2,2-Difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one derivatives as pesticides

Abstract

The present invention relates to a compound represented by formula (I) TIFF2024531177000113.tif28152 (wherein Q is Qa, Qb or Qc TIFF2024531177000114.tif46145) relates to 2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one derivatives. Exemplary compounds include, for example, 6-[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P1). TIFF2024531177000115.tif37157. The present invention further relates to agrochemical compositions comprising the compounds of formula (I), to the preparation of these compositions and to the use of the compounds or compositions for combating, preventing or controlling animal pests, including in particular arthropods such as insects, mollusks, nematodes or representatives of the order Acarina, in agriculture or horticulture.

Description

[Technical Field]

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

[0002] Heterocyclic aromatic dihydropyrrolone and phthalimide derivatives having sulfur-containing substituents have been described in literature, such as J. Org. Chem. 2003, 62, 8240 and Bull. Chem Soc. Chim. Belg. 1997, 106, 151. However, none of these literatures describe their pesticidal effects. Structurally different pesticidal heterocyclic derivatives having sulfur-containing substituents have been described in, for example, WO 2012 / 012086848, WO 2013 / 018928, WO 2019 / 131575, and WO 2020 / 013147.

[0003] Surprisingly, it has now been found that certain novel pesticidally active derivatives having sulfur-containing substituents have favorable properties as pesticides. Summary of the Invention [Means for solving the problem]

[0004] The present invention therefore provides a compound of formula I [ka] (In the formula, Q is a function of the formula Qa, Qb and Qc [ka] where the arrow indicates the point of attachment to the nitrogen atom of the tricyclic ring. is a group selected from the group consisting of: and, A, A1 and A2 are, independently of one another, CH or N; X is S, SO, or SO; R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl; R3, R4, R5 and R6 are each independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, C1-C6 cyanoalkoxy, cyano, C1-C4 alkoxy, C1-C6 haloalkoxy, -N(R9R 10 ) or -N(R9)C(=O)R 10 and; R9 and R 10 are each independently hydrogen, C1-C4 alkyl, C1-C6 haloalkyl, or C3-C6 cycloalkyl; R7 and R8 are each independently hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, C1-C6 cyanoalkoxy, cyano, C1-C4 alkoxy, C1-C6 haloalkoxy, or -N(R 11 )C(=O)R 12 and R 11 and R 12 are each independently hydrogen, C1-C4 alkyl, C1-C6 haloalkyl, or C3-C6 cycloalkyl. to provide.

[0005] The present invention also provides agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of compounds of formula I. DETAILED DESCRIPTION OF THE INVENTION

[0006] Compounds of formula I having at least one basic centre can, for example, form acid addition salts with strong inorganic acids, such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrohalic acids; strong organic carboxylic acids, for example C1-C4 alkanecarboxylic acids which are unsubstituted or substituted, for example, by halogens, such as acetic acid; saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid; hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or for example benzoic acid; or organic sulfonic acids, for example C1-C4 alkane- or arylsulfonic acids which are unsubstituted or substituted, for example, by halogens, such as methane- or p-toluenesulfonic acid. Compounds of formula I having at least one acidic group can, for example, form salts with bases, for example inorganic salts, for example alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or organic amines, for example morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or mono-, di- or trihydroxy-lower alkylamines, for example mono-, di- or triethanolamine.

[0007] In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form as N-oxides, or in salt form, for example in agriculturally usable salt form.

[0008] N-oxides are oxidized forms of tertiary amines or nitrogen-containing aromatic heterocyclic compounds, as described, for example, in the book "Heterocyclic N-oxides", A. Albini and S. Pietra, CRC Press, Boca Raton 1991.

[0009] The compounds of formula I according to the present invention also include the hydrates which may be formed during salt formation.

[0010] When substituents themselves are described as being further substituted, this means that they bear one or more equal or different substituents, for example, 1 to 4 substituents. Typically, no more than three such optional substituents are present at one time. Preferably, no more than two such substituents are present at one time (i.e., the group is substituted with one or two of the listed substituents). When the additional substituent is a larger group such as cycloalkyl or phenyl, it is most preferred that only one of such optional substituents is present. When a group, e.g., alkyl, is described as being substituted, this includes groups that are part of another group, e.g., alkyl in alkylthio.

[0011] As used herein, "C1-C n The term "alkyl" refers to a saturated straight or branched hydrocarbon group having 1 to n carbon atoms attached via any of the carbon atoms, such as any one of the following groups: methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n-pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, or 1-ethyl-2-methylpropyl.

[0012] As used herein, "C1-C nThe term "haloalkyl" refers to a straight or branched saturated alkyl group (as defined above) having 1 to n carbon atoms attached via any of the carbon atoms, 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, 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, and any one of 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl, and nonafluorobutyl. Thus, the term "C1-C2 fluoroalkyl" refers to a C1-C2 alkyl group having 1, 2, 3, 4 or 5 fluorine atoms, such as any one of difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl or pentafluoroethyl.

[0013] As used herein, "C1-C nThe term "alkoxy" refers to a straight or branched saturated alkyl group (as defined above) having 1 to n carbon atoms attached through an oxygen atom, i.e., any one of, for example, methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy, or 1,1-dimethylethoxy.

[0014] As used herein, "C1-C n The term "haloalkoxy" refers to any of the above C1-C alkyl groups partially or fully substituted with fluorine, chlorine, bromine and / or iodine. n alkoxy groups, i.e., for example, 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, 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.

[0015] As used herein, "C1-C nThe term "cyanoalkyl" refers to a linear or branched saturated alkyl group having 1 to n carbon atoms (as defined above) substituted with a cyano group, such as cyanomethylene, cyanoethylene, 1,1-dimethylcyanomethyl, cyanomethyl, cyanoethyl, cyanoisopropyl, and 1-dimethylcyanomethyl.

[0016] "C1~C n The term "cyanoalkoxy" refers to a straight or branched saturated cyanoalkyl group having 1 to n carbon atoms (as defined above) attached through an oxygen atom.

[0017] As used herein, the term "C3-C6 cycloalkyl" refers to 3- to 6-membered cycloylkyl groups such as cyclopropane, cyclobutane, cyclopropane, cyclopentane, and cyclohexane.

[0018] "C3~C n The suffix "-C1~C" following a term such as "cycloalkyl" n "Alkyl" (where n is an integer from 1 to 6) as used herein means a C3 to C n It refers to a linear or branched saturated alkyl group substituted with a cycloalkyl. C3-C n Cycloalkyl-C1~C n An example of alkyl is, for example, cyclopropylmethyl.

[0019] As used herein, the term "C3-C6 cycloalkyl" mono-substituted with cyano refers to a 3- to 6-membered cycloylkyl group (as defined above) substituted with a cyano group. An example of a C3-C6 cycloalkyl mono-substituted with cyano is 1-cyanocyclopropyl.

[0020] Halogen is generally fluorine, chlorine, bromine or iodine. This applies correspondingly to halogen in combination with other meanings, such as haloalkyl.

[0021] Certain embodiments of the present invention are provided as described below.

[0022] Embodiment 1 provides a compound of formula I, as defined above, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof.

[0023] 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 X, R, R, R, R, and R are as defined below. 10 has preferred values ​​for

[0024] 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 X, R1, R5, R6, R9, and R10, as described below, are independently selected from the group consisting of: 10 has preferred values ​​for

[0025] Embodiment 4 provides a compound according to embodiment 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof, wherein Q is Qc, and A, A1, A2, X, R1, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29, R30, R31, R32, R33, R34, R35, R36, R37, R38, R39, R40, R41, R42, R43, R44, R45, R46, R47, R48, R49, R50, R51, R52, R53, R54, R55, R5 11 and R 12 has preferred values ​​for

[0026] Regarding embodiments 1 to 4, X, R1, A, A1, A2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 and R 12 Preferred values ​​of , in any of these combinations, are as follows:

[0027] Preferably, X is S or SO2.

[0028] Most preferably, X is SO2.

[0029] Preferably, R1 is C1-C4 alkyl or cyclopropyl-C1-C4 alkyl.

[0030] More preferably, R1 is ethyl or cyclopropylmethyl.

[0031] Most preferably, R1 is ethyl.

[0032] Preferably, R3 and R4 are each independently hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, C1-C6 cyanoalkoxy, cyano, C1-C4 alkoxy, C1-C6 haloalkoxy, or -N(R9)C(=O)R 10 is.

[0033] More preferably, R3 and R4 are each independently hydrogen, halogen, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3.

[0034] Even more preferably, R4 is hydrogen and R3 is hydrogen, halogen, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3; or R3 is hydrogen and R4 is halogen, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3.

[0035] Most preferably, R4 is hydrogen and R3 is hydrogen, halogen, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3; or R3 is hydrogen and R4 is trifluoromethyl, halogen, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3.

[0036] Preferably, R5 and R6 are each independently hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, C1-C6 cyanoalkoxy, cyano, C1-C4 alkoxy, C1-C6 haloalkoxy, or -N(R9)C(=O)R 10 is.

[0037] More preferably, R5 and R6 are each independently hydrogen, halogen, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3.

[0038] Even more preferably, R6 is hydrogen and R5 is hydrogen, halogen, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3; or R5 is hydrogen and R6 is halogen, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3.

[0039] Most preferably, R6 is hydrogen and R5 is hydrogen, halogen, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3; or R5 is hydrogen and R6 is halogen, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3.

[0040] Preferably, R and R 10 are each independently hydrogen or C1-C4 alkyl.

[0041] More preferably, R and R 10 are each independently hydrogen or methyl.

[0042] Most preferably, R9 is hydrogen or methyl and R 10 is methyl.

[0043] Preferably, A is CH or N.

[0044] Most preferably, A is N.

[0045] Preferably, A1 is CH or N.

[0046] Preferably, A2 is CH or N.

[0047] It is also preferred that A1 is CH and A2 is N.

[0048] It is also preferred that A1 is N and A2 is CH.

[0049] It is more preferred that both A1 and A2 are N.

[0050] Most preferably, A1 and A2 are both CH.

[0051] Preferably, R7 and R8 are each independently hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, C1-C6 cyanoalkoxy, cyano, C1-C4 alkoxy, C1-C6 haloalkoxy, or -N(R 11 )C(=O)R 12 is.

[0052] More preferably, R7 and R8 are each independently hydrogen, halogen, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3.

[0053] Even more preferably, R8 is hydrogen and R7 is hydrogen, halogen, trifluoromethyl, 1,1-difluoroethyl, —OCHF2, —OCH2CHF2, —OCH2CF3, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, —CHF2, —OC(CH3)2CN, —NHC(O)CH3 or —NCH3C(O)CH3; or R7 is hydrogen and R8 is trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3.

[0054] Most preferably, R8 is hydrogen and R7 is hydrogen, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3; or R7 is hydrogen and R8 is trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3.

[0055] Preferably, R 11 and R 12 are each independently hydrogen or C1-C4 alkyl.

[0056] More preferably, R 11 and R 12 are each independently hydrogen or methyl.

[0057] Most preferably, R 11 is hydrogen or methyl, and R12 is methyl.

[0058] Further embodiments of the present invention are provided as described below.

[0059] A preferred group of compounds of formula I is the compound of formula I-1 [ka] (Wherein, X, R1, R3, R4, R9 and R 10 is as defined in formula I above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide of a compound of formula I-1.

[0060] In a preferred group of compounds of formula I-1, R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl; X is S or SO2; R3 and R4 are each independently hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, C1-C6 cyanoalkoxy, cyano, C1-C4 alkoxy, C1-C6 haloalkoxy, or -N(R9)C(=O)R 10 and R9 and R 10 are each independently hydrogen or C1-C4 alkyl; preferably, R9 and R 10 are, independently of each other, hydrogen or methyl; more preferably, R is hydrogen or methyl and R 10 is methyl.

[0061] In another preferred group of compounds of formula I-1, R1 is ethyl or cyclopropylmethyl, preferably R1 is ethyl; X is S or SO2, preferably X is SO2; and R3 and R4 are, independently of one another, hydrogen, fluoro, chloro, bromo, iodo, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3.

[0062] In all of the compounds of formula I-1 and preferred embodiments of compounds of formula I-1 described herein, X, R, R, R, R, and R are independently selected from the group consisting of aryl, ... 10 is as defined in Formula I above.

[0063] Other preferred embodiments of compounds of formula I-1 are those in which R1 is ethyl; and X is SO2.

[0064] Also preferred are compounds of formula I-1 in which R4 is hydrogen and R3 is hydrogen, fluoro, chloro, bromo, iodo, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3; or compounds of formula I-1 in which R3 is hydrogen and R4 is trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3.

[0065] Compounds of formula I-1 in which R4 is hydrogen and R3 is hydrogen, fluoro, chloro, bromo, iodo, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3; or R Further preferred are compounds of formula I-1 in which 3 is hydrogen and R4 is fluoro, chloro, bromo, iodo, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3.

[0066] Another preferred group of compounds of formula I is the compounds of formula I-2 [ka] (Wherein, X, R1, R5, R6, R9 and R 10 is as defined in Formula I above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide of a compound of Formula I-2.

[0067] In a preferred group of compounds of formula I-2, R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl; X is S or SO2; R5 and R6 are each independently hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, C1-C6 cyanoalkoxy, cyano, C1-C4 alkoxy, C1-C6 haloalkoxy, or -N(R9)C(=O)R 10 and R9 and R 10 are each independently hydrogen or C1-C4 alkyl; preferably, R9 and R 10are each independently hydrogen or methyl, more preferably R is hydrogen or methyl and R 10 is methyl.

[0068] In another preferred group of compounds of formula I-2, R1 is ethyl or cyclopropylmethyl, preferably R1 is ethyl; X is S or SO2, preferably X is SO2; R5 and R6 are, independently of one another, hydrogen, fluoro, chloro, bromo, iodo, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3.

[0069] In all of the compounds of formula I-2 and preferred embodiments of compounds of formula I-2 described herein, X, R, R, R, R, and R are independently selected from the group consisting of aryl, ... 10 is as defined in Formula I above.

[0070] Other preferred embodiments of compounds of formula I-2 are those in which R1 is ethyl; and X is SO2.

[0071] Also preferred are compounds of formula I-2 in which R6 is hydrogen and R5 is hydrogen, fluoro, chloro, bromo, iodo, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3; or compounds of formula I-2 in which R5 is hydrogen and R6 is trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3.

[0072] Further preferred are compounds of formula I-2 in which R6 is hydrogen and R5 is hydrogen, fluoro, chloro, bromo, iodo, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3; or compounds of formula I-2 in which R5 is hydrogen and R6 is trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3.

[0073] Another preferred group of compounds of formula I is the compounds of formula I-3 [ka] (In the formula, A, A1, A2, X, R1, R7, R8, R 11 and R 12 is as defined in Formula I above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide of a compound of Formula I-3.

[0074] In a preferred group of compounds of formula I-3, A is CH or N; A1 is CH or N; A2 is CH or N; R1 is C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl; X is S or SO2; R7 and R8 are each independently hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, C1-C6 cyanoalkoxy, cyano, C1-C4 alkoxy, C1-C6 haloalkoxy, or -N(R 11 )C(=O)R 12 and R 11and R 12 are each independently hydrogen or C1-C4 alkyl; preferably, R 11 and R 12 are, independently of one another, hydrogen or methyl; more preferably, R 11 is hydrogen or methyl, and R 12 is methyl.

[0075] In another preferred group of compounds of formula I-3, A is CH or N, preferably A is N; A is CH or N; A is CH or N; R is ethyl or cyclopropylmethyl, preferably R is ethyl; X is S or SO, preferably X is SO; R and R are, independently of one another, hydrogen, trifluoromethyl, 1,1-difluoroethyl, -OCHF, -OCHCHF, -OCHCF, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF, -OC(CH)CN, -NHC(O)CH or -NCHC(O)CH.

[0076] In all of the compounds of formula I-3 and preferred embodiments of compounds of formula I-3 described herein, unless otherwise specified, A, A1, A2, X, R1, R7, R8, R 11 and R 12 is as defined in Formula I above.

[0077] Other preferred embodiments of compounds of formula I-3 are those in which R1 is ethyl; and X is SO2.

[0078] or compounds of formula I-3 in which R8 is hydrogen and R7 is hydrogen, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3; or Compounds of formula I-3 in which R7 is hydrogen and R8 is trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3 are preferred.

[0079] Compounds of formula I-3 in which R8 is hydrogen and R7 is hydrogen, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3; or Further preferred are compounds of formula I-3 in which R7 is hydrogen and R8 is trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3.

[0080] A further preferred group of compounds according to this embodiment are compounds of formula I-3 or compounds of formula (I-3a), which are any of the preferred embodiments of compounds of formula I-3, where A is CH.

[0081] Another preferred group of compounds according to this embodiment are compounds of formula I-3 or compounds of formula (I-3b), which are any of the preferred embodiments of compounds of formula I-3, where A is N.

[0082] Yet another preferred group of compounds according to this embodiment are compounds of formula I-3 or compounds of formula (I-3c), which are any of the preferred embodiments of compounds of formula I-3, wherein A1 is CH and A2 is N.

[0083] A further preferred group of compounds according to this embodiment are compounds of formula I-3 or compounds of formula (I-3d), which are any of the preferred embodiments of compounds of formula I-3, where A1 is N and A2 is CH.

[0084] A further preferred group of compounds according to this embodiment are compounds of formula I-3 or compounds of formula (I-3e), which are any of the preferred embodiments of compounds of formula I-3, wherein A1 and A2 are both N.

[0085] Most preferred are compounds of formula (I-3f) according to this embodiment, which are compounds of formula I-3 or any of the preferred embodiments of compounds of formula I-3, wherein A1 and A2 are both CH.

[0086] Another preferred group of compounds of formula I is the compounds of formula I-4 [ka] (In the formula, Q1 is a group of the formulas Q1a, Q1b and Q1c [ka] where the arrow indicates the point of attachment to the nitrogen atom of the tricyclic ring. is a group selected from the group consisting of: and A, A1, A2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 and R 12 is as defined in Formula I above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide of a compound of Formula I-4.

[0087] In all of the compounds of formula I-4 and preferred embodiments of compounds of formula I-4 described herein, unless otherwise specified, A, A1, A2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 and R 12is as defined in Formula I above.

[0088] A preferred group of compounds of formula I-4 are compounds of formula (I-4a), which are either compounds of formula I-4 or preferred embodiments of compounds of formula I-4, wherein Q is Q1a, R4 is hydrogen, and R3 is hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, C1-C6 cyanoalkoxy, cyano, C1-C4 alkoxy, C1-C6 haloalkoxy, —N(R9R 10 ) or -N(R9)C(=O)R 10 and R9 and R 10 are, independently of each other, hydrogen, C1-C4 alkyl, C1-C6 haloalkyl or C3-C6 cycloalkyl; or Q is Q1a, R3 is hydrogen, and R4 is hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, C1-C6 cyanoalkoxy, cyano, C1-C4 alkoxy, C1-C6 haloalkoxy, -N(R9R 10 ) or -N(R9)C(=O)R 10 and R9 and R 10 are each independently hydrogen, C1-C4 alkyl, C1-C6 haloalkyl or C3-C6 cycloalkyl.

[0089] Further preferred are compounds of formula I-4a, wherein R4 is hydrogen and R3 is hydrogen, halogen, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3, or -NCH3C(O)CH3; or compounds of formula I-4a, wherein R3 is hydrogen and R4 is trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3, or -NCH3C(O)CH3.

[0090] Another preferred group of compounds of formula I-4 are compounds of formula (I-4b), which are either compounds of formula I-4 or preferred embodiments of compounds of formula I-4, wherein Q is Q1b, R6 is hydrogen, and R5 is hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, C1-C6 cyanoalkoxy, cyano, C1-C4 alkoxy, C1-C6 haloalkoxy, —N(R9R 10 ) or -N(R9)C(=O)R 10 and R9 and R 10 are, independently of each other, hydrogen, C1-C4 alkyl, C1-C6 haloalkyl or C3-C6 cycloalkyl; or Q is Q1b, R5 is hydrogen, and R6 is hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, C1-C6 cyanoalkoxy, cyano, C1-C4 alkoxy, C1-C6 haloalkoxy, -N(R9R 10 ) or -N(R9)C(=O)R 10 and R9 and R 10are each independently hydrogen, C1-C4 alkyl, C1-C6 haloalkyl or C3-C6 cycloalkyl.

[0091] Further preferred are compounds of formula I-4b, wherein R6 is hydrogen and R5 is hydrogen, halogen, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3, or -NCH3C(O)CH3; or compounds of formula I-4b, wherein R5 is hydrogen and R6 is trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3, or -NCH3C(O)CH3.

[0092] Another preferred group of compounds of formula I-4 are compounds of formula (I-4c), which are either compounds of formula I-4 or preferred embodiments of compounds of formula I-4, where Q is Q1c, R8 is hydrogen, and R7 is hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, C1-C6 cyanoalkoxy, cyano, C1-C4 alkoxy, C1-C6 haloalkoxy, or -N(R 11 )C(=O)R 12 and R 11 and R 12 are, independently of each other, hydrogen, C1-C4 alkyl, C1-C6 haloalkyl or C3-C6 cycloalkyl; or Q is Q1c, R7 is hydrogen, and R8 is hydrogen, halogen, C1-C4 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl monosubstituted with cyano, C1-C6 cyanoalkyl, C1-C6 cyanoalkoxy, cyano, C1-C4 alkoxy, C1-C6 haloalkoxy, or -N(R 11 )C(=O)R 12 and R 11 and R 12 are each independently hydrogen, C1-C4 alkyl, C1-C6 haloalkyl or C3-C6 cycloalkyl.

[0093] Compounds of formula I-4c, wherein R8 is hydrogen and R7 is hydrogen, trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3, or -NCH3C(O)CH3; or Further preferred are compounds of formula I-4c in which R7 is hydrogen and R8 is trifluoromethyl, 1,1-difluoroethyl, -OCHF2, -OCH2CHF2, -OCH2CF3, cyclopropyl, 1-cyanocyclopropyl, 1-cyano-1-methyl-ethyl, trifluoromethoxy, -CHF2, -OC(CH3)2CN, -NHC(O)CH3 or -NCH3C(O)CH3.

[0094] A further preferred group of compounds according to this embodiment are compounds of formula II-4c or compounds of formula (I-4c-1), which are any of the preferred embodiments of compounds of formula II-4c, where A is CH.

[0095] Another preferred group of compounds according to this embodiment are compounds of formula II-4c or compounds of formula (I-4c-2), which are any of the preferred embodiments of compounds of formula II-4c, where A is N.

[0096] Yet another preferred group of compounds according to this embodiment are compounds of formula II-4c or compounds of formula (I-4c-3), which are any of the preferred embodiments of compounds of formula II-4c, wherein A1 is CH and A2 is N.

[0097] A further preferred group of compounds according to this embodiment are compounds of formula II-4c or compounds of formula (I-4c-4), which are any of the preferred embodiments of compounds of formula II-4c, where A1 is N and A2 is CH.

[0098] A further preferred group of compounds according to this embodiment are compounds of formula II-4c or compounds of formula (I-4c-5), which are any of the preferred embodiments of compounds of formula II-4c, wherein A1 and A2 are both N.

[0099] Another preferred group of compounds according to this embodiment are compounds of formula II-4c or compounds of formula (I-4c-6), which are any of the preferred embodiments of compounds of formula II-4c, where A1 and A2 are both CH.

[0100] The compounds of the present invention may have any number of benefits, including, inter alia, advantageous levels of biological activity for protecting plants against insects, or excellent properties for use as agrochemical active ingredients (e.g., high biological activity, advantageous activity spectrum, high safety profile, improved physicochemical properties, or high biodegradability or environmental profile). In particular, it has been unexpectedly found that certain compounds of formula (I) may exhibit advantageous safety profiles against non-target arthropods, particularly pollinators such as honeybees, solitary bees, and bumblebees. Most particularly, the European honeybee (Apis mellifera).

[0101] In another aspect, the present invention provides a composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), as defined in embodiments by compounds of formulae (I), (I-1), (I-2), (I-3) and (I-4) (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and optionally an adjuvant or diluent.

[0102] In a further aspect, the present invention provides a method for combating and controlling insects, acaridae, nematodes or molluscs, which method comprises applying to the pest, the pest's habitat or plants susceptible to attack by the pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), as defined in any of the embodiments of the compounds of formula (I), (I), (I-1), (I-2), (I-3) and (I-4) (above), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, or a composition as defined above.

[0103] In a further aspect, the present invention provides a method for protecting plant propagation material from attack by insects, mites, nematodes or mollusks, comprising the step of treating the propagation material or the site where the propagation material is to be planted with a composition as defined above.

[0104] The process for preparing the compounds of formula I according to the present invention is basically carried out by methods known to those skilled in the art. More specifically, a subgroup of compounds of formula I, in which X is SO (sulfoxide) and / or SO (sulfone), can be obtained by oxidation of the corresponding sulfide compounds of formula I, in which X is S, using reagents such as metachloroperbenzoic acid (mCPBA), hydrogen peroxide, oxone, sodium periodate, sodium hypochlorite or tert-butyl hypochlorite, among other oxidizing agents (Schemes 1a, 1b and 2). Scheme 1a: [ka] Scheme 1b: [ka] Scheme 2: [ka] This oxidation reaction is generally carried out in the presence of a solvent. Examples of solvents used in this reaction include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform; alcohols such as methanol and ethanol; acetic acid; water; and mixtures thereof. The amount of oxidizing agent used in this reaction is generally 1 to 3 moles, preferably 1 to 1.2 moles, based on 1 mole of sulfide compound I to produce sulfoxide compound I, and preferably 2 to 2.2 moles of oxidizing agent based on 1 mole of sulfide compound I to produce sulfone compound I. Such oxidation reactions are disclosed, for example, in WO 2013 / 018928.

[0105] Compounds of formula I, where Q is as defined in formula I above, can be prepared by reacting a compound of formula VII with a compound of formula VIII, where Q is as defined in formula I above and 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 tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide or acetonitrile at a temperature between 0 and 150°C, optionally under microwave irradiation (Scheme 3).Alternatively, a compound of formula I (wherein Q is as defined in formula I above) can be reacted with a compound of formula VII and a compound of formula VIII (wherein Q is as defined in formula I above and LG3 is a halogen (or pseudohalogen leaving group such as triflate), preferably bromo or iodo), in the presence of a base such as sodium carbonate, potassium carbonate or cesium carbonate or potassium t-butoxide, in the presence of a metal catalyst such as a copper catalyst, for example copper(I) iodide, optionally in the presence of a ligand, for example a diamine ligand (for example in the presence of, for example, N,N'-dimethylethylenediamine or trans-cyclohexyldiamine) or dibenzylideneacetone (dba) or 1,10-phenanthroline at temperatures between 30 and 180°C, optionally under microwave irradiation, or with a palladium catalyst, for example, palladium(II) acetate, bis(dibenzylideneacetone)palladium(0) (Pd(dba)2) or tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3, optionally in the form of the chloroform adduct), or with, for example, t-BuBrettPhos Pd G3 [(2-di-t-butylphosphino-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl)-2-(2'-amino-1,1'-biphenyl)]palladium(II) methanesulfonate or BrettPhos Pd G3 [(2-dicyclohexylphosphino-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl)-2-(2'-amino-1,1'-biphenyl)] palladium (II) methanesulfonate, and optionally in the presence of a ligand such as SPhos, t-BuBrettPhos, or Xantphos, can be prepared by reacting at a temperature of 60 to 120 ° C, optionally under microwave irradiation. The reaction can be carried out in the presence of a solvent such as toluene, dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), dioxane, or tetrahydrofuran (THF), and is described in, for example, WO 2012031004, WO 2009042907, and Synthetic Communications 2011, 41:67-72. Scheme 3: [ka]

[0106] Alternatively, compounds of formula I (wherein Q is as defined in formula I above) can be prepared by reacting a compound of formula VI (wherein LG2 is a leaving group, for example, Br, Cl, or I (preferably bromo), and R is a C-C alkyl, benzyl, or phenyl group) with a compound of formula IX (wherein Q is as defined in formula I) in the presence of a base such as sodium carbonate, potassium carbonate, or cesium carbonate, or sodium hydride, N,N-diisopropylethylamine, or KOtBu, and in the presence of a solvent such as ethanol, methanol, dioxane, toluene, DMF, DMA, DMSO, or THF, at a temperature between 0 and 150°C, optionally under microwave irradiation. Such reactions proceed via nucleophilic substitution and subsequent cyclization and have been reported in the literature, for example in WO2009042907.

[0107] Alternatively, compounds of formula I, where Q is as defined in formula I above, can be prepared by cyclizing compounds of formula X, where Q is as defined in formula I, in the presence of, for example, phosphorus oxychloride, optionally in the presence of a solvent or diluent such as toluene or xylene, at a temperature between 0 and 180°C, preferably between 20 and 120°C.

[0108] Scheme 4: [ka] Compounds of formula I, where Q is as defined in formula I above, can also be prepared by reacting a compound of formula Xa, where Q is as defined in formula I above, and where X0 is a halogen, preferably chlorine, or X0 is X 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 and 50°C. 01 or X 02 (Scheme 4) Certain bases, such as pyridine and triethylamine, can be conveniently employed as both the base and the solvent.

[0109] Compounds of formula Xa, wherein Q is as defined in formula I above, and wherein X is a halogen, preferably chlorine, or X is X 01 or X 02Compounds of formula X (where Q is as defined in formula I above) can be prepared by activation of compounds of formula X (where Q is as defined in formula I above) by methods known to those skilled in the art and described, for example, in Tetrahedron, 2005, 61(46), 10827-10852. The formation of activated species Xa (where Q is as defined in formula I above and where X is a halogen, preferably chlorine) is preferred. For example, compound Xa (where X is a halogen, preferably chlorine) is formed by treatment of X with, for example, oxalyl chloride (COCl) or thionyl chloride (SOCl) in the presence of a catalytic amount of N,N-dimethylformamide (DMF) in an inert solvent such as methylene chloride (CH2Cl2) or tetrahydrofuran (THF) at a temperature of 20-100°C, preferably 25°C. Alternatively, treatment of compounds of formula X with, for example, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide EDC or dicyclohexylcarbodiimide DCC in an inert solvent such as pyridine or tetrahydrofuran THF, optionally in the presence of a base such as triethylamine, at temperatures between 50 and 180° C., affords activated species Xa (where X0 is, respectively, X 01 or X 02 ) is generated.

[0110] Compounds of formula VII can be prepared by reacting compounds of formula VI (wherein LG2 is a leaving group such as Br, Cl or I (preferably bromo) and R is a C1-C6 alkyl, benzyl or phenyl group) with ammonia or an ammonia surrogate such as NH4OH in the presence of a solvent such as ethanol, methanol, dioxane, toluene, DMF, DMA, DMSO and THF at a temperature between 0 and 150°C, optionally under microwave irradiation.

[0111] Compounds of formula X (wherein Q is as defined in formula I above) can be prepared by nucleophilic substitution reaction of compounds of formula VI (wherein LG2 is a leaving group such as Br, Cl or I (preferably bromo) and R is a C1-C6 alkyl, benzyl or phenyl group) with amino compounds of formula IX (or compounds of formula IX-boc) (wherein Q is as defined in formula I above, followed by deprotection of the BOC functionality after the reaction), followed by in situ hydrolysis of intermediate esters of formula XVII (wherein Q is as defined in formula I above and R is a C1-C6 alkyl, benzyl or phenyl group). [ka]

[0112] The in situ generated unhydrolyzed ester compound of formula XVII can be isolated and also converted to the carboxylic acid of formula X via saponification in the presence of a suitable base, e.g., NaOH, LiOH, Ba(OH). 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, among others, and in the presence of a solvent, e.g., dioxane, DMF, DMA, DMSO, THF, at temperatures between −30 and 150° C. Compounds of formula VI, where LG2 is a leaving group, e.g., Br, Cl, or I (preferably bromo), and R is a C1-C6 alkyl, benzyl, or phenyl group, can be prepared by radical-induced benzylic halogenation of compounds of formula V, where R is a C1-C6 alkyl, benzyl, or phenyl group. Such reactions are well known to those skilled in the art and can be carried out in the presence of electrophilic halogenating agents such as Br, NBS, Cl, NIS, and radical initiators such as AIBN (azobisisobutyronitrile) and benzoyl peroxide, or under photochemical conditions, at temperatures ranging from 20°C to the boiling point of the solvent, and in the presence of solvents such as toluene, xylene, acetonitrile, hexane, dichloroethane, or carbon tetrachloride. This reaction is known as the Wohl-Ziegler bromination and has been reported in the literature, for example, in Synthesis, 2015, 47, 1280-1290 and J. Am. Chem. Soc., 1963, 85(3), pp. 354-355.

[0113] Compounds of formula V, where R is a C1-C6 alkyl, benzyl or phenyl group, can be prepared by a Suzuki reaction, which involves, for example, reacting compounds of formula IVa, where LG1 is a halogen Br, Cl, I, preferably Cl, and R is a C1-C6 alkyl, benzyl or phenyl group, with other methyl borate equivalents, especially trimethylboroxine or potassium methyltrifluoroborate. This reaction can be catalyzed by a palladium-based catalyst, such as tetrakis(triphenylphosphine)palladium(0), (1,1'-bis(diphenylphosphino)ferrocene)dichloropalladium-dichloromethane (1:1 complex), or chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (XPhos palladacycle), in the presence of a base such as sodium carbonate, tripotassium phosphate, or cesium fluoride, in a solvent or solvent mixture such as dioxane, acetonitrile, N,N-dimethylformamide, a mixture of 1,2-dimethoxyethane and water, or a dioxane / water mixture, or a toluene / water mixture, preferably under an inert atmosphere. The reaction temperature can 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 are reviewed, for example, in J. Organomet. Chem. 576, 1999, 147-168.

[0114] Alternatively, compounds of formula V, where R is a C1-C6 alkyl, benzyl, or phenyl group, can be prepared according to Scheme 3a. Scheme 3a [ka]

[0115] In Scheme 3a, compounds of formula V, where R is a C1-C6 alkyl, benzyl, or phenyl group, can be prepared from compounds of formula Va via an esterification reaction involving the reaction of compounds of formula Va with R—OH, where R is a C1-C6 alkyl, benzyl, or phenyl group, in the presence of an acid catalyst, for example, sulfuric acid or a Lewis acid, such as Sc(OTf)3 or FeCl3. Such a reaction is well known to those skilled in the art and is known as the Fischer esterification reaction, and has been reported in the literature, for example, in Org. Chem., 2006, 71, 3332-3334; Chem. Commun., 1997, 351-352; and Synthesis, 2008, 3407-3410. Such an esterification reaction can also be carried out by reacting a compound of formula III with TMSCHN2 to form a compound of formula V (where R is methyl), as reported in Angew. Chem. Int. Ed. 2007, 46, 7075. Compounds of formula Va can be prepared by oxidation of compounds of formula Vb. Such reactions are well known to those skilled in the art. Examples of reagents that promote such transformations include oxone, KMnO4, NaClO2 (known as Pinnick oxidation), AgNO3 in the presence of a metal hydroxide or Ag2O (known as Tollens' reagent). Such reactions are known in the literature and are described, for example, in Acta Chem. Scand. 1973, 27:888-890; Tetrahedron 1981, 37(11):2091-2096; Ber. Deut. Chem. Gessel., 15(1882), pp. 1635-1639; Org. Synth. 1953, 33, 94. Compounds of formula Vb can be prepared from compounds of formula Vc via a procedure similar to that described in Scheme 3 for the conversion of compounds of formula IVa to compounds of formula V. Compounds of formula Vc can be prepared from compounds of formula Vd via halogenation and in situ oxidation using halogenating agents such as iodine, bromine, chlorine, N-chlorosuccinimide, N-bromosuccinimide, among others.Alternatively, halogenation can be carried out and in a subsequent step, an oxidation reaction can be carried out using an oxidation reagent to form a compound of formula Vc in two steps from a compound of formula Vd, which is known in the literature under CAS Registry Number 72768-97-9.

[0116] Compounds of formula IVa (wherein LG1 is a halogen, such as Br, Cl, or I, preferably Cl, and R is a C1-C6 alkyl, benzyl, or phenyl group) can be prepared by reacting compounds of formula IV (wherein R is a 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 3). This transformation is preferably carried out in an inert solvent, such as acetonitrile, a halogenated solvent, such as 1,2-dichloroethane, or water, at a temperature between 0 and 150°C, preferably between room temperature and the boiling point of the reaction mixture. Compounds of formula IV (wherein R is C1-C6 alkyl, benzyl, or phenyl) can be prepared from compounds of formula III (wherein LG1 is a halogen, preferably Br, Cl, or I) by methods such as those found in WO 2016 / 020286, which involve a carbonylation reaction in which a compound of formula III 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 the presence of 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 and 180°C. Compounds of formula III (wherein LG is a halogen, preferably Br, Cl, or I) can be prepared, for example, by a halogenation reaction of compounds of formula II with a halogenating agent such as N-chlorosuccinimide (NCS), N-bromo-halosuccinimide (NBS), or N-iodosuccinimide (NIS), or alternatively with 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 temperatures between 20 and 200°C, preferably between room temperature and 100°C.

[0117] Compound of Formula VI [ka] (wherein LG2 is a leaving group, for example Br, Cl or I, and R is C1-C6 alkyl, benzyl or phenyl) is novel and has been specially developed for the preparation of compounds of formula I according to the invention and therefore represents a further object of the present invention. The preferences and preferred embodiments of the substituents of compounds of formula I are also valid for compounds of formula VI. Preferably, LG2 is bromo or chloro; even more preferably, LG2 is bromo. Preferably, R is C1-C6 alkyl; even more preferably, R is methyl or ethyl.

[0118] Alternatively, compounds of formula I, where Q is as defined in formula I above, can be prepared according to Scheme 5. Scheme 5: [ka]

[0119] In Scheme 5, a compound of formula I (wherein Q is as defined in Formula I above) can be prepared from a compound of formula X (wherein Q is as defined in Formula I above) by the method described in Scheme 4 above (Scheme 6). A compound of formula X can be prepared by reacting a compound of formula XII with a compound of formula IX (wherein Q is as defined in Formula I above) under reductive amination conditions (Scheme 6). This reaction can be carried out in the presence of a reducing agent, such as sodium cyanoborohydride or sodium triacetoxyborohydride, among others, and optionally in the presence of an acid, such as trifluoroacetic acid, formic acid, acetic acid, etc., at a temperature ranging from 0° C. to the boiling point of the solvent. This reaction can be carried out in the presence of an inert solvent, such as ethanol, methanol, dioxane, or tetrahydrofuran. Such a reaction, which involves a two-step conversion of a compound of formula XII to a compound of formula I, is described in the literature, for example in Bioorganic & Medicinal Chemistry Letters 26 (2016) 5947-5950.

[0120] Compounds of formula XII can be prepared from compounds of formula XI (wherein LG2 is chloro, bromo, or iodo, preferably bromo, and R is a C1-C6 alkyl, benzyl, or phenyl group) by hydrolysis and subsequent intramolecular cyclization. This reaction can be carried out under basic conditions using metal hydroxides, for example, using aqueous sodium hydroxide in the presence of a solvent such as dioxane, tetrahydrofuran, or water at a temperature in the range of 20-150°C, as reported in Synlett 1992, (6), 531-533, or under aqueous acidic conditions, for example, using acetic acid, hydrochloric acid, or sulfuric acid in the presence of a solvent such as water, dioxane, or a halogenated solvent such as dichloroethane, as reported in Tetrahedron 62 (2006) 9589-9602. Compounds of formula XI, where LG2 is chloro, bromo or iodo, preferably bromo, and R is a C1-C6 alkyl, benzyl or phenyl group, can be prepared from compounds of formula V, where R is a C1-C6 alkyl, benzyl or phenyl group, by methods similar to those described in Scheme 3 for the conversion of compounds of formula V to compounds of formula VI. Scheme 6: [ka]

[0121] Alternatively, compounds of formula I above, where Q is as defined in formula I, can be prepared from compounds of formula XV above, where Q is as defined in formula I, via selective reduction of the carbonyl functionality (Scheme 7). Scheme 7: [ka]

[0122] This reaction can be carried out in the presence of a reducing agent such as NaBH, LiAlH, or palladium on carbon, in the presence of hydrogen, or in the presence of a combination of two reducing agents such as NaBH followed by triethylsilane. Such reactions are described, for example, in U.S. Patent Application Publication No. 20100160303. Compounds of formula XV above (wherein Q is as defined in formula I) can be prepared from compounds of formula XIV above (wherein Q is as defined in formula I) by a hydrolysis reaction followed by a cyclization reaction, as described in Scheme 4 for the conversion of compounds of formula X to compounds of formula I. Compounds of formula XIV (wherein Q is as defined in formula I above and R is C1-C6 alkyl, benzyl, or phenyl) can be prepared by reacting compounds of formula XIII (wherein R is C1-C6 alkyl, benzyl, or phenyl) with compounds of formula IX (wherein Q is as defined in formula I) via the amidation reaction previously described in Scheme 4. Compounds of formula XIII (wherein R is C1-C6 alkyl, benzyl, or phenyl) can be prepared by benzylic oxidation of compounds of formula V (wherein R is C1-C6 alkyl, benzyl, or phenyl). This reaction can be carried out in the presence of an oxidizing agent such as KMNO4, nBu4MnO4, K2S2O8, or the like, in the presence of oxygen, or under photochemical conditions, at temperatures ranging from 20°C to the boiling point of the solvent. This reaction can be carried out in the presence of an inert solvent such as acetonitrile, ethyl acetate, DMSO, dichloroethane, etc. Such reactions are known in the literature, for example, in Synthesis, 2017, 49, 4007-4016, Synthesis, 2006, 1757-1759, and IOSR Journal of Applied Chemistry, 2014, 7, 16-27.

[0123] Alternatively, compounds of formula I, where Q is as defined in formula I above, can be prepared by cyclization of compounds of formula XVII, where Q is as defined in formula I above and R is C1-C6 alkyl, benzyl, or phenyl (Scheme 8). Scheme 8: [ka]

[0124] The reaction can be carried out in the presence of a base such as potassium tert-butoxide, lithium diisopropylamide, sodium hydride, and similar others, 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, etc. Such a reaction is reported in Synlett 2006(4):591-594. Compounds of formula XVII (wherein Q is as defined in formula I above and R is C1-C6 alkyl, benzyl, or phenyl) can be prepared by reacting compounds of formula XVI (wherein R is C1-C6 alkyl, benzyl, or phenyl) with compounds of formula IX (wherein Q is as defined in formula I) under Mitsunobu conditions. Such reactions are well known to those skilled in the art and can be carried out, inter alia, in the presence of a phosphine reagent such as triphenylphosphine, tributylphosphine, or polymer-supported triphenylphosphine, and in the presence of an azodicarboxylate reagent such as diethyl azodicarboxylate or diisopropyl azodicarboxylate, at a temperature between 0°C and 100°C, and in the presence of an inert solvent such as acetonitrile, dichloromethane, tetrahydrofuran, or toluene. Such reactions are reported, for example, in Synthesis, 1981(1), 1-28. Compounds of formula XVI (wherein R is C1-C6 alkyl, benzyl, or phenyl) can be prepared by reacting compounds of formula XIII (wherein R is C1-C6 alkyl, benzyl, or phenyl) with a reducing agent. The reaction can be carried out using a reducing agent, for example, a metal hydride such as lithium aluminum hydride (DIBAL-H), or a borane, such as diborane, borane tetrahydrofuran, among others, at a temperature between 0° C. and 150° C. in the presence of an inert solvent, such as tetrahydrofuran, dioxane, etc. Such a reaction is reported in Tetrahedron Letters, 1982, 23, 2475-2478.

[0125] Compound of Formula XVII-a [ka] (In the formula, Q is as defined above in Formula I, and R a is hydrogen, C1-C6 alkyl, benzyl or phenyl) is novel and was developed in particular for the preparation of compounds of formula I according to the invention and therefore represents a further object of the invention. The preferences and preferred embodiments of the substituents of compounds of formula I are also valid for compounds of formula XVII-a. Preferably, Ra is hydrogen or C1-C6 alkyl; even more preferably, Ra is hydrogen, methyl or ethyl.

[0126] Compounds of formula IX, where Q is as defined in formula I, can be prepared by deprotection of the tert-butyl group of compounds of formula XIX, where Q is as defined in formula I (Scheme 9). Scheme 9: [ka]

[0127] This reaction can be carried out in the presence of an acid catalyst such as trifluoroacetic acid, hydrochloric acid, or sulfuric acid, and others. Compounds of formula IX (where Q is as defined in formula I) can be prepared by reacting compounds of formula XVIII (where Q is as defined in formula I) with an organic azide in the presence of a suitable base (t-BuOH) and 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. This reaction can be carried out in the presence of a coupling agent such as T3P, or via activation of the carboxylic acid with SOCl2, oxalyl chloride, or other coupling agents described in Scheme 6 for the conversion of compounds of formula X to compounds 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, inter alia, Zn(OTf)2, Sc(OTf)2, or Cu(OTf)2. The compound of formula XIX can also be prepared by reacting the compound of formula XVIII with diphenylphosphoryl azide in the presence of an organic base such as triethylamine, diisopropylethylamine, or the like, and in the presence of tert-butanol, in an inert solvent such as a halogenated solvent, for example, a cyclic ether such as dichloromethane, dichloroethane, or tetrahydrofuran, among others, at a temperature ranging from 50° C. to the boiling point of the solvent. This reaction for converting a carboxylic acid to an amine is known to those skilled in the art as the Curtius reaction, and has been 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, where Q is as defined in formula I, can also be prepared from compounds of formula XX, where Q is as defined in formula I, by a Hofmann rearrangement reaction.This reaction can be carried out in the presence of a base, such as a metal hydroxide, e.g., aqueous sodium hydroxide or potassium hydroxide, or an organic base, e.g., DBU (1,8-diazabicyclo(5.4.0)undec-7-ene), and an electrophilic halogenating agent, e.g., chlorine, bromine, or N-bromo-halosuccinimide, at a temperature ranging from 20°C to the boiling point of the solvent. This reaction is known as the Hoffmann rearrangement and has been reported in the literature, e.g., Chem. Ber. 1881, 14, 2725. Compounds of formula XX (where Q is as defined in formula I) can be prepared by reacting compounds of formula XVIII with ammonia, e.g., NHOH, NH, or other ammonia substitutes, in the presence of a carboxylic acid activating agent, as described in Scheme 4.

[0128] A subgroup of compounds of formula XVIII (wherein Q is Qa, where R3, R4, X and R1 are as defined in formula I) can be defined as compounds of formula XVIII-a (Scheme 8). Such compounds of formula XVIII-a are known in the literature or they can be prepared according to Scheme 8 using methods and conditions similar to those described, for example, in WO 2017 / 061497 and WO 2018 / 052136. Scheme 8: [ka]

[0129] A subgroup of compounds of formula XVIII (wherein Q is Qb, where R5, R6, X and R1 are as defined in formula I) can be defined as compounds of formula XVIII-b (Scheme 9a). Such compounds of formula XVIII-b are known in the literature or they can be prepared according to Scheme 9a, for example, using methods and conditions similar to those described in WO2019162174A1. Scheme 9a: [ka]

[0130] Alternatively, compounds of formula XVIII-b (wherein R, X, R and R are as defined in formula I) can be prepared according to scheme 9b using methods and conditions similar to those described in the literature, for example in WO2009095253A1. Scheme 9b: [ka]

[0131] A subgroup of compounds of formula IX (wherein Q is Qb, where R5, R6 and R1 are as defined in formula I, and X is SO2) can be defined as compounds of formula IX-b (wherein R1, R5 and R6 are as defined in formula I, and X is SO2) (Scheme 9c). Such compounds of formula IX-b (wherein R1, R5 and R6 are as defined in formula I, and X is SO2) can be prepared according to Scheme 9c. Scheme 9c: [ka]

[0132] In Scheme 9c, compounds of formula IX-b (wherein R5, R6, and R1 are as defined in formula I, and X is SO2) can be prepared from compounds of formula XXXXI (wherein R5, R6, and R1 are as defined in formula I, and X is SO2) via deprotection of the tert-butoxycarbonyl group. Such reactions can be carried out in the presence of other acid catalysts, such as trifluoroacetic acid, hydrochloric acid, and, optionally, in the presence of a solvent such as dichloromethane, toluene, or trifluorotoluene, among others. Compounds of formula XXXXI (wherein R5, R6, and R1 are as defined in formula I, and X is SO2) can be prepared via oxidation of compounds of formula XXXXI (wherein R5, R6, and R1 are as defined in formula I, and X is S) by following a procedure similar to that described in Scheme 1a. Compounds of formula XXXXI, wherein R5, R6 and R1 are as defined in formula I and X is S, can be optionally reacted in the presence of a suitable base such as an alkali metal carbonate, for example sodium carbonate and potassium carbonate, or an alkali metal hydride, for example sodium hydride, or an alkali metal hydroxide, for example sodium hydroxide and potassium hydroxide, or sodium or potassium tert-butoxide, in an inert solvent, preferably at a temperature of 25 to 120°C, Reagent of formula XXXXa R1-SH(XXXXa) or a salt thereof (wherein R1 is as defined in formula I) by a substitution reaction or cross-coupling reaction of a compound of formula XXXIX (wherein R5 and R6 are as defined in formula I, PG1 is an amino-protecting group such as acetyl, benzyl, benzoyl, and LG6 is a leaving group, preferably Cl, Br, or I). Examples of solvents used include ethers such as tetrahydrofuran THF, ethylene glycol dimethyl ether, tert-butyl methyl ether, and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, nitriles such as acetonitrile, or polar aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone NMP, or dimethyl sulfoxide. Examples of salts of compounds of formula XXXXa include compounds of the following formula: R1-SM(XXXXb) (wherein R1 is as defined above and M is, for example, sodium or potassium). Such a process for preparing a compound of formula XXXXb from a compound of formula XXXXa can be found, for example, in WO 16 / 091731.

[0133] Alternatively, this reaction of a compound of formula XXXIX to form a compound of formula XXXXI using R1-SH(XXXXa) or R1-SM(XXXXb) can be carried out in the presence of a palladium catalyst such as tris(dibenzylideneacetone)dipalladium(0), in the presence of a phosphine ligand such as xantphos, in the presence of a base such as N,N-diisopropylethylamine, and in the presence of an inert solvent such as xylene, at a temperature of 100-160° C., preferably 140° C., as described in Tetrahedron 2005, 61, 5253-5259. During the conversion of a compound of formula XXXIX to a compound of formula XXXXI, the amino protecting group PG1 is cleaved under the reaction conditions described above or can be subsequently cleaved using suitable reagents well known to those skilled in the art, for example, an acetyl protecting group can be cleaved under basic conditions using other bases, such as NaOH, KOH, Cs2CO3, K2CO3, among others.

[0134] Compounds of formula XXXIX (wherein R5 and R6 are as defined in formula I, PG1 is an amino protecting group, such as acetyl, benzyl, benzoyl, and LG6 is a leaving group, preferably Cl, Br, or I) can be prepared by reaction of compounds of formula XXXVIII (wherein R5 and R6 are as defined in formula I, PG1 is an amino protecting group, such as acetyl, benzyl, benzoyl, and LG6 is a leaving group, preferably Cl, Br, or I) with di-tert-butyl decarbonate, optionally in the presence of a base such as triethylamine, 4-dimethylaminopyridine, among others, and a solvent such as dichloromethane, acetonitrile, toluene, tetrahydrofuran, among others. Compounds of formula XXXVIII (wherein R5 and R6 are as defined in formula I, PG1 is an amino-protecting group, such as acetyl, benzyl, benzoyl, and LG6 is a leaving group, preferably Cl, Br, or I) can be prepared by reacting compounds of formula XXXVII (wherein R5 and R6 are as defined in formula I, and PG1 is an amino-protecting group, such as acetyl, benzyl, benzoyl, with a suitable halogenating reagent, such as N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, among others, in the presence of a solvent such as dichloromethane, acetonitrile, tetrahydrofuran, DMF, among others. Such reactions are well known to those skilled in the art. Compounds of formula XXXVII (wherein R5 and R6 are as defined in formula I and PG1 is an amino-protecting group such as acetyl, benzyl, benzoyl) can be prepared by reacting compounds of formula XXXVI (wherein R5 and R6 are as defined in formula I) with a suitable amino-protecting group reagent, for example, using acetyl chloride in the presence of pyridine.

[0135] Compounds of formula XXXVI (wherein R5 and R6 are as defined in formula I) can be prepared from compounds of formula XXXIV (wherein R5 and R6 are as defined in formula I) in two steps, including the N-amination reaction of compounds of formula XXXIV with an aminating reagent such as, inter alia, hydroxylamine-O-sulfonic acid, O-(mesitylsulfonyl)hydroxylamine to form compounds of formula XXXV (wherein R5 and R6 are as defined in formula I), followed by intramolecular cyclization of compounds of formula XXXV (wherein R5 and R6 are as defined in formula I) in the presence of a base such as, inter alia, sodium hydride, KOH, NaOH, potassium carbonate, cesium carbonate, and in the presence of a solvent such as, inter alia, dichloromethane, dichloroethane, methanol, tetrahydrofuran, dimethylformamide. Such two-step reactions have been reported in the literature, for example as described in Tetrahedron Letters (2014), 55(43), 5963-5966.

[0136] Compounds of formula XXXIV (where R5 and R6 are as defined in formula I) can be prepared from compounds of formula XXXI (where R5 and R6 are as defined in formula I and LG5 is a halogen (or a pseudohalogen leaving group such as triflate)) by reaction with an acetonitrile anion equivalent in the presence of a metal catalyst. A variety of acetonitrile anion equivalents can be used in such reactions. Examples are tri-n-butylstannylacetonitrile, which can be coupled with compounds of formula (XXXI) under Stille reaction conditions, as described by Mitiga et al. (Chem. Lett. 1984, 15 11), or trimethylsilylacetonitrile in the presence of a palladium catalyst such as tris(dibenzylideneacetone)dipalladium(0), Xantphos Pd G3 ([(4,5-bis(diphenylphosphino)-9,9-dimethylxanthene)-2-(2'-amino-1,1'-biphenyl)]palladium(II) methanesulfonate), and a ligand such as Xantphos or P(i-Bu)3, and a fluoride source such as ZnF2, in a dipolar aprotic solvent such as DMF at temperatures between 80 and 120°C. Such reactions are well precedented in the literature (see, for example, Hartwig et al. (J. Am. Chem. Soc. 2002, 124, 9330 and J. Am. Chem. Soc. 2005, 727, 15824)) (Scheme 9c). Metal cyanoacetates such as potassium cyanoacetate or sodium cyanoacetate can also be used as acetonitrile anion equivalents, and the coupling reaction takes place in the presence of a palladium catalyst such as [Pd2(dba)3] (tris(dibenzylideneacetone)dipalladium(0)), [Pd(allyl)Cl]2 (allylpalladium(II) chloride dimer), among others, and in the presence of ligands such as SPhos, Xantphos, or P(i-Bu)3 or P(tert-butyl)3. Such reactions are known in the literature and are described, for example, in Angew. Chem. Int. Ed. 2011, 50, 4470-4474.

[0137] Yet another method for preparing a compound of formula XXXIV from a compound of formula XXXI is shown below (Scheme 9c-1). Scheme 9c-1: [ka]

[0138] in the presence of a base such as sodium carbonate, potassium carbonate or cesium carbonate or sodium hydride, sodium methoxide or ethoxide, potassium tert-butoxide, optionally under palladium (including, for example, Pd(PPh3)2Cl2) or copper (including, for example, CuI) catalyst, in a suitable solvent such as, for example, toluene, dioxane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone NMP or dimethyl sulfoxide DMSO, optionally in a solvent such as, for example, tetrabutylammonium chloride; Reaction of a compound of formula XXXI (where R5 and R6 are as defined in formula I, and LG5 is a halogen (or a pseudohalogen leaving group such as triflate)) with a reagent of formula XXXII (where R is a C1-C6 alkyl) in the presence of a phase transfer catalyst PTC, such as ammonium bromide or triethylbenzyl ammonium chloride TEBAC, at temperatures between room temperature and 180°C can provide a compound of formula XXXIII (where R5 and R6 are as described in formula I above, and R is a C1-C6 alkyl). Similar chemistry is described, for example, in Synthesis 2010, No. 19, 3332-3338.

[0139] Compounds of formula XXXIV (wherein R5 and R6 are as described above in formula I) can be prepared under conditions known to those skilled in the art, such as, for example, using aqueous sodium hydroxide, potassium hydroxide, or lithium hydroxide in methanol, ethanol, tetrahydrofuran, or dioxane at room temperature or reflux; followed by acidification of the reaction mixture under standard aqueous acid conditions, or under acidic conditions, for example, in the presence of HCl or paratoluenesulfonic acid. The compounds of formula XXXIV can be prepared by saponification / decarboxylation of compounds of formula XXXIII (where R5 and R6 are as described in formula I above and R is C1-C6 alkyl) in a solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, or dimethyl sulfoxide (DMSO) with a halide anion, preferably a chloride anion, e.g., from lithium chloride or sodium chloride, optionally in the presence of additional water, to give compounds of formula XXXIV. The reaction temperature for such a transformation (Krapko O-dealkylation / decarboxylation) is preferably in the range of 20°C to the boiling point of the reaction mixture, or the reaction can be carried out under microwave irradiation. Similar chemistry is described, for example, in Synthesis 2010, No. 19, 3332-3338.

[0140] Alternatively, compounds of formula IX-b (wherein R5, R6, and R1 are as defined in formula I, and X is SO2) can be prepared according to Scheme 9d. In Scheme 9d, compounds of formula IX-b (wherein R5, R6, and R1 are as defined in formula I, and X is SO2) can be prepared from compounds of formula XXXXIII (wherein R5 and R6 are as defined in formula I) following a similar procedure as described in Scheme 9c for the conversion of compounds of formula XXXVII to compounds of formula IX-b. Scheme 9d: [ka]

[0141] Compounds of formula XXXXIII (wherein R5 and R6 are as defined in formula I) can be prepared from compounds of formula XXXIV (wherein R5 and R6 are as defined in formula I) via a four-step process that includes reaction with hydroxylamine to form compounds of formula XXXXII, acetylation reaction to form compounds of formula XXXXIIa, base-catalyzed oxadiazole synthesis to form compounds of formula XXXXIIb, and finally, intramolecular cyclization / rearrangement to compounds of formula XXXXIII. Such reactions are reported in, for example, WO 2012146657, WO 2012146659, or Tetrahedron Letters (2017), 58(3), 202-205. Compounds of formula XXXIV can be prepared from compounds of formula XXXI as described in Scheme 9c.

[0142] A subgroup of the compounds of formula IX (wherein Q is Qc, and R7, R8, X, R1, A, A1 and A2 are as defined in formula I) can be defined as compounds of formula IX-c (wherein R7, R8, X, R1, A, A1 and A2 are as defined in formula I). ​​Compounds of formula IX-c can be prepared from compounds of formula XVIII-c, which are a subgroup of compounds of formula XVIII (wherein Q is Qc, and R7, R8, X, R1, A, A1 and A2 are as defined in formula I), according to Scheme 9. Compounds of formula XVIII-c are known in the literature or can be prepared according to methods similar to those described, for example, in WO 2016 / 142326 A1 and WO 2016091731 A1. [ka]

[0143] A subgroup of compounds of formula IX (wherein Q is Qc, where R7, R8, X, R1, A1 and A2 are as defined in formula I, and A is N) can be defined as compounds of formula IX-c-1 (wherein R7, R8, X, R1, A1 and A2 are as described in formula I). ​​Compounds of formula IX-c-1 can be prepared according to Scheme 9e. Scheme 9e: [ka]

[0144] The compound of formula IX-c-1 (wherein R7, R8, X, R1, A1 and A2 are as described in formula I) can be optionally reacted in the presence of a base such as sodium carbonate, potassium carbonate or cesium carbonate or potassium tert-butoxide, and optionally in the presence of a metal catalyst, for example a copper catalyst such as copper(I) iodide, copper powder, copper sulfate, and optionally in the presence of a diamine ligand (for example N,N'-dimethylethylenediamine or trans-cyclohexyldiamine) or in the presence of ligands such as dibenzylideneacetone (dba) or 1,10-phenanthroline at temperatures between 30 and 180°C, optionally under microwave irradiation, under sealed conditions, or with, for example, palladium(II) acetate, bis(dibenzylideneacetone)palladium(0) (Pd(dba)2) or tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3, optionally in the form of the chloroform adduct), or, for example, tert-BuBrettPhosPd G3 [(2-di-tert-butylphosphino-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl)-2-(2'-amino-1,1'-biphenyl)]palladium(II) methanesulfonate or BrettPhos Pd G3 can be prepared by reacting a compound of formula XXXXIX (where R7, R8, X, R1, A1 and A2 are as described in formula I, and wherein LG8 is a halogen, preferably bromo or chloro) with ammonia, aqueous ammonia or an ammonia substitute such as NH4OH (or by using protected ammonia such as tert-butyl carbamate followed by deprotection after formation of the product) in the presence of a palladium catalyst, such as a palladium pre-catalyst, such as [(2-dicyclohexylphosphino-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl)-2-(2'-amino-1,1'-biphenyl)]palladium(II) methanesulfonate, and optionally a ligand, such as SPhos, t-BuBrettPhos or Xantphos, at a temperature of 60-120°C, optionally under microwave irradiation.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, for example, Tetrahedron (1987), 43 (21), 4931-46, Organic Letters (2013), 15 (14), 3734-3737, Organic Letters (2015), 17 (23), 5934-5937, and WO 2004035549 A1.

[0145] Compounds of formula XXXXIX (wherein R7, R8, X, R1, A1 and A2 are as described in formula I, and where LG3 is halogen, preferably bromo or chloro) can be prepared by reacting compounds of formula XXXXVIII (wherein R7, R8, X, R1, A1 and A2 are as described in formula I) with a halogenating reagent such as POCl3, POBr3 or trichloroacetonitrile in the presence of other halogenating reagents, especially triphenylphosphine, capable of converting heteroaryl N-oxides to halo-functionalized derivatives. Such reactions are well known in the literature and are described, for example, in Tetrahedron Letters (2014), 55(51), 7130-7132, Tetrahedron (2005), 61(38), 9042-9051, and European Journal of Organic Chemistry (2016), 2016(8), 1606-1611. Compounds of formula XXXXVIII (wherein R7, R8, X, R1, A1, and A2 are as described in formula I) can be prepared by reacting compounds of formula XXXXVII (wherein R7, R8, X, R1, A1, and A2 are as described in formula I) with other oxidizing reagents, such as urea-H2O2, m-CPBA, among others, in the presence of solvents such as acetonitrile, tetrahydrofuran, dichloromethane, dichloroethane, among others. Such reactions are well known in the literature and are described, for example, in Organic Letters (2018), 20(8), 2346-2350, Dalton Transactions (2014), 43(21), 8054-8061, and Chemische Berichte (1992), 125(8), 1965-6.Compounds of formula XXXXVII (wherein R7, R8, X, R1, A1 and A2 are as described in formula I) can be prepared from compounds of formula XXXXVI (wherein R7, R8, X, R1, A1 and A2 are as described in formula I and where LG7 is a halogen (or a pseudohalogen leaving group such as triflate)) according to the procedure described in Scheme 9c for the conversion of compounds of formula XXXIX to compounds of formula XXXXI.

[0146] Compounds of formula I, where Q is Qa and R, X, R, and R are as defined above in formula I, can be defined as compounds of formula Ia. Such compounds of formula Ia can be prepared according to Scheme 10. Scheme 10: [ka]

[0147] In certain situations in Scheme 10, R3 is -N(R9)C(=O)R 10 (Wherein R9 and R 10 is as defined in Formula I), a compound of formula Ia (wherein R1, R3 and R4 are as defined in Formula I, and X is SO or SO2) can be converted to a compound of formula XXXXXa-1 (wherein R1 and R4 are as defined in Formula I, and X is SO or SO2, and X b is a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an aryl- or alkylsulfonate such as trifluoromethanesulfonic acid) to HN(R)C(=O)R 10 (Wherein R9 and R 10can be prepared by reaction of the compound (as defined in Formula I) with an equivalent of the reagent R3-H(XXXXXIa) (CN bond formation). Such reactions can be carried out in the presence of a base such as potassium carbonate, cesium carbonate, sodium hydroxide, or the like, in an inert solvent such as toluene, dimethylformamide (DMF), N-methylpyrrolidine (NMP), dimethyl sulfoxide (DMSO), dioxane, tetrahydrofuran (THF), or the like, optionally with, for example, palladium(II) acetate, bis(dibenzylideneacetone)palladium(0) (Pd(dba)2) or tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3, optionally in the form of the chloroform adduct), or, for example, tert-BuBrettPhosPd G3 [(2-di-tert-butylphosphino-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl)-2-(2'-amino-1,1'-biphenyl)]palladium(II) methanesulfonate or BrettPhos Pd In the presence of a catalyst, such as a palladium precatalyst, for example G3[(2-dicyclohexylphosphino-3,6-dimethoxy-2',4',6'-triisopropyl-1,1'-biphenyl)-2-(2'-amino-1,1'-biphenyl)]palladium(II) methanesulfonate, and optionally in the presence of a ligand, for example SPhos, t-BuBrettPhos or Xantphos, at a temperature of 60-120°C, optionally under microwave irradiation.

[0148] In certain situations in Scheme 10, R3 is -N(R9R 10 ) (wherein R9 and R 10 is as defined in Formula I), a compound of formula Ia (wherein R1, R3 and R4 are as defined in Formula I, and X is SO or SO2) can be converted to a compound of formula XXXXXa-1 (wherein R1 and R4 are as defined in Formula I, and X is SO or SO2, and X b is a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an aryl- or alkylsulfonate such as trifluoromethanesulfonic acid) to HN(R10 ) or a salt thereof (such as a hydrohalide salt, preferably a hydrochloride or hydrobromide salt, or a trifluoroacetate salt, or any other equivalent salt), wherein R and R 10 can be prepared by reaction of the compound (as defined in Formula I) with an equivalent of the reagent R3-H(XXXXXIa) (CN bond formation). Such reactions are typically carried out in inert solvents 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, toluene, water or mixtures thereof, at temperatures between 0 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, for example, a diamine ligand (e.g., N,N'-dimethylethylenediamine or trans-cyclohexyldiamine), dibenzylideneacetone (dba) or 1,10-phenanthroline, and optionally in the presence of a base such as potassium phosphate.

[0149] Reagent HN(R9R 10 ) or HN(R9)COR 10 (Wherein R9 and R 10 is as defined in Formula I) are known, commercially available, or can be prepared by methods known to those skilled in the art.

[0150] Alternatively, a compound of formula Ia (wherein R1, R3 and R4 are as defined in formula I, and X is SO or SO2) can be prepared, for example, by the addition of a compound of formula XXXXXa-1 (wherein R1 and R4 are as defined in formula I, and X is SO or SO2, and X bis a leaving group such as, for example, chlorine, bromine or iodine (preferably chlorine or bromine), or an aryl- or alkylsulfonate such as trifluoromethanesulfonic acid) with a compound of formula (XXXXXI), where R3 is as defined in formula I and Y b1 is, for example, B(OH)2 or B(OR b1 )2(where R b1 can be a C1-C4 alkyl group, or two groups OR b1 can be prepared by a Suzuki reaction comprising reacting (which can be a boron-derived functional group such as ) with (which can be, together with the boron atom, forming a five-membered ring (e.g., a boronic acid pinacol ester). This reaction can be catalyzed by a palladium catalyst, such as tetrakis(triphenylphosphine)palladium(0), (1,1'-bis(diphenylphosphino)ferrocene)dichloropalladium-dichloromethane (1:1 complex), or chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (XPhos palladacycle), in the presence of a base such as sodium carbonate, tripotassium phosphate, or cesium fluoride, in a solvent or solvent mixture such as dioxane, acetonitrile, N,N-dimethylformamide, a mixture of 1,2-dimethoxyethane and water, a dioxane / water mixture, or a toluene / water mixture, preferably under an inert atmosphere. The reaction temperature can preferably 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 are reviewed, for example, in J. Organomet. Chem. 576, 1999, 147-168.

[0151] Conversion of a compound of formula XXXXXa-1 (wherein R1 and R4 are as defined in formula I, and where X is S, and X is S) to a compound of formula XXXXXa-1 (wherein X is SO or SO2) with a suitable oxidizing agent. bis a leaving group such as, for example, chlorine, bromine, or iodine (preferably chlorine or bromine), or an aryl- or alkylsulfonate such as trifluoromethanesulfonic acid), oxidation of which can be achieved under the conditions already described above in Scheme 1a.

[0152] Many compounds of formula (XXXXXI) and (XXXXXIa) are commercially available or can be prepared by one skilled in the art.

[0153] Alternatively, compounds of formula I (where X is SO or SO) can be prepared from compounds of formula XXXXXa-1 (where X is S (sulfide)) with the same chemistry as above by changing the order of steps (i.e., performing the sequence of XXXXXa-1 (X is S) to Ia (X is S) via Suzuki or C-N bond formation, followed by an oxidation step to form Ia (X is SO or SO)).

[0154] Alternatively, compounds of formula Ia (wherein R1, X, R3 and R4 are as defined in formula I above) can be prepared according to Scheme 11. Scheme 11: [ka]

[0155] The chemistry described in Scheme 10 leading to compounds of formula Ia from compounds of formula XXXXXa-1 is equally applicable to the preparation of compounds of formula Ia from compounds of formula XXXXXa-2 (wherein all previously described substituent definitions remain valid) (Scheme 11).

[0156] Compounds of formula I, where Q is Qb and R1, X, R5, and R6 are as defined for formula I above, can be defined as compounds of formula I-aa. Such compounds of formula I-aa can be prepared according to Schemes 12 and 13. The chemistry described in Schemes 10 and 11 for the preparation of compounds of formula Ia is equally applicable to the preparation of compounds of formula I-aa in Schemes 12 and 13. Scheme 12: [ka] Scheme 13: [ka]

[0157] Compounds of formula I, where Q is Qc and R, X, A, A, A, R, and R are as defined for formula I above, can be defined as compounds of formula I-aaa. Such compounds of formula I-aaa can be prepared according to Schemes 14 and 15. The chemistry described in Schemes 10 and 11 for the preparation of compounds of formula Ia is equally applicable to the preparation of compounds of formula I-aaa in Schemes 14 and 15. Scheme 14: [ka] Scheme 15: [ka]

[0158] Depending on the method or reaction conditions, the reactants can be reacted in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamides, alkylenediamides, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxide and carbocyclic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0159] The reactants can be reacted with each other as they are, i.e., without the addition of a solvent or diluent. However, in most cases, it is advantageous to add an inert solvent or diluent or a mixture thereof. When the reaction is carried out in the presence of a base, the base used in excess, such as triethylamine, pyridine, N-methylmorpholine, or N,N-diethylaniline, can also serve as the solvent or diluent.

[0160] The reaction is advantageously carried out in the temperature range of about -80°C to about +140°C, preferably about -30°C to about +100°C, and in many cases in the range of room temperature to about +80°C.

[0161] Compounds of formula I can be converted into other compounds of formula I in a manner known per se by conventional methods by replacing one or more substituents of the starting compound of formula I by other substituents according to the invention, as well as by subsequent modification of the compound by reactions such as oxidation, alkylation, reduction, acylation and other methods known to those skilled in the art.

[0162] Depending on the respective suitable reaction conditions and the choice of starting materials, it is possible, for example, to simply replace one substituent with another substituent according to the invention in one reaction step, or multiple substituents can be replaced with other substituents according to the invention in the same reaction step.

[0163] Salts of compounds of formula I can be prepared in a manner known per se: thus, for example, acid addition salts of compounds of formula I can be obtained by treatment with a suitable acid or with a suitable ion exchange reagent, and base salts can be obtained by treatment with a suitable base or with a suitable ion exchange reagent.

[0164] Salts of compounds of formula I can be converted in a customary manner into acid addition salts of the free compounds I, for example by treatment with suitable basic compounds or suitable ion exchange reagents, and into salts with bases, for example by treatment with suitable acids or suitable ion exchange reagents.

[0165] Salts of compounds of formula I may be converted into other salts, such as acid addition salts, of compounds of formula I in a manner known per se, for example by treating the inorganic acid salt, such as the hydrochloride, with a suitable metal salt, such as the sodium, barium or silver salt of the acid, for example silver acetate, in a suitable solvent in which the inorganic salt that forms silver chloride is insoluble and therefore precipitates from the reaction mixture.

[0166] Depending on the procedure or reaction conditions, compounds of formula I having salt-forming properties may be obtained in free form or in salt form.

[0167] The compounds of formula I and, where appropriate, their tautomers, can exist in the form of one of the possible isomers or as mixtures thereof, in the form of pure isomers, such as enantiomers and / or diastereomers, or as isomeric mixtures, such as enantiomeric mixtures, such as racemates, diastereomeric mixtures or racemic mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms occurring in the molecule and / or depending on the configuration of non-aromatic double bonds occurring in the molecule, in each case in free form or in salt form; the invention relates to the pure isomers and also to all possible isomeric mixtures, and is to be understood in this sense above and below, respectively, even if details of the stereochemistry are not specifically stated in each case.

[0168] Diastereomeric or racemic mixtures of compounds of formula I, in free or salt form, obtained depending on which starting materials and procedures are selected, can be separated in known manner into pure diastereomers or racemates on the basis of the physical chemical differences of the components, for example, by fractional crystallization, distillation, and / or chromatography.

[0169] Enantiomeric mixtures, such as racemates, obtained in a similar manner can be resolved into their optical antipodes by known methods, for example by recrystallization from optically active solvents, by chromatography on chiral adsorbents, for example by high-performance liquid chromatography (HPLC) on acetylcellulose using suitable microorganisms, by cleavage with specific immobilized enzymes via the formation of inclusion compounds, for example with chiral crown ethers, in which only one enantiomer is complexed, or by conversion to diastereomeric salts, for example by reacting the basic final product racemate with an optically active acid, such as a carboxylic acid, for example camphoric acid, tartaric acid or malic acid, or a sulfonic acid, for example camphorsulfonic acid, and separating the diastereomeric mixtures thus obtained, for example by fractional crystallization based on their different solubilities, to give diastereomers from which the desired enantiomer can be released by the action of a suitable substance, for example a basic substance.

[0170] Pure diastereomers or enantiomers can be obtained according to the present invention not only by separating the appropriate isomeric mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, e.g. by carrying out the process according to the present invention using stereochemically characterized starting materials.

[0171] The N-oxides can be prepared by reacting the compounds of formula I with a suitable oxidizing agent, such as the H2O2 / urea adduct, in the presence of an acid anhydride, such as trifluoroacetic anhydride. Such oxidations are known from the literature, for example, J. Med. Chem., 32(12), 2561-73, 1989 or WO 2000 / 15615.

[0172] When the individual components have different biological activities, it may be advantageous to isolate or synthesize the respective more biologically active isomer, e.g., enantiomer or diastereomer, or mixture of isomers, e.g., mixture of enantiomers or diastereomers.

[0173] The compounds of formula I and, where appropriate, their tautomers, may also be obtained in free or salt form, optionally in the form of hydrates, and / or contain other solvents, for example solvents that may have been used for the crystallization of compounds present in solid form.

[0174] The compounds of formula I according to the following tables A-1 to A-3, B-1 to B-3, C-1 to C-3, D-1 to D-3, E-1 to E-3 and F-1 to F-3 can be prepared according to the above methods. The following examples are intended to illustrate the invention and to show preferred compounds of formula I in the form of compounds of formula Ia-Qa to Ib-Qc.

[0175] The following table shows certain compounds of the invention.

[0176] The following Tables A-1 to A-3 show specific compounds of the present invention.

[0177] [ka] Table A-1 provides 14 compounds A-1.001 to A-1.014 of formula Ia-Qa, where X is S, R1 is ethyl, and R3 is as defined in Table M.

[0178] [Table 1]

[0179] Table A-2 provides 14 compounds A-2.001 to A-2.014 of formula Ia-Qa, where X is SO, R1 is ethyl, and R3 is as defined in Table M.

[0180] Table A-3 provides 14 compounds A-3.001 to A-3.014 of formula Ia-Qa, where X is SO2, R1 is ethyl, and R3 is as defined in Table M.

[0181] The following Tables B-1 to B-3 show further specific compounds of the present invention.

[0182] [ka] Table B-1 provides 14 compounds B-1.001 to B-1.014 of formula Ib-Qa, where X is S, R1 is ethyl, and R4 is as defined in Table N.

[0183] [Table 2]

[0184] Table B-2 provides 14 compounds B-2.001 to B-2.014 of formula Ib-Qa, where X is SO, R1 is ethyl, and R4 is as defined in Table N.

[0185] Table B-3 provides 14 compounds B-3.001 to B-3.014 of formula Ib-Qa, where X is SO2, R1 is ethyl, and R4 is as defined in Table N.

[0186] The following Tables C-1 to C-3 show further specific compounds of the present invention.

[0187] [ka] Table C-1 provides 14 compounds C-1.001 to C-1.014 of formula Ia-Qb, where X is S, R1 is ethyl, and R5 is as defined in Table O.

[0188] [Table 3]

[0189] Table C-2 provides 18 compounds C-2.001 to C-2.018 of formula Ia-Qb, where X is SO, R1 is ethyl, and R5 is as defined in Table O.

[0190] Table C-3 provides 18 compounds C-3.001 to C-3.018 of formula Ia-Qb, where X is SO2, R1 is ethyl, and R5 is as defined in Table O.

[0191] The following Tables D-1 to D-3 show further specific compounds of the present invention.

[0192] [ka] Table D-1 provides 14 compounds D-1.001 to D-1.014 of formula Ib-Qb, where X is S, R1 is ethyl, and R6 is as defined in Table P1.

[0193] [Table 4]

[0194] Table D-2 provides 18 compounds D-2.001 to D-2.018 of formula Ib-Qb, where X is SO, R1 is ethyl, and R6 is as defined in Table P1.

[0195] Table D-3 provides 18 compounds D-3.001 to D-3.018 of formula Ib-Qb, where X is SO2, R1 is ethyl, and R6 is as defined in Table P1.

[0196] Tables E-1 to E-3 below show further specific compounds of the invention.

[0197] [ka] Table E-1 provides 14 compounds E-1.001 to E-1.014 of formula Ia-Qc, where X is S, R1 is ethyl, and R7 is as defined in Table Q.

[0198] [Table 5]

[0199] Table E-2 provides 14 compounds E-2.001 to E-2.014 of formula Ia-Qc, where X is SO, R1 is ethyl, and R7 is as defined in Table Q.

[0200] Table E-3 provides 14 compounds E-3.001 to E-3.014 of formula Ia-Qc, where X is SO2, R1 is ethyl, and R7 is as defined in Table Q.

[0201] Tables F-1 to F-3 below show further specific compounds of the invention.

[0202] [ka] Table F-1 provides 14 compounds F-1.001 to F-1.014 of formula Ib-Qc, where X is S, R1 is ethyl, and R8 is as defined in Table R.

[0203] [Table 6]

[0204] Table F-2 provides 14 compounds F-2.001 to F-2.014 of formula Ib-Qc, where X is SO, R1 is ethyl, and R8 is as defined in Table R.

[0205] Table F-3 provides 14 compounds F-3.001 to F-3.014 of formula Ib-Qc, where X is SO2, R1 is ethyl, and R8 is as defined in Table R.

[0206] The compounds of formula I according to the invention are preventively and / or therapeutically useful active ingredients in the field of pest control, even at low application rates, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded animal species, fish, and plants. The active ingredients according to the invention act not only against normally susceptible animal pests, such as insects or representatives of the order Acarina, but also against all or individual developmental stages of resistant animal pests. The insecticidal or acaricidal activity of the active ingredients according to the invention can be manifested directly (i.e., killing of the pest immediately or only after a certain period of time, for example, during molting) or indirectly (e.g., by reducing egg production and / or hatching rate, a good activity corresponding to a killing rate (mortality) of at least 50-60%).

[0207] Examples of the above animal pests are: From the order Acarina, for example: Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp., Eotetranychus spp. spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus spp.), Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp., Tarsonemus spp. and Tetranychus spp.; From the order Anoplura, for example: Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; From the order Coleoptera, for example: Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotoma spp., Conoderus spp., Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp.), Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa ​​decemLineata, Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Maladera castanea, Megascelis spp. spp., Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp., Phlyctinus spp., Popillia spp.), Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabaeidae, Sitophilus spp., Sitotroga spp., Somaticus spp., Sphenophorus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp. and Trogoderma spp.;. From the order Diptera, for example: Aedes spp., Anopheles spp., Antherigona soccata, Bactrocea oleae, Bibio hortulanus, Bradysia spp., Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp., Drosophila melanogaster, Fannia spp. spp.), Gastrophilus spp., Geomyza tripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp. spp.), Rhagoletis spp., Rivelia quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; From the order Hemiptera, for example: Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Amblypelta nitida, Bathycoelia thalassina, Blissus spp., Cimex spp., Clavigrella tomentosicollis, Creontiades spp., Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp., Euschistus spp. spp.), Eurydema pulchrum, Eurygaster spp., Brown marmorated stink bugs (Halyomorpha halys), Horcias nobilellus, Leptocorisa spp., Mire bugs (Lygus spp.), Margarodes spp., Murgantia histrionic, Neomegalotomus spp., Nesidiocoris tenuis, Nezara spp., Nysius simulans, Oebalus insularis, Piesma spp. spp.), Piezodorus spp., Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp., Thyanta spp., Triatoma spp.), Vatiga illudens;. Acyrthosium pisum, Adalges spp., Agalliana ensigera, Agonoscena targionii, Aleurodicus spp., Aleurocanthus spp., Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp. spp.), Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp., Brachycaudus spp., Brevicoryne brassicae, Cacopsylla spp., Cavariella aegopodii Scop., Ceroplaster spp.), Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp., Cofana spectra, Cryptomyzus spp., Cicadulina spp., Coccus hesperidum, Dalbulus maidis, Dialeurodes spp., Diaphorina citri, Diuraphis noxia, Dysaphis spp., Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae, Hyalopterus spp., Hyperomyzus pallidus, Idioscopus clypealis, Jacobiasca lybica, Laodelphax spp., Lecanium corni, Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp., Mahanarva spp., Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp.), Neotoxoptera spp., Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter, Bayberry whitefly (Parabemisia myricae), Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Corn planthopper (Peregrinus maidis), Perkinsiella spp., Hop wart aphid (Phorodon humuli, Phylloxera spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp., Scaphoideus spp. spp.), Schizaphis spp., Sitobion spp.), Sogatella furcifera, Spisstilus festinus, Tarophagus Proserpina, Toxoptera spp., Trialeurodes spp., Tridiscus sporoboli, Trionymus spp., Trioza erytreae, Unaspis citri, Zygina flammigera, Zyginidia scutellaris; From the order Hymenoptera, for example: Acromyrmex ants, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis ants, Neodiprion spp., Pogonomyrmex spp., Slenopsis invicta, Solenopsis spp. and Vespa spp.; From the order Isoptera, for example: Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Solenopsis geminate From the order Lepidoptera, for example: Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp., Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis perspectalis, Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea, Earias spp., Eldana saccharina, Ephestia spp.), Epinotia spp., Estigmene acrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltia jaculiferia, Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Herpetogramma spp., Hyphantria cunea, Keiferia lycopersicella lycopersicella, Lasmopalpus lignosellus, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostege bifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Mythimna spp., Noctua spp., Operophtera spp., Orniodes indica indica), European corn borer (Ostrinia nubilalis), Pammene spp., Pandemis spp.), pine sawyer moth (Panolis flammea), Papaipema nebris, pink bollworm (Pectinophora gossypiela), coffee leafminer (Perileucoptera coffeella), Pseudaletia unipuncta, potato tuber moth (Phthorimaea operculella), cabbage white butterfly (Pieris rapae), Pieris spp., diamondback moth (Plutella xylostella), Prays spp., Pseudoplusia spp., Rachiplusia nu, Richia albicosta, Scirpophaga spp., Sesamia spp.), Sparganothis spp., Spodoptera spp., Sylepta derogate, Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tuta absoluta and Yponomeuta spp.;. From the order Mallophaga, for example: Damalinea spp. and Trichodectes spp.; From the order Orthoptera, for example: Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscus spp. and Schistocerca spp.; From the order Psocoptera, for example: Liposcelis spp.; From the order Siphonaptera, for example: Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis; From the order Thysanoptera, for example: Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp.; From the order Thysanura, for example, Lepisma saccharina.

[0208] The active ingredients according to the invention can be used to control, i.e. suppress or destroy, pests of the above-mentioned types occurring in particular on plants, in particular on useful plants and ornamental plants in agriculture, horticulture and forestry, or on organs such as the fruits, flowers, leaves, stems, tubers or roots of such plants, in some cases even plant organs formed at a later time remaining protected from these pests.

[0209] Suitable target crops are, in particular, cereals such as wheat, barley, rye, oats, rice, maize or sorghum; beets such as sugar beet or fodder beet; fruits, such as pome fruits, stone fruits or soft fruits, for example apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; legumes, such as beans, lentils, peas or soybeans; rapeseed, mustard, poppy, olive, sunflower, palm, castor, cocoa or groundnut. citrus fruits such as oranges, lemons, grapefruits or tangerines; vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes or peppers; plants of the Lauraceae family such as avocado, cinnamon or camphor; and also tobacco, tree nuts, coffee, eggplant, sugarcane, tea, pepper, grapes, hops, plantains and latex plants.

[0210] The compositions and / or methods of the present invention may be used on any ornamental and / or vegetable crop, including flowers, shrubs, broadleaf trees and evergreen trees.

[0211] For example, the present invention relates to the use of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g., B. elatior, B. semperflorens, B. tubereux), Bougainvillea spp., Brachycome spp. spp.), Brassica spp. (ornamental), Calceolaria spp., Capsicum annuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemum spp., Cineraria spp. (C. maritime), Coreopsis spp., Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Bleeding hearts spectabilis, Dorotheantus spp., Lisianthus (Eustoma grandiflorum), Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Globetrotter (Gomphrena globosa), Heliotropium spp., Helianthus spp., Hibiscus spp.), Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (I. Walleriana), Iresines spp., Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp. spp.), Nemesia spp., Tagetes spp., Dianthus spp. (carnations), Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (ivy geranium (P. peltatum), P. Zonale), Viola spp. (pansies), Petunia spp., Phlox spp., Plecthranthus spp., Poinsettia spp. spp.), Parthenocissus spp. (American Creeper (P. quinquefolia), Ivy (P. tricuspidata)), Primula spp., Ranunculus spp., Rhododendron spp., Rosa spp. (roses), Rudbeckia spp., Saintpaulia spp., Salvia spp.), Scaevola aemola, Schizanthus wisetonensis, Sedum spp., Solanum spp., Surfinia spp., Tagetes spp., Nicotinia spp., Verbena spp., Zinnia spp., and other bedding plants.

[0212] For example, the present invention relates to the use of the following vegetable species: Allium spp. (garlic (A. sativum), onion (A. cepa), shallot (A. oschaninii), leek (A. porrum), scallion (A. ascalonicum), green onion (A. fistulosum)), chervil (Anthriscus cerefolium), celery (Apium graveolus), asparagus (Asparagus officinalis), beet (Beta vulgarus), Brassica spp. (B. oleracea, Chinese cabbage (B. pekinensis), turnip (B. rapa)), chili pepper (Capsicum annuum), chickpea (Cicer arietinum), endive (Cichorium endivia), Cichorum spp. spp.) (chicory (C. intybus), endive (C. endivia)), watermelon (Citrillus lanatus), Cucumis spp. (saffron (C. sativus), melon (C. melo)), Cucurbita spp. (Cucurbita pepo, Cucurbita maxima), Cyanara spp. (artichoke (C. scolymus), cardoon (C. cardunculus)), carrot (Daucus carota), fennel (Foeniculum vulgare), Hypericum spp., lettuce (Lactuca sativa), tomato spp. spp.) (tomato (L. esculentum), tomato (L. lycopersicum)), mint species (Mentha spp.), basil (Ocimum basilicum), parsley (Petroselinum crispum), Phaseolus species (Phaseolus spp.) (P. vulgaris, runner bean (P.The present invention may be used in any of the following plants: pea (Pisum sativum), radish (Raphanus sativus), rhubarb (Rheum rhaponticum), rosemary (Rosemarinus spp.), salvia (Salvia spp.), yellow rosemary (Scorzonera hispanica), eggplant (Solanum melongena), spinach (Spinacea oleracea), Valerianella spp. (V. locusta, V. eriocarpa), and broad bean (Vicia faba).

[0213] Preferred ornamental species include Saintpaulia, Begonia, Dahlia, Gerbera, Hydrangea, Vervain, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hydrangea, Rosemary, Sage, St. John's Wort, Mint, Bell Pepper, Tomato, and Cucumber.

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

[0215] The active ingredients according to the invention are particularly suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetables, corn, rice and soybean crops. The active ingredients according to the invention are particularly suitable for controlling Mamestra (preferably on vegetables), codling moth (Cydia pomonella) (preferably on apple), Empoasca (preferably on vegetables and vineyards), Leptinotarsa ​​(preferably on potato) and Chilo supressalis (preferably on rice).

[0216] In a further aspect, the present invention also relates to plant parasitic nematodes (endoparasitic, semi-endoparasitic and ectoparasitic nematodes), in particular the root-knot nematode Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; cyst-forming nematodes Globodera rostochiensis and other Globodera species; wheat cyst nematode Heterodera avenae, soybean cyst nematode Heterodera glycines, sugar beet cyst nematode Heterodera schachtii, clover cyst nematode Heterodera trifolii and other cyst nematodes (Heterodera species); seed gall nematodes, Anguina species; stem and peel nematodes, Aphelenchoides species; sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; pine wood nematode, Bursaphelenchus xylophilus and other Bursaphelenchus species; ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; fire nematodes, Dolichodorus species;Screw nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Spear nematodes, Hoploaimus species; False root-knot nematodes, Nacobbus species; Tylenchidae, Longidorus elongatus elongatus and other Longidorus species; pin nematodes, Pratylenchus species; root-lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; root-lesion nematodes, Radopholus similis and other Radopholus species; false nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species; Scutellonema species; Trichodorus primitivus and other Trichodorus species, Paratrichodorus species;Plant-parasitic nematodes such as the claytonid nematode, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, and other Tylenchorhynchus species; the burrowing nematode, Tylenchulus species; the giant sting nematode, Xiphinema species; and plant-parasitic nematodes such as Subanguina species, Hypsoperine species, Macroposthonia species, Melinius species, Punctodera species, and Quinisulcius species. The present invention may also relate to a method for preventing damage to plants and parts thereof by other plant-parasitic nematode species, such as Pseudomonas spp.;

[0217] The compounds of the present invention may also have activity against mollusks, such as, for example, the family Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena furticum); fruticum); Cepaea (C. hortensis, C. nemoralis); Ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum) tum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H. obvia); Helicidae (Helicigona albustrum) arbustorum); Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Monoa These include the genera Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.

[0218] The term "crop plant" should also be understood to include crop plants that have been transformed by the use of recombinant DNA techniques so as to be capable of synthesizing one or more selectively acting toxins, such as those known to be derived from toxin-producing bacteria, particularly bacteria of the genus Bacillus.

[0219] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or δ-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, insecticidal proteins from Bacillus thuringiensis or plant insecticidal proteins (Vip), such as Vip1, Vip2, Vip3 or Vip3A; or bacterial-colonizing nematodes, such as Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus, etc. insecticidal proteins of Azotoxins; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and neurotoxins specific to other insects; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectin, barley lectin or snowdrop lectin; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin and papain inhibitors; ricin, corn-RIP, abrin, rufin, saporin ribosome-inactivating proteins (RIPs) such as erythrin or bryodin; steroid metabolic enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers such as blockers of sodium channels or calcium channels, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

[0220] In the context of the present invention, delta-endotoxins are understood to mean, for example, Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or plant insecticidal proteins (Vip), such as Vip1, Vip2, Vip3, or Vip3A, and also specifically hybrid toxins, truncated toxins, and modified toxins. Hybrid toxins are produced recombinantly by combining different domains of these proteins (see, for example, WO 02 / 15701). Truncated toxins, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the native toxin are replaced. In such amino acid substitutions, preferably a non-naturally occurring protease recognition sequence is inserted into the toxin, for example, in the case of Cry3A055, a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see WO 03 / 018810).

[0221] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP 0 374 753, WO 93 / 07278, WO 95 / 34656, EP 0 427 529, EP 451 878 and WO 03 / 052073.

[0222] Methods for the preparation of such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above. Deoxyribonucleic acids of the CryI type and their preparation are known, for example, from WO 95 / 34656, EP 0 367 474, EP 0 401 979 and WO 90 / 13651.

[0223] The toxins contained in the transgenic plants confer resistance to pests found in a range of insect taxa, but are particularly common in beetles (Coleoptera), two-winged insects (Diptera), and moths (Lepidoptera).

[0224] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known, and some of them are commercially available. Examples of such plants include YieldGard® (a corn variety expressing the Cry1Ab toxin); YieldGard Rootworm® (a corn variety expressing the Cry3Bb1 toxin); YieldGard Plus® (a corn variety expressing the Cry1Ab and Cry3Bb1 toxins); Starlink® (a corn variety expressing the Cry9C toxin); Herculex I® (a corn variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) for tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety expressing the Cry1Ac toxin); Bollgard I® (a cotton variety expressing the Cry1Ac toxin); Bollgard II® (a cotton variety expressing Cry1Ac and Cry2Ab toxins); VipCot® (a cotton variety expressing Vip3A and Cry1Ab toxins); NewLeaf® (a potato variety expressing Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), and Protecta®.

[0225] Further examples of such transgenic crops are: 1. Bt11 maize, registration number C / FR / 96 / 05 / 10, manufactured by Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St. Sauveur, France). This genetically modified maize is resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) through the transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also genetically expresses the enzyme PAT to confer tolerance to the herbicide glufosinate ammonium.

[0226] 2. Bt176 maize, registration number C / FR / 96 / 05 / 10, manufactured by Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St. Sauveur, France). This genetically modified maize is resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) through transgenic expression of the Cry1Ab toxin. Bt176 maize also genetically expresses the enzyme PAT to confer tolerance to the herbicide glufosinate ammonium.

[0227] 3. MIR604 maize, registration number C / FR / 96 / 05 / 10, manufactured by Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St. Sauveur, France). This maize has been made insect-resistant by transgenic expression of a modified Cry3A toxin. The toxin is Cry3A055, modified by the insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03 / 018810.

[0228] 4. MON 863 maize, registration number C / DE / 02 / 9, manufactured by Monsanto Europe SA (270-272 Avenue de Tervuren, B-1150 Brussels, Belgium). MON 863 expresses the Cry3Bb1 toxin and confers resistance to certain Coleoptera insects.

[0229] 5. IPC 531 cotton, registration number C / ES / 96 / 02, manufactured by Monsanto Europe SA (270-272 Avenue de Tervuren, B-1150 Brussels, Belgium).

[0230] 6. 1507 Maize, registration number C / NL / 00 / 10, manufactured by Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium. Genetically modified maize for expression of the protein Cry1F for resistance to certain Lepidoptera insects and the protein PAT for resistance to the herbicide glufosinate ammonium.

[0231] 7. NK603 x MON 810 maize, registration number C / GB / 02 / M3 / 03, manufactured by Monsanto Europe SA (270-272 Avenue de Tervuren, B-1150 Brussels, Belgium). This maize consists of a conventionally bred hybrid maize variety by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 maize also genetically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which confers resistance to the herbicide Roundup® (containing glyphosate), and the Cry1Ab toxin, obtained from Bacillus thuringiensis subsp. kurstaki, which confers resistance to certain Lepidoptera, including the European corn borer.

[0232] 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).

[0233] The term "crop plant" should also be understood to include crop plants that have been transformed by the use of recombinant DNA technology so as to be able to synthesize antipathogenic substances with selective action, such as, for example, so-called "pathogenicity-related proteins" (PRPs, see, for example, EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesizing such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95 / 33818 and EP-A-0 353 191. Methods for producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the above-mentioned publications.

[0234] Crops can also be improved to increase resistance to fungal (e.g., Fusarium, anthracnose, or Phytophthora), bacterial (e.g., Pseudomonas), or viral (e.g., potato leaf curl virus, tomato spotted wilt virus, cucumber mosaic virus) pathogens.

[0235] Crops also include those that have a high resistance to nematodes, such as the soybean cyst nematode.

[0236] Crops that are tolerant to abiotic stress include those that have increased tolerance to drought, high salinity, high temperature, low temperature, frost, or light due to, for example, expression of NF-YB or other proteins known in the art.

[0237] Antipathogenic substances that can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers of sodium or calcium channels, e.g., viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; so-called "pathogenesis-related proteins" (PRPs; see, for example, EP 0 392 225); antipathogenic substances produced by microorganisms, such as peptide or heterocyclic antibiotics (see, for example, WO 95 / 33818) or proteins or polypeptide factors involved in plant pathogen defense (the so-called "plant disease resistance genes" described in WO 03 / 000906).

[0238] Further fields of use of the compositions according to the invention are the protection of stored goods and storage rooms and of raw materials (such as wood and textiles), floor coverings and buildings, and in the hygiene sector, in particular the protection of humans, domestic animals and productive livestock from pests of the above-mentioned types.

[0239] The present invention also provides methods for controlling pests (such as mosquitoes and other disease vectors; see also http: / / www.who.int / malaria / vector_control / irs / en / ). In one embodiment, the method for controlling pests comprises applying a composition of the present invention to the target pest, its habitat, or a surface or substrate by brushing, rolling, spraying, painting, or dipping. By way of example, IRS (indoor residual spray) application of surfaces such as walls, ceilings, or floors is contemplated by the method of the present invention. In another embodiment, it is contemplated to apply such compositions to substrates such as nonwoven or woven materials in the form of (or in a form that can be used to manufacture) netting, clothing, bedding, curtains, and tents.

[0240] In one embodiment, a method for controlling such pests comprises applying a pesticidally effective amount of a composition of the present invention to a target pest, its habitat, or a surface or substrate to provide effective, residual pest control activity to the surface or substrate. Such application may be by brushing, rolling, spraying, painting, or dipping the pesticidal composition of the present invention. For example, IRS application to surfaces such as walls, ceilings, or floors is contemplated by the method of the present invention to provide effective, residual pest control activity to the surface. In another embodiment, the application of such compositions for residual pest control on substrates such as fabric materials in the form of (or in the form that can be used to manufacture) netting, clothing, bedding, curtains, and tents is contemplated.

[0241] The substrates to be treated, including nonwovens, fabrics, or nets, can be made of natural fibers such as cotton, raffia, jute, flax, sisal, hemp, or wool, or synthetic fibers such as polyamide, polyester, polypropylene, or polyacrylonitrile. Polyesters are particularly suitable. Methods for treating textiles are known, for example, from WO 2008 / 151984, WO 2003 / 034823, U.S. Pat. No. 5,631,072, WO 2005 / 64072, WO 2006 / 128870, EP 1 724 392, WO 2005 113 886, or WO 2007 / 090739.

[0242] A further field of use for the compositions according to the invention is that of trunk injection / trunk treatment of all ornamental trees and all kinds of fruit and nut-bearing trees.

[0243] In the field of trunk injection / trunk treatment, the compounds according to the invention are particularly suitable against wood-boring insects of the above-mentioned orders Lepidoptera and Coleoptera, in particular the woodborers listed in Tables A and B below.

[0244] [Table 7]

[0245] [Table 8] TIFF2024531177000051.tif251147 TIFF2024531177000052.tif63154

[0246] The present invention may be used to control any insect pest that may be present in turfgrass, including, for example, beetles, caterpillars, fire ants, ground pearls, millipedes, pill bugs, mites, mole crickets, scale insects, mealybugs, mites, boxworms, southern chinch bugs, and grubs. The present invention may also be used to control insect pests in various stages of their life cycle, including eggs, larvae, nymphs, and adults.

[0247] In particular, the present invention relates to the treatment of grubs (Cyclocephala spp. (e.g., masked chafer, C. lurida), Rhizotrogus spp. (e.g., European chafer, R. majalis), Cotinus spp. (e.g., blue swallowtail, C. nitida), Popillia spp. (e.g., Japanese beetle, P. japonica), Phyllophaga spp. (e.g., May / June beetle), Ataenius spp., and the like). spp. (e.g., Black turfgrass ataenius, A. spretulus), Maladera spp. (e.g., red-veined scarab beetle, M. castanea) and Tomarus spp.), cotton bollworms (Margarodes spp.), mole crickets (tawny, southern and brachypterous; Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula The compounds may be used to control insect pests that feed on the roots of turfgrass, including Pseudomonas spp.

[0248] The present invention may also be used to control straw-dwelling insect pests of turfgrass, including cutworms (such as Spodoptera frugiperda and the common armyworm (Pseudaletia unipuncta)), cutworms, weevils (such as Sphenophorus spp., S. venatus verstitus, and S. parvulus) and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis).

[0249] The present invention may also be used to control insect pests that live on the ground and feed on turfgrass leaves, including the lesser stink bug (such as the southern kinkbag, Blissus insularis), bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug (Antonina graminis), two-lined spittlebug (Propsapia bicincta), leafhoppers, cutworms (Noctuidae), and greengrass aphids.

[0250] The present invention may also be used to control other pests of turfgrass, such as the red fire ant (Solenopsis invicta), which creates ant mounds in turfgrass.

[0251] In the hygiene field, the compositions according to the invention are effective against ectoparasites such as hard ticks, soft ticks, scabies mites, chiggers, flies (stable flies and licking flies), parasitic fly larvae, lice, pubic lice, biting lice and fleas.

[0252] Examples of such parasites are: Among the Anoplurida, the genera Haematopinus, Linognathus, Pediculus, Phtirus, and Solenopotes are included.

[0253] From the order Mallophagida, the genera Trimenopon, Menopon, Trinoton, Bovicola, Werneckiella, Lepikentron, Damalina, Trichodectes and Felicola.

[0254] Among the order Diptera and its suborders Nematocerina and Brachycerina, for example, the genera Aedes, Anopheles, Culex, Simulium, Eusimulium, Phlebotomus, Lutzomyia, Culicoides, Chrysops, Hybomitra, Atylotus, Tabanus, Haematopota, spp.), Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp.), sheep flies (Oestrus spp.), cow flies (Hypoderma spp.), bot flies (Gasterophilus spp.), hood flies (Hippobosca spp.), deer flies (Lipoptena spp.) and sheep hood flies (Melophagus spp.).

[0255] Among the Siphonapterida, for example, the human flea genus (Pulex spp.), the dog flea genus (Ctenocephalides spp.), the mouse flea genus (Xenopsylla spp.), and the long flea genus (Ceratophyllus spp.).

[0256] From the order Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp., and Panstrongylus spp.

[0257] From the order Blattaria, for example, the Asian cockroach (Blatta orientalis), the American cockroach (Periplaneta americana), the German cockroach (Blattela germanica) and the genus Supella.

[0258] Among the subclass Acaria (Acarida) and the suborder Metastigmata and Mesostigmata, for example, the genera Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp. spp.), Pneumonyssus spp., Sternostoma spp. and Varroa spp.

[0259] From the orders Actinedida (Prostigmata) and Acaridida (Astigmata), for example, the genera Acarapis, Cheyletiella, Ornithocheyletia, Myobia, Psorergates, Demodex, Trombicula, Listrophorus, Acarus, Tyrophagus, Caloglyphus, Hypodectes spp.), Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

[0260] The compositions according to the invention are also suitable for protecting against insect infestation in materials such as wood, textiles, plastics, adhesives, glues, paints, paper and cardboard, leather, floor coverings and building materials.

[0261] The compositions according to the invention can be used, for example, against the following pests: European house borer (Hylotrupes bajulus), Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, pine wood beetle (Ernobius mollis), longhorn beetle (Priobium carpini), flat-headed beetle (Lyctus brunneus), African flat-headed beetle (Lyctus africanus), American flat-headed beetle (Lyctus planicollis), oak flat-headed beetle (Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis, Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec.and Dinoderus minutus, as well as hymenopteran insects such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, and Urocerus augur, as well as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, and other insects of the genus Kalotermes. Termites such as Mastotermes darwiniensis, Zootermopsis nevadensis, and Coptotermes formosanus, as well as wood mites such as Lepisma saccharina.

[0262] Although the compounds of the present invention can be used as pesticides in their native form, they are generally formulated into compositions using formulation aids such as carriers, solvents, and surfactants in various ways. The formulations can be in various physical forms, such as dustable powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-based flowables, aqueous dispersions, oil-based dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (containing water or a water-miscible organic solvent as a carrier), impregnated polymer films, or other forms known from, for example, the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can be used directly or diluted before use. Dilution can be carried out, for example, with water, liquid fertilizers, trace elements, biological materials, oils, or solvents.

[0263] The formulations can be prepared by mixing the active ingredient with formulation aids to obtain a composition in the form of, for example, finely divided solids, granules, solutions, dispersions, or emulsions. The active ingredient can also be formulated with other adjuvants, such as finely divided solids, mineral oil, vegetable or animal oil, modified vegetable or animal oil, organic solvent, water, surfactant, or combinations thereof.

[0264] The active ingredient can also be contained in extremely fine microcapsules. Microcapsules contain the active ingredient in a porous carrier, allowing the active ingredient to be released into the environment in controlled amounts (e.g., sustained release). Microcapsules typically have diameters of 0.1 to 500 microns. They contain the active ingredient in an amount of about 25 to 95% by weight of the capsule. The active ingredient can be in the form of a bulk solid, fine particles in a solid or liquid dispersion, or a suitable solution. The encapsulating membrane can comprise, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymer, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane, or chemically modified polymers, and starch xanthate, or other polymers known to those skilled in the art. Alternatively, extremely fine microcapsules can be formed containing the active ingredient in the form of fine particles in a base solid matrix, but the microcapsules themselves are not encapsulated.

[0265] The formulation auxiliaries suitable for preparing the compositions according to the invention are known per se. Examples of liquid carriers include water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietic acid, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-Trichloroethane, 2-heptanone, α-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate Examples of suitable solvents include ethanol, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol and high molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, and N-methyl-2-pyrrolidone.

[0266] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, Kiesslager, limestone, calcium carbonate, bentonite, calcium montmorillonite, cotton hulls, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin, and similar materials.

[0267] Many surface-active substances can be used advantageously in both solid and liquid formulations, especially in formulations that can be diluted with a carrier before use. The surface-active substances can be anionic, cationic, nonionic, or polymeric, and they can be used as emulsifying agents, wetting agents, or suspending agents, or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates such as calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide adducts such as nonylphenol ethoxylate; alcohol / alkylene oxide adducts such as tridecyl alcohol ethoxylate; soaps such as sodium stearate; salts of alkylnaphthalenesulfonates such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinates such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters such as sorbitol oleate; quaternary amines such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkyl phosphate esters; and further substances described, for example, in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood, New Jersey (1981).

[0268] Additional adjuvants that may be used in the pest control formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, antifoaming agents, complexing agents, neutralizing or pH adjusting and buffering agents, corrosion inhibitors, fragrances, wetting agents, uptake enhancers, trace elements, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze agents, fungicides and liquid and solid fertilizers.

[0269] The compositions of the present invention may contain additives including vegetable or animal oils, mineral oils, alkyl esters of such oils, or mixtures of such oils and oil derivatives. The amount of oil additive in the compositions of the present invention is generally 0.01 to 10% based on the mixture to be applied. For example, the oil additive can be added to the spray tank at the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oils or vegetable oils such as rapeseed oil, olive oil, or sunflower oil, emulsified vegetable oils, alkyl esters of vegetable oils such as methyl derivatives, or animal oils such as fish oil or beef tallow. Preferred oil additives are C8 to C 22 Alkyl esters of fatty acids, especially C 12 ~C 18 Methyl derivatives of fatty acids, including, for example, the methyl esters of lauric acid, palmitic acid, and oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Many oil derivatives are listed in the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.

[0270] The compositions of the present invention generally comprise 0.1 to 99% by weight, especially 0.1 to 95% by weight, of the compounds of the present invention and 1 to 99.9% by weight of formulation aids, which preferably include 0 to 25% by weight of surfactants. Although commercial products may preferably be formulated as concentrates, end users will typically utilize diluted formulations.

[0271] The application rates vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pests to be controlled, the prevailing weather conditions and other factors which depend on the method, time of application and the target crop. As a general guideline, the compounds may be applied in amounts of 1 to 2000 l / ha, especially 10 to 1000 l / ha.

[0272] A preferred formulation may have the following composition (by weight): Emulsifiable concentrate: Active ingredient: 1-95%, preferably 60-90% Surface active agent: 1 to 30%, preferably 5 to 20% Liquid carrier: 1 to 80%, preferably 1 to 35%

[0273] Powder: Active ingredient: 0.1 to 10%, preferably 0.1 to 5% Solid carrier: 99.9 to 90%, preferably 99.9 to 99%

[0274] Suspension concentrate: Active ingredient: 5-75%, preferably 10-50% Water: 94-24%, preferably 88-30% Surface active agent: 1 to 40%, preferably 2 to 30%

[0275] Wettable powder: Active ingredient: 0.5 to 90%, preferably 1 to 80% Surface active agent: 0.5 to 20%, preferably 1 to 15% Solid carrier: 5 to 95%, preferably 15 to 90%

[0276] Granules: Active ingredient: 0.1 to 30%, preferably 0.1 to 15% Solid carrier: 99.5 to 70%, preferably 97 to 85%

[0277] The following examples further illustrate, but do not limit, the present invention.

[0278] [Table 9]

[0279] The complex is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to obtain a wettable powder that can be diluted with water to obtain a suspension of the desired concentration.

[0280] [Table 10]

[0281] The complex is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to obtain a powder that can be used directly as a seed treatment.

[0282] [Table 11]

[0283] Emulsions of any required dilution that can be used for plant protection are available from this concentrate by dilution with water.

[0284] [Table 12]

[0285] Ready-to-use dusts are obtained by mixing the complex with a carrier and grinding the mixture in a suitable mill. Such powders can also be used as dry seed dressings.

[0286] [Table 13]

[0287] The compound is mixed and ground with the adjuvant, the mixture is moistened with water, the mixture is extruded and then dried in a stream of air.

[0288] [Table 14]

[0289] In a mixer, the finely ground composite is applied uniformly to kaolin moistened with polyethylene glycol, resulting in coated, dust-free granules.

[0290] [Table 15]

[0291] The finely ground composite is thoroughly mixed with adjuvants to give a suspension concentrate which can be diluted with water to give a suspension of any desired dilution, and such dilutions can be used to treat and protect living plants and plant propagation material against microbial infestation by spraying, pouring or dipping.

[0292] [Table 16]

[0293] The finely ground composite is thoroughly mixed with adjuvants to give a suspension concentrate which can be diluted with water to give a suspension of any desired dilution, and such dilutions can be used to treat and protect living plants and plant propagation material against microbial infestation by spraying, pouring or dipping.

[0294] slow-release capsule suspension 28 parts of the composite are mixed with 2 parts aromatic solvent and 7 parts toluene diisocyanate / polymethylene-polyphenylisocyanate (8:1) mixture. This mixture is emulsified in a mixture of 1.2 parts polyvinyl alcohol, 0.05 parts defoamer, and 51.6 parts water until the desired particle size is achieved. A mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts water is added to this emulsion. The mixture is stirred until the polymerization reaction is complete. The resulting capsule suspension is stabilized by adding 0.25 parts thickener and 3 parts dispersant. The capsule suspension formulation contains 28% active ingredient. The diameter of the medium-sized capsules is 8 to 15 microns. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for this purpose.

[0295] Formulation types include emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water dispersible granules (WG), emulsifiable granules (EG), emulsions, water-in-oil (EO), emulsions, oil-in-water (EW), microemulsions (ME), oil dispersions (OD), oil-miscible flowables (OF), oil-miscible liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), technical concentrates (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG) or any technically preferred formulation in combination with agriculturally acceptable adjuvants. [Example]

[0296] Preparation example: "Mp" means melting point (°C). The free radical represents a methyl group. 1 H NMR measurements were recorded on a Brucker 400 MHz spectrometer and chemical shifts are given in ppm relative to a TMS standard. Spectra were run in deuterated solvents as specified. Compounds were characterized using one of the following LCMS methods. The unique LCMS values ​​obtained for each compound consist of the retention time ("Rt", reported in minutes) and the observed molecular ion (M+H). + or (M+H) - It was.

[0297] LCMS method: Method 1: Spectra were recorded on a Waters mass spectrometer (SQD single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative ion, 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: 110–800 Da) and a Waters H-class UPLC: quaternary pump, heated column compartment, and diode-array detector. Column: Acquity UPLC HSS T3 C18, 1.8 μm, 30 × 2.1 mm; Temperature: 40 °C; DAD wavelength range (nm): 200–400; Solvent gradient: A = water + 5% acetonitrile + 0.1% HC(O)OH, B = acetonitrile + 0.05% HC(O)OH; 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.

[0298] Method 2: Spectra were recorded on an Agilent Technologies mass spectrometer (6410 Triple Quadrupole Mass Spectrometer) equipped with an electrospray source (polarity: positive or negative ion, MS2 Scan, capillary: 4.00 kV, fragmentor: 100 V, desolvation temperature: 350 °C, gas flow: 11 L / min, nebulizer gas: 45 psi, mass range: 110–1000 Da) and an Agilent 1200 Series HPLC: 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): 210–400; Solvent gradient: A = water + 5% acetonitrile + 0.1% HC(O)OH, B = acetonitrile + 0.1% HC(O)OH; Gradient: 0 min 10% B, 90% A; 0.9–1.8 min 100% B; 1.8–2.2 min 100–10% B; 2.2–2.5 min 10% B; Flow rate (mL / min) 1.8.

[0299] Method 3: Spectra were recorded on a Waters mass spectrometer (Acquity QDa mass spectrometer) equipped with an electrospray source (polarity: anode and cathode switched), capillary: 0.8 kV, cone range: 25 V, extractor: V (no extractor voltage for the QDa detector), source temperature: 120 °C, desolvation temperature: 600 °C, cone gas flow: 50 L / h, desolvation gas flow: 1000 L / h, mass range: 110–850 Da) and a Waters Acquity UPLC: Quaternary solvent manager, heated column compartment, and diode-array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm; Temperature: 40 °C; PDA wavelength range (nm): 230–400; Solvent gradient: A = water + 0.1% formic acid:acetonitrile: 95:5 v / v; B = acetonitrile + 0.05% formic acid; Gradient: 0 min–1.0 min, 10% B–90% A; 1.0 min–4.50 min, 10% B–100% B; 4.51 min–5.30 min, 100% B, 0% A; 5.31 min–5.50 min, 100% B–10% B; 5.51 min–6.00 min, 10% B, 90% A; Flow rate (ml / min) 0.6.

[0300] Method 4: Spectra were recorded on an Agilent Technologies mass spectrometer (6410 Triple Quadrupole Mass Spectrometer) equipped with an electrospray source (polarity: positive or negative ion, MS2 Scan, capillary: 7.00 kV, fragmentor: 120 V, desolvation temperature: 350 °C, gas flow: 11 L / min, nebulizer gas: 40 psi, mass range: 110–1000 Da) and an Agilent 1200 Series HPLC: quaternary pump, heated column compartment, and diode-array detector. Column: KINETEX EVO C18, 2.6 μm, 50 × 4.6 mm; Temperature: 40 °C; Detector VWD wavelength: 254 nm; Solvent gradient: A = water + 5% acetonitrile + 0.1% HC(O)OH, B = acetonitrile + 0.1% HC(O)OH; Gradient: 0 min 10% B, 90% A; 0.9–1.8 min 100% B; 1.8–2.2 min 100–10% B; 2.2–2.5 min 10% B; Flow rate (mL / min) 1.8.

[0301] Example P1: Preparation of 6-[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P1) [ka] Step A1: Preparation of (2,2-difluoro-1,3-benzodioxol-5-yl)methanol (Intermediate I-1) [ka] To a solution of 2,2-difluoro-1,3-benzodioxole-5-carbaldehyde (CAS 656-42-8) (15 g, 76.56 mmol) in methanol (75 mL) cooled to 0° C., sodium borohydride (4.57 g, 114.84 mmol) was added slowly. The reaction mixture was stirred at room temperature overnight. After completion, the reaction mass was concentrated in vacuo, quenched with aqueous ammonium chloride solution, and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated in vacuo to give (2,2-difluoro-1,3-benzodioxol-5-yl)methanol as a colorless liquid. 1 H NMR(400MHz,CDCl3)δ ppm:1.91(br s,1H),4.69(br s,2H),7.03-7.09(m,2H),7.14(s,1H).

[0302] Step A2: Preparation of 6-chloro-2,2-difluoro-1,3-benzodioxole-5-carbaldehyde (Intermediate I-2) [ka] To a solution of (2,2-difluoro-1,3-benzodioxol-5-yl)methanol (intermediate I-1 prepared as above) (10 g, 50.49 mmol) in acetonitrile (60 mL) was added N-chlorosuccinimide (17.20 g, 126.24 mmol). The reaction mixture was stirred at room temperature overnight. After completion, the reaction mass was concentrated in vacuo, triturated with cyclohexane, filtered through a Buchner funnel, and the filtrate was concentrated in vacuo. The crude compound was purified by combiflash (silica gel, 0-30% ethyl acetate in cyclohexane) to give pure 6-chloro-2,2-difluoro-1,3-benzodioxole-5-carbaldehyde as a colorless liquid. 1 H NMR(400MHz,CDCl3)δ ppm:7.22(s,1H),7.66(s,1H),10.41(s,1H).

[0303] Step A3: Preparation of 2,2-difluoro-6-methyl-1,3-benzodioxole-5-carbaldehyde (Intermediate I-3) [ka] To a solution of 6-chloro-2,2-difluoro-1,3-benzodioxole-5-carbaldehyde (intermediate I-2, prepared as described above) (1 g, 4.30 mmol) in toluene (10 mL) was added methylboronic acid (1.14 g, 17.22 mmol) followed by a solution of potassium carbonate (1.78 g, 12.92 mmol) in water (3 mL) over 10 minutes while purging with nitrogen. 1,1'-Bis(diphenylphosphino)ferrocene-palladium(II) dichloride dichloromethane complex (0.18 g, 0.21 mmol) was added and the reaction mixture was heated at 90°C for 15 hours. The reaction mixture was cooled to room temperature and concentrated in vacuo. The reaction mass was diluted with water and extracted with ethyl acetate. The organic layer was washed with water followed by brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by combiflash (silica gel, 0-30% ethyl acetate in cyclohexane) to give 2,2-difluoro-6-methyl-1,3-benzodioxole-5-carbaldehyde as a brown oil. 1H NMR(400MHz,CDCl3)δ ppm:2.72(s,3H),6.99(s,1H),7.56(s,1H),10.27(s,1H).

[0304] Step A4: Preparation of 2,2-difluoro-6-methyl-1,3-benzodioxole-5-carboxylic acid (Intermediate I-4) [ka] To a solution of silver nitrate (0.57 g, 3.22 mmol) in water (6.8 mL) was added a solution of sodium hydroxide (0.33 g, 8.06 mmol) in water (6.8 mL) dropwise at room temperature. 2,2-Difluoro-6-methyl-1,3-benzodioxole-5-carbaldehyde (Intermediate I-3 prepared as described above) (0.34 g, 1.61 mmol) was added to the reaction mixture in portions over a period of 20 minutes. The reaction mixture was stirred at room temperature for 2 hours. After completion, the reaction mixture was filtered through Celite, and the filtrate was acidified with 2N aqueous hydrochloric acid. The solid formed was filtered, washed with cold water, and dried in vacuo to give 2,2-difluoro-6-methyl-1,3-benzodioxole-5-carboxylic acid as a white solid. LCMS (Method 2): Rt = 1.42 min, m / z = 215 (MH). - . 1 H NMR(400MHz,DMSO-d6)δ ppm:2.54(s,3H),7.41(s,1H),7.77(s,1H).

[0305] Step A5: Preparation of ethyl 2,2-difluoro-6-methyl-1,3-benzodioxole-5-carboxylate (Intermediate I-5) [ka] A solution of 2,2-difluoro-6-methyl-1,3-benzodioxole-5-carboxylic acid (intermediate I-4 prepared as above) (0.23 g, 1.01 mmol) in ethanol (10 mL) was stirred at room temperature for 15 minutes. To this reaction mass, sulfuric acid (0.02 mL, 0.40 mmol) was added dropwise (exotherm was observed). The reaction mixture was heated at 60° C. for 12 hours. After completion, the reaction mass was concentrated in vacuo, neutralized with aqueous sodium bicarbonate, and the product was extracted twice with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo to give ethyl 2,2-difluoro-6-methyl-1,3-benzodioxole-5-carboxylate. The crude product was used directly in the next step. 1 H NMR(400MHz,CDCl3)δ ppm:1.41(t,3H),2.64(s,3H),4.37(q,2H),6.97(s,1H),7.67(s,1H).

[0306] Step A6: Preparation of ethyl 6-(bromomethyl)-2,2-difluoro-1,3-benzodioxole-5-carboxylate (Intermediate I-6) [ka] To a solution of ethyl 2,2-difluoro-6-methyl-1,3-benzodioxole-5-carboxylate (intermediate I-5, prepared as described above) (0.25 g, 0.97 mmol) in benzotrifluoride (3 mL) was added N-bromosuccinimide (0.196 g, 1.06 mmol) and azobisisobutyronitrile (0.016 g, 0.097 mmol) at room temperature. The reaction mixture was heated at 90 °C for 3 h. The reaction mixture was cooled to room temperature and concentrated in vacuo. The crude product was purified by combiflash (silica gel, 0-30% ethyl acetate in cyclohexane) to give ethyl 6-(bromomethyl)-2,2-difluoro-1,3-benzodioxole-5-carboxylate as a gummy mass. 1H NMR(400MHz,CDCl3)δ ppm:1.39-1.47(m,3H),4.38-4.45(m,2H),4.97(s,2H),7.20(s,1H),7.71(s,1H).

[0307] Step B1: Preparation of ethyl 6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylate (Intermediate I-7) [ka] To a solution of 5-(trifluoromethyl)pyridin-2-amine (4.0 g, 25 mmol) in ethanol (40 mL) was added ethyl 3-bromo-2-oxo-propanoate (3.7 mL, 30 mmol) and sodium bicarbonate (4.1 g, 49 mmol) at room temperature. The reaction mass was heated at 85° C. for 4 hours. After completion, the reaction mass was added to ice-cold water and the solid formed was filtered through a Buchner funnel to give ethyl 6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylate. This material was used directly in the next step. LCMS (Method 2): Rt=1.35 min, m / z=259 (M+H). + .

[0308] Step B2: Preparation of ethyl 3-chloro-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylate (Intermediate I-8) [ka] To a solution of ethyl 6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylate (intermediate I-7 prepared as above) (8.5 g, 33 mmol) in N,N-dimethylformamide (85 mL) was added 1-chloropyrrolidine-2,5-dione (5.3 g, 40 mmol) at room temperature. The reaction mass was heated at 40° C. for 4 hours. After completion, the reaction mass was quenched with ice-cold water, and the solid formed was filtered through a Buchner funnel and dried in vacuo to give ethyl 3-chloro-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylate as a solid. LCMS (Method 2): Rt=1.45 min, m / z=293 (M+H). + .

[0309] Step B3: Preparation of ethyl 3-ethylsulfanyl-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylate (Intermediate I-9) [ka] To a solution of ethyl 3-chloro-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylate (intermediate I-8 prepared as above) (6.0 g, 21 mmol) in N,N-dimethylformamide (60 mL) cooled to 0 °C, sodiothioethane (2.1 g, 25 mmol) was added at room temperature. The reaction mass was stirred at room temperature for 5 hours. After completion, the reaction mass was added to ice-cold water, and the solid formed was filtered through a Buchner funnel and dried in vacuo to give ethyl 3-ethylsulfanyl-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylate. This material was used directly in the next step. LCMS (Method 2): Rt = 1.49 min, m / z = 319 (M+H). + .

[0310] Step B4: Preparation of ethyl 3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylate (Intermediate I-10) [ka] To a solution of ethyl 3-ethylsulfanyl-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylate (intermediate I-9, prepared as described above) (6.5 g, 20 mmol) in ethanol (65 mL) cooled to 0 °C, 3-chloroperbenzoic acid (11 g, 45 mmol, 70% by weight) was added. The reaction mixture was stirred at 0 °C for 4 h. The reaction mass was diluted with water (50 mL) and basified with 2 N aqueous sodium hydroxide solution. The aqueous phase was extracted with ethyl acetate (2 × 50 mL). The combined organic layers were washed with brine (20 mL), dried over sodium sulfate, and concentrated in vacuo. The crude product was purified by combiflash (silica gel, 30–40% ethyl acetate in cyclohexane) to give ethyl 3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylate. LCMS (method 2): Rt=1.43 min, m / z=351(M+H) + .

[0311] Step B5: Preparation of 3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylic acid (Intermediate I-11) [ka] To a solution of ethyl 3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylate (Intermediate I-10, prepared as above) (4.2 g, 12 mmol) in tetrahydrofuran (42 mL) was added a solution of lithium hydroxide monohydrate (1.00 g, 24 mmol) in water (17 mL) at 0-5 °C. The reaction mixture was stirred at room temperature for 4 h. The reaction mixture was acidified with 2 N aqueous hydrochloric acid, and the solid that formed was filtered through a Buchner funnel and dried in vacuo to give 3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylic acid. This material was used directly in the next step. LCMS (Method 2): Rt = 0.37 min, m / z = 323 (M+H). + . 1H NMR(400MHz,DMSO-d6)δ ppm:1.27(t,3H),3.77(q,2H),7.95(dd,1H),8.10(d,1H),9.34(s,1H).

[0312] Step B6: Preparation of tert-butyl N-[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]carbamate (Intermediate I-12) and 3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-amine (Intermediate I-13) [ka] To a solution of 3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridine-2-carboxylic acid (intermediate I-11 prepared as above) (4.1 g, 13 mmol) in tert-butanol (8.2 mL) was added triethylamine (2.1 g, 120 mmol) at room temperature, and the reaction mass was heated at 90 °C for 10 minutes. To this was then added diphenylphosphoryl azide (5.7 g, 20 mmol) dropwise over 15 minutes, and the reaction mixture was further stirred at 90 °C for 40 minutes. The reaction mass was cooled to room temperature and quenched with ice-cold water (100 mL) and brine (50 mL), and the product was extracted with ethyl acetate (3 × 100 mL). The combined organic layers were dried over sodium, filtered, and concentrated in vacuo. The crude products were purified by combiflash (silica gel, ethyl acetate in cyclohexane) to give pure tert-butyl N-[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]carbamate and 3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-amine, respectively.

[0313] tert-Butyl N-[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]carbamate (Intermediate I-12): LCMS (Method 2): Rt = 1.49 min, m / z = 392 (M−H) - . 1H NMR(400MHz,DMSO-d6)δ ppm:1.21-1.34(m,3H),1.48(s,9H),3.74(d,2H),7.85-7.94(m,2H),9.05(s,1H),9.60(s,1H).

[0314] 3-Ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-amine (Intermediate I-13): LCMS (Method 2): Rt = 1.22 min, m / z = 294 (M+H) + . 1 H NMR(400MHz,DMSO-d6)δ ppm:1.17(t,3H),3.42(q,2H),6.37(s,2H),7.56(d,1H),7.71(dd,1H),8.77(s,1H).

[0315] Step B7: Preparation of tert-butyl N-[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]carbamate (Intermediate I-12) [ka] To a solution of 3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-amine (Intermediate I-13, prepared as described above) (1 g, 3.23 mmol) in N,N-dimethylformamide (10 mL) cooled to 0 °C was added sodium hydride (0.310 g, 7.12 mmol), and the reaction mixture was stirred at 0 °C for 30 min. A solution of tert-butoxycarbonyl tert-butyl carbonate (0.94 mL, 3.88 mmol) in N,N-dimethylformamide (3 mL) was added at 0 °C, and the mixture was stirred at room temperature overnight. After completion, the reaction mixture was quenched with ice water, and the product was extracted with ethyl acetate (3 × 50 mL). The combined organic layers were washed with water and brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by combiflash (silica gel, 10-70% ethyl acetate in cyclohexane) to give tert-butyl N-[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]carbamate as a white solid. LCMS (Method 2): Rt=1.51 min, m / z=392 (M−H)−.

[0316] Step C-1: Preparation of ethyl 6-[[tert-butoxycarbonyl-[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylate (Intermediate I-14) [ka] To a solution of tert-butyl N-[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]carbamate (Intermediate I-12, prepared as described above) (0.3 g, 0.724 mmol) in acetonitrile (10 mL) was added ethyl 6-(bromomethyl)-2,2-difluoro-1,3-benzodioxole-5-carboxylate (Intermediate I-6, prepared as described above) (0.295 g, 0.869 mmol) and cesium carbonate (0.472 g, 1.44 mmol) at room temperature. The reaction mixture was heated at 50 °C for 3 hours, then diluted with water, and the product was extracted with ethyl acetate. The organic layer was washed twice with water, then with brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by combiflash (silica gel, 10-50% ethyl acetate in cyclohexane) to give ethyl 6-[[tert-butoxycarbonyl-[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylate as a gum. LCMS (Method 1): Rt = 1.34 min, m / z = 658.41 (M+Na)+.

[0317] Step C-2: Preparation of ethyl 6-[[[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylate (Intermediate I-15) [ka] A solution of ethyl 6-[[tert-butoxycarbonyl-[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylate (Intermediate I-14, prepared as described above) (0.431 g, 0.6442 mmol) in trifluoroacetic acid (3 mL, 38.6 mmol) was stirred at room temperature for 3 hours. After completion, the reaction mass was neutralized with aqueous sodium bicarbonate. The aqueous layer was extracted with ethyl acetate (twice), and the combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo to give ethyl 6-[[[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylate. The crude product was used directly in the next step. LCMS (Method 1): Rt=1.25 min, m / z=536(M+H)+.

[0318] Step C-3: Preparation of 6-[[[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylic acid (Intermediate I-16) [ka] To a solution of ethyl 6-[[[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylate (Intermediate I-15 prepared as above) (0.3 g, 0.532 mmol) in tetrahydrofuran (6 mL) was added a solution of lithium hydroxide monohydrate (0.094 g, 2.129 mmol) in water (2 mL) at 10 °C. The reaction mixture was stirred at room temperature for 12 hours. After completion, the reaction mass was concentrated in vacuo, acidified with 1N aqueous hydrochloric acid, and the product was extracted with ethyl acetate. The organic layer was washed with water (twice) followed by brine, dried over sodium sulfate, filtered, and concentrated in vacuo to give 6-[[[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylic acid. The crude product was used directly in the next step. LCMS (Method 1): Rt=1.13 min, m / z=508 (M+H)+.

[0319] Step C-4: Preparation of 6-[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P1) [ka] To a solution of 6-[[[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylic acid (intermediate I-16 prepared as above) (0.39 g, 0.7302 mmol) in pyridine (2 mL) cooled to 0 °C, phosphorus oxychloride (0.1375 mL, 1.460 mmol) was added. The mixture was allowed to reach room temperature and stirred under a nitrogen atmosphere for 2 hours. The reaction mass was acidified with 2 N aqueous hydrochloric acid (15 mL), and the product was extracted with ethyl acetate (2 × 30 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by combiflash (silica gel, 50% ethyl acetate in cyclohexane) to give 6-[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one as a white solid. LCMS (Method 1): Rt=1.13 min, m / z=490 (M+H)+. 1 H NMR(400MHz,CDCl3)δ ppm:1.55(t,3H),3.89(q,2H),5.10(s,2H),7.29(s,1H),7.62(s,1H),7.68(dd,1H),7.82(d,1H),9.27(s,1H).

[0320] Example P2: Preparation of 6-(3-ethylsulfonyl-2-quinolyl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P2) [ka] Step-1: Preparation of 3-ethylsulfanylquinoline (Intermediate I-17) [ka] To a solution of 3-bromoquinoline (5.2 g, 25 mmol) in toluene (52 mL) that had been degassed with nitrogen for 10 minutes, sodiothioethane (2.5 g, 30 mmol), N,N-diisopropylethylamine (15 mL, 87 mmol), tris(dibenzylideneacetone)dipalladium(0) (1.5 g, 1.6 mmol), and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (1.6 g, 2.7 mmol) were added. The reaction mixture was again degassed with nitrogen for an additional 5 minutes and then heated at 100°C for 3 hours and then at 80°C overnight. The reaction mass was quenched with water, and the product was extracted with ethyl acetate (twice). The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The crude compound was purified by combiflash (silica gel, 0-15% ethyl acetate in cyclohexane) to give 3-ethylsulfanylquinoline as an oil. LCMS (Method 1): Rt=1.03 min, m / z=190 (M+H). + .

[0321] Step-2: Preparation of 3-ethylsulfonyl-1-oxide-quinolin-1-ium (Intermediate I-18) [ka] To a solution of 3-ethylsulfanylquinoline (intermediate I-17 prepared as above) (2.8 g, 15 mmol) in dichloromethane (40 mL) was added 3-chloroperbenzoic acid (12 g, 47 mmol, 70% by weight), and the reaction mass was stirred at room temperature overnight. The reaction mass was diluted with water and then basified with saturated sodium bicarbonate solution. The aqueous phase was extracted with dichloromethane (3 x 50 mL), and the combined organic layers were washed with brine (30 mL), dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by combiflash (silica gel, 40% ethyl acetate in cyclohexane) to give 3-ethylsulfonyl-1-oxide-quinolin-1-ium. LCMS (Method 1): Rt = 0.55 min, m / z = 238 (M+H). + .

[0322] Step-3: Preparation of 2-chloro-3-ethylsulfonyl-quinoline (Intermediate I-19) [ka] To 3-ethylsulfonyl-1-oxide-quinolin-1-ium (intermediate I-18, prepared as above) (2.59 g, 10.93 mmol) cooled to 0 °C under a nitrogen atmosphere was added phosphoryl chloride (25.93 mL) dropwise. The reaction mixture was warmed to room temperature and stirred under a nitrogen atmosphere for 2 h. The reaction mixture was poured into ice-cold water, and the product was extracted with ethyl acetate (3 × 60 mL). The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by combiflash (silica gel, 0-40% ethyl acetate in cyclohexane) to give 2-chloro-3-ethylsulfonyl-quinoline. LCMS (Method 1): Rt = 1.01 min, m / z = 256 / 258 (M+H). + .

[0323] Step-4: Preparation of 3-ethylsulfonylquinolin-2-amine (Intermediate I-20) [ka] To a solution of 2-chloro-3-ethylsulfonyl-quinoline (intermediate I-19 prepared as above) (2 g, 7.82 mmol) in tetrahydrofuran (12 mL) in an Eyela vessel was added copper(II) sulfate (0.249 g, 1.56 mmol), copper (0.099 g, 1.56 mmol), and ammonium hydroxide (13.71 g, 117.3 mmol) at room temperature. The Eyela vessel was closed, and the mixture was stirred at 105 °C for 6 h. Upon completion, the apparatus was cooled to room temperature, and the pressure was carefully released. The reaction mass was diluted with water, and the product was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by combiflash (silica gel, 50% ethyl acetate in cyclohexane) to give 3-ethylsulfonylquinolin-2-amine as a solid. LCMS (method 2): Rt=0.48 min, m / z=237(M+H)+ .

[0324] Step-5: Preparation of tert-butyl N-(3-ethylsulfonyl-2-quinolyl)carbamate (Intermediate I-21) [ka] To a solution of 3-ethylsulfonylquinolin-2-amine (intermediate I-20 prepared as above) (1.20 g, 5.08 mmol) in N,N-dimethylformamide (20 mL) was added sodium hydride (0.467 g, 11.7 mmol, 60% by weight) at 0° C. After stirring for 30 minutes at 0° C., a solution of tert-butoxycarbonyl tert-butyl carbonate (1.33 g, 6.09 mmol) in N,N-dimethylformamide (0.5 mL) was added at 0° C. The reaction mixture was warmed to room temperature and stirred for 3 hours. Upon completion, the reaction mass was quenched with ice water, and the product was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by combiflash (silica gel, 40% ethyl acetate in cyclohexane) to give tert-butyl N-(3-ethylsulfonyl-2-quinolyl)carbamate as a pale yellow solid. LCMS (Method 1): Rt = 1.06 min, m / z = 281 [(M+H) + -56].

[0325] Step-6: Preparation of ethyl 6-[[tert-butoxycarbonyl-(3-ethylsulfonyl-2-quinolyl)amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylate (Intermediate I-22) [ka] To a solution of tert-butyl N-(3-ethylsulfonyl-2-quinolyl)carbamate (intermediate I-21 prepared as above) (0.450 g, 1.338 mmol) in acetonitrile (20 mL) was added ethyl 6-(bromomethyl)-2,2-difluoro-1,3-benzodioxole-5-carboxylate (intermediate I-6 prepared as above) (0.54 g, 1.67 mmol) and cesium carbonate (0.65 g, 2.00 mmol) under a nitrogen atmosphere. The mixture was heated at 50° C. for 3.5 hours. The reaction mass was diluted with water (50 mL), and the product was extracted with ethyl acetate (3×50 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo to give ethyl 6-[[tert-butoxycarbonyl-(3-ethylsulfonyl-2-quinolyl)amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylate as a gum. The crude product was used directly in the next step. LCMS (Method 1): Rt = 1.37 min, m / z = 479 [(M+H) + -100].

[0326] Step-7: Preparation of ethyl 6-[[(3-ethylsulfonyl-2-quinolyl)amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylate (Intermediate I-23) [ka] To a solution of ethyl 6-[[tert-butoxycarbonyl-(3-ethylsulfonyl-2-quinolyl)amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylate (intermediate I-22 prepared as above) (0.855 g, 1.48 mmol) in trifluoromethylbenzene (10 mL) was added trifluoroacetic acid (1.79 mL, 22.2 mmol) at 0 °C. The reaction mass was stirred at room temperature for 10 hours. After completion, the reaction mass was concentrated in vacuo, diluted with water (50 mL), and quenched with aqueous sodium bicarbonate (30 mL). The aqueous layer was extracted with ethyl acetate (2 × 50 mL), and the combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by combiflash (silica gel, 0-30% ethyl acetate in cyclohexane) to give ethyl 6-[[(3-ethylsulfonyl-2-quinolyl)amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylate as a white solid. LCMS (Method 1): Rt = 1.35 min, m / z = 479 (M+H). + .

[0327] Step-8: Preparation of 6-[[(3-ethylsulfonyl-2-quinolyl)amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylic acid (Intermediate I-24) [ka] To a solution of ethyl 6-[[(3-ethylsulfonyl-2-quinolyl)amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylate (Intermediate I-23 prepared as above) (0.49 g, 1.024 mmol) in tetrahydrofuran (10 mL) was added a solution of lithium hydroxide monohydrate (0.1809 g, 4.096 mmol) in water (3.5 mL) at room temperature. The reaction mixture was stirred overnight at room temperature. Additional lithium hydroxide monohydrate (0.042 g, 1.024 mmol) was added and stirring was continued for another 18 hours. After completion, the reaction mass was concentrated in vacuo, acidified with 1N aqueous hydrochloric acid, and the product was extracted with ethyl acetate (2 × 50 mL). The combined organic layers were washed with water (50 mL) followed by brine, dried over sodium sulfate, filtered, and concentrated in vacuo to give 6-[[(3-ethylsulfonyl-2-quinolyl)amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylic acid as an off-white solid. The crude product was used directly in the next step. LCMS (Method 1): Rt = 1.10 min, m / z = 451 (M+H). + .

[0328] Step-9: Preparation of 6-(3-ethylsulfonyl-2-quinolyl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P2) [ka] To a solution of 6-[[(3-ethylsulfonyl-2-quinolyl)amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylic acid (intermediate I-24 prepared as above) (0.40 g, 0.894 mmol) in pyridine (2 mL) at 0 °C, phosphorus oxychloride (0.168 mL, 1.79 mmol) was added. The reaction mixture was stirred at 0-10 °C for 40 min under a nitrogen atmosphere. The reaction mass was quenched with ice-cold water (60 mL), and the product was extracted with ethyl acetate (2 × 25 mL). The combined organic layers were washed with brine (30 mL), dried over sodium sulfate, filtered, and concentrated in vacuo. The crude compound was purified by combiflash (silica gel, 0-30% ethyl acetate in cyclohexane) to give 6-(3-ethylsulfonyl-2-quinolyl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one as a white solid. LCMS (Method 1): Rt=1.07 min, m / z=433 (M+H)+. 1 H NMR(400MHz,CDCl3)δ ppm:1.38(t,3H),3.55(q,2H),5.09(s,2H),7.25(s,1H),7.60(s,1H),7.78(td,1H),7.96(ddd,1H),8.09(d,1H),8.14(d,1H),9.02(s,1H).

[0329] Example P3: Preparation of 6-[3-ethylsulfonyl-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P3) [ka] Step-1: Preparation of tert-butyl 2-cyano-2-[5-(trifluoromethyl)-2-pyridyl]acetate (Intermediate I-25) [ka] To a stirred solution of 2-chloro-5-(trifluoromethyl)pyridine (10.0 g, 55.1 mmol) in dimethyl sulfoxide (50 mL) was added potassium carbonate (11.4 g, 82.6 mmol) followed by tert-butyl 2-cyanoacetate (9.33 g, 66.1 mmol) at room temperature. The reaction mass was stirred at 100° C. for 5 hours. After completion, the reaction mass was quenched with ice-cold water and stirred for 10 minutes. The precipitate that formed was filtered through a Buchner funnel, washed with n-pentane, and dried in vacuo to give tert-butyl 2-cyano-2-[5-(trifluoromethyl)-2-pyridyl]acetate as a yellow solid. LCMS (Method 1): Rt=1.09 min, m / z=285 (M−H). - .

[0330] Step-2: Preparation of 2-[5-(trifluoromethyl)-2-pyridyl]acetonitrile (Intermediate I-26) [ka] To a stirred solution of tert-butyl 2-cyano-2-[5-(trifluoromethyl)-2-pyridyl]acetate (intermediate I-25 prepared as above) (10.00 g, 34.94 mmol) in acetonitrile (100 mL) was added 4-methyl-benzenesulfonic acid (3.04 g, 17.47 mmol) at room temperature. The reaction mass was stirred at 87 °C for 1 h. The mixture was quenched with ice-cold water (100 mL) and the product was extracted with ethyl acetate (2 x 100 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The crude compound was purified by combiflash (silica gel, 20% ethyl acetate in cyclohexane) to give 2-[5-(trifluoromethyl)-2-pyridyl]acetonitrile as yellow crystals. LCMS (Method 1): Rt = 1.00 min, m / z = 187 (M+H). + .

[0331] Step-3: Preparation of 2-[1-amino-5-(trifluoromethyl)pyridin-1-ium-2-yl]acetonitrile; 2,4,6-trimethylbenzenesulfonate (Intermediate I-27) [ka] To a solution of ethyl N-(mesitylsulfonyl)oxyacetimidate (5.0 g, 17.52 mmol) in 1,4-dioxane (15 mL) at 0 °C, perchloric acid (2.147 mL, 21.34 mmol) was added dropwise, and the reaction mixture was stirred at 0 °C for 30 minutes. Ice-cold water was added to the reaction mass, which was then extracted with dichloromethane (2 × 25 mL). The combined organic layers were dried over sodium sulfate and filtered to give a solution of amino 2,4,6-trimethylbenzenesulfonate (I-27a). To a solution of this freshly prepared amino 2,4,6-trimethylbenzenesulfonate (I-27a) in dichloromethane (50 mL), 2-[5-(trifluoromethyl)-2-pyridyl]acetonitrile (intermediate I-26 prepared as above) (2.17 g, 11.66 mmol) was added dropwise at room temperature. The reaction mass was stirred at room temperature for 16 hours. After completion, the mixture was used directly in the next step as a solution of 2-[1-amino-5-(trifluoromethyl)pyridin-1-ium-2-yl]acetonitrile; 2,4,6-trimethylbenzenesulfonate in dichloromethane. LCMS (Method 1): Rt=0.99 min, m / z=202 (M). + .

[0332] Step-4: Preparation of 6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-amine (Intermediate I-28) [ka] To a stirred solution of 2-[1-amino-5-(trifluoromethyl)pyridin-1-ium-2-yl]acetonitrile; 2,4,6-trimethylbenzenesulfonate (intermediate I-27 prepared as above) (7 g, 17.44 mmol) in dichloromethane (50 mL) was added methanol (35 mL) and potassium carbonate (4.820 g, 34.88 mmol) at room temperature. The reaction mass was stirred at room temperature for 4 hours, then quenched with ice-cold water, and the organic layer was separated. The aqueous layer was extracted with ethyl acetate (2 × 80 mL), and the combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. The crude compound was purified by combiflash (silica gel, 0–30% ethyl acetate in cyclohexane) to give 6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-amine as a solid. LCMS (method 1): Rt=0.97 min, m / z=202(M+H) + .

[0333] Step-5: Preparation of N-[6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]acetamide (Intermediate I-29) [ka] To a solution of 6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-amine (intermediate I-28, prepared as above) (2.58 g, 12.83 mmol) in pyridine (25 mL) at 0 °C, acetyl chloride (1.86 mL, 25.65 mmol) was added dropwise, and the reaction mixture was stirred at 0-10 °C for 1 h under a nitrogen atmosphere. The reaction mass was diluted with water and ethyl acetate, and the organic layer was then separated. The aqueous layer was extracted with ethyl acetate (2 × 50 mL), and the combined organic layers were washed with water, dried over sodium sulfate, filtered, and concentrated in vacuo. The crude compound was purified by combiflash (silica gel, 0-40% ethyl acetate in cyclohexane) to give N-[6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]acetamide. LCMS (Method 1): Rt = 0.99 min, m / z = 244 (M+H). + .

[0334] Step-6: Preparation of N-[3-iodo-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]acetamide (Intermediate I-30) [ka] To a solution of N-[6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]acetamide (Intermediate I-29 prepared as above) (2.63 g, 10.83 mmol) in acetonitrile (26.3 mL) was added 1-iodopyrrolidine-2,5-dione (2.92 g, 12.99 mmol) in several portions, and the reaction mass was stirred at room temperature for 1.5 hours. After completion, the reaction mass was diluted with water, and the product was extracted with ethyl acetate (twice). The combined organic layers were washed with sodium thiosulfate solution, followed by brine, dried over sodium sulfate, filtered, and concentrated in vacuo to give N-[3-iodo-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]acetamide as a solid. The crude product was used directly in the next step. LCMS (Method 1): Rt = 1.01 min, m / z = 370 (M+H). + .

[0335] Step-7: Preparation of tert-butyl N-acetyl-N-[3-iodo-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]carbamate (Intermediate I-31) [ka] To a solution of N-[3-iodo-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]acetamide (intermediate I-30 prepared as above) (3.77 g, 10.23 mmol) in acetonitrile (35 mL) at 0 °C, 4-dimethylaminopyridine (0.127 g, 1.02 mmol) was added, followed by di-tert-butyl dicarbonate (2.76 g, 12.27 mmol). The mixture was stirred at room temperature for 2 hours. The reaction mass was concentrated in vacuo, quenched with ice-cold water, and the product was extracted with ethyl acetate (3 × 50 mL). The combined organic layers were washed with saturated bicarbonate solution, dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by combiflash (silica gel, 0-30% ethyl acetate in cyclohexane) to give tert-butyl N-acetyl-N-[3-iodo-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]carbamate as a yellow solid. LCMS (Method 1): Rt = 1.21 min, m / z = 370 [(M+H) + -100].

[0336] Step-8: Preparation of tert-butyl N-[3-ethylsulfanyl-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]carbamate (Intermediate I-32) [ka] To a solution of tert-butyl N-acetyl-N-[3-iodo-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]carbamate (intermediate I-31 prepared as above) (4.41 g, 9.40 mmol) in anhydrous 1,4-dioxane (40 mL) was added N-ethyl-N-isopropyl-propan-2-amine (4.18 mL, 24.44 mmol) and (5-diphenyl-phosphanyl-9,9-dimethyl-xanthen-4-yl)-diphenyl-phosphane (0.435 g, 0.752 mmol) at room temperature over 5 minutes while purging with nitrogen. Tris(dibenzylideneacetone)dipalladium(0) (0.602 g, 0.658 mmol) was added, and the solution was degassed with nitrogen for an additional 5 minutes. Sodiothioethane (1.63 g, 18.80 mmol) was then added under a nitrogen atmosphere, and the reaction mixture was stirred at 105 °C for 5 hours. The reaction mass was diluted with ethyl acetate, filtered through Celite, and the residue was washed with ethyl acetate. The filtrate was washed with water, followed by brine, and the organic layer was separated. The aqueous layer was extracted with ethyl acetate, and the combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. The crude compound was purified by combiflash (silica gel, 0-20% ethyl acetate in cyclohexane) to give tert-butyl N-[3-ethylsulfanyl-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]carbamate as a gum. LCMS (Method 1): Rt = 1.23 min, m / z = 306 [(M+H) + -56].

[0337] Step-9: Preparation of tert-butyl N-[3-ethylsulfonyl-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]carbamate (Intermediate I-33) [ka] To a solution of tert-butyl N-[3-ethylsulfanyl-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]carbamate (intermediate I-32 prepared as above) (3.21 g, 8.88 mmol) in acetonitrile (30 mL) at 0 °C was added 3-chloroperbenzoic acid (4.82 g, 19.5 mmol, 70% by weight). The mixture was stirred at 0-10 °C for 1.5 h. The reaction mass was concentrated in vacuo (the water bath temperature was maintained below 25 °C). The residue was diluted with water (60 mL) and basified with 2 N aqueous sodium hydroxide solution. The aqueous phase was extracted with ethyl acetate (2 × 50 mL), and the combined organic layers were washed with brine (60 mL), dried over sodium sulfate, and concentrated in vacuo. The crude compound was purified by combiflash (silica gel, 0-30% ethyl acetate in cyclohexane) to give tert-butyl N-[3-ethylsulfonyl-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl] as an off-white solid. The crude product was used directly in the next step. LCMS (Method 1): Rt = 1.14 min, m / z = 338 [(M+H) + -56].

[0338] Step-10: Preparation of ethyl 6-[[tert-butoxycarbonyl-[3-ethylsulfonyl-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylate (Intermediate I-34) [ka] To a solution of tert-butyl N-[3-ethylsulfonyl-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]carbamate (Intermediate I-33, prepared as described above) (0.60 g, 1.52 mmol) in acetonitrile (10 mL) was added cesium carbonate (0.746 g, 2.28 mmol) and ethyl 6-(bromomethyl)-2,2-difluoro-1,3-benzodioxole-5-carboxylate (Intermediate I-6, prepared as described above) (0.616 g, 1.90 mmol) at room temperature. The mixture was heated at 50 °C for 3.5 h, then quenched with ice-cold water (30 mL), and the product was extracted with ethyl acetate (3 × 50 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo to give ethyl 6-[[tert-butoxycarbonyl-[3-ethylsulfonyl-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylate as a gum. LCMS (Method 2): Rt = 1.66 min, m / z = 536 [(M+H) + -100].

[0339] Step-11: Preparation of ethyl 6-[[[3-ethylsulfonyl-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylate (Intermediate I-35) [ka] To a solution of ethyl 6-[[tert-butoxycarbonyl-[3-ethylsulfonyl-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylate (Intermediate I-34 prepared as above) (1.22 g, 1.92 mmol) in trifluoromethylbenzene (10 mL) at 0 °C, trifluoroacetic acid (2.32 mL, 28.8 mmol) was added, and the mixture was stirred at room temperature for 12 hours. The reaction mass was concentrated in vacuo, diluted with water (50 mL), and neutralized with aqueous sodium bicarbonate (20 mL). The aqueous layer was extracted with ethyl acetate (2 × 50 mL), and the combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by combiflash (silica gel, 0-30% ethyl acetate in cyclohexane) to give ethyl 6-[[[3-ethylsulfonyl-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylate as a gum. LCMS (Method 1): Rt=1.22 min, m / z=536 (M+H)+.

[0340] Step-12: Preparation of 6-[[[3-ethylsulfonyl-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylic acid (Intermediate I-36) [ka] To a solution of ethyl 6-[[[3-ethylsulfonyl-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylate (Intermediate I-35, prepared as described above) (0.751 g, 1.403 mmol) in tetrahydrofuran (10 mL) was added a solution of lithium hydroxide monohydrate (0.123 g, 2.80 mmol) in water (3.5 mL) at room temperature overnight. Additional lithium hydroxide monohydrate (0.123 g, 2.80 mmol) was added and stirring was continued at room temperature for another 6 hours. After completion, the reaction mass was concentrated in vacuo, acidified with 1N aqueous hydrochloric acid, and the product was extracted with ethyl acetate (2 × 30 mL). The combined organic layers were washed with water (20 mL), followed by brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by combiflash (silica gel, 80% ethyl acetate in cyclohexane) to give 6-[[[3-ethylsulfonyl-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylic acid. LCMS (Method 1): Rt = 1.10 min, m / z = 508 (M+H). + .

[0341] Step-13: Preparation of 6-[3-ethylsulfonyl-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P3) [ka] To a solution of 6-[[[3-ethylsulfonyl-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]amino]methyl]-2,2-difluoro-1,3-benzodioxole-5-carboxylic acid (intermediate I-36 prepared as above) (0.332 g, 0.654 mmol) in pyridine (1.66 mL) at 0 °C, phosphorus oxychloride (0.12 mL, 1.309 mmol) was added, and the reaction mass was stirred at 0-10 °C for 25 min under a nitrogen atmosphere. The mixture was quenched with ice-cold water (60 mL), and the product was extracted with ethyl acetate (3 × 25 mL). The combined organic layers were washed with brine (30 mL), dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by combiflash (silica gel, 0-30% ethyl acetate in cyclohexane) to give 6-[3-ethylsulfonyl-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one as an off-white solid. LCMS (Method 1): Rt=1.23 min, m / z=490 (M+H)+. 1 H NMR(400MHz,CDCl3)δ ppm:1.43(t,3H),3.66(q,2H),5.01(s,2H),7.24(s,1H),7.61(s,1H),7.65(dd,1H),8.24(d,1H),8.83(s,1H).

[0342] [Table 17] TIFF2024531177000104.tif250164 TIFF2024531177000105.tif92163

[0343] The activity of the compositions according to the invention can be considerably broadened and adapted to epidemic situations by adding other insecticidally, acaricidally and / or fungicidal active ingredients. Mixtures of compounds of formula I with other insecticidally, acaricidally and / or fungicidal active ingredients can also have further unexpected advantages, which can be described in a broader sense as synergistic activity, such as better plant resistance, lower herbicidal activity, the ability to control insects at different stages of development, or better behavior during their preparation, for example during grinding or mixing, during their storage, or during their use.

[0344] Suitable additives for the active ingredients here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, urea, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylurea, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.

[0345] The following mixtures of compounds of formula I with active ingredients are preferred (the abbreviation "TX" means "one compound selected from the group consisting of the compounds listed in Tables A-1 to A-3, B-1 to B-3, C-1 to C-3, D-1 to D-3, E-1 to E-3, F-1 to F-3 and Table P of the present invention"): An adjuvant selected from the group of substances consisting of petroleum (alternative name) (628) + TX; Abamectin +TX, Acequinocyl +TX, Acetamiprid +TX, Acetoprole +TX, Acrinathrin +TX, Acinonapyr +TX, Afidopiropen +TX, Afoxolaner +TX, Alanycarb +TX, Allethrin +TX, α-Cypermethrin +TX, Alphamethrin +TX, Amidoflumet +TX, Aminocarb +TX, Azocyclotine +TX, Bensultap +TX, Benzoximate +TX, Benzpyrimoxane + TX, beta-cyfluthrin + TX, beta-cypermethrin + TX, bifenazate + TX, bifenthrin + TX, binapacryl + TX, bioallethrin + TX, S bioallethrin + TX, bioresmethrin + TX, bistrifluron + TX, brofuranilide + TX, brofluthrinate + TX, bromophos-ethyl + TX, buprofezin + TX, butocarboxim + TX, cadusafos + TX, carbaryl + TX, carbosulfan + TX, Kartap+TX, CAS number: 1632218-00-8+TX, CAS number: 1808115-49-2+TX, CAS number: 2032403-97-5+ TX, CAS number:2044701-44-0+TX, CAS number:2128706-05-6+TX, CAS number:2095470-94-1+TX, CAS number:2 377084-09-6+TX, CAS number: 1445683-71-5+TX, CAS number: 2408220-94-8+TX, CAS number: 2408220-91- 5+TX, CAS number: 1365070-72-9+TX, CAS number: 2171099-09-3+TX, CAS number: 2396747-83-2+TX, CAS number :2133042-31-4+TX, CAS number:2133042-44-9+TX, CAS number:1445684-82-1+TX, CAS number:1445684- 82-1+TX, CAS number:1922957-45-6+TX, CAS number:1922957-46-7+TX, CAS number:1922957-47-8+TX, CA S number: 1922957-48-9+TX, CAS number: 2415706-16-8+TX, CAS number: 1594624-87-9+TX, CAS number: 159463 7-65-6+TX, CAS number: 1594626-19-3+TX, CAS number: 1990457-52-7+TX, CAS number: 1990457-55-0+TX,CAS No.: 1990457-57-2+TX, CAS No.: 1990457-77-6+TX, CAS No.: 1990457-66-3+TX, CAS No.: 1990457-85-6+TX, CAS No.: 2220132-55-6+TX, CAS No.: 1255091-74-7+TX, CAS No.: RNA (Colorado potato beetle (Leptinotarsa decemLineata)-specific recombinant double-stranded interference (GS2) + TX, CAS No.: 2719848-60-7 + TX, CAS No.: 1956329-03-5 + TX, chlorantraniliprole + TX, chlordane + TX, chlorfenapyr + TX, chlorprallethrin + TX, chromafenozide + TX, clenpirin + TX, cloetocarb + TX, clothianidin + TX, 2-chlorophenyl N-methylcarbamate (CPMC) + TX, cyanofenphos +TX, cyantraniliprole +TX, cyclaniliprole +TX, cyclobutrifluram +TX, cycloprothrin +TX, cycloxapride +TX, cyenopyrafen +TX, cetopyrafen (or ethopyrafen) +TX, cyflumetofen +TX, cyfluthrin +TX, cyhalodiamide +TX, cyhalothrin +TX, cypermethrin +TX, cyphenothrin +TX, cyprofanilide +TX, cyromazine +TX, deltamethrin +TX, diafenthin Uron + TX, Dialifos + TX, Dibrom + TX, Dichloromezothiaz + TX, Diflobidazin + TX, Diflubenzuron + TX, Dinpropylidaz + TX, Dinactin + TX, Dinocap + TX, Dinotefuran + TX, Dioxabenzophos + TX, Emamectin (or Emamectin benzoate) + TX, Empenthrin + TX, Epsilon-Monfluorothrin + TX, Epsilon-Metofluthrin + TX, Esfenvalerate + TX, Ethion + TX, Ethion Tiprole +TX, Etofenprox +TX, Etoxazole +TX, Famflur +TX, Fenazaquin +TX, Fenfluthrin +TX, Fenmezodithiaz +TX, Fenitrothion +TX, Fenobucarb +TX, Fenothiocarb +TX, Fenoxycarb +TX, Fenpropathrin +TX, Fenpyroximate +TX, Fensulfothion +TX, Fenthion +TX, Fentin acetate +TX, Fenvalerate +TX, Fipronil +TX,flometoquine +TX, flonicamid +TX, fluacrypyrim +TX, fluazaindolizine +TX, fluazuron +TX, flubendiamide +TX, flubenzoimine +TX, fluchlordiniliprole +TX, flucythrinate +TX, flucycloxuron +TX, flucythrinate +TX, fluensulfone +TX, flufenerim +TX, flufenprox +TX, flufiprole +TX, fluhexafon +TX, flumethrin +TX, fluopyram +TX, flupentiofenox +TX, flupyradifuron +TX, flupirimine +TX, fluralaner +TX, fluvalinate +TX, fluxamethamide +T X, fosthiazate + TX, gamma-cyhalothrin + TX, guadipyr + TX, halofenozide + TX, halfenprox + TX, heptafluthrin + TX, hexythiazox + TX, hydramethylnon + TX, imicyafos + TX, imidacloprid + TX, imiprothrin + TX, indazapiroxameth + TX, indoxacarb + TX, iodomethane + TX, iprodione + TX, isocycloceram + TX, isothioate + TX, ivermectin + TX, kappa-bifenthrin + TX, kappa-tefluthrin + TX, lambda-cyhalothrin + TX, lepimectin + TX, lotilaner + TX, lufenuron + TX, Metaflumizone +TX, metaldehyde +TX, metam +TX, methomyl +TX, methoxyfenozide +TX, metofluthrin +TX, metolcarb +TX, mexacarbate +TX, milbemectin +TX, momfluorotrin +TX, niclosamide +TX, nicofluprole +TX, nitenpyram +TX, nithiazine +TX, omethoate +TX, oxamyl +TX, oxazosulfil +TX, parathion ethyl +TX, permethrin +TX, fenothrin +TX, phosphocarb +TX, piperonyl butoxide +TX, pirimicarb +TX, pirimi Phosphol-ethyl + TX, Pirimiphos-methyl + TX, Polyhedrovirus + TX, Prallethrin + TX, Profenofos + TX, Profluthrin + TX, Propargite + TX, Propetamphos + TX, Propoxur + TX, Prothiofos + TX, Protrifenbut + TX, Piflubumid + TX, Pymetrozine + TX, Pyraclofos + TX, Pyrafluprole + TX, Pyridaben + TX, Pyridalyl + TX, Pyrifluquinazon + TX, Pyrimidifen + TX, Pyriminostrobin + TX, Pyriprole + TX, Pyriproxyfen + TX, Resmethrin + TX, sarolaner + TX, selamectin + TX, silafluofen + TX, spinetoram + TX, spinosad + TX, spirobudifen + TX, spirodiclofen + TX, spiromesifen + TX, spiropydione + TX, spirotetramat + TX, spidoxamat + TX, sulfoxaflor + TX, tebufenozide + TX, tebufenpyrad + TX, tebupirimifos + TX, tefluthrin + TX, temephos + TX, tetrachlorantraniliprole + TX, tetradifon + TX, tetramethrin + TX, tetramethylfluthrin + TX, tetra Nactin + TX, tetraniliprole + TX, theta-cypermethrin + TX, thiacloprid + TX, thiamethoxam + TX, thiocyclam + TX, thiodicarb + TX, thiofanox + TX, thiometon + TX, thiosultap + TX, tigoraner + TX, thioantraniliprole + TX, thioxazaphen + TX, tolfenpyrad + TX, toxaphene + TX, tralomethrin + TX, transfluthrin + TX, triazamate + TX, triazophos + TX, trichlorfon + TX, trichloronate + TX, trichlorfon + TX,Trifluenfronate +TX, Triflumezopyrim +TX, Cyclopyrazoflor +TX, Zeta-cypermethrin +TX, Seaweed extract and fermentation product from Melasse +TX, Seaweed extract and fermentation product from Melasse containing urea +TX, Amino acids +TX, Potassium and molybdenum and EDTA-chelated manganese +TX, Seaweed extract and fermented plant product +TX, Seaweed extract and fermented plant product containing plant hormones +TX, Vitamins +TX, EDTA-chelated copper +TX, Zinc +TX, and Iron +TX, Azadirachtin +TX, Bacillus aizawai +TX, Bacillus chitinosporus AQ746 (NRRL Accession Number B-21618) +TX, Bacillus firmus +TX, Bacillus kurstaki kurstaki + TX, Bacillus mycoides AQ726 (NRRL accession number B-21664) + TX, Bacillus pumilus (NRRL accession number B-30087) + TX, Bacillus pumilus AQ717 (NRRL accession number B-21662) + TX, Bacillus sp. AQ178 (ATCC accession number 53522) + TX, Bacillus sp. AQ175 (ATCC accession number 55608) + TX, Bacillus sp. AQ177 (ATCC accession number 55609) + TX, Bacillus subtilis subtilis unspecified + TX, Bacillus subtilis AQ153 (ATCC accession number 55614) + TX, Bacillus subtilis AQ30002 (NRRL accession number B-50421) + TX, Bacillus subtilis AQ30004 (NRRL accession number B-50455) + TX, Bacillus subtilis AQ713 (NRRL accession number B-21661) + TX, Bacillus subtilis AQ743 (NRRL accession number B-21665) + TX,Bacillus thuringiensis AQ52 (NRRL accession number B-21619) + TX, Bacillus thuringiensis BD#32 (NRRL accession number B-21530) + TX, Bacillus thuringiensis subspec. kurstaki BMP123 + TX, Beauveria bassiana + TX, D-limonene + TX, granulovirus + TX, harpin + TX, Helicoverpa armigera nucleopolyhedrovirus + TX, Helicoverpa zea nucleopolyhedrovirus + TX, Heliothis virescens nucleopolyhedrovirus + TX, Heliothis punctigera punctigera nucleopolyhedrovirus +TX, Metarhizium spp. +TX, Muscodor albus 620 (NRRL accession number 30547) +TX, Muscodor roseus A3-5 (NRRL accession number 30548) +TX, Neem tree lineage product +TX, Paecilomyces fumosoroseus +TX, Paecilomyces lilacinus +TX, Pasteuria nishizawae +TX, Pasteuria penetrans +TX, Pasteuria ramosa +TX, Pasteuria sorneyi thornei) + TX, Pasteuria usgae + TX, P-cymene + TX, Plutella xylostella granulosis virus + TX, Plutella xylostella nucleopolyhedrovirus + TX, polyhedrovirus + TX, pyrethrum + TX, QRD420 (terpenoid blend) + TX, QRD452 (terpenoid blend) + TX,QRD460 (terpenoid blend) + TX, Quillaja saponaria + TX, Rhodococcus globerulus AQ719 (NRRL accession number B-21663) + TX, Spodoptera frugiperda nucleopolyhedrovirus + TX, Streptomyces galbus (NRRL accession number 30232) + TX, Streptomyces sp. (NRRL accession number B-30145) + TX, terpenoid blend + TX, and Verticillium spp. + TX; an algicide selected from the group of substances consisting of bethoxadin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, sibutrin [CCN] + TX, dichloron (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamide (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX; an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomate (1011) + TX, cyclobutrifluram + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX; an avian repellent selected from the group of substances consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX; 1-Hydroxy-1H-pyridine-2-thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodisin (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargafen (alternative name) [CCN] + T a fungicide selected from the group of substances consisting of X, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX, and thiomersal (alternative name) [CCN] + TX; Adoxophyes orana GV (alternate name) (12) + TX, Agrobacterium radiobacter (alternate name) (13) + TX, Amblyseius spp. (alternate name) (19) + TX, Anagrapha falcifera NPV (alternate name) (28) + TX, Anagrus atomus (alternate name) (29) + TX, Aphelinus abdominalis (alternate name) (33) + TX, Aphidius colemani (alternate name) (34) + TX, Aphidoletes aphidimyza (alternate name) (35) + TX, Autographa californica californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (48) + TX, Bacillus sphaericus Neide (scientific name) (49) + TX, Bacillus thuringiensis Berliner (scientific name) (51) + TX, Bacillus thuringiensis subsp. aizawai (scientific name) (51) + TX, Bacillus thuringiensis subsp. israelensis (scientific name) (51) + TX, Bacillus thuringiensis subsp. japonensis subsp. japonensis) (scientific name) (51) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51) + TX, Bacillus thuringiensis subsp. tenebrionis (Bacillus thuringiensis subsp.tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alternate name) (53) + TX, Beauveria brongniartii (alternate name) (54) + TX, Chrysoperla carnea (alternate name) (151) + TX, Cryptolaemus montrouzieri (red ladybird beetle) (alternate name) (178) + TX, Cydia pomonella GV (alternate name) (191) + TX, Dacnusa sibirica (alternate name) (212) + TX, Diglyphus isaea (alternate name) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus (alternate name) (300) + TX, Helicoverpa zea NPV (alternate name) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alternate name) (433) + TX, Hippodamia convergens (alternate name) (442) + TX, Leptomastix dactylopii (alternate name) (488) + TX, Macrolophus caliginosus (alternate name) (491) + TX, Mamestra brassicae brassicae NPV (alternate name) (494) + TX, Metaphycus helvolus (alternate name) (522) + TX, Metarhizium anisopliae var. acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. leconti (N.lecontei NPV (alternate name) (575) + TX, Orius spp. (alternate name) (596) + TX, Paecilomyces fumosoroseus (alternate name) (613) + TX, Phytoseiulus persimilis (alternate name) (644) + TX, Spodoptera exigua multicapsid nucleopolyhedrovirus (scientific name) (741) + TX, Steinernema bibionis (alternate name) (742) + TX, Steinernema carpocapsae (alternate name) (742) + TX, Steinernema felziae feltiae (alternate name) (742) + TX, Steinernema glaseri (alternate name) (742) + TX, Steinernema riobrave (alternate name) (742) + TX, Steinernema riobravis (alternate name) (742) + TX, Steinernema scapterisci (alternate name) (742) + TX, Steinernema spp. (alternate name) (742) + TX, Trichogramma spp. (alternate name) (826) + TX, Typhlodromus occidentalis a biological agent selected from the group of substances consisting of Verticillium lecanii (alternative name) (848) + TX; a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX; chemical disinfectants selected from the group of substances consisting of Apholate [CCN] + TX, Visadyl (alternative name) [CCN] + TX, Busulfan (alternative name) [CCN] + TX, Diflubenzuron (250) + TX, Dimatif (alternative name) [CCN] + TX, Hemel [CCN] + TX, Hempa [CCN] + TX, Metepa [CCN] + TX, Methiotepa [CCN] + TX, Methyl Apholate [CCN] + TX, Morzide [CCN] + TX, Penfluron (alternative name) [CCN] + TX, Tepa [CCN] + TX, Thiohempa (alternative name) [CCN] + TX, Thiotepa (alternative name) [CCN] + TX, Tretamine (alternative name) [CCN] and Uredepa (alternative name) [CCN] + TX; (E)-Deca-5-en-1-yl acetate and (E)-dec-5-en-1-ol (IUPAC name) (222) + TX, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, (E,Z)-tetradec-4,1 0-Dien-1-yl acetate (IUPAC name) (779) + TX, (Z)-Dodec-7-en-1-yl acetate (IUPAC name) (285) + TX, (Z)-Hexadec-11-enal (IUPAC name) (436) + TX, (Z)-Hexadec-11-en-1-yl acetate (IUPAC name) (437) + TX, (Z)-Hex Sadec-13-en-11-yn-1-yl acetate (IUPAC name) (438) + TX, (Z)-Icos-13-en-10-one (IUPAC name) (448) + TX, (Z)-tetradec-7-en-1-al (IUPAC name) (782) + TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783) + TX, ( Z)-Tetradeca-9-en-1-yl acetate (IUPAC name) (784) + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283) + TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780) + TX, (9Z,12E)-tetradeca-9,12-Dien-1-yl acetate (IUPAC name) (781) + TX, 14-methyloctadec-1-ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol and 4-methylnonan-5-one (IUPAC name) (544) + TX, alpha-multistriatin (alternative name) [CCN] + TX, Brevicomin (alternative name) [CCN] + TX, Codrelure (alternative name) [CCN] + TX, Codlemone (alternative name) (167) + TX, Cure (alternative name) (179) + TX , Disparlure (277) + TX, Dodec-8-en-1-yl acetate (IUPAC name) (286) + TX, Dodec-9-en-1-yl acetate (IUPAC name) (287) + TX, Dodec-8 + TX, 10-dien-1-yl acetate (IUPAC name) (284) + TX, Dominicalure (alternative name) [CCN] + TX, Ethyl 4-methyloctanoate (IUPAC name) (317) + TX, Eugenol (alternative name) [CCN] + TX, Frontalin (alternative name) [CCN] + T X, a 1:1 mixture of the (Z,E) and (Z,Z) isomers of Gossyplure® (alternative name: hexadeca-7,11-dien-1-yl-acetate) (420) + TX, Grandolure (421) + TX, Grandolure I (alternative name) (421) + TX, Grandolure II (alternative name) (421) + TX, Grandolure III (alternative name) (421) + TX, Grandolure IV (alternative name) (421) + TX, Hexalure [CCN] + TX, Ipsdienol (alternative name) [CCN] + TX, Ipsenol (alternative name) [CCN] + TX, Japonirua (alternative name) (481) + TX, Lineatin (alternative name) [CCN] + TX, Litirua (alternative name) [CCN] + TX, Lupulua (alternative name) [CCN] + TX, Medurua [CCN] + TX, Megatomoic acid (alternative name) [CCN] + TX, Methyleugenol (alternative name) (540) + TX, Muscalua (563) + TX, Octadeca-2,13-dien-1-yl acetate (IUPAC name) (588) + TX, Octadeca-3,13-Dien-1-yl acetate (IUPAC name) (589) + TX, Olfrulure (alternative name) [CCN] + TX, Orictalure (alternative name) (317) + TX, Ostramon (alternative name) [CCN] + TX, Siglua [CCN] + TX, Soldigin (alternative name) (736) + TX, Sulcatol (alternative name) [CCN] + TX, Tetradec-11-en-1-yl acetate (IU an insect pheromone selected from the group of substances consisting of Trimedulla (PAC name) (785) + TX, Trimedulla (839) + TX, Trimedulla A (alternate name) (839) + TX, Trimedulla B1 (alternate name) (839) + TX, Trimedulla B2 (alternate name) (839) + TX, Trimedulla C (alternate name) (839) and Trunk-call (alternate name) [CCN] + TX; an insect repellent selected from the group of substances consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, diethyltoluamide [CCN] + TX, dimethylcarbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexamide [CCN] + TX, methoquin-butyl (1276) + TX, methylneodecanamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX; Bis(tributyltin)oxide (IUPAC name) (913) + TX, Bromoacetamide [CCN] + TX, Calcium arsenate [CCN] + TX, Cloethocarb (999) + TX, Copper acetarsenite [CCN] + TX, Copper sulfate (172) + TX, Fentin (347) + TX, Ferric phosphate (IUPAC name) (352) + TX, Metaldehyde (518) + TX, Methiocarb (530) + TX, Niclosamide (576) + TX, Niclosamide-olamine (576) + TX, Pentachloroethylene (Phenylalanine) a molluscicide selected from the group of substances consisting of: chlorophenol (623) + TX, sodium pentachlorophenoxide (623) + TX, thazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, triphenmorph (1454) + TX, trimethacarb (840) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, pyriprole [394730-71-3] + TX; AKD-3088 (compound code) + TX, 1,2-dibromo-3-chloropropane (IUPAC / Chemical Abstracts Name) (1045) + TX, 1,2-dichloropropane (IUPAC / Chemical Abstracts Name) (1062) + TX, 1,2-dichloropropane and 1,3-dichloropropene (IUPAC Name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC / Chemical Abstracts Name) (1065) + TX, 3-(4-chlorophenyl) -5-Methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alternative name) (210) + TX, abamectin (1) + TX, acetoprole [CCN] + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxicarb (863) + TX, AZ60541 (compound code) + TX, benclotiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alternative name) + TX, Cadusafos (109) + TX, Carbofuran (118) + TX, Carbon Disulfide (945) + TX, Carbosulfan (119) + TX, Chloropicrin (141) + TX, Chlorpyrifos (145) + TX, Cloetocarb (999) + TX, Cyclobutrifluram + TX, Cytokinin (alternative name) (210) + TX, Dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, Diamidafos (1044) + TX, Diclofenthion (1051) + TX, Dicrifos (alternative name) + TX, Dimethoate (262) + T X, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ethoprophos (312) + TX, ethylene dibromide (316) + TX, fenamiphos (326) + TX, fenpyrad (alternative name) + TX, fensulfothion (1158) + TX, fosthiazate (408) + TX, fostietan (1196) + TX, furfural (alternative name) [CCN] + TX, GY-81 (development code) (423) + TX, heterophos [CCN] + TX,Iodomethane (IUPAC name) (542) + TX, Isamidophos (1230) + TX, Isazophos (1231) + TX, Ivermectin (alternative name) [CCN] + TX, Kinetin (alternative name) (210) + TX, Mecarfone (1258) + TX, Metam (519) + TX, Metam-potassium (alternative name) (519) + TX, Metam-sodium (519) + TX, Methyl bromide (537) + TX, Methyl isothiocyanate (543) + TX, Milbemycin oxime (alternative name) [CCN] + TX, Moxidectin (alternative name [CCN] + TX, Myrothecium verrucaria) Composition (alternative name) (565) + TX, NC-184 (compound code) + TX, Oxamyl (602) + TX, Phorate (636) + TX, Phosphamidon (639) + TX, Phosphocarb [CCN] + TX, Cebufos (alternative name) + TX, Selamectin (alternative name) [CCN] + TX, Spinosad (737) + TX, Terbam (alternative name) + TX, Terbufos (773) + TX, Tetrachlorothiophene (IUP a nematicide selected from the group of substances consisting of AC / Chemical Abstracts Name) (1422) + TX, Thiafenox (alternative name) + TX, Thionazine (1434) + TX, Triazophos (820) + TX, Triazuron (alternative name) + TX, Xylenol [CCN] + TX, YI-5302 (compound code) and Zeatin (alternative name) (210) + TX, Fluensulfone [318290-98-1] + TX, Fluopyram + TX; a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX; a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX; 2-Isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, alpha-chlorohydrin [CCN] + TX, aluminum phosphide (640) + TX, anthracene (880) + TX, arsenic trioxide (882) + TX, barium carbonate (891) + TX, bisthiosemi (912) + TX, brodifacoium (89) + TX, bromadiolone (including alpha-bromadiolone) +TX, Bromethalin (92) +TX, Calcium cyanide (444) +TX, Chloralose (127) +TX, Chlorophacinone (140) +TX, Cholecalciferol (alternative name) (850) +TX, Coumacrol (1004) +TX, Coumafuryl (1005) +TX, Coumatetralyl (175) +TX, Crimidine (1009) +TX, Difenacoum (246) +TX, Difethialone (249) +TX, Diphacinone (273) +TX, Ergocalciferol (301) +TX, Flo Coumaphene (357) + TX, Fluoroacetamide (379) + TX, Flupropaline (1183) + TX, Flupropaline Hydrochloride (1183) + TX, gamma-HCH (430) + TX, HCH (430) + TX, Hydrogen Cyanide (444) + TX, Iodomethane (IUPAC name) (542) + TX, Lindane (430) + TX, Magnesium Phosphide (IUPAC name) (640) + TX, Methyl Bromide (537) + TX, Norbormide (1318) + TX, Fosacetim (1336) + TX, Fosacetim a rodenticide selected from the group of substances consisting of sphingosine (IUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371) + TX, sciliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851) and zinc phosphide (640) + TX; a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934) + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol and nerolidol (alternative names) (324) + TX, MB-599 (development code) (498) + TX, MGK264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piperotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesamolin (1394) and sulfoxide (1406) + TX; an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetate (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN], and ziram (856) + TX; a virucidal agent selected from the group of substances consisting of Imanin (alternative name) [CCN] and Ribavirin (alternative name) [CCN] + TX; a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octilinone (590) and thiophanate-methyl (802) + TX; 1,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX, 2,4-dichlorophenylbenzenesulfonate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 4-chlorophenylphenylsulfone + TX, acetoprole + TX, aldoxicarb + TX, amidithione + TX, amidothioate + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, alamite + TX, arsenic oxide + TX, azobenzene + TX, azotoate + TX, benomyl + TX, benoxaphos + TX, ben Dibenzoate + TX, Bixafen + TX, Brofenvalerate + TX, Bromocyclen + TX, Bromophos + TX, Bromopropylate + TX, Buprofezin + TX, Butocarboxim + TX, Butoxycarboxim + TX, Butylpyridaben + TX, Calcium polysulfide + TX, Camphechlor + TX, Carbanolate + TX, Carbophenothion + TX, Cimiazol + TX, Thiomethionate + TX, Chlorbeside + TX, Chlordimeform + TX, Chlordimeform hydrochloride + TX, Chlorphenetole + TX, Chlor Fenson +TX, Chlorphenesulfide +TX, Chlorobenzilate +TX, Chlormebform +TX, Chlormethiuron +TX, Chloropropylate +TX, Chlorthiophos +TX, Cinerin I +TX, Cinerin II +TX, Cinerins +TX, Closantel +TX, Coumaphos +TX, Crotamiton +TX, Crotoxyphos +TX, Kufraeb +TX, Cyanthoate +TX, DCPM +TX, DDT +TX, Demefion +TX, Demefion-O +TX, Demefion-S +TX, Demeton-methyl +TX, Demeton-O +TX, Demeton- O-Methyl + TX, Demeton-S + TX, Demeton-S-methyl + TX, Demeton-S-methyl sulfone + TX, Dichlofluanid + TX, Dichlorvos + TX, Dicrifos + TX, Dienochlor + TX, Dimefox + TX, Zinex + TX, Zinex-Diclexin + TX, Dinocap-4 + TX, Dinocap-6 + TX, Dinocton + TX, Dinopenton + TX, Dinosulfone + TX, Dinotervon + TX, Dioxathion + TX, Diphenylsulfone + TX, Disulfiram + TX, DNOC + TX, Dofenapine + TX, Doramectin + TX,Endothion + TX, Epirinomectin + TX, Ethoate-methyl + TX, Etrimphos + TX, Fenazaflor + TX, Fenbutatin oxide + TX, Fenothiocarb + TX, Fenpyrad + TX, Fen-pyroximate + TX, Fenpyrazamine + TX, Fenson + TX, Fentrifanil + TX, Flubenzimine + TX, Flucycloxuron + TX, Fluenethyl + TX, Fluorobenside + TX, FMC 1137+TX, formetanate+TX, formetanate hydrochloride+TX, formparanate+TX, gamma-HCH+TX, gliodin+TX, halfenprox+TX, hexadecylcyclopropanecarboxylate+TX, isocarbophos+TX, jasmolin I+TX, jasmolin II+TX, jodofenphos+TX, lindane+TX, malonoven+TX, mecarbam+TX, mefosfolan+TX, mesulfen+TX, Methacrifos + TX, methyl bromide + TX, metolcarb + TX, mexacarbate + TX, milbemycin oxime + TX, mipafox + TX, monocrotophos + TX, morphothion + TX, moxidectin + TX, naled + TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, nifururizide + TX, nikkomycin + TX, nitrilacarb + TX, nitrilocarb Liracarb 1:1 zinc chloride complex +TX, omethoate +TX, oxydeprophos +TX, oxydisulfoton +TX, pp'-DDT +TX, parathion +TX, permethrin +TX, fenkapton +TX, phosalone +TX, phospholan +TX, phosphamidon +TX, polychloroterpenes +TX, polynactin +TX, proclonol +TX, promacyl +TX, propoxur +TX, protidathion +TX, prothoate +TX, pyrethrins I+TX, Pyrethrin II+TX, Pyrethrin+TX, Pyridaphenthion+TX, Pirimitate+TX, Quinalphos+TX, Quinthiofos+TX, R-1492+TX, Phosglycine+TX, Rotenone+TX, Schladan+TX, Cebufos+TX, Selamectin+TX, Sofamid+TX, SSI-121+TX, Sulfiram+TX, Sulfuramide+TX, Sulfotep+TX, Sulfur+TX, Diflobidazine+TX, Tau-Fluvalinate+TX,TEPP+TX, Terbam+TX, Tetradifon+TX, Tetrasul+TX, Thiafenox+TX, Thiocarboxim+TX, Thiofanox+TX, Thiometon+TX, Thioquinox+TX, Thuringiensin+TX, Triamiphos+TX, Triaten+TX, Triazophos+TX, Triazuron + TX, Trifenofos + TX, Trinactin + TX, Vamidothion + TX, Vaniliprole + TX, Bethoxazin + TX, Copper dioctanoate + TX, Copper sulfate + TX, Sibutrin + TX, Dichlorn + TX, Dichlorophen + TX, Endothal + TX, Fentin + TX, Slaked lime + TX, Nabam + TX, Quinoclamine + TX, Quinoneamide + TX, Simazine + TX, Triphenyltin acetate + TX, Triphenyltin hydroxide + TX, Crufomate + TX, Piperazine + TX, Thiophanate + TX, Chloralose + TX, Fenthion + TX, Pyridin-4-amine + TX, Strychnine + TX, 1-Hydroxy-1H-pyridine-2-thione + TX, 4-(Quinoxalin-2-ylamino)benzene Sulfonamides + TX, 8-hydroxyquinoline sulfate + TX, Bronopol + TX, Copper hydroxide + TX, Cresol + TX, Dipyrithione + TX, Doditin + TX, Fenaminosulf + TX, Formaldehyde + TX, Hydralgafen + TX, Kasugamycin + TX, Kasugamycin hydrochloride hydrate + TX, Nickel bis(dimethyldithiocarbamate) + TX, Nitrapyrin + TX, Octilinone + TX, Oxolinic acid + TX, Oxytetracycline + TX, Hydroxyquinoline potassium sulfate + TX, Probenazole + TX, Streptomycin + TX, Streptomycin sesquisulfate + TX, Tecloftalam + TX, Thiomersal + TX, Adoxophyes orana GV+TX, Agrobacterium radiobacter+TX, Amblyseius spp.) + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, Autographa californica NPV + TX, Bacillus sphaericus Neide + TX, Beauveria brongniartii + TX, Chrysoperla carnea + TX, Cryptolaemus montrouzieri + TX, Codling moth Cydia pomonella GV+TX, Dacnusa sibirica+TX, Diglyphus isaea+TX, Encarsia formosa+TX, Eretmocerus eremicus+TX, Heterorhabditis bacteriophora and H. megidis+TX, Hippodamia convergens+TX, Leptomastix dactylopii+TX, Macrolophus caliginosus+TX, Mamestra brassicae NPV+TX, Metaphycus herbolis helvolus) + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, pine sawfly (Neodiprion sertifer) NPV and N. leconti (N.lecontei NPV + TX, Orius spp. + TX, Paecilomyces fumosoroseus + TX, Phytoseiulus persimilis + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema skapterischii + TX, scapterisci) + TX, Steinernema spp.) + TX, Trichogramma spp.) + TX, Typhlodromus occidentalis + TX, Verticillium lecanii lecanii) + TX, apholate + TX, Visadil + TX, busulfan + TX, Dimatif + TX, Hemel + TX, Hempa + TX, Metepa + TX, Methiotepa + TX, methyl apholate + TX, Molzide + TX, Penfluron + TX, Tepa + TX, Thiohempa + TX, Thiotepa + TX, Tretamine + TX, Uredepa + TX, (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol + TX, (E)-tridec-4-en-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E,Z)-tetradec-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en-1-yl acetate ate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-icos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradec-9,12-dien-1-yl acetate + TX. 14-Methyloctadec-1-ene + TX, 4-methylnonan-5-ol and 4-methylnonan-5-one + TX, alpha-multistriatin + TX, Brevicomin + TX, Codrelle + TX, Codlemone + TX, Querle + TX, Disparlure + TX, Dodec-8-en-1-yl acetate + TX, Dodec-9-en-1-yl acetate + TX, Dodec-8 + TX, 10-dien-1-yl acetate + TX, Dominicalure + TX, Ethyl 4-methyloctanoate + TX, Eugenol + TX, Frontalin + TX, Grandolure + TX , Grandolure I + TX, Grandolure II + TX, Grandolure III + TX, Grandolure IV + TX, Hexalure + TX, Ipsdienol + TX, Ipsenol + TX, Japonilure + TX, Lineatin + TX, Litirure + TX, Lupulure + TX, Medulure + TX, Megatomoic acid + TX, Methyleugenol + TX, Muscalure + TX, Octadeca-2,13-dien-1-yl acetate + TX, Octadeca-3,13-dien-1-yl acetate + TX, Olfrulure + TX, Orictalure + TX, Ostramon + TX, Siglua + TX, Soldigin + TX, Sulcatol + TX, Tetradec-11-en-1-yl acetate + TX, Trimedlure + TX, Trimedlure A + TX, Trimedlure B1 + TX, Trimedlure B2 + TX, Trimedlure C + TX, Trunc-call + TX, 2-(octylthio)-ethanol + TX, Butapyronoxyl + TX, Butoxy(polypropylene glycol) + TX, Dibutyl adipate + TX, Dibutyl phthalate + TX, Dibutyl succinate + TX, Diethyl toluamide + TX, Dimethylcarbate + TX, Dimethylphthalate ester + TX, ethyl hexanediol + TX, hexamide + TX, methoquin-butyl + TX, methyl neodecaneamide + TX, oxamate + TX, picaridin + TX, 1-dichloro-1-nitroethane + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)-ethane + TX, 1,2-dichloropropane and 1,3-dichloropropene + TX, 1-bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methylphosphate + TX,2-(1,3-dithiolan-2-yl)phenyl dimethyl carbamate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methyl carbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidone + TX, 2-isovalerylindan-1,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenyl methyl carbamate + TX, 2-thiocyanatoethyl laurate + TX, 3-bromo-1-chloro Prop-1-ene + TX, 3-methyl-1-phenylpyrazol-5-yldimethylcarbamate + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate + TX, 5,5-dimethyl-3-oxocyclohex-1-enyldimethylcarbamate + TX, acetione + TX, acrylonitrile + TX, aldrin + TX, allosamidin + TX, alixycarb + TX, α-ecdysone + TX, aluminum phosphide + TX, aminocarb + TX, anabasine + TX, atidathion + TX, azamethiphos + TX, Bacillus thuringiensis (Bacillus thuringiensis) delta-endotoxin +TX, barium hexafluorosilicate +TX, barium polysulfide +TX, bartholin +TX, Bayer 22 / 190 +TX, Bayer 22408 +TX, beta-cyfluthrin +TX, beta-cypermethrin +TX, bioethanometrin +TX, biopermethrin +TX, bis(2-chloroethyl) ether +TX, borax +TX, bromfenvinphos +TX, bromo-DDT +TX, bufencarb +TX, butacarb +TX, butathiophos +TX, butonate +TX, calcium arsenate +TX, calcium cyanide +TX, carbon disulfide +TX, carbon tetrachloride +TX, cartap hydrochloride +TX, sevadin +TX, chlorbicyclen +TX, chlordane +TX, chlordecone +TX, chloroform +TX, chloropicrin +TX, chlorphoxim +TX, chlorprazophos +TX, cis-resmethrin +TX, cismethrin +TX, clocitrin +TX, copper acetoarsenite +TX, copper arsenate +TX, copper oleate +TX, chumithoate +TX, cryolite +TX,CS708+TX, cyanofenphos+TX, cyanophos+TX, cyclethrin+TX, cythioate+TX, d-tetramethrin+TX, DAEP+TX, dazomet+TX, decarbofuran+TX, diamidaphos+TX, dikapton+TX, dichlorophenthion+TX, dicresyl+TX, dicyclanil+TX, dieldrin+TX, diethyl 5-methylpyrazol-3-yl phosphate+TX, dilol+TX, dimefluthrin+TX, dimethane+TX, dimethrin+TX, dimethylvinphos+TX, dimethyllan+TX, dinoprop+TX, dinosam+TX, dinoseb+TX, diofenolan+TX, dioxabenzophos+TX, dicyclophos+TX, DSP+TX, ecdysterone+TX, EI 1642+TX, EMPC+TX, EPBP+TX, Ethaphos+TX, Ethiofencarb+TX, Ethyl formate+TX, Ethylene dibromide+TX, Dichloroethane+TX, Ethylene oxide+TX, EXD+TX, Fenchlorphos+TX, Fenetacarb+TX, Fenitrothion+TX, Fenoxacrim+TX, Fenpyrithrin+TX, Fensulfothion+TX, Fenthion-ethyl+TX, Flucofuron+TX, Fosmetilan+TX, Fospirate+TX, Fostietan+TX, Furathiocarb+TX, Frethrin+TX, Guazatine+TX, Guazatine acetate+TX, Sodium tetrathiocarbonate+TX, Halfenprox+TX, HCH+TX, HEOD+TX, Heptachlor+TX, Heterofos+TX, HHDN+TX, Sodium tetrathiocarbonate+TX Hydrogen anhydride +TX, Hikincarb +TX, IPSP +TX, Isazophos +TX, Isobenzane +TX, Isodrin +TX, Isofenphos +TX, Isolane +TX, Isoprothiolane +TX, Isoxathion +TX, Juvenile hormone I +TX, Juvenile hormone II +TX, Juvenile hormone III +TX, Kelevan +TX, Kinoprene +TX, Lead arsenate +TX, Leptophos +TX, Lilimphos +TX, Ritidathion +TX, m-Cumenylmethylcarbamate +TX, Magnesium phosphide +TX, Magidox +TX, Mecarfone +TX, Menasone +TX, Mercurous chloride +TX, Mesulfenphos +TX, Metam +TX, Metam-potassium +TX, Metam-sodium +TX, Methanesulfonyl fluoride +TX, Metocrotophos +TX, Methoprene +TX, Methotrin +TX,Methoxychlor + TX, methyl isothiocyanate + TX, methyl chloroform + TX, methylene chloride + TX, methoxadiazone + TX, Mirex + TX, naphthalophos + TX, naphthalene + TX, NC-170 + TX, nicotine + TX, nicotine sulfate + TX, nithiazine + TX, nornicotine + TX, O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate + TX, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate + TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate + TX, O,O,O',O'-tetrapropyl dithiopyrophosphate + TX, oleic acid + TX, para-dichlorobenzene + TX, Parathion-methyl + TX, Pentachlorophenol + TX, Pentachlorophenyl laurate + TX, PH60-38 + TX, Fenkapton + TX, Fosnichlor + TX, Phosphine + TX, Phoxim-methyl + TX, Pyrimetaphos + TX, Polychlorodicyclopentadiene Isomers + TX, Potassium Arsenite + TX, Potassium Thiocyanate + TX, Precocene I + TX, Precocene II + TX, Precocene III + TX, Pyrimidophos + TX, Profluthrin + TX, Promecarb + TX, Prothiofos + TX, Pyrazophos + TX, Pyresmethrin + TX, Cassia + TX, Quinalphos-methyl + TX, Quinothione + TX, Rafoxanide + TX, Resmethrin + TX, Rotenone + TX, Kadetrin + TX, Riania + TX, Ryanodine + TX, Sabadila + TX, Shradan + TX, Cebufos + TX, SI-0009 + TX, Tiapronil + TX, Sodium arsenite + TX, Sodium cyanide + TX, Sodium fluoride + TX, Sodium hexafluorosilicate + TX, Pentachlorophenoxide sodium salt + TX, Sodium selenate + TX, Sodium thiocyanate + TX, Sulcofuron + TX, Sulcofuron-sodium +TX, Sulfuryl fluoride +TX, Sulprofos +TX, Tar oil +TX, Thazimcarb +TX, TDE +TX, Tebupirimfos +TX, Temephos +TX, Telarethrin +TX, Tetrachloroethane +TX, Cyclofos +TX, Thiocyclam +TX, Thiocyclam hydrogen oxalate +TX, Thionazine +TX, Thiosultap +TX, Thiosultap-sodium +TX, Tralomethrin +TX, Transpermethrin +TX, Triazamate +TX, Trichlormethaphos-3 +TX, Trichloronaphthalene +TX, Trimethacarb + TX, tolprocarb + TX, triclopyricarb + TX, triplen + TX, veratridine + TX, veratrine + TX, XMC + TX, zetamethrin + TX, zinc phosphide + TX, zolaprofos + TX, meperfluthrin + TX, tetramethylfluthrin + TX, bis(tributyltin) oxide + TX, bromoacetamide + TX, ferric phosphate + TX, niclosamide-olamine + TX, tributyltin oxide + TX, pyrimorph + TX, triphenmorph + TX, 1,2-dibromo-3-chloropropane + TX, 1,3-dichloropropene + TX,3,4-Dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, 2-fluoro-N-(3-methoxyphenyl)-9H-purin-6-amine + TX, benclothiaz + TX, cytokinin + TX, DCIP + TX, rufural + TX, isamidophos + TX, kinetin + TX, Myrothecium verrucaria composition + TX, tetrachlorothiophene + TX, xylenol + TX, zeatin + TX, potassium ethylxanthate + TX, acibenzolar + TX, acibenzolar-S-methyl + TX, Reynoutria sachalinensis) extract +TX, alpha-chlorohydrin +TX, anth +TX, barium carbonate +TX, bisthiosemi +TX, brodifacoum +TX, bromadiolone +TX, bromethalin +TX, chlorophacinone +TX, cholecalciferol +TX, coumachlor +TX, coumafuryl +TX, coumatetralyl +TX, crimidine +TX, difenacoum +TX, difethialone +TX, diphacinone +TX, ergocalciferol +TX, flocoumafen +TX, fluoroacetamide +TX, flupropazine +TX, flupropazine hydrochloride +TX, norbormide +TX, fosacetim +TX, phosphorus +TX, pindone +TX, pyrinuron +TX, sciliroside +TX, sodium -fluoroacetate ium + TX, thallium sulfate + TX, warfarin + TX, 2-(2-butoxyethoxy)ethyl piperonylate + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, farnesol and nerolidol + TX, berubutin + TX, MGK264 + TX, piperonyl butoxide + TX, piprotal + TX, propyl isomer + TX, S421 + TX, sesamex + TX, sesasmolin + TX, sulfoxide + TX, anthraquinone + TX, copper naphthenate + TX, copper oxychloride + TX, dicyclopentadiene + TX, thiram + TX, zinc naphthenate + TX, ziram + TX, imanin + TX, ribavirin + TX, chlorinconazide + TX, mercury(II) oxide + TX,Thiophanate-methyl + TX, azaconazole + TX, bitertanol + TX, bromuconazole + TX, cyproconazole + TX, difenoconazole + TX, diniconazole + TX, epoxiconazole + TX, fenbuconazole + TX, fluquinconazole + TX, flusilazole + TX, flutriafol + TX, furametpyr + TX, hexaconazole + TX, imazalil + TX, imibenconazole + TX, ipconazole + TX, metconazole + TX, myclobutanil + TX, paclobutrazol + TX, pefurazoate + TX , penconazole +TX, prothioconazole +TX, pyrifenox +TX, prochloraz +TX, propiconazole +TX, pyrisoxazole +TX, simeconazole +TX, tebuconazole +TX, tetraconazole +TX, triadimefon +TX, triadimenol +TX, triflumizole +TX, triticonazole +TX, ancymidol +TX, fenarimol +TX, nuarimol +TX, bupirimate +TX, dimethirimol +TX, ethirimol +TX, dodemorph +TX, fenpropidin +TX, fenpropimorph +TX, Pyroxamine + TX, tridemorph + TX, cyprodinil + TX, mepanipyrim + TX, pyrimethanil + TX, fenpiclonil + TX, fludioxonil + TX, benalaxyl + TX, furalaxyl + TX, -metalaxyl- + TX, R-metalaxyl + TX, ofrace + TX, oxadixyl + TX, carbendazim + TX, debacarb + TX, fuberidazole + TX, thiabendazole + TX, chlozolinate + TX, dichlozolin + TX, mycozolin + TX, procymidone + TX, vinclozolin + TX, boscalid + TX, carboxy rham + TX, flutolanil + TX, mepronil + TX, oxycarboxin + TX, penthiopyrad + TX, thifluzamide + TX, dodine + TX, iminoctadine + TX, azoxystrobin + TX, dimoxystrobin + TX, enestrobulin + TX, phenaminestrobin + TX, flufenoxystrobin + TX, fluoxastrobin + TX, kresoxim-methyl + TX, metominostrobin + TX, trifloxystrobin + TX, oryzastrobin + TX, picoxystrobin + TX, pyraclostrobin + TX,Pyrametstrobin +TX, pyraoxystrobin +TX, ferbam +TX, mancozeb +TX, maneb +TX, metiram +TX, propineb +TX, zineb +TX, captafol +TX, captan +TX, fluoroimide +TX, folpet +TX, tolylfluanid +TX, Bordeaux mixture +TX, copper oxide +TX, mancopper +TX, oxine-copper +TX, nitrothal-isopropyl +TX, edifenphos +TX, Iprobenfos +TX, Fosdifen +TX, Turcofos-methyl +TX, Anilazine +TX, Benthiavalicarb +TX, Blasticidin-S +TX, Chloroneb +TX, Chlorothalonil +TX, Cyflufenamid +TX, Cymoxanil +TX, Diclocymet +TX, Diclomedine +TX, Dicloran +TX, Diethofencarb +TX, Dimethomorph-+TX, Flumorph +TX, Dithianon +TX, Ethaboxam + TX, Etridiazole + TX, Famoxadone + TX, Fenamidon + TX, Fenoxanil + TX, Ferimzone + TX, Fluazinam + TX, Fluopicolide + TX, Flusulfamide + TX, Fluxapyroxad + TX, Fenhexamid + TX, Fosetyl-aluminum + TX, Hymexazole + TX, Iprovalicarb + TX, Cyazofamid + TX, Metasulfocarb + TX, Metrafenone + TX, Pencycuron + TX, Phthalide + TX, Polyoxin + TX X, propamocarb +TX, pyribencarb +TX, proquinazide +TX, pyroquilon +TX, pyriophenone +TX, quinoxyfen +TX, quintozene +TX, tiadinil +TX, triazoxide +TX, tricyclazole +TX, triforine +TX, validamycin +TX, valifenalate +TX, zoxamide +TX, mandipropamide +TX, flubeneteram +TX, isopyrazam +TX, sedaxane +TX, benzovindiflupir +TX, pydiflumetofen +TX, 3-difluoxetine Fluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, isoflucipram + TX, isotianil + TX, dipimethitrone + TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile + TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 4-(2,6 -difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluorophenyl)-1,3-Dimethyl-1H-pyrazol-5-amine + TX, Fluindapyr + TX, Dimethoxystrobin (Jiaxiangjunzhi) + TX, Rubenmixianan + TX, Diclobenthiazox + TX, Mandestrobin + TX, 3-(4,4-Difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone + TX, 2-[2-Fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propane -2-ol + TX, oxathiapiproline + TX, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, pyraziflumide + TX, inpirfluxam + TX, turolprocarb + TX, mefentrifluconazole + TX, ipfentrifluconazole + TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl]methanesulfonic acid +TX, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate +TX, ethyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate +TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine +TX, pyridaclomethyl +TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-Trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX, aminopyrifen + TX, ametoctrazine + TX, amisulbrom + TX, penflufen + TX, (Z,2E) -5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX, furylpicoxamide + TX, fenpicoxamide + TX, tebufloquine + TX, ipulfenoquine + TX, quinofumelin + TX, isofetamide + TX, ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate + TX (prepared from the method described in WO 2020 / 056090). obtained from the method described in WO 2020 / 056090), ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enoxy]phenyl]methyl]pyrazole-3-carboxylate + TX (which may be prepared from the method described in WO 2020 / 056090), methyl N-[[4-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate + TX (which may be prepared from the method described in WO 2020 / 097012), methyl N-[[4-[1-(2,6-difluoro- 4-isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate + TX (which may be prepared from the method described in WO 2020 / 097012), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide + TX (which may be prepared from the method described in WO 2020 / 109391), 6-chloro-N-[2-(2-chloro-4-methyl-phenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide + TX (which may be prepared from the method described in WO 2020 / 109391), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide + TX (which may be prepared from the method described in WO 2020 / 109391), N-[2-[2,4-dichloro N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, Benzothiostrobin + TX, Fenamacryl + TX, 5-Amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, Fluopyram + TX, Flufenoxadiazam + TX, Flutianil + TX, Fluopimomide + TX, Pirapropoin + TX, Picarburazox + TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, Methyltetraprole + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidinemethanol + TX, fluoxapiprolin + TX, enoxastrobin + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop-2-enoate + TX, methyl (Z)-3-methoxy-2- [2-methyl-5-(4-propyltriazol-2-yl)phenoxy]prop-2-enoate + TX, methyl (Z)-2-[5-(3-isopropylpyrazol-1-yl)-2-methyl-phenoxy]-3-methoxy-prop-2-enoate + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-(3-propylpyrazol-1-yl)phenoxy]prop-2-enoate + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]prop-2-enoate methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate + TX (these compounds may be prepared from the method described in WO 2020 / 079111), methyl (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate + TX (these compounds may be prepared from the method described in WO 2020 / 193387), 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + T X, trinexapac + TX, cumoxystrobin + TX, zhongshengmycin + TX, copper thiodiazole + TX, zinc thiazole + TX, amethotractin + TX, iprodione + TX, seboxylamine + TX; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]- N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds can be prepared by the method described in WO 2015 / 155075; N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared by the method described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine + TX, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds can be prepared by the method described in WO 2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoro N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1- benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline Phosphorus-3-carboxamide + TX, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX (these compounds can be prepared by the method described in WO 2017 / 153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trimethylpyrazole-3-yl ... Trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4, 4-Difluoro-3,3-dimethyl-isoquinoline + TX (these compounds can be prepared by the method described in WO 2017 / 025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline + TX, 4, 4-Difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole + TX (these compounds can be prepared by the method described in WO 2016 / 156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N,2-Dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate + TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine + TX. The compounds in this paragraph can be prepared by the methods described in WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 093348 and WO 2017 / 118689; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound can be prepared by the method described in WO 2017 / 029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound can be prepared by the method described in WO 2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carbo, xylate + TX (this compound can be prepared by the method described in WO 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone + TX (this compound can be prepared by the method described in WO 2011 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide + TX; N- Methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX (this compound can be prepared by the method described in WO 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX; N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared by the method described in WO 2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX (this compound can be prepared by the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX (these compounds can be prepared by the method described in WO 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX (this compound can be prepared by the method described in WO 2018 / 06 5414); ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate + TX (this compound can be prepared by the method described in WO 2018 / 158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX a biologically active agent selected from N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX (these compounds can be prepared by the methods described in WO 2018 / 202428); Microorganisms including: Acinetobacter lwoffii + TX, Acremonium alternatum + TX, Acremonium cephalosporium + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, Adoxophyes orana granulovirus (AdoxGV) (Capex®) + TX, Agrobacterium radiobacter strain K84 (Galltrol-A®) + TX, Alternaria alternata + TX, Alternaria cassia + TX, cassia) + TX, Alternaria destruens (Smolder®) + TX, Ampelomyces quisqualis (AQ10®) + TX, Aspergillus flavus AF36 (AF36®) + TX, Aspergillus flavus NRRL21882 (Aflaguard®) + TX, Aspergillus spp.) + TX, Aureobasidium pullulans + TX, Azospirillum + TX, (MicroAZ® + TX, TAZO B®) + TX, Azotobacter + TX, Azotobacter chroocuccum (Azotomeal®) + TX, Azotobacter cysts (Bionatural Blooming Blossoms®) + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus chitinosporus strain CM-1 + TX, Bacillus chitinosporus strain AQ746+TX, Bacillus licheniformis strain HB-2 (Biostart™ Rhizoboost®)+TX, Bacillus licheniformis strain 3086 (EcoGuard®+TX, Green Releaf®)+TX, Bacillus circulans+TX, Bacillus firmus (BioSafe®+TX, BioNem-WP®+TX, VOTiVO®)+TX, Bacillus firmus strain I-1582+TX, Bacillus macerans+TX, Bacillus marismortii (Bacillus marismortui + TX, Bacillus megaterium + TX, Bacillus mycoides strain AQ726 + TX, Bacillus papillae (Milky Spore Powder®) + TX, Bacillus pumilus spp.) +TX, Bacillus pumilus strain GB34 (Yield Shield®) +TX, Bacillus pumilus strain AQ717 +TX, Bacillus pumilus strain QST 2808 (Sonata® +TX, Ballad Plus®) +TX, Bacillus spahericus (VectoLex®) +TX, Bacillus spp. +TX, Bacillus spp. strain AQ175 +TX, Bacillus spp. strain AQ177 +TX, Bacillus spp. spp. strain AQ178+TX, Bacillus subtilis strain QST 713 (CEASE®+TX, Serenade®+TX, Rhapsody®)+TX, Bacillus subtilis strain QST 714 (JAZZ®)+TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilis strain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis var. amyloliquefaciensamyloliquefaciens strain FZB24 (Taegro® +TX, Rhizopro®) +TX, Bacillus thuringiensis Cry2Ae +TX, Bacillus thuringiensis Cry1Ab +TX, Bacillus thuringiensis aizawai GC91 (Agree®) +TX, Bacillus thuringiensis israelensis (BMP123® +TX, Aquabac® +TX, VectoBac®) +TX, Bacillus thuringiensis kurstaki Bacillus thuringiensis kurstaki (Javelin® + TX, Deliver® + TX, CryMax® + TX, Bondide® + TX, Scutella WP® + TX, Turilav WP® + TX, Astuto® + TX, Dipel WP® + TX, Biobit® + TX, Foray®) + TX, Bacillus thuringiensis kurstaki BMP 123 (Baritone®) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF / 3P®) + TX, Bacillus thuringiensis strain BD#32 ... thuringiensis strain AQ52+TX, Bacillus thuringiensis var. aizawai (XenTari®+TX, DiPel®)+TX, Bacteria spp.) (GROWMEND® +TX, GROWSWEET® +TX, Shootup®) +TX, Clavipacter michiganensis bacteriophage (AgriPhage®) +TX, Bakflor® +TX,. Beauveria bassiana (Beaugenic® +TX, Brocaril WP®) +TX, Beauveria bassiana GHA (Mycotrol ES® +TX, Mycotrol O® +TX, BotaniGuard®) +TX, Beauveria brongniartii (Engerlingspilz® +TX, Schweizer Beauveria® +TX, Melocont®) +TX, Beauveria spp. +TX, Botrytis cineria +TX, Bradyrhizobium japonicum (TerraMax®) +TX, Brevibacillus brevis brevis + TX, Bacillus thuringiensis tenebrionis (Novodor®) + TX, BtBooster + TX, Burkholderia cepacia (Deny® + TX, Intercept® + TX, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp.) + TX, Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima pulcherrima + TX, Candida reukaufii + TX, Candida saitoana (Bio-Coat® + TX, Biocure®) + TX, Candida sake + TX, Candida spp.) + TX, Candida tenius + TX, Cedecea dravisae + TX, Cellulomonas flavigena + TX, Chaetomium cochliodes (Nova-Cide®) + TX, Chaetomium globosum (Nova-Cide®) + TX, Chromobacterium subtsugae strain PRAA4-1T (Grandevo®) + TX, Cladosporium cladosporioides + TX, Cladosporium oxysporum + TX, Cladosporium chlorocephalum chlorocephalum + TX, Cladosporium spp. + TX, Cladosporium tenuissimum + TX, Clonostachys rosea (EndoFine®) + TX, Colletotrichum acutatum + TX, Coniothyrium minitans (Cotans WG®) + TX, Coniothyrium spp.) + TX, Cryptococcus albidus (YIELDPLUS®) + TX, Cryptococcus humicola + TX, Cryptococcus infirmo-miniatus + TX, Cryptococcus laurentii + TX, Cryptophlebia leucotreta granulovirus (Cryptex®) + TX, Cupriavidus campinensis + TX, Cydia pomonella granulovirus (CYD-X®) + TX, Cydia pomonella granulovirus (Madex® + TX, Madex Plus® + TX, Madex Max / Carpovirusine®) + TX, Cylindrobasidium laeve (Stumpout®) + TX, Cylindrocladium + TX, Debaryomyces hansenii + TX, Drechslera hawaiinensis + TX, Enterobacter cloacae + TX, Enterobacteriaceae + TX, Entomophtora virulenta (Vektor®) + TX, Epicoccum nigrum nigrum) + TX, Epicoccum purpurascens + TX, Epicoccum spp.) + TX, Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum + TX, Fusarium oxysporum (Fusaclean® / Biofox C®) + TX, Fusarium proliferatum + TX, Fusarium spp. + TX, Galactomyces geotrichum + TX, Gliocladium catenulatum (Primastop® + TX, Prestop®) + TX, Gliocladium roseum roseum + TX, Gliocladium spp. (SoilGard®) + TX, Gliocladium virens (Soilgard®) + TX, Granulovirus (Granupom®) + TX, Halobacillus halophilus + TX, Halobacillus litoralis + TX, Halobacillus trueperi + TX, Halomonas spp.) + TX, Halomonas subglaciescola + TX, Halovibrio variabilis + TX, Hanseniaspora uvarum + TX, Helicoverpa armigera nucleopolyhedrovirus (Helicovex®) + TX, Helicoverpa zea nucleopolyhedrovirus (Gemstar®) + TX, isoflavone-formononetin (Myconate®) + TX, Kloeckera apiculata + TX, Kloeckera spp.) + TX, Lagenidium giganteum (Laginex®) + TX, Greenhouse whitefly (Lecanicillium longisporum) (Vertiblast®) + TX, Lecanicillium muscarium (Vertikil®) + TX, Gypsy moth (Lymantria dispar) nucleopolyhedrovirus (Disparvirus®) + TX, Marinococcus halophilus + TX, Meira geulakonigii + TX, Metarhizium anisopliae (Met52®) + TX, Metarhizium anisopliae (Destruxin®) + TX, WP®) + TX, Metschnikowia fruticola (Shemer®) + TX, Metschnikowia pulcherrima + TX, Microdochium dimerum (Antibot®) + TX, Micromonospora coerulea + TX, Micromonospora coerulea + TX, Microsphaeropsis ochracea + TX, Muscodor albus 620 (Muscudor®) + TX, Muscodor roseus strain A3-5 + TX, Mycorrhizae spp.) (AMykor® +TX, Root Maximizer®) +TX, Myrothecium verrucaria strain AARC-0255 (DiTera®) +TX, BROS PLUS® +TX, Ophiostoma piliferum strain D97 (Sylvanex®) +TX, Paecilomyces farinosus +TX, Paecilomyces fumosoroseus (PFR-97® +TX, PreFeRal®) +TX, Paecilomyces linacinus (Biostat WP®) +TX, Paecilomyces lilacin. us strain 251 (MeloCon WG®) + TX, Paenibacillus polymyxa + TX, Pantoea agglomerans (BlightBan C9-1®) + TX, Pantoea spp. + TX, Pasteuria spp. (Econem®) + TX, Pasteuria nishizawae + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart® + TX, TagTeam®) + TX, Penicillium brevicompactum brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp. + TX, Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, Phosphosomal (Phosphomeal®) + TX, Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala anomala) + TX, Pichia guilermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofaciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Pseudomonas fluorescens strain A506 (BlightBan A506®) + TX, Pseudomonas putida + TX, Pseudomonas reactans + TX, Pseudomonas species spp.) + TX, Pseudomonas syringae (Bio-Save®) + TX, Pseudomonas viridiflava + TX, Pseudomonas fluorescens (Zequanox®) + TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®) + TX, Puccinia canaliculata + TX, Puccinia thlaspeos (Wood Warrior®) + TX, Pythium paroecandrum + TX, Pythium oligandrum) (Polygandron® + TX, Polyversum®) + TX, Pythium periplocum + TX, Rhanella aquatilis + TX, Rhanella spp.) + TX, rhizobia (Dormal® + TX, Vault®) + TX, Rhizoctonia spp. + TX, Rhodococcus globerulus strain AQ719 + TX, Rhodosporidium diobovatum + TX, Rhodosporidium toruloides + TX, Rhodotorula spp. + TX, Rhodotorula glutinis + TX, Rhodotorula graminis + TX, Rhodotorula mucilagnosa + TX, Rhodotorula rubra + TX, Saccharomyces cerevisiae + TX, Salinococcus roseus + TX, Sclerotinia minor + TX, Sclerotinia minor (SARRITOR®) + TX, Scytalidium spp. + TX, Scytalidium uredinicola + TX, Spodoptera exigua nucleopolyhedrovirus (Spod-X® + TX, Spexit®) + TX, Serratia marcescens + TX, Serratia plymuthica + TX, Serratia spp.) + TX, Sordaria fimicola + TX, Spodoptera littoralis nuclear polyhedrosis virus (Littovir®) + TX, Sporobolomyces roseus + TX, Stenotrophomonas maltophilia + TX, Streptomyces ahygroscopicus + TX, Streptomyces albaduncus + TX, Streptomyces exfoliates + TX, Streptomyces galbus + TX, Streptomyces griseoplanus griseoplanus + TX, Streptomyces griseoviridis (Mycostop®) + TX, Streptomyces lydicus (Actinovate®) + TX, Streptomyces lydicus WYEC-108 (ActinoGrow®) + TX, Streptomyces violaceus + TX, Tilletiopsis minor + TX, Tilletiopsis spp.) + TX, Trichoderma asperellum (T34 Biocontrol®) + TX, Trichoderma gamsii (Tenet®) + TX, Trichoderma atroviride (Plantmate®) + TX, Trichoderma hamatum TH 382 + TX, Trichoderma harzianum rifai (Mycostar®) + TX, Trichoderma harzianum T-22 (Trianum-P® + TX, PlantShield HC® + TX, RootShield® + TX, Trianum-G®) + TX, Trichoderma harzianum harzianum) T-39 (Trichodex®) + TX, Trichoderma inhamatum + TX, Trichoderma koningii + TX, Trichoderma spp.) LC 52 (Sentinel®) + TX, Trichoderma lignorum + TX, Trichoderma longibrachiatum + TX, Trichoderma polysporum (Binab T®) + TX, Trichoderma taxi + TX, Trichoderma virens + TX, Trichoderma virens (formerly Gliocladium virens GL-21) (SoilGuard®) + TX, Trichoderma viride + TX, Trichoderma viride strain ICC 080 (Remedier®) + TX, Trichosporon pullulans + TX, Trichosporon spp. + TX, Trichothecium spp.) + TX, Trichothecium roseum + TX, Typhula phacorrhiza strain 94670 + TX, Typhula phacorrhiza strain 94671 + TX, Ulocladium atrum + TX, Ulocladium oudemansii (Botry-Zen®) + TX, Ustilago maydis + TX, various bacteria and supplemental micronutrients (Natural II®) + TX, various fungi (Millennium Microbes®) + TX, Verticillium chlamydosporium + TX, Verticillium lecanii lecanii (Mycotal® + TX, Vertalec®) + TX, Vip3Aa20 (VIPtera®) + TX, Virgibaclillus marismortui + TX, Xanthomonas campestris pv. Poae (Camperico®) + TX, Xenorhabdus bovienii + TX, Xenorhabdus nematophilus; Plant extracts including: pine oil (Retenol®) +TX, azadirachtin (Plasma), Neem Oil® +TX, AzaGuard® +TX, MeemAzal® +TX, Molt-X® +TX, botanical insect growth regulators (Neemazad® +TX, Neemix®) +TX, rapeseed oil (Lilly Miller Vegol®) +TX, American ant's weed (Chenopodium ambrosioides near ambrosioides) (Requiem®) +TX, Chrysanthemum extract (Crisant®) +TX, neem oil extract (Trilogy®) +TX, Labiatae essential oil (Botania®) +TX, clove, rosemary, peppermint, and thyme oil extracts (Garden insect killer®) + TX, glycine betaine (Greenstim®) + TX, garlic + TX, lemongrass oil (GreenMatch®) + TX, neem oil + TX, catnip (Nepeta cataria) (catnip oil) + TX, catnip (Nepeta catarina) + TX, nicotine + TX, oregano oil (MossBuster®) + TX, sesame (Pedaliaceae) oil (Nematon®) + TX, pyrethrum + TX, soapberry (Quillaja saponaria) (NemaQ®) + TX, giant knotweed (Reynoutria sachalinensis) (Regalia® + TX, Sakalia®) + TX, rotenone (Eco Roten®) + TX, Rutaceae extract (Soleo®) + TX, soybean oil (Ortho ecosense®) +TX, tea tree oil (Timorex Gold®) +TX, thyme oil +TX, AGNIQUE® MMF +TX, BugOil® +TX, a mixture of rosemary, sesame, peppermint, thyme and cinnamon extracts (EF300®) + TX, a mixture of clove rosemary and peppermint extracts (EF 400®) + TX, a mixture of clove peppermint garlic oil and mint (Soil Shot®) + TX, kaolin (Screen®) + TX, brown algae storage glucan (Laminarin®); Pheromones, including: blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®) + TX, codling moth pheromone (Paramount dispenser-(CM) / Isomate C-Plus®) + TX, grape berry moth pheromone (3M MEC-GBM Sprayable Pheromone®) + TX, leafroller pheromone (3M MEC-LR Sprayable Pheromone®) + TX, muscamone (Snip7 Fly Bait® + TX, Starbar Premium Fly Bait®) + TX, oriental fruit moth pheromone (3M oriental fruit moth sprayable pheromone®) + TX, peachtree Borer pheromone (Isomate-P®) + TX, Tomato Pinworm pheromone (3M Sprayable pheromone®) + TX, Entostat powder (palm tree extract) (Exosex CM®) + TX, (E+TX,Z+TX,Z)-3+TX,8+TX,11-tetradecatrienyl acetate + TX, (Z+TX,Z+TX,E)-7+TX,11+TX,13-hexadecatrienal + TX, (E+TX,Z)-7+TX,9-dodecadien-1-yl acetate + TX, 2-methyl-1-butanol + TX, calcium acetate + TX, Scenturion® + TX, Biolure® + TX, Check-Mate® + TX, lavandulyl senecioate; Macroorganisms including: Aphelinus abdominalis + TX, Aphidius ervi (Aphelinus-System®) + TX, Acerophagus papaya + TX, Adalia bipunctata (Adalia-System®) + TX, Adalia bipunctata (Adaline®) + TX, Adalia bipunctata (Aphidalia®) + TX, Ageniaspis citricola + TX, Ageniaspis fuscicollis + TX, Amblyseius andersoni (Anderline® + TX, Andersoni-System®) + TX, Amblyseius californicus californicus (Amblyline® + TX, Spical®) + TX, Amblyseius cucumeris (Thripex® + TX, Bugline cucumeris®) + TX, Amblyseius fallacis (Fallacis®) + TX, Amblyseius swirskii (Bugline swirskii® + TX, Swirskii-Mite®) + TX, Amblyseius womersleyi (WomerMite®) + TX, Amitus hesperidum + TX, Anagrus atomus + TX, Anagyrus fusciventris fusciventris) + TX, Anagyrus kamali + TX, Anagyrus loecki + TX, Anagyrus pseudococcus (Anagyruspseudococci (Citripar®) + TX, Anicetus benefices + TX, Anisopteromalus calandrae + TX, Anthocoris nemoralis (Anthocoris-System®) + TX, Aphelinus abdominalis (Apheline® + TX, Aphiline®) + TX, Aphelinus asychis + TX, Aphidius colemani (Aphipar®) + TX, Aphidius ervi (Ervipar®) + TX, Aphidius gifuensis + TX, Aphidius matricariae matricariae (Aphipar-M®) + TX, Aphidoletes aphidimyza (Aphidend®) + TX, Aphidoletes aphidimyza (Aphidoline®) + TX, Aphytis lingnanensis + TX, Aphytis melinus + TX, Aprostocetus hagenowii + TX, Atheta coriaria (Staphyline®) + TX, Bombus spp. + TX, Bombus terrestris (Natupol Beehive® + TX, Bombus terrestris (Beeline® + TX, Tripol®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus + TX, Chrysoperlacarnea (Chrysoline®) + TX, Chrysoperla carnea (Chrysopa®) + TX, Chrysoperla rufilabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichus phyllocnistoides + TX, Closterocerus chamaeleon + TX, Closterocerus spp. + TX, Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug® + TX, Cryptoline®) + TX, Cybocephalus nipponicus (Dacnusa sibirica) + TX, Dacnusa sibirica (Minusa®) + TX, Diglyphus isaea (Diminex®) + TX, Delphastus catarinae (Delphastus catalinae) (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsisjucunda + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea + TX, Diglyphus isaea (Miglyphus® + TX, Digline®) + TX, Dacnusa sibirica (DacDigline® + TX, Minex®) + TX, Diversinervus spp. + TX, Encarsia citrina + TX, Encarsia formosa (Encarsia max® + TX, Encarline® + TX, En-Strip®) + TX, Eretmocerus eremicus (Enermix®) + TX, Encarsia guadeloupae + TX, Encarsia haitiensis + TX, Episyrphus balteatus (Syrphidend®) + TX, Eretmoceris siphonini + TX, Eretmocerus californicus + TX, Eretmocerus eremicus (Ercal® + TX, Eretline e®) + TX, Eretmocerus eremicus (Bemimix®) + TX, Eretmocerus hayati + TX, Eretmocerus mundus (Bemipar® + TX, Eretline m®) + TX, Eretmocerus siphonini + TX, Exochomus quadripustulatus + TX, Feltiella acarisuga (Spidend®) + TX, Feltiella acarisuga (Feltiline®) + TX, Fopius arisanus + TX, Fopius ceratitivorus + TX, Formononetin (Wirless Beehome®) + TX, Franklinothrips vespiformis (Vespop®) + TX, Galendromus occidentalis + TX, Goniozus legneri + TX, Habrobracon hebetor + TX, Harmonia axyridis (HarmoBeetle®) + TX, Heterorhabditis spp. (Lawn Patrol®) + TX, Heterorhabditis bacteriophora (NemaShield®) + TX, HB® + TX, Nemaseek® + TX, Terranem-Nam® + TX, Terranem® + TX, Larvanem® + TX, B-Green® + TX, NemAttack® + TX, Nematop® + TX, Heterorhabditis megidis (Nemasys H® + TX, BioNem H® + TX, Exhibitline hm® + TX, Larvanem-M®) + TX, Hippodamiaconvergens + TX, Hypoaspis aculeifer (Aculeifer-System® + TX, Entomite-A®) + TX, Hypoaspis miles (Hypoline m® + TX, Entomite-M®) + TX, Lbalia leucospoides + TX, Lecanoideus floccissimus + TX, Lemophagus errabundus + TX, Leptomastidea abnormis + TX, Leptomastix dactylopii (Leptopar®) + TX, Leptomastix epona + TX, Lindorus lophanthae + TX, Lipolexis oregmae + TX, Lucilia caesar (Natufly®) + TX, Lysiphlebus testaceipes + TX, Macrolophus caliginosus (Mirical-N® + TX, Macroline c® + TX, Mirical®) + TX, Mesoseiulus longipes + TX, Metaphycus flavus + TX, Metaphycus lounsburyi + TX, Micromus angulatus (Milacewing®) + TX, Microterys flavus + TX, Muscidifurax raptorellus and Spalangia cameronicameroni (Biopar®) + TX, Neodryinus typhlocybae + TX, Neoseiulus californicus + TX, Neoseiulus cucumeris (THRYPEX®) + TX, Neoseiulus fallacis + TX, Nesideocoris tenuis (NesidioBug® + TX, Nesibug®) + TX, Ophyra aenescens (Biofly®) + TX, Orius insidiosus (Thripor-I® + TX, Oriline i®) + TX, Orius laevigatus (Thripor-L® + TX, Oriline l®) + TX, Orius majusculus (Oriline m®) + TX, Orius strigicollis (Thripor-S®) + TX, Pauesia juniperorum + TX, Pediobius foveolatus + TX, Phasmarhabditis hermaphrodita (Nemaslug®) + TX, Phymastichus coffea + TX, Phytoseiulus macropilus + TX, Phytoseiulus persimmon (Phytoseiulus persimilis (Spidex® + TX, Phytoline p®) + TX, Podisus maculiventris (Podisus®) + TX, Pseudacteon curvatus + TX, Pseudacteon obtususobtusus + TX, Pseudacteon tricuspis + TX, Pseudaphycus maculipennis + TX, Pseudleptomastix mexicana + TX, Psyllaephagus pilosus + TX, Psyttalia concolor (complex) + TX, Quadrastichus spp. + TX, Rhyzobius lophanthae + TX, Rodolia cardinalis + TX, Rumina decollate + TX, Semielacher petiolatus + TX, Sitobion avenae (Ervibank®) + TX, Steinernema carpocapsae (Nematac C® + TX, Millennium® + TX, BioNem C®+TX, NemAttack®+TX, Nemastar®+TX, Capsanem®+TX, Steinernema feltiae (NemaShield®+TX, Nemasys F®+TX, BioNem F®+TX, Steinernema-System®+TX, NemAttack®+TX, Nemaplus®+TX, Exhibitline sf®+TX, Scia-rid®+TX, Entonem®)+TX, Steinernema kraussei (Nemasys L®+TX, BioNem L®+TX, Exhibitline srb®)+TX, Steinernema riobrave riobrave) (BioVector® + TX, BioVektor®) + TX, Steinernema scapterisci (Nematac S®) + TX, Steinernema spp. + TX, Steinernema spp.) (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX, Trichogramma brassicae (Tricho-Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator;. Other biological agents include: abscisic acid +TX, bioSea® +TX, Chondrostereum purpureum (Chontrol Paste®) +TX, Colletotrichum gloeosporioides (Collego®) +TX, copper octanoate (Cueva®) +TX, delta traps (Trapline d®) +TX, Erwinia amylovora (Harpin) (ProAct® +TX, Ni-HIBIT Gold CST®) +TX, fatty acids derived from natural by-products of extra virgin olive oil (FLIPPER®) +TX, ferric phosphate (Ferri-phosphate) (Ferramol®) +TX, funnel traps (Trapline y®) +TX, Gallex® +TX, Grower's Secret® +TX, Homo-brassonolide +TX, Iron phosphate (Lilly Miller Worry Free Ferramol Slug & Snail Bait®) +TX, MCP hail trap (Trapline f®) +TX, Microctonus hyperodae +TX, Mycoleptodiscus terrestris (Des-X®) +TX, BioGain® +TX, Aminomite® +TX, Zenox® +TX, pheromone trap (Thripline ams®) + TX, potassium bicarbonate (MilStop®) + TX, potassium salts of fatty acids (Sanova®) + TX, potassium silicate solution (Sil-Matrix®) + TX, potassium iodide + potassium thiocyanate (Enzicur®) + TX, SuffOil-X® + TX, spider venom + TX, Nosema locustae (Semaspore Organic Grasshopper)Control®) + TX, sticky traps (Trapline YF® + TX, Rebell Amarillo®) + TX and traps (Takitrapline y+b®) + TX; (1) an antibacterial agent selected from the group consisting of: (1.1) Examples of such bacteria are: Bacillus mojavensis strain R3B (accession number NCAIM(P)B001389) from Certis USA LLC (a subsidiary of Mitsui & Co., Ltd.) (WO 2013 / 034938) + TX; Bacillus pumilus, in particular the strain BU F-33 with NRRL accession number 50185 (available as part of the CARTISSA® range from BASF, EPA registration number 71840-19) + TX; Bacillus subtilis, in particular the strain QST713 / AQ713 (SERENADE OPTI or SERENADE OPTI® from Bayer CropScience LP, US). No. 6,060,051 (available as ASO, NRRL accession number B21661) +TX; Bacillus subtilis strain BU1814 (available as VELONDIS® PLUS, VELONDIS® FLEX, and VELONDIS® EXTRA from BASF SE) +TX; Bacillus subtilis var. amyloliquefaciens strain FZB24 (available as TAEGRO® or TAEGRO® ECO (EPA registration number 70127-5) from Novozymes) +TX, with accession number DSM10271 +TX; Bacillus subtilis CX-9060 from Certis USA LLC (a subsidiary of Mitsui & Co., Ltd.) +TX; Bacillus sp. sp.), in particular strain D747 (available as DOUBLE NICKEL® from Kumiai Chemical Industry Co., Ltd.), having accession number FERM BP-8234, U.S. Pat. No. 7,094,592+TX; Paenibacillus sp., having accession number NRRL B-50972 or accession number NRRL B-67129) strain, WO 2016 / 154297 +TX; Paenibacillus polymyxa, in particular strain AC-1 (e.g., TOPSEED® from Green Biotech Company Ltd.) +TX; Pantoea agglomerans, in particular strain E325 (accession number NRRL B-21856) (available as BLOOMTIME BIOLOGICAL™ FD BIOPESTICIDE from Northwest Agri Products) +TX; Pseudomonas proradix from Sourcon Padena (e.g., PRORADIX®) +TX; and (1.2) Examples are fungi: Aureobasidium pullulans, in particular blastospores of the strain DSM 14940, blastospores of the strain DSM 14941 or a mixture of blastospores of the strains DSM 14940 and DSM 14941 (for example BOTECTOR® and BLOSSOM PROTECT® from bio-ferm, CH) + TX; Pseudozyma aphidis (disclosed in WO 2011 / 151819 by Yissum Research Development Company of the Hebrew University of Jerusalem) + TX; Saccharomyces cerevisiae from Lesaffre et Compagnie, FR. cerevisiae), in particular strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938 or CNCM No. 1-3939 (WO 2010 / 086790); (2) A biological bactericide or fungicide selected from the following group: (2.1) Examples are bacteria such as: Agrobacterium radiobacter strain K84 (e.g., GALLTROL-A® from AgBioChem, CA) + TX; Agrobacterium radiobacter strain K1026 (e.g., NOGALL® from BASF SE) + TX; Bacillus subtilis var. amyloliquefaciens strain FZB24 with accession number DSM10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA registration number 70127-5)) + TX; Bacillus amyloliquefaciens, in particular strain D747 (available as Double Nickel™ from Kumiai Chemical Industry Co., Ltd., with accession number FERM BP-8234, U.S. Pat. No. 7,094,592) +TX; Bacillus amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL accession number B-50768, WO 2014 / 028521) (STARGUS® from Marrone Bio Innovations) +TX; Bacillus amyloliquefaciens strain FZB42, accession number DSM 23117 (available as RHIZOVITAL® from ABiTEP, DE) +TX; Bacillus amyloliquefaciens isolate B246 (e.g. AVOGREEN™ from the University of Pretoria) +TX; Bacillus licheniformis, in particular strain SB3086 with accession number ATCC 55406, WO 2003 / 000051 (available as ECOGUARD™ Biofungicide and GREEN RELEAF™ from Novozymes) +TX +TX;Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (QUARTZO® (WG) and PRESENCE® (WP) from FMC Corporation) + TX; Bacillus methylotrophicus strain BAC-9912 (from the Chinese Academy of Sciences' Institute of Applied Ecology) + TX; Bacillus mojavensis strain R3B (accession number NCAIM(P)B001389) from Certis USA LLC (a subsidiary of Mitsui & Co., Ltd.) (WO 2013 / 034938) + TX; Bacillus mycoides mycoides, isolate, having accession number B-30890 (available from Certis USA LLC, a subsidiary of Mitsui & Co., Ltd., as BMJ TGAI® or WG and LifeGard®) +TX; Bacillus pumilus, particularly strain QST2808 (available from Bayer CropScience LP, US as SONATA®, having accession number NRRL B-30087, and described in U.S. Pat. No. 6,245,551) +TX; Bacillus pumilus, particularly strain GB34 (available from Bayer AG, DE as Yield Shield®) +TX; Bacillus pumilus, particularly strain BU, having NRRL accession number 50185 F-33 ​​(available as part of the CARTISSA product line from BASF, EPA registration number 71840-19) + TX; Bacillus subtilis, specifically strain QST713 / AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, US, with NRRL accession number B21661, as described in U.S. Pat. No. 6,060,051) + TX;Bacillus subtilis Y1336 (available from BioNTech, Taiwan as BIOBAC® WP, registered in Taiwan as a biological fungicide under registration numbers 4764, 5454, 5096, and 5277) +TX; Bacillus subtilis strain MBI 600 (available from BASF SE as SUBTILEX), having accession number NRRL B-50595, U.S. Pat. No. 5,061,495 +TX; Bacillus subtilis strain GB03 (available from Bayer AG, DE as Kodiak®) +TX; Bacillus subtilis strain BU1814 (available from BASF SE as SUBTILEX), having accession number NRRL B-50595, U.S. Pat. No. 5,061,495 +TX; available as VELONDIS® PLUS, VELONDIS® FLEX, and VELONDIS® EXTRA from SE (+TX); Bacillus subtilis CX-9060 from Certis USA LLC (a subsidiary of Mitsui & Co., Ltd.); Bacillus subtilis KTSB strain (FOLIACTIVE® from Donaghys) (+TX); Bacillus subtilis IAB / BS03 (AVIV® from STK Bio-Ag Technologies, PORTENTO® from Idai Nature) (+TX); Bacillus subtilis strain Y1336 (available as BIOBAC® WP from BioNTech, Taiwan, registered as a biological fungicide in Taiwan under registration numbers 4764, 5454, 5096, and 5277) + TX; Paenibacillus epiphyticus from BASF SE (WO 2016 / 020371) + TX; Paenibacillus polymyxa ssp. plantarum from BASF SE (WO 2016 / 020371) + TX;Paenibacillus sp. strains having accession number NRRL B-50972 or accession number NRRL B-67129, WO 2016 / 154297 +TX; Pseudomonas chlororaphis strain AFS009, having accession number NRRL B-50897, WO 2017 / 019448 (e.g., HOWLER™ and ZIO™ from AgBiome Innovations, US) +TX; Pseudomonas chlororaphis, in particular strain MA342 (e.g., CEDOMON™, CERALL™ and CEDRESS™ from Bioagri and Koppert) +TX; Pseudomonas fluorescens Pseudomonas fluorescens strain A506 (e.g., BLIGHTBAN® A506 by NuFarm) +TX; Pseudomonas proradix (e.g., PRORADIX® from Sourcon Padena) +TX; Streptomyces griseoviridis strain K61 (also known as Streptomyces galbus strain K61) (accession number DSM7206) (MYCOSTOP® from Verdera, PREFENCE® from BioWorks, see Crop Protection 2006, 25, 468-475) +TX; Streptomyces lydicus strain WYEC108 (Streptomyces lydicus strain WYCD108US) (ACTINO-IRON® and ACTINOVATE® manufactured by Novozymes) +TX; and (2.2) Examples of fungi are: Ampelomyces quisqualis, in particular the strain AQ 10 (for example AQ 10® from IntrachemBio Italia) + TX; Ampelomyces quisqualis strain AQ10 with accession number CNCM1-807 (for example AQ 10® from IntrachemBio Italia) + TX; Aspergillus flavus strain NRRL 21882 (product known as AFLA-GUARD® from Syngenta / ChemChina) + TX; Aureobasidium pullulans, in particular blastospores of the strain DSM 14940 + TX; Aureobasidium pullulans, in particular the strain DSM Aureobasidium pullulans, in particular a mixture of blastospores of strains DSM 14940 and DSM 14941 (e.g., Botector® by bio-ferm, CH) + TX; Chaetomium cupreum (accession number CABI 353812) (e.g., BIOKUPRUM® by AgriLife) + TX; Chaetomium globosum (available as RIVADIOM® by Rivale) + TX; Cladosporium cladosporioides, strain H39, with accession number CBS122244, as described in US Patent Application Publication No. 2010 / 0291039 (Stichting Dienst Landbouwkundig). Onderzoek) + TX; Coniothyrium minitans, in particular the strain CON / M / 91-8 (accession number DSM 9660, e.g. Contans® from Bayer CropScience Biologics GmbH) + TX;Cryptococcus flavescens, strain 3C (NRRL Y-50378) (B2.2.99) + TX; Dactylaria Candida + TX; Dilophosphora alopecuri (available as TWIST FUNGUS®) + TX; Fusarium oxysporum, strain Fo47 (available as FUSACLEAN® by Natural Plant Protection) + TX; Gliocladium catenulatum (syn: Clonostachys rosea f. catenulata) + TX; f. catenulate) strain J1446 (e.g., Prestop® by Lallemand) + TX; Gliocladium roseum (also known as Clonostachys rosea f. rosea), in particular strain 321U from the fungal Adjuvants Plus, strain ACM941 disclosed by Xue (Efficacy of Clonostachys rosea strain ACM941 and fungicide seed treatments for controlling the root complex of field pea, Can Jour Plant Sci 83(3):519-524) or strain IK726 (Jensen DF, et al. Development of a biocontrol agent for plant disease control with special emphasis on the near commercial fungal antagonist Clonostachys rosea strain 'IK726', Australasian Plant Pathol.2007,36:95-101)+TX;Lecanicillium lecanii (formerly known as Verticillium lecanii) conidia of strain KV01 (e.g. Vertalec® by Koppert / Arysta) + TX; Metschnikowia fructicola, in particular strain NRRL Y-30752, (B2.2.3) + TX; Microsphaeropsis ochracea + TX; Muscodor roseus, in particular strain A3-5 (accession number NRRL 30548) + TX; Penicillium stickii from BASF SE steckii (DSM27859, WO 2015 / 067800) + TX; Penicillium vermiculatum + TX; Phlebiopsis gigantea strain VRA 1992 (ROTSTOP® C from Danstar Ferment) + TX; Pichia anomala, strain WRL-076 (NRRL Y-30842), U.S. Pat. No. 7,579,183 + TX; Pseudozyma flocculosa, strain PF-A22 UL (available as SPORODEX® L from Plant Products Co., CA) + TX; Saccharomyces cerevisiae, particularly strain LASO2 (Agro-Levures et Derives), strain LAS117 cell walls (CEREVISANE® from Lesaffre, ROMEO® from BASF SE), strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938, CNCM No. 1-3939 from Lesaffre et Compagnie, FR (WO 2010 / 086790) +TX; Simplicillium lanosoniveum +TX;Talaromyces flavus, strain V117b +TX; Trichoderma asperelloides JM41R (accession number NRRL B-50759) (TRICHO PLUS® from BASF SE) +TX; Trichoderma asperellum, in particular the strain kd (e.g. T-Gro from Andermatt Biocontrol) +TX; Trichoderma asperellum, in particular the strain SKT-1, with accession number FERM P-16510 (e.g. ECO-HOPE® from Kumiai Chemical Industry Co., Ltd.), strain T34 (e.g. T34 Biocontrol from Biocontrol Technologies SL, ES) or strain ICC from Isagro. 012 +TX; Trichoderma atroviride, in particular the strain SC1 (with accession number CBS 122089, WO 2009 / 116106 and U.S. Pat. No. 8,431,120 (Bi-PA)), strain 77B (T77 from Andermatt Biocontrol) or strain LU132 (e.g. Sentinel from Agrimm Technologies Limited) +TX; Trichoderma atroviride, strain CNCM 1-1237 (e.g. Esquive® WP from Agrauxine, FR) +TX; Trichoderma atroviride, strain number V08 / 002387 +TX; Trichoderma atroviride atroviride), strain NMI number V08 / 002388+TX; Trichoderma atroviride, strain NMI number V08 / 002389+TX; Trichoderma atroviride, strain NMI number V08 / 002390+TX;Trichoderma atroviride, strain LC52 (e.g., Tenet by Agrimm Technologies Limited) + TX; Trichoderma atroviride, strain ATCC 20476 (IMI 206040) + TX; Trichoderma atroviride, strain T11 (IMI352941 / CECT20498) + TX; Trichoderma atroviride, strain SKT-1 (FERM P-16510), JP 11-253151 A + TX; Trichoderma atroviride, strain SKT-2 (FERM P-16511), JP 11-253151 A + TX; Trichoderma atroviride, strain SKT-3 (FERM P-17021), JP 11-253151 A + TX; Trichoderma fertile (e.g., the product TrichoPlus from BASF) + TX; Trichoderma gamsii (formerly known as T. viride); strain ICC080 (IMI CC 392151 CABI, e.g. BioDerma from AGROBIOSOL DE MEXICO, SADE CV) +TX; Trichoderma gamsii (formerly T. viride), strain ICC 080 (IMI CC 392151 CABI) (available as BIODERMA® from AGROBIOSOL DE MEXICO, SADE CV) +TX; Trichoderma harmatum +TX; Trichoderma harmatum with accession number ATCC 28012 +TX; Trichoderma harzianum strain T-22 (e.g. Trianum-P from Andermatt Biocontrol or Koppert) or strain Cepa SimbT5 (Simbiose Agro) +TX; Trichoderma harzianum +TX; Trichoderma harzianum rifai T39 (e.g. Trichodex® from Makhteshim, US) +TX; Trichoderma harzianum, strain ITEM 908 (e.g. Trianum-P from Koppert) +TX; Trichoderma harzianum, strain TH35 (e.g. Root-Pro by Mycontrol) +TX; Trichoderma harzianum, strain DB 103 (available as T-GRO® 7456 from Dagutat Biolab) +TX; Trichoderma polysporum, strain IMI 206039 (e.g., Binab TF WP by BINAB Bio-Innovation AB, Sweden) + TX; Trichoderma stromaticum with accession number Ts3550 (e.g., Tricovab by CEPLAC, Brazil) + TX;Trichoderma virens (also known as Gliocladium virens), in particular strain GL-21 (e.g., SoilGard by Certis, US) + TX; Trichoderma virens strain G-41, formerly known as Gliocladium virens (accession number ATCC 20906) (e.g., ROOTSHIELD® PLUS WP and TURFSHIELD® PLUS WP by BioWorks, US) + TX; Trichoderma viride, strain TV1 (e.g., Trianum-P by Koppert) + TX; Trichoderma viride, in particular strain B35 (Pietr et al., 1993, Zesz. Nauk. AR w Szczecinie 161:125-137) +TX; a mixture of Trichoderma asperellum strain ICC 012 (also known as Trichoderma harzianum ICC012), with accession number CABI CC IMI 392716, Trichoderma gamsii (formerly T. viride) strain ICC 080, with accession number IMI 392151 (e.g., BIO-TAM™ from Isagro USA, Inc. and BIODERMA® from Agrobiosol de Mexico, SA de CV) +TX; Ulocladium oudemansii (Ulocladium oudemansii), with accession number NM 99 / 06216 oudemansii strain U3 (e.g., BOTRY-ZEN® by Botry-Zen Ltd, New Zealand and BOTRYSTOP® by BioWorks, Inc.)+TX;Verticillium albo-atrum (formerly V. dahliae), strain WCS850 with accession number WCS850, deposited at the Central Bureau for Fungi Cultures (e.g., DUTCH TRIG® from Tree Care Innovations) +TX; Verticillium chlamydosporium +TX; (3) A biological control agent having the effect of improving plant growth and / or plant health selected from the following group: (3.1) Examples of bacteria include Azospirillum brasilense (e.g., VIGOR® from KALO, Inc.) + TX; Azospirillum lipoferum (e.g., VERTEX-IF® from TerraMax, Inc.) + TX; Azorhizobium caulinodans, in particular the strain ZB-SK-5 + TX; Azotobacter chroococcum, in particular the strain H23 + TX; Azotobacter vinelandii, in particular the strain ATCC 12837 + TX; Azotobacter vinelandii and Clostridium pasteurianum. a mixture of Bacillus pasteurianum (available as INVIGORATE® from Agrinos) + TX; Bacillus amyloliquefaciens pm414 (LOLI-PEPTA® from Biofilm Crop Protection) + TX; Bacillus amyloliquefaciens SB3281 (ATCC #PTA-7542, WO 2017 / 205258) + TX; Bacillus amyloliquefaciens TJ1000 (available as QUIKROOTS® from Novozymes) + TX; Bacillus Bacillus amyloliquefaciens, in particular the strain IN937a + TX; Bacillus amyloliquefaciens, in particular the strain FZB42 (e.g. RHIZOVITAL® from ABiTEP, DE) + TX; Bacillus amyloliquefaciens BS27 (accession number NRRL B-5015) + TX;Bacillus cereus family member EE128 (NRRL No. B-50917) + TX; Bacillus cereus family member EE349 (NRRL No. B-50928) + TX; Bacillus cereus, in particular strain BP01 (ATCC 55675, e.g., MEPICHLOR® from Arysta Lifescience, US) + TX; Bacillus firmus, in particular strain CNMC 1-1582 (e.g., VOTIVO® from BASF SE) + TX; Bacillus mycoides BT155 (NRRL No. B-50921) + TX; Bacillus mycoides EE118 (Bacillus mycoides Bacillus mycoides EE118 (NRRL No. B-50918) + TX; Bacillus mycoides EE141 (NRRL No. B-50916) + TX; Bacillus mycoides BT46-3 (NRRL No. B-50922) + TX; Bacillus pumilus, particularly strain QST2808 (Accession No. NRRL No. B-30087) + TX; Bacillus pumilus, particularly strain GB34 (e.g., YIELD SHIELD® from Bayer Crop Science, DE) + TX; Bacillus siamensis, particularly strain KCTC 13613T + TX; Bacillus subtilis subtilis, particularly strain QST713 / AQ713 (having NRRL accession number B-21661 and described in U.S. Pat. No. 6,060,051, available from Bayer CropScience LP, US as SERENADE® OPTI or SERENADE® ASO) + TX; Bacillus subtilis, particularly strain AQ30002 (having NRRL accession number B-50421 and described in U.S. Patent Application Publication No. 13 / 330,576) + TX;Bacillus subtilis, particularly strain AQ30004 (and described in NRRL B-50455 and U.S. Patent Application Publication No. 13 / 330,576) +TX; Bacillus subtilis strain BU1814, (available as TEQUALIS® from BASF SE), Bacillus subtilis rm303 (RHIZOMAX® from Biofilm Crop Protection) +TX; Bacillus thuringiensis BT013A (NRRL No. B-50924) (also known as Bacillus thuringiensis 4Q7) +TX; Bacillus licheniformis FMCH001 (Bacillus licheniformis a mixture of Bacillus subtilis FMCH001 and Bacillus subtilis FMCH002 (available from FMC Corporation as QUARTZO® (WG), PRESENCE® (WP)) + TX; Bacillus subtilis, particularly the strain MBI 600 (e.g., SUBTILEX® from BASF SE) + TX; Bacillus tequilensis, particularly the strain NII-0943 + TX; Bradyrhizobium japonicum (e.g., OPTIMIZE® from Novozymes) + TX; Delftia acidovorans, particularly the strain RAY209 (e.g., BIOBOOST® from Brett Young Seeds) + TX; Mesorhizobium Lactobacillus sp. (e.g., LACTOPLANT® from LactoPAFI) + TX;Rhizobium leguminosarium biovar viciae (e.g. NODULATOR from BASF SE) + TX; Pseudomonas proradix (e.g. PRORADIX® from Sourcon Padena) + TX; Pseudomonas aeruginosa, in particular the strain PN1 + TX; Rhizobium leguminosarum, in particular the bv.viceae strain Z25 (accession number CECT 4585) + TX; Paenibacillus polymyxa, in particular the strain AC-1 (e.g. TOPSEED® from Green Biotech Company Ltd.) + TX; Serratia marcescens, in particular the strain SRM (accession number MTCC 8708) + TX; Sinorhizobium meliloti strain NRG-185-1 (NITRAGIN® GOLD from Bayer CropScience) + TX; Thiobacillus sp. (e.g., CROPAID® from Cropaid Ltd UK) + TX; and (3.2) Examples of fungi are: Purpureocillium lilacinum (formerly known as Paecilomyces lilacinus) strain 251 (AGAL 89 / 030550, e.g. BioAct from Bayer CropScience Biologics GmbH) +TX; Penicillium bilaii, strain ATCC 22348 (e.g. JumpStart® from Acceleron BioAg), Talaromyces flavus, strain V117b +TX; Trichoderma atroviride strain CNCM 1-1237 (e.g. Esquive® WP from Agrauxine, FR), Trichoderma viride viride), e.g., strain B35 (Pietr et al., 1993, Zesz. Nauk.AR w Szczecinie 161:125-137) +TX; Trichoderma atroviride strain LC52 (also known as Trichoderma atroviride strain LU132, e.g. Sentinel from Agrimm Technologies Limited) +TX; Trichoderma atroviride strain SC1 as described in International Patent Application PCT / Italian Patent Application Publication No. 2008 / 000196 +TX; Trichoderma asperellum strain kd (e.g. T-Gro from Andermatt Biocontrol) +TX; Trichoderma asperellum strain Eco-T (Plant Health Products, ZA), Trichoderma harzianum harzianum strain T-22 (e.g. Trianum-P from Andermatt Biocontrol or Koppert) + TX; Myrothecium verrucaria strain AARC-0255 (e.g. DiTera™ from Valent Biosciences) + TX; Penicillium bilaii strain ATCC ATCC20851 + TX; Pythium oligandrum strain M1 (ATCC38472, e.g. Polyversum from Bioprepraty, CZ) + TX; Trichoderma virens strain GL-21 (e.g. SoilGard™ from Certis, USA) + TX; Verticillium alboatrum albo-atrum (formerly V. dahliae) strain WCS850 (CBS276).92, e.g. Dutch Trig from Tree Care Innovations) +TX; Trichoderma atroviride, in particular strain number V08 / 002387, strain number NMI number V08 / 002388, strain number NMI number V08 / 002389, strain number NMI number V08 / 002390 +TX; Trichoderma harzianum strain ITEM 908, Trichoderma harzianum strain TSTh20 +TX; Trichoderma harzianum strain 1295-22 +TX; Pythium oligandrum strain DV74 +TX; Rhizopogon amylopogon amylopogon (e.g., in Myco-Sol from Helena Chemical Company) + TX; Rhizopogon fulvigleba (e.g., in Myco-Sol from Helena Chemical Company) + TX; Trichoderma virens strain GI-3 + TX; (4) an insecticidally effective biological control agent selected from the following: (4.1) Examples are bacteria such as: Agrobacterium radiobacter strain K84 (Galltrol from AgBiochem Inc.) + TX; Bacillus amyloliquefaciens, in particular the strain PTS-4838 (e.g. AVEO from Valent Biosciences, US) + TX; Bacillus firmus, in particular the strain CNMC1-1582 (e.g. VOTIVO® from BASF SE) + TX; Bacillus mycoides, isolate J. (e.g. BmJ from Certis USA LLC (a subsidiary of Mitsui & Co., Ltd.)) + TX; Bacillus sphaericus, in particular the serotype H5a5b strain 2362 (strain ABTS-1743) (e.g. Valent Biosciences, US) + TX; BioSciences, US) + TX; Bacillus thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372, e.g., XENTARI® from Valent BioSciences) + TX; Bacillus thuringiensis subsp. aizawai, in particular serotype H-7 (e.g., FLORBAC® WG from Valent BioSciences, US) + TX; Bacillus thuringiensis israelensis strain BMP 144 (e.g., AQUABAC® from Becker Microbial Products, IL) + TX; Bacillus thuringiensis subsp. israelensis (Bacillus thuringiensis subsp.israelensis (serotype H-14) strain AM65-52 (accession number ATCC 1276) (e.g., VECTOBAC® from Valent BioSciences, US) +TX; Bacillus thuringiensis subsp. aizawai strain GC-91 +TX; Bacillus thuringiensis var. colmeri (e.g., TIANBAOBTC from Changzhou Jianghai Chemical Factory) +TX; Bacillus thuringiensis var. japonensis strain Buibui +TX; Bacillus thuringiensis subsp. kurstaki strain BMP 123 +TX from Becker Microbial Products, IL; Bacillus thuringiensis subsp. kurstaki strain BMP 123 by Bayer CropScience, Inc., IL, e.g., BARITONE+TX from Bayer CropScience; Bacillus thuringiensis subsp. kurstaki strain HD-1 (e.g., DIPEL® ES from Valent BioSciences, US)+TX; Bacillus thuringiensis var. kurstaki strain EVB-113-19 (e.g., BIOPROTEC® from AEF Global)+TX; Bacillus thuringiensis subsp. kurstaki strain ABTS351 ...kurstaki strain PB 54 + TX; Bacillus thuringiensis subsp. kurstaki strain SA 11 (JAVELIN from Certis, US) + TX; Bacillus thuringiensis subsp. kurstaki strain SA 12 (THURICIDE from Certis, US) + TX; Bacillus thuringiensis subsp. kurstaki strain EG2348 (LEPINOX from Certis, US) + TX; Bacillus thuringiensis subsp. kurstaki strain EG 7841 (CRYMAX from Certis, US) + TX; Bacillus thuringiensis subsp. tenebrionis thuringiensis subsp. tenebrionis strain NB176 (SD-5428, e.g. NOVODOR® FC from BioFa DE) + TX; Brevibacillus laterosporus (LATERAL from Ecolibrium Biologicals) + TX; Burkholderia spp.), in particular Burkholderia rinojensis strain A396 (also known as Burkholderia rinojensis strain MBI 305) (Accession No. NRRL B-50319 +TX; WO 2011 / 106491 and WO 2013 / 032693 +TX; e.g., MBI206 TGAI and ZELTO® +TX from Marrone Bio Innovations); Chromobacterium subtsugae, in particular strain PRAA4-1T (MBI-203 +TX; e.g., GRANDEVO® from Marrone Bio Innovations) +TX; Lecanicillium muscarium Ve6 (Lecanicillium muscarium Ve6) (MYCOTAL from Koppert) + TX; Paenibacillus popilliae (formerly Bacillus popilliae) + TX; e.g., MILKY SPORE POWDER™ and MILKY SPORE GRANULAR™ from St. Gabriel Laboratories + TX; Pasteuria nishizawae strain Pn1 (CLARIVA from Syngenta / ChemChina) + TX; Serratia entomophila (e.g., INVADE® by Wrightson Seeds) + TX; Serratia marcescens, particularly strain SRM (accession number MTCC 8708) + TX; Trichoderma asperellum asperellum (TRICHODERMAX from Novozymes) + TX; Wolbachia pipientis ZAP strain (e.g., ZAP MALES® from MosquitoMate) + TX; and (4.2) Examples of fungi are: Beauveria bassiana strain ATCC 74040 (e.g. NATURALIS® from Intrachem Bio Italia) + TX; Beauveria bassiana strain GHA (accession number ATCC 74250, e.g. BOTANIGUARD® ES and MYCONTROL-O® from Laverlam International Corporation) + TX; Beauveria bassiana strain ATP02 (accession number DSM24665) + TX; Isaria fumosorosea (formerly known as Paecilomyces fumosoroseus) strain Apopka from SePRO. 97) PREFERAL + TX; Metarhizium anisopliae 3213-1 (deposited under NRRL accession number 67074) (WO 2017 / 066094 + TX; Pioneer Hi-Bred International) + TX; Metarhizium robertsii 15013-1 (deposited under NRRL accession number 67073) + TX; Metarhizium robertsii 23013-3 (deposited under NRRL accession number 67075) + TX; Paecilomyces lilacinus strain 251 (MELOCON from Certis, US) + TX; Zooftora radicans + TX; (5) A virus selected from the group consisting of: Adoxophyes orana (smaller apple tortrix) granulosis virus (GV) + TX; Cydia pomonella (codling moth) granulosis virus (GV) + TX; Helicoverpa armigera (cotton bollworm) nucleopolyhedrovirus (NPV) + TX; Spodoptera exigua (beet armyworm) mNPV + TX; Spodoptera frugiperda (stalk armyworm) mNPV + TX; Spodoptera littoralis (Egyptian armyworm) NPV + TX; (6) Bacteria and fungi that can be added as an "inoculant" to plants or plant parts or plant tissues and that promote plant growth and plant health due to their specific properties, selected from the following: Agrobacterium spp. + TX; Azorhizobium caulinodans + TX; Azospirillum spp. + TX; Azotobacter spp. + TX; Bradyrhizobium spp. + TX; Burkholderia spp., in particular Burkholderia cepacia (formerly known as Pseudomonas cepacia) + TX; Gigaspora spp. spp.) or Gigaspora monosporum + TX; Glomus spp. + TX; Laccaria spp. + TX; Lactobacillus buchneri + TX; Paraglomus spp. + TX; Pisolithus tinctorus + TX; Pseudomonas spp. + TX; Rhizobium spp., especially Rhizobium trifolii + TX; Rhizopogon spp. + TX; Scleroderma spp. + TX; Suillus spp.) + TX;Streptomyces spp.) + TX; (7) Plant extracts and products formed by microorganisms containing proteins and secondary metabolites that can be used as biological control agents, selected from the following: garlic (Allium sativum) (NEMGUARD from Eco-Spray) + TX; BRALIC from ADAMA) + TX; Armour-Zen + TX; Artemisia absinthium + TX; azadirachtin (e.g. AZATIN XL from Certis, US) + TX; Biokeeper WP + TX; Brassicaceae extracts, in particular rapeseed powder or mustard powder + TX; Cassia nigricans + TX; Celastrus angulatus + TX; Chenopodium anthelminticum + TX; chitin + TX; Dryopteris filix-mas) + TX; Horsetail (Equisetum arvense) + TX; Fortune Aza + TX; Fungastop + TX; Heads Up (Quinoa (Chenopodium quinoa) saponin extract) + TX; PROBLAD (Natural Blad Polypeptide from Lupine Seed), Certis EU + TX; FRACTURE (Natural Blad Polypeptide from Lupine Seed), FMC + TX; Calyx / Pyrethrin + TX; Quassia amara + TX; Quercus (Quercus spp.) + TX; Quillaja (Quillaja) extract (QL AGRI 35 from BASF) + TX; Giant Knotweed (Reynoutria sachalinensis) extract (REGALLIA / REGALIA from Marrone Bio) MAXX) + TX; "Requiem™ Insecticide" + TX; Rotenone + TX; Ryania / Ryanodine + TX; Comfrey (Symphytum officinale) + TX; Tansy (Tanacetum vulgare) + TX; Thymol + TX; Thymol mixed with geraniol (CEDROZ from Eden Research) + TX;Thymol mixed with geraniol and eugenol (MEVALONE from Eden Research) +TX; Triact 70 +TX; TriCon +TX; nasturtium (Tropaeulum majus) +TX; Melaleuca alternifolia extract (TIMOREX GOLD from STK) +TX; nettle (Urtica dioica) +TX; veratrine +TX; and mistletoe (Viscum album) +TX; and Safeners such as benoxacor + TX, cloquintocet (including cloquintocet-mexyl) + TX, cyprosulfamide + TX, dichlormid + TX, fenchlorazole (including fenchlorazole-ethyl) + TX, fenclorim + TX, fluxofenim + TX, furilazole + TX, isoxadifen (including isoxadifen-ethyl) + TX, mefenpyr (including mefenpyr-diethyl) + TX, metcamifen + TX and oxabetrinil + TX.

[0346] The mixture can be used in a method of controlling pests, the method comprising the step of applying a composition comprising the mixture to the pest or its environment, excluding methods of treatment of the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body.

[0347] Mixtures comprising a compound of formula I selected from Tables A-1 to A-3, B-1 to B-3, C-1 to C-3, D-1 to D-3, E-1 to E-3, and F-1 to F-3 and Table P and one or more of the active ingredients described above can be applied, for example, in a single ready-mix form, as a combined spray mixture made up of separate formulations of a single active ingredient, such as a "tank mix," and in combination with the single ...

Claims

1. Compounds of formula (I): 【Chemical 1】 (In the formula, Q is a group of the formulas Qa, Qb and Qc 【Chemistry 2】 where the arrow indicates the point of attachment to the nitrogen atom of the tricyclic ring. is a group selected from the group consisting of: and, A, A 1 and A 2 are, independently of each other, CH or N; X is S, SO, or SO 2 and R 1 is C 1 ~C 4 Alkyl or C 3 ~C 6 Cycloalkyl-C 1 ~C 4 is alkyl; R 3 , R 4 , R 5 and R 6 are each independently hydrogen, halogen, C 1 ~C 4 Alkyl, C 1 ~C 6 Haloalkyl, C 3 ~C 6 Cycloalkyl, monosubstituted with cyano 3 ~C 6 Cycloalkyl, C 1 ~C 6 Cyanoalkyl, C 1 ~C 6 Cyanoalkoxy, cyano, C 1 ~C 4 Alkoxy, C 1 ~C 6 haloalkoxy, —N(R 9 R 10 ) or -N(R 9 ) C(=O)R 10 and R 9 and R 10 are each independently hydrogen, C 1 ~C 4 Alkyl, C 1 ~C 6 Haloalkyl or C 3 ~C 6 is cycloalkyl; R 7 and R 8 are each independently hydrogen, halogen, C 1 ~C 4 Alkyl, C 1 ~C 6 Haloalkyl, C 3 ~C 6 Cycloalkyl, monosubstituted with cyano 3 ~C 6 Cycloalkyl, C 1 ~C 6 Cyanoalkyl, C 1 ~C 6 Cyanoalkoxy, cyano, C 1 ~C 4 Alkoxy, C 1 ~C 6 haloalkoxy or —N(R 11 ) C(=O)R 12 and R 11 and R 12 are each independently hydrogen, C 1 ~C 4 Alkyl, C 1 ~C 6 Haloalkyl or C 3 ~C 6 cycloalkyl).

2. Compound of formula I-1: 【Chemistry 3】 (In the formula, X, R 1 , R 3 , R 4 , R 9 and R 10 is as defined in formula I in claim 1), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of the compound of formula I-1.

3. R 3 and R 4 are each independently hydrogen, halogen, C 1 ~C 4 Alkyl, C 1 ~C 6 Haloalkyl, C 3 ~C 6 Cycloalkyl, monosubstituted with cyano 3 ~C 6 Cycloalkyl, C 1 ~C 6 Cyanoalkyl, C 1 ~C 6 Cyanoalkoxy, cyano, C 1 ~C 4 Alkoxy, C 1 ~C 6 haloalkoxy or —N(R 9 ) C(=O)R 10 and R 9 and R 10 are each independently hydrogen or C 1 ~C 4 alkyl; preferably, R 9 and R 10 are, independently of each other, hydrogen or methyl; more preferably, R 9 is hydrogen or methyl, and R 10 3. The compound of claim 1, wherein is methyl.

4. R 4 is hydrogen, and R 3 is hydrogen, trifluoromethyl, 1,1-difluoroethyl, —OCHF 2 , -OCH 2 CHF 2 , -OCH 2 CF 3 , cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF 2 , -OC(CH 3 ) 2 CN, -NHC(O)CH 3 or -NCH 3 C(O)CH 3 or a compound according to claim 1 or claim 2, 3 is hydrogen, and R 4 is trifluoromethyl, 1,1-difluoroethyl, -OCHF 2 , -OCH 2 CHF 2 , -OCH 2 CF 3 , cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF 2 , -OC(CH 3 ) 2 CN, -NHC(O)CH 3 or -NCH 3 C(O)CH 3 The compound of formula I-1,

5. Compound of formula I-2: 【Chemistry 4】 (In the formula, X, R 1 , R 5 , R 6 , R 9 and R 10 is as defined in formula I in claim 1), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of a compound of formula I-2.

6. R 5 and R 6 are each independently hydrogen, halogen, C 1 ~C 4 Alkyl, C 1 ~C 6 Haloalkyl, C 3 ~C 6 Cycloalkyl, monosubstituted with cyano 3 ~C 6 Cycloalkyl, C 1 ~C 6 Cyanoalkyl, C 1 ~C 6 Cyanoalkoxy, cyano, C 1 ~C 4 Alkoxy, C 1 ~C 6 haloalkoxy or —N(R 9 ) C(=O)R 10 and R 9 and R 10 are each independently hydrogen or C 1 ~C 4 alkyl; preferably, R 9 and R 10 are each independently hydrogen or methyl, more preferably R 9 is hydrogen or methyl, and R 10 6. The compound of claim 1, wherein is methyl.

7. R 6 is hydrogen, and R 5 is hydrogen, trifluoromethyl, 1,1-difluoroethyl, —OCHF 2 , -OCH 2 CHF 2 , -OCH 2 CF 3 , cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF 2 , -OC(CH 3 ) 2 CN, -NHC(O)CH 3 or -NCH 3 C(O)CH 3 or a compound according to claim 1 or claim 5, 5 is hydrogen, and R 6 is trifluoromethyl, 1,1-difluoroethyl, -OCHF 2 , -OCH 2 CHF 2 , -OCH 2 CF 3 , cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF 2 , -OC(CH 3 ) 2 CN, -NHC(O)CH 3 or -NCH 3 C(O)CH 3 The compound of formula I-2, wherein

8. Compound of formula I-3: 【Chemistry 5】 (In the formula, A, A 1 , A 2 , X, R 1 , R 7 , R 8 , R 11 and R 12 is as defined in formula I in claim 1), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of the compound of formula I-3.

9. R 7 and R 8 are each independently hydrogen, halogen, C 1 ~C 4 Alkyl, C 1 ~C 6 Haloalkyl, C 3 ~C 6 Cycloalkyl, monosubstituted with cyano 3 ~C 6 Cycloalkyl, C 1 ~C 6 Cyanoalkyl, C 1 ~C 6 Cyanoalkoxy, cyano, C 1 ~C 4 Alkoxy, C 1 ~C 6 haloalkoxy or —N(R 11 ) C(=O)R 12 and R 11 and R 12 are each independently hydrogen or C 1 ~C 4 alkyl; preferably, R 11 and R 12 are, independently of each other, hydrogen or methyl; more preferably, R 11 is hydrogen or methyl, and R 12 9. The compound of claim 1 or claim 8, wherein is methyl.

10. R 8 is hydrogen, and R 7 is hydrogen, trifluoromethyl, 1,1-difluoroethyl, —OCHF 2 , -OCH 2 CHF 2 , -OCH 2 CF 3 , cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF 2 , -OC(CH 3 ) 2 CN, -NHC(O)CH 3 or -NCH 3 C(O)CH 3 or a compound according to claim 1 or claim 8, wherein R 7 is hydrogen, and R 8 is trifluoromethyl, 1,1-difluoroethyl, -OCHF 2 , -OCH 2 CHF 2 , -OCH 2 CF 3 , cyclopropyl, cyanocyclopropyl, cyanoisopropyl, trifluoromethoxy, -CHF 2 , -OC(CH 3 ) 2 CN, -NHC(O)CH 3 or -NCH 3 C(O)CH 3 The compound of formula I-3,

11. 9. The compound of claim 1 or claim 8, wherein A is N.

12. A 1 and A 2 and are both CH.

13. A 1 and A 2 and are both N.

14. A 1 is N, and A 2 is CH; or A 1 is CH, and A 2 is N.

15. X is S or SO 2 and preferably, X is SO 2 and R 1 is ethyl or cyclopropylmethyl; preferably, R 1 The compound of claim 1 , wherein is ethyl.

16. Compound of formula I-4: 【Chemistry 6】 (In the formula, Q1 is a group of the formula Q1a, Q1b and Q1c 【Chemistry 7】 where the arrow indicates the point of attachment to the nitrogen atom of the tricyclic ring. is a group selected from the group consisting of: As well as A, A 1 , A 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 is as defined in formula I in claim 1), or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide of the compound of formula I-4.

17. 6-[3-ethylsulfonyl-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P1); 6-(3-ethylsulfonyl-2-quinolyl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P2); 6-[3-ethylsulfonyl-6-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P3); 6-(6-cyclopropyl-3-ethylsulfonyl-pyrazolo[1,5-a]pyridin-2-yl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P4); 6-[3-ethylsulfonyl-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P5); 6-[3-ethylsulfonyl-5-(trifluoromethyl)pyrazolo[1,5-a]pyridin-2-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P6); 6-[6-(1,1-difluoroethyl)-3-ethylsulfonyl-imidazo[1,2-a]pyridin-2-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P7); 6-[7-(1,1-difluoroethyl)-3-ethylsulfonyl-imidazo[1,2-a]pyridin-2-yl]-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P8); 6-(7-Bromo-3-ethylsulfonyl-imidazo[1,2-a]pyridin-2-yl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P9); 6-(6-Bromo-3-ethylsulfonyl-imidazo[1,2-a]pyridin-2-yl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P10); 6-(6-chloro-3-ethylsulfonyl-imidazo[1,2-a]pyridin-2-yl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P11); 6-(6-Bromo-3-ethylsulfonyl-pyrazolo[1,5-a]pyridin-2-yl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P12); 6-(7-chloro-3-ethylsulfonyl-imidazo[1,2-a]pyridin-2-yl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P13); 6-(6-chloro-3-ethylsulfonyl-pyrazolo[1,5-a]pyridin-2-yl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P14); 6-(5-chloro-3-ethylsulfonyl-pyrazolo[1,5-a]pyridin-2-yl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P15); 6-(3-ethylsulfonyl-7-iodo-imidazo[1,2-a]pyridin-2-yl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P16); 6-(3-ethylsulfonyl-6-iodo-imidazo[1,2-a]pyridin-2-yl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P17); and 6-(3-Ethylsulfonylimidazo[1,2-a]pyridin-2-yl)-2,2-difluoro-5H-[1,3]dioxolo[4,5-f]isoindol-7-one (compound P18) 2. The compound of formula I according to claim 1, selected from the group consisting of:

18. 10. A composition comprising an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) according to claim 1, or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, and optionally an auxiliary or diluent.

19. 19. A method for combating and controlling insects, acaridae, nematodes or molluscs, the method comprising the step of applying to the pest, the pest's habitat or plants susceptible to attack by the pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as defined in claim 1 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, or a composition as defined in claim 18.

20. 20. A method for protecting plant propagation material from attack by insects, mites, nematodes or mollusks, comprising treating the propagation material or the location where the propagation material is planted with the composition of claim 18.

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