14, or an agrochemically acceptable salt thereof, and optionally, an adjuvant or diluent.

16. A method for combating and controlling insects, acarines, nematodes or molluscs, the method comprising applying to the pest, the locus of the pest or a plant susceptible to attack by the pest an insecticidal, acaricidal, nematicidal or molluscicidal effective amount of a compound of formula (I) as defined in any one of claims 1 to 14, or an agrochemically acceptable salt thereof, or a composition as defined in claim 15, wherein methods for treating the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body are excluded.

17. A method for protecting plant propagation material from attack by insects, mites, nematodes or molluscs, the method comprising treating the propagation material or the site where the propagation material is planted with a composition according to claim 15.

18. A compound having formula XVII-a in R2, G1, G2 and Q are as defined in claim 1 under formula I; and R a It is hydrogen, C1-C6 alkyl, benzyl or phenyl.

19. A compound having formula IX-a in R1 and X are as defined in claim 1 under formula I; and Q 1a It is 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl or 2-pyridyloxy.

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