Pesticidal Active Diazine-Amide Compounds

Abstract

The compounds of formula (I) wherein the substituents are as defined in claim 1 and the agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of these compounds may be used as insecticides. TIFF2024524883000102.tif47105

Description

[Technical Field]

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

[0002] WO 2020 / 070049, WO 2020 / 201398 and WO 2021 / 068179 describe certain diazine-amide compounds.

[0003] Novel pesticidally active bispyrazine amide compounds have now been discovered. Summary of the Invention [Means for solving the problem]

[0004] Thus, in a first aspect, the present invention provides a compound of formula I [ka] (In the formula, X is O or S; R1 is H, C1-C6 alkyl, C1-C6 cyanoalkyl, aminocarbonylC1-C6 alkyl, hydroxycarbonylC1-C6 alkyl, trimethylsilylC1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C4 cycloalkylC1-C2 alkyl, C3-C4 cycloalkylC1-C2 alkyl (wherein the C3-C4 cycloalkyl group is substituted with 1 or 2 halo atoms), oxetan-3-yl-CH2-, benzyl, or benzyl substituted with halogen; R 2ais H, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 haloalkylthio, C1-C3 alkoxy, C1-C3 haloalkoxy, SF5, CN, C3-C6 cycloalkyl; C3-C6 cycloalkyl substituted by 1 to 3 substituents independently selected from C1-C3 alkyl, C1-C3 haloalkyl, cyano, C1-C3 alkoxy, and halogen; C3-C6 cycloalkylC1-C4 alkyl; C1-C3 alkyl, C1-C C3-C6 cycloalkylC1-C4 alkyl substituted by 1-5 substituents independently selected from haloalkyl, cyano, and halogen; C1-C5 cyanoalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfinyl, C1-C4 haloalkylsulfinyl, C3-C6 cycloalkylsulfanyl, C3-C6 cycloalkylsulfinyl, or C3-C6 cycloalkylsulfonyl; R 2b is H, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 haloalkylthio, C1-C3 alkoxy, C1-C3 haloalkoxy, SF5, or CN; A is N or CR 2c and; R 2c is H, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; R3 is C1-C3 alkyl or C1-C3 haloalkyl; R4 is [ka] where R 4a is hydrogen, halogen, CN, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, and C(=O)NR 4aa R 4ab (where R 4aa and R 4ab are each independently selected from hydrogen, C1-C3 alkyl, C3-C5 cycloalkyl, or R 4aa and R4ab together with the nitrogen atom to which they are attached, form a 3- to 12-membered saturated or partially unsaturated heterocyclyl which may further contain a heteroatom selected from oxygen and sulfur, and the heterocyclyl is optionally substituted with 1 to 3 substituents. Selected from; R 4b is hydrogen, halogen, CN, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, and C(=O)NR 4aa R 4ab (where R 4aa and R 4ab are each independently selected from hydrogen, C1-C3 alkyl, C3-C5 cycloalkyl, or R 4aa and R 4ab together with the nitrogen atom to which they are attached, form a 3- to 12-membered saturated or partially unsaturated heterocyclyl which may further contain a heteroatom selected from oxygen and sulfur, and the heterocyclyl is optionally substituted with 1 to 3 substituents. Selected from; R 4c is hydrogen, halogen, CN, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, and C1-C3 haloalkoxy, or R 4a , and R 4c Selected from; R 5a and R 5b are each independently selected from hydrogen, halogen, CN, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, and C1-C3 haloalkoxy. or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer and N-oxide of a compound of formula I. DETAILED DESCRIPTION OF THE INVENTION

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

[0006] 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.

[0007] 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.

[0008] The compounds of formula I according to the present invention also include the hydrates which may be formed during salt formation.

[0009] As used herein, "C1-C n The term "alkyl" refers to a saturated straight or branched hydrocarbon radical having 1 to n carbon atoms attached via any of the carbon atoms, such as any one of the radicals 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.

[0010] As used herein, "C1-C nThe term "haloalkyl" refers to a straight or branched saturated alkyl radical having 1 to n carbon atoms bonded via any of the carbon atoms (as defined above), wherein some or all of the hydrogen atoms in these radicals 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. The term "C1-C2 fluoroalkyl" refers to a C1-C2 alkyl radical 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.

[0011] As used herein, "C1-C nThe term "alkoxy" refers to a straight or branched saturated alkyl radical having 1 to n carbon atoms (as defined above) 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 radicals. As used herein, "haloC1-C n The term "alkoxy" refers to a C1-C alkyl radical in which one or more hydrogen atoms on the alkyl radical are replaced by the same or different halo atoms. n refers to an alkoxy radical (examples include trifluoromethoxy, 2-fluoroethoxy, 3-fluoropropoxy, 3,3,3-trifluoropropoxy, 4-chlorobutoxy).

[0012] As used herein, "C1-C n The term "cyanoalkyl" refers to a linear or branched saturated C1-C alkyl group having 1 to n carbon atoms. n It refers to alkyl radicals (as defined above) in which one of the hydrogen atoms in these radicals is replaced by a cyano group, for example, cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, 3-cyanopropyl, 1-(cyanomethyl)-2-ethyl, 1-(methyl)-2-cyanoethyl, 4-cyanobutyl, and the like.

[0013] As used herein, "C3-C n The term "cycloalkyl" refers to a 3 to n-membered cycloalkyl group, such as cyclopropane, cyclobutane, cyclopentane, and cyclohexane.

[0014] As used herein, the term "C3-C4 cycloalkyl-C1-C2 alkyl-" refers to a 3- or 4-membered cycloalkyl group having either a methylene or ethylene group attached to the remainder of the molecule, where the C3-C4 cycloalkyl-C1-C2 alkyl- group is substituted and the substituents can be on the cycloalkyl group and / or the alkyl group.

[0015] As used herein, "aminocarbonyl C1-C n The term "alkyl" refers to an alkyl radical, wherein one of the hydrogen atoms in the radical is replaced by a CONH2 group.

[0016] As used herein, "hydroxycarbonyl C1-C n The term "alkyl" refers to an alkyl radical in which one of the hydrogen atoms in the radical has been replaced by a COOH group.

[0017] As used herein, "C1-C n The term "alkylsulfanyl" refers to a C1-C alkyl group bonded through a sulfur atom. n Similarly, as used herein, "C1-C" refers to an alkyl moiety. n Haloalkylthio" or "C1-C n The term "haloalkylsulfanyl" refers to a C1-C alkyl group bonded through a sulfur atom. n It refers to the haloalkyl moiety. Similarly, "C3-C n The term "cycloalkylsulfanyl" refers to a 3 to n-membered cycloalkyl moiety attached through a sulfur atom.

[0018] As used herein, "C1-C n The term "alkylsulfinyl" refers to a C1-C alkyl group bonded through the sulfur atom of the S(=O) group. n Similarly, as used herein, "C1-C" refers to an alkyl moiety. n Haloalkylsulfinyl" or "C1-C n The term "haloalkylsulfinyl" refers to a C1-C alkyl group bonded through the sulfur atom of the S(=O) group. n It refers to the haloalkyl moiety. Similarly, "C3-C n The term "cycloalkylsulfinyl" refers to a 3 to n-membered cycloalkyl moiety attached through the sulfur atom of an S(=O) group.

[0019] As used herein, "C1-C n The term "alkylsulfonyl" refers to a C1-C alkyl group bonded through the sulfur atom of the S(=O)2 group. n Similarly, as used herein, "C1-C" refers to an alkyl moiety. n Haloalkylsulfonyl" or "C1-C n The term "haloalkylsulfonyl" refers to a C1-C2 alkyl group bonded through the sulfur atom of the S(=O)2 group. n It refers to the haloalkyl moiety. Similarly, "C3-C n The term "cycloalkylsulfonyl" refers to a 3- to n-membered cycloalkyl moiety attached through the sulfur atom of an S(=O)2 group.

[0020] As used herein, "trimethylsilyl C1-C n The term "alkyl" refers to C1-C n It refers to a radical in which one of the hydrogen atoms in the radical is replaced by a -Si(CH3)3 group.

[0021] As used herein, "C2-C n The term "alkenyl" refers to a straight or branched alkenyl chain having 2 to n carbon atoms and one or two double bonds, for example ethenyl, prop-1-enyl, but-2-enyl.

[0022] As used herein, "C2-C n The term "haloalkenyl" refers to a C-C alkyl group substituted with one or more halo atoms, which may be the same or different. n Refers to the alkenyl moiety.

[0023] As used herein, "C2-C n The term "alkynyl" refers to a straight or branched alkynyl chain having 2 to n carbon atoms and one triple bond, for example, ethynyl, prop-2-ynyl, but-3-ynyl.

[0024] As used herein, "C2-Cn The term "haloalkynyl" refers to a C-C alkyl group substituted with one or more halo atoms, which may be the same or different. n Refers to the alkynyl moiety.

[0025] R 4aa and R4 ab The term "heterocyclyl" as used herein in connection with 2-oxa-6-azaspiro[3.3]heptan-6-yl, 6-oxa-3-azabicyclo[3.1.1]heptan-3-yl, 1,4-oxazepan-4-yl, thiomorpholin-4-yl, 1,1-dioxidethiomorpholin-4-yl, 4-methylpiperazin-1-yl, morpholin-4-yl, piperidin-1-yl, pyrrolidin-1-yl, azetidin-1-yl, 3-oxopiperazin-1-yl, 4-methyl ... -methyl-3-oxo-piperazin-1-yl, 3,5-dioxopiperazin-1-yl, 3,3-dimethyl-1,3-azasilinan-1-yl, thiomorpholin-4-yl, wherein morpholin-4-yl, piperidin-1-yl, pyrrolidin-1-yl and azetidin-1-yl may be optionally substituted with 1 to 4 substituents selected from the group consisting of fluorine, hydroxy, methyl, methoxy, 1,2,4-oxadiazolyl, and 2-methylpyrazolyl.

[0026] Halogen or "halo" is generally fluorine, chlorine, bromine or iodine. This applies correspondingly to the combination of halogen with other meanings, such as haloalkyl.

[0027] As used herein, the term "control" refers to reducing the number of pests so that damage to plants or plant-derived products is reduced, eradicating pests, and / or preventing further pest damage.

[0028] As used herein, the wavy lines, for example in R4 and K-1, represent the points of attachment / connection to the remainder of the compound.

[0029] As used herein, the term "pest" refers to insects and mollusks found in agriculture, horticulture, forestry, and storage of plant-derived products (such as fruit, grain, and lumber); and pests associated with damage to man-made structures. The term pest encompasses all stages in the life cycle of a pest.

[0030] As used herein, the term "effective amount" refers to that amount of a compound or salt thereof that produces a desired effect in single or multiple applications.

[0031] An effective amount is readily determined by one skilled in the art by the use of known techniques and by observing results obtained under analogous circumstances. Determining an effective amount takes into account numerous factors, including, but not limited to, the type of plant or plant-derived product to which it is applied; the pest to be controlled and its life cycle; the particular compound applied; the type of application; and other relevant circumstances.

[0032] As one of ordinary skill in the art would understand, compounds of formula I contain a stereogenic center, as indicated by an asterisk in the structure below: [ka] In the formula, A, X, R1, R 2a , R 2b , R3, R4, R 5a and R 5b is as defined in the first aspect.

[0033] The present invention contemplates both the racemate and the individual enantiomers. Compounds with preferred stereochemistry are shown below. [ka]

[0034] Particularly preferred compounds of the invention have formula I'a: (In the formula, A, X, R1, R 2a , R 2b, R3, R4, R 5a and R 5b is as defined in the first aspect) and the stereoisomers, enantiomers, tautomers and N-oxides of the compounds of formula (I'a), and agrochemically acceptable salts thereof.

[0035] As used herein, the term "optionally substituted" means that the group to which it is being referred is unsubstituted or optionally substituted with specified substituents; for example, "C3-C4 cycloalkyl optionally substituted with 1 or 2 halo atoms" means C3-C4 cycloalkyl, C3-C4 cycloalkyl substituted with 1 halo atom, and C3-C4 cycloalkyl substituted with 2 halo atoms.

[0036] Embodiments according to the present invention are provided as follows.

[0037] In one embodiment of each aspect of the invention, X is O.

[0038] In one embodiment of each aspect of the invention, R1 is A. hydrogen, methyl, ethyl, n-propyl, isobutyl, cyclopropylmethyl, or HCH≡CCH2-; or B. hydrogen, methyl, or cyclopropylmethyl; or C. hydrogen; or D. Methyl; or E. cyclopropylmethyl (i.e., C3H5CH2); or F. Hydrogen or methyl is.

[0039] In one embodiment of each aspect of the invention, A is AN; or BC-R 2c where R 2c is hydrogen or halogen (such as Cl, F, Br and I); preferably, R 2cis hydrogen; or C.CH is.

[0040] In one embodiment of each aspect of the invention, R 2a teeth, A. halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 haloalkylthio, C1-C3 alkoxy, C1-C3 haloalkoxy, CN, C3-C6 cycloalkyl; C3-C6 cycloalkyl substituted with 1 to 3 substituents independently selected from C1-C3 alkyl, C1-C3 haloalkyl, cyano, C1-C3 alkoxy, and halogen; C3-C6 cycloalkyl C1-C4 alkyl; C1-C3 alkyl, C1-C3 haloal C3-C6 cycloalkylC1-C4 alkyl substituted with 1 to 5 substituents independently selected from alkyl, cyano, and halogen; C1-C5 cyanoalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfinyl, C1-C4 haloalkylsulfinyl, C3-C6 cycloalkylsulfanyl, C3-C6 cycloalkylsulfinyl, or C3-C6 cycloalkylsulfonyl; or B. halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 haloalkylthio, C1-C3 alkoxy, C1-C3 haloalkoxy, CN, C3-C6 cycloalkyl; C3-C6 cycloalkyl substituted with 1 or 2 substituents independently selected from C1-C3 haloalkyl, cyano, C1-C3 alkoxy, and halogen; C3-C6 cycloalkyl C1-C4 alkyl; C3-C6 cycloalkyl C1-C4 alkyl substituted with 1 to 3 substituents independently selected from C1-C3 haloalkyl, cyano, and halogen; C1-C5 cyanoalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfinyl, C1-C4 haloalkylsulfinyl, C3-C6 cycloalkylsulfanyl, C3-C6 cycloalkylsulfinyl, or C3-C6 cycloalkylsulfonyl; or C. halogen, C1-C3 haloalkyl, C1-C3 haloalkylthio, C1-C3 haloalkoxy, C3-C6 cycloalkyl; C3-C6 cycloalkyl substituted with 1 or 2 substituents independently selected from C1-C3 haloalkyl, cyano, C1-C3 alkoxy, and halogen; C3-C6 cycloalkylC1-C4 alkyl; C3-C6 cycloalkylC1-C4 alkyl substituted with 1 to 3 substituents independently selected from C1-C3 haloalkyl, cyano, and halogen; C1-C5 cyanoalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfinyl, C1-C4 haloalkylsulfinyl, C3-C6 cycloalkylsulfanyl, C3-C6 cycloalkylsulfinyl, or C3-C6 cycloalkylsulfonyl; or D. halogen, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C5 cyanoalkyl, or C1-C4 haloalkylsulfonyl; or E. chlorine, bromine, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, 1-cyano-cyclopropyl, or trifluoromethylsulfonyl; or F. chlorine, bromine, iodine, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, 1-cyano-cyclopropyl, 1-cyano-1-methylethyl, methylsulfonyl, or trifluoromethylsulfonyl; or

[0041] In one embodiment of each aspect of the invention, R 2b teeth, A. halogen, C1-C3 haloalkyl, C1-C3 haloalkylthio, C1-C3 alkoxy, C1-C3 haloalkoxy, or CN; or B. halogen, C1-C3 haloalkyl, or C1-C3 haloalkoxy; or C. halogen or C1-C3 haloalkyl; or D. chlorine, bromine, trifluoromethyl, or difluoromethyl; or E. chlorine, bromine, or trifluoromethyl; or F. Chlorine, bromine, iodine, trifluoromethoxy, difluoromethoxy, or trifluoromethyl is.

[0042] In one embodiment of each aspect of the invention, R3 is A. C1-C3 alkyl or C1-C3 haloalkyl; or B. Methyl is.

[0043] In one embodiment of each aspect of the invention, R 4a teeth, A. hydrogen, halogen, CN, C1-C3 haloalkyl, or C1-C3 haloalkoxy; or B. hydrogen, halogen, CN, CF3, O-CF3, or O-CHF2; C. hydrogen, Cl, Br, CN, or CF3; or D. hydrogen, Cl, or CN; or E. Hydrogen is.

[0044] In one embodiment of each aspect of the invention, R 4b teeth, A. hydrogen, halogen, CN, C1-C3 haloalkyl, or C1-C3 haloalkoxy; or B. hydrogen, halogen, CN, CF3, O-CF3, or O-CHF2; C. hydrogen, Cl, Br, CN, or CF3; or D. Hydrogen is.

[0045] In one embodiment of each aspect of the invention, R 4c teeth, A. hydrogen, halogen, CN, C1-C3 haloalkyl, or C1-C3 haloalkoxy; or B. hydrogen, halogen, CN, CF3, O-CF3, or O-CHF2; C. hydrogen, Cl, Br, CN, or CF3; or D. Hydrogen is.

[0046] In one embodiment of each aspect of the invention, with reference to Table Z below, R4 is A. R4-1, R4-2, R4-3, R4-4, or R4-5; or B. R4-1, R4-2, or R4-4; or C.R4-4; or D.R4-2; or E.R4-1; or

[0047] In one embodiment of each aspect of the invention, R 5a and R 5b are independently of each other and independently of Q1 to Q4, A. selected from hydrogen, halogen, C1-C3 alkyl, C1-C3 alkoxy, and C1-C3 haloalkoxy; or B. selected from hydrogen, halogen, methyl, methoxy, and halomethoxy; or C. selected from hydrogen, Cl, methyl, methoxy, and OCF2H; or D. selected from methyl and hydrogen.

[0048] In one embodiment of each aspect of the invention, R 5a is methyl and R 5b is hydrogen.

[0049] In one embodiment of each aspect of the invention, R 5a is hydrogen and R 5b is hydrogen.

[0050] The present invention therefore provides the substituents R, R as defined above. 2a , R 2b , R3, R 4a , R 4b , R 4c , R 5a , R 5b, X, and A in any combination / permutation thereof. Thus, for example, compounds of formula I are available in which A is in the first embodiment (i.e., A is N or CR 2c where R 2c is H, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; X is O or S; R1 is embodiment B (i.e., hydrogen, methyl, or cyclopropylmethyl); R 2a is embodiment C (i.e., C1-C3 haloalkyl, C1-C3 haloalkylthio, C1-C3 haloalkoxy, C3-C6 cycloalkyl; C3-C6 cycloalkyl substituted with 1 or 2 substituents independently selected from C1-C3 haloalkyl, cyano, C1-C3 alkoxy, and halogen; C3-C6 cycloalkylC1-C4 alkyl; C3-C6 cycloalkylC1-C4 alkyl substituted with 1 to 3 substituents independently selected from C1-C3 haloalkyl, cyano, and halogen; C1-C5 cyanoalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfinyl, C1-C4 haloalkylsulfinyl, C3-C6 cycloalkylsulfanyl, C3-C6 cycloalkylsulfinyl, or C3-C6 cycloalkylsulfonyl); R 2b is embodiment B (i.e., halogen, C1-C3 haloalkyl, or C1-C3 haloalkoxy); R3 is embodiment B (i.e., methyl); R 4a , R 4b , and R 4c are, independently of each other, a first aspect (i.e., R 4a , R 4b , and R 4c are each independently selected from hydrogen, halogen, CN, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, and C1-C3 haloalkoxy; R 5a is embodiment A (i.e., selected from hydrogen, halogen C1-C3 alkyl, C1-C3 alkoxy, and C1-C3 haloalkoxy); R 5bCompounds of Formula I are available in which is embodiment C (ie, selected from hydrogen, Cl, methyl, methoxy, and OCF2H).

[0051] In one embodiment, the compound of formula I is [ka] where R1, R3, R 4a , R 4b , R 4c , R 5a , and R 5b is as defined in the first aspect, X is O, R2 is as defined in the first aspect, A and the substituent R 2a and R 2b is a cyclic group containing

[0052] In one embodiment of each aspect of the invention, R2 (A and the substituent R 2a and R 2b A cyclic group containing AK-1 to K-24, and K-25 to K-41: [ka] [ka] is selected from selected from BK-1, K-2, K-3, K-5, K-6, K-7, K-9, K-10, K-11, K-12, K-14, K-16, K-18, K-21, K-22, K-23, and K-24; or selected from CK-1, K-2, K-5, K-7, K-9, K-10, K-11, K-12, K-14, K-16, K-18, K-21, K-22, and K-23; or selected from DK-1, K-5, K-9, K-12, K-14, K-16, K-21 and K-23; or selected from EK-1, K-7, K-9, K-10, K-11, K-13, K-18, K-21, and K-23; or selected from FK-1, K-7, K-10, K-11, K-18, K-21, and K-23; or selected from GK-1, K-9, K-10, K-14, K-21 and K-23; or selected from HK-1, K-9, K-10, K-11, K-21, and K-23; or IK-1; or JK-10; or KK-9; or K-1, K-3, K-4, K-5, K-7, K-8, K-9, K-10, K-11, K-13, K-14, K-17, K-19, K-21, K-23, K-24, K-25, K-26, K-27, K-28, K-29, K-30, K-31, K-32, K-33, K-34, K-35, K-36, K-37, K-38, K-39, K-40, and K-41; or selected from MK-3, K-7, K-19, K-20, K-27, K-28, K-29, or K-30; or selected from NK-11, K-17, K-24, or K-34; or selected from OK-1, K-3, K-4, K-5, K-7, K-8, K-9, K-11, K-13, K-14, K-17, K-19, K-23, K-24, K-25, K-26, K-27, K-28, K-29, K-30, K-31, K-32, K-33, K-34, K-35, K-36, K-37, K-38, K-39, K-40, and K-41; or selected from PK-23, K-32, K-33, K-36, K-37, K-38, K-39, K-40, and K-41; or selected from QK-14, K-25, K-27, K-28, and K-41; or selected from RK-1, K-3, K-4, K-5, K-7, K-8, K-9, K-11, K-13, K-14, K-17, K-19, K-26, K-31, K-32, K-33; or Selected from SK-7, K-8, K29, K-30, and K-31.

[0053] In one embodiment of each aspect of the invention, the compound of formula I has as X oxygen; and as R1 hydrogen, methyl, ethyl, n-propyl, isobutyl, cyclopropylmethyl, or HCH≡CCH2-; R 2a as halogen, C1-C3 haloalkyl, C1-C3 haloalkylthio, C1-C3 haloalkoxy, C3-C6 cycloalkyl; C3-C6 cycloalkyl substituted with 1 or 2 substituents independently selected from C1-C3 haloalkyl, cyano, C1-C3 alkoxy, and halogen; C3-C6 cycloalkylC1-C4 alkyl; C3-C6 cycloalkylC1-C4 alkyl substituted with 1 to 3 substituents independently selected from C1-C3 haloalkyl, cyano, and halogen; C1-C5 cyanoalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfinyl, C1-C4 haloalkylsulfinyl, C3-C6 cycloalkylsulfanyl, C3-C6 cycloalkylsulfinyl, or C3-C6 cycloalkylsulfonyl; R 2b as halogen or C1-C3 haloalkyl; A has: N, CCl, CBr, CF, Cl or CH; R3 has methyl; R 4a , R 4b , and R 4c are each independently hydrogen, halogen, CN, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; R 5a and R 5b are each independently selected from hydrogen, halogen, C1-C3 alkyl, C1-C3 alkoxy, and C1-C3 haloalkoxy.

[0054] In one embodiment of each aspect of the invention, the compound of formula I has X as oxygen; R1 as hydrogen, methyl, or cyclopropylmethyl; R 2aas halogen, C1-C3 haloalkyl, C1-C3 haloalkylthio, C1-C3 haloalkoxy, C3-C6 cycloalkyl; C3-C6 cycloalkyl substituted with 1 or 2 substituents independently selected from C1-C3 haloalkyl, cyano, C1-C3 alkoxy, and halogen; C3-C6 cycloalkylC1-C4 alkyl; C3-C6 cycloalkylC1-C4 alkyl substituted with 1 to 3 substituents independently selected from C1-C3 haloalkyl, cyano, and halogen; C1-C5 cyanoalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfinyl, C1-C4 haloalkylsulfinyl, C3-C6 cycloalkylsulfanyl, C3-C6 cycloalkylsulfinyl, or C3-C6 cycloalkylsulfonyl; R 2b as halogen or C1-C3 haloalkyl; A has N or CH; R3 has methyl; R 4a , R 4b , and R 4c are each independently hydrogen, halogen, CN, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; R 5a and R 5b are each independently selected from hydrogen, halogen, C1-C3 alkyl, C1-C3 alkoxy, and C1-C3 haloalkoxy.

[0055] In one embodiment of each aspect of the invention, the compound of formula I has X as oxygen; R1 as hydrogen, methyl, or cyclopropylmethyl; R 2aas halogen, C1-C3 haloalkyl, C1-C3 haloalkylthio, C1-C3 haloalkoxy, C3-C6 cycloalkyl; C3-C6 cycloalkyl substituted with 1 or 2 substituents independently selected from C1-C3 haloalkyl, cyano, C1-C3 alkoxy, and halogen; C3-C6 cycloalkylC1-C4 alkyl; C3-C6 cycloalkylC1-C4 alkyl substituted with 1 to 3 substituents independently selected from C1-C3 haloalkyl, cyano, and halogen; C1-C5 cyanoalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfinyl, C1-C4 haloalkylsulfinyl, C3-C6 cycloalkylsulfanyl, C3-C6 cycloalkylsulfinyl, or C3-C6 cycloalkylsulfonyl; R 2b as halogen or C1-C3 haloalkyl; A has N or CH; R3 has methyl; R 4a , R 4b , and R 4c are each independently hydrogen, halogen, CN, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; R 5a and R 5b are independently selected from hydrogen, Cl, methyl, methoxy, and OCF2H.

[0056] In one embodiment of each aspect of the invention, the compound of formula I has X as oxygen; R1 as hydrogen, methyl, or cyclopropylmethyl; R 2a as halogen, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C5 cyanoalkyl, or C1-C4 haloalkylsulfonyl; R 2b as halogen or C1-C3 haloalkyl; A has N or CH; R3 has methyl; R 4a , R 4b , and R 4c are each independently hydrogen, halogen, CN, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; R 5a and R 5b are independently selected from hydrogen, Cl, methyl, methoxy, and OCF2H.

[0057] In one embodiment of each aspect of the invention, the compound of formula I has X as oxygen; R1 as hydrogen, methyl, or cyclopropylmethyl; R 2a as halogen, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C5 cyanoalkyl, or C1-C4 haloalkylsulfonyl; R 2b as halogen or C1-C3 haloalkyl; A has N or CH; R3 has methyl; R 4a , R 4b , and R 4c R are, independently of one another, hydrogen, halogen, CN, CF3, O-CF3, or O-CHF2; 5a and R 5b are independently selected from hydrogen, Cl, methyl, methoxy, and OCF2H.

[0058] In one embodiment of each aspect of the invention, the compound of formula I has X as oxygen; R1 as hydrogen, methyl, or cyclopropylmethyl; R 2a as halogen, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C5 cyanoalkyl, or C1-C4 haloalkylsulfonyl; R 2b as halogen or C1-C3 haloalkyl; A has N or CH; R3 has methyl; R 4a , R 4b , and R 4c R are independently hydrogen, Cl, Br, CN, or CF; 5a and R 5b are independently selected from hydrogen, Cl, methyl, methoxy, and OCF2H.

[0059] In one embodiment of each aspect of the invention, the compound of formula I has X as oxygen; R1 as hydrogen, methyl, or cyclopropylmethyl; R 2a as halogen, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C5 cyanoalkyl, or C1-C4 haloalkylsulfonyl; R 2b as halogen or C1-C3 haloalkyl; A has N or CH; R3 has methyl; R 4b and R 4c and each having hydrogen; R 4a as hydrogen, halogen, CN, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; R 5a and R 5b are independently selected from hydrogen, Cl, methyl, methoxy, and OCF2H.

[0060] In one embodiment of each aspect of the invention, the compound of formula I has X as oxygen; R1 as hydrogen, methyl, or cyclopropylmethyl; R 2a as halogen, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C5 cyanoalkyl, or C1-C4 haloalkylsulfonyl; R 2b as halogen or C1-C3 haloalkyl; A has N or CH; R3 has methyl; R 4b and R 4c as, each with hydrogen; R 4a as hydrogen, halogen, CN, CF3, O-CF3, or O-CHF2; R 5a and R 5b are independently selected from hydrogen, Cl, methyl, methoxy, and OCF2H.

[0061] In one embodiment of each aspect of the invention, the compound of Formula I-1 or Formula I-1′a has as R1 hydrogen, methyl, ethyl, n-propyl, isobutyl, cyclopropylmethyl, or HCH≡CCH2—; As R2, have one of K-1 to K-24; R3 has methyl; R 4a , R 4b , and R 4c are each independently hydrogen, halogen, CN, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; R 5a and R 5b are each independently selected from hydrogen, halogen, C1-C3 alkyl, C1-C3 alkoxy, and C1-C3 haloalkoxy.

[0062] In one embodiment of each aspect of the invention, the compound of Formula I-1 or Formula I-1′a has, as R1, hydrogen, methyl, or cyclopropylmethyl; As R2, have one of K-1 to K-24; R3 has methyl; R 4a , R 4b , and R 4c are each independently hydrogen, halogen, CN, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; R 5a and R5b are each independently selected from hydrogen, halogen, C1-C3 alkyl, C1-C3 alkoxy, and C1-C3 haloalkoxy.

[0063] In one embodiment of each aspect of the invention, the compound of Formula I-1 or Formula I-1′a has, as R1, hydrogen, methyl, or cyclopropylmethyl; As R2, have one of K-1 to K-24; R3 has methyl; R 4a , R 4b , and R 4c as, independently of one another, hydrogen, halogen, CN, CF3, O-CF3, or O-CHF2; R 5a and R 5b are each independently selected from hydrogen, halogen, C1-C3 alkyl, C1-C3 alkoxy, and C1-C3 haloalkoxy.

[0064] In one embodiment of each aspect of the invention, the compound of Formula I-1 or Formula I-1′a has, as R1, hydrogen, methyl, or cyclopropylmethyl; As R2, have one of K-1 to K-24; R3 has methyl; R 4b and R 4c as, each with hydrogen; R 4a R is hydrogen, halogen, CN, C1-C3 alkyl, C1-C3 haloalkyl, C3-C4 cycloalkyl, C1-C3 alkoxy, or C1-C3 haloalkoxy; 5a and R 5b are each independently selected from hydrogen, halogen, C1-C3 alkyl, C1-C3 alkoxy, and C1-C3 haloalkoxy.

[0065] In one embodiment of each aspect of the invention, the compound of Formula I-1 or Formula I-1′a has, as R1, hydrogen, methyl, or cyclopropylmethyl; As R2, have one of K-1 to K-24; R3 has methyl; R 4b and R 4c as, each with hydrogen; R 4a R has hydrogen, halogen, CN, CF3, O-CF3, or O-CHF2; 5a and R 5b are each independently selected from hydrogen, halogen, C1-C3 alkyl, C1-C3 alkoxy, and C1-C3 haloalkoxy.

[0066] Also, for example, compounds of formula I are made available, where A is CH or N; X is O; R is hydrogen or methyl; 2a is bromine, chlorine, iodine, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, 1-cyano-1-methylethyl, 1-cyanocyclopropyl, methylsulfonyl, or difluoromethylsulfonyl; R 2b is bromine, chlorine, iodine, trifluoromethyl, difluoromethoxy, or trifluoromethoxy; R is methyl; R 4a is H, Cl or cyano; R 4b , R 4c , R 5a and R 5b are hydrogen atoms.

[0067] Further, for example, compounds of formula I are made available, where A is CH; X is O; R is hydrogen; 2a is bromine, chlorine, iodine, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, 1-cyano-1-methylethyl, 1-cyanocyclopropyl, methylsulfonyl, or difluoromethylsulfonyl; R 2b is chlorine, trifluoromethyl, difluoromethoxy, or trifluoromethoxy; R is methyl; R 4a is H, Cl or cyano, for example, R 4a is H;R4b , R 4c , R 5a and R 5b are hydrogen atoms.

[0068] Also, for example, compounds of formula I are made available, where A is CH; X is O; R is hydrogen; 2a is chlorine, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, 1-cyano-1-methylethyl, 1-cyanocyclopropyl, methylsulfonyl, or difluoromethylsulfonyl; R 2b is chlorine, trifluoromethyl, difluoromethoxy, or trifluoromethoxy; R is methyl; R 4a is H;R 4b , R 4c , R 5a and R 5b are hydrogen atoms.

[0069] Further, for example, compounds of formula I are made available, where A is N; X is O; R is hydrogen or methyl; 2a is chlorine, 1-cyano-1-methylethyl, or 1-cyanocyclopropyl; R 2b is bromine, chlorine, or trifluoromethyl; R is methyl; R 4a is H;R 4b , R 4c , R 5a and R 5b are hydrogen atoms.

[0070] Also, for example, compounds of formula I are made available, where A is N; X is O; R is hydrogen; 2a is 1-cyano-1-methylethyl or 1-cyanocyclopropyl; R 2b is bromine, chlorine, or trifluoromethyl; R is methyl; R 4a is H;R 4b , R 4c , R 5a and R 5bare hydrogen atoms.

[0071] Also, for example, compounds of formula I are made available, where A is N; X is O; R is hydrogen; 2a is difluoromethyl or trifluoromethyl; R 2b is bromine, chlorine, or trifluoromethyl; R is methyl; R 4a is H;R 4b , R 4c , R 5a and R 5b are hydrogen atoms.

[0072] Also, for example, compounds of formula I are made available, where A is N; X is O; R is hydrogen; 2a is difluoromethyl or trifluoromethyl; R 2b is bromine or trifluoromethyl; R is methyl; R 4a is H;R 4b , R 4c , R 5a and R 5b are hydrogen atoms.

[0073] In a second aspect, the present invention makes available a composition comprising a compound of formula I as defined in the first aspect, one or more adjuvants and diluents and optionally one or more other active ingredients.

[0074] In a third aspect, the present invention makes available a method for combating and controlling insects, acaridae, nematodes or molluscs, which 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 as defined in the first aspect or a composition as defined in the second aspect.

[0075] In a fourth aspect, the present invention makes available a method for the protection of plant propagation material from attack by insects, mites, nematodes or mollusks, which comprises treating the propagation material or the locus in which the propagation material is planted with an effective amount of a compound of formula I as defined in the first aspect or a composition as defined in the second aspect.

[0076] In a fifth aspect, the present invention makes available plant propagation material, such as seeds, which comprises, has been treated with or has attached thereto a compound of formula I as defined in the first aspect or a composition as defined in the second aspect.

[0077] In a further aspect, the present invention provides a method of controlling parasites in or on an animal in need thereof, the method comprising administering an effective amount of a compound of formula I as defined in the first aspect. The present invention further provides a method of controlling ectoparasites on an animal in need thereof, the method comprising administering an effective amount of a compound of the first aspect. The present invention further provides a method of preventing and / or treating diseases transmitted by ectoparasites, the method comprising administering to an animal in need thereof an effective amount of a compound of formula I as defined in the first aspect.

[0078] Compounds of formula I can be prepared by those skilled in the art by following known methods. More specifically, compounds and intermediates of formula I and I'a can be prepared as described below in the schemes and examples. The specific stereogenic centers are left unspecified for the sake of brevity and are not intended to limit the teachings of the schemes in any way.

[0079] The processes for preparing the compounds of formula I according to the invention are carried out by methods known to those skilled in the art.

[0080] Formula I [ka] The compound of formula II [ka] (wherein R1, R3, R4, R 5a , and R 5b is as defined in formula I), or a salt thereof (e.g., a hydrohalide, preferably a hydrochloride or hydrobromide, or a trifluoroacetate, or any other equivalent salt), with a compound of formula III [ka] A carboxylic acid derivative of the formula (wherein A, R 2a , R 2b and X is as defined in Formula I. The chemical reaction is described in more detail in Scheme 1, where X is oxygen. Scheme 1: [ka]

[0081] In Scheme 1, a compound of formula III (wherein R 2a , R 2b、 and A are as defined in formula I) are activated to compounds of formula IIIa by methods known to those skilled in the art and described, for example, in Tetrahedron, 61(46), 10827-10852, 2005. For example, compounds where X is a halogen are formed by treatment of compounds of formula III with, for example, oxalyl chloride or thionyl chloride in an inert solvent such as dichloromethane (DCM) or tetrahydrofuran (THF) in the presence of a catalytic amount of DMF at a temperature between 20° C. and 100° C., preferably 25° C. Compounds of formula II (where R, R, R, R 5a , and R 5bis as defined in formula I), or a salt thereof (e.g., a hydrohalide, preferably hydrochloride or hydrobromide, or a trifluoroacetate, or any other equivalent salt), optionally in the presence of a base such as sodium, potassium, or cesium carbonate, or for example, triethylamine, diisopropylethylamine, or pyridine, provides compounds of formula I. This reaction can be carried out neat or in a solvent, preferably an organic solvent such as ethyl acetate, acetonitrile, N,N-dimethylformamide, or N,N-dimethylacetamide, or mixtures thereof, at a temperature range of −100 to +300° C., preferably 0° C. to 100° C. Alternatively, compounds of formula I can be prepared by the activation of IIIa (where X is X 01 or X 02

[0033] Furthermore, acids of formula III can be prepared by treating compounds of formula IIIa (wherein X is X) with dicyclohexylcarbodiimide (DCC) or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) in an inert solvent, such as pyridine or THF, optionally in the presence of a base, such as triethylamine, at temperatures between 50 and 180°C, to give compounds of formula IIIa (wherein X is X), as described, for example, in Synthesis 2013, 45, 1569 and Journal Prakt. Chemie 1998, 340, 581. 03 or X 04 The amines of formula II can also be activated by reaction with coupling reagents such as propanephosphonic anhydride (T3P®) or O-(7-aza-1-benzotriazolyl)-N,N,N',N'-tetramethyluronium-hexafluorophosphate (HATU), which affords the compounds of formula I. Subsequent reaction with amines of formula II affords compounds of formula I.

[0082] An intermediate of formula II (wherein R1, R3, R4, R 5a and R 5b is as defined in Formula I) can be prepared according to Scheme 2. Scheme 2: [ka]

[0083] Compound IVm (where M is a metal and R, R 5a and R 5b is as defined in formula I) and compounds Vm (where M is a metal and R 4a , R 4b and R 4c Compounds of formula IV (where X is as defined above) are known or they can be prepared by the process of 05 is a leaving group such as chlorine, bromine, iodine, arylsulfonate, alkylsulfonate, or trifluoromethanesulfonate; R, R 5a and R 5b is as defined in formula I) or compound V (wherein X 05 is a leaving group such as chlorine, bromine, iodine, arylsulfonate, alkylsulfonate, or trifluoromethanesulfonate, and R 4a , R 4b and R 4cM can also be prepared by known metalation reactions from M(OH) (as defined above). Such compounds and transformations can be found in the literature, for example, where M is zinc (e.g., ZnCl) (see WO 2008019357), M is magnesium (e.g., MgCl) (see Angewandte Chemie, International Edition (2020), 59(19), 7372-7376), and M is boron (e.g., B(OH)2 (see Bioorganic & Medicinal Chemistry Letters (2010), 20(7), 2326-2329). Such metallation reactions can be carried out, for example, by treatment of a heteroaromatic halide (e.g., a bromide) with butyllithium, or magnesium, or isopropylmagnesium chloride, or pinacolborane, or bispinacolborane, in the presence or absence of a transition metal catalyst, such as a palladium catalyst, with or without a base, in a solvent such as tetrahydrofuran, at temperatures ranging from −100° C. to 200° C., preferably −78° C. to 100° C., with or without microwave heating. Many such transformations are well known to those skilled in the art.

[0084] A compound of formula VI (wherein R3, R4, R 5a , and R 5b (wherein is as defined in Formula I) can be prepared by a CC coupling reaction between a compound of Formula IV and a compound of Formula Vm, or between a compound of Formula IVm and a compound of Formula V. Typically, such a CC coupling reaction is carried out in the presence of a catalyst, for example, a palladium catalyst. The CC coupling reaction can be accomplished in an inert solvent such as DMF, acetonitrile, or dioxane, in the presence of a base such as cesium carbonate or sodium tert-butoxide, optionally in the presence of a copper salt such as copper(I) iodide, at a temperature between 20 and 180°C, preferably between 60 and 120°C. Additional methods, including transition metal catalyzed methods, can be found in the literature. Many such transformations are well known to those skilled in the art.

[0085] The compound of formula VI may be treated with a compound of formula VII (wherein R1 is as defined in formula I) in the presence of NaBH(OAc)3 or NaBH3CN, preferably with NaBH3CN as a reducing agent, at room temperature in a suitable solvent, preferably acetic acid, to give a compound of formula II (wherein R1, R3, R4, R 5a and R 5b is as defined in Formula I). ​​Another reagent system for reductive amination uses a combination of Ti(OiPr)4 and NaBH4 in the presence of an amine of Formula VII to give a compound of Formula II (see Synthesis 2003(14), 2206).

[0086] Alternatively, an intermediate of formula II (wherein R1, R3, R4, R 5a and R 5b is as defined in Formula I) can be prepared according to Scheme 3. Scheme 3: [ka]

[0087] In an alternative process (Scheme 3), a ketone of formula VI (where R3, R4, R 5a , and R 5b is as defined in formula I) can be reduced to an alcohol of formula VIII in the usual manner (see, for example, WO 2012 / 082997, page 141), for example by reduction with NaBH4, preferably in MeOH as solvent. Subsequent activation of the alcohol of formula VIII with a compound of formula X (where Y is CH3, CF3 or p-CH3-CH4) in an inert solvent, preferably dichloromethane or tetrahydrofuran, and in the presence of a base, for example triethylamine, gives a compound of formula IX (where X 07Alcohols of formula VIII can also be converted to alkyl halides X (where X is chlorine or bromine) by treatment with phosphorus compounds such as P(X) (where X is chlorine or bromine) by methods known to those skilled in the art. 07 is Cl or Br). Such general functional group transformations are described, for example, in Organische Chemie. 4. Auflage, Wiley-VCH Verlag, Weinheim 2005, p. 393 ff. and Chem Commun. 2014, 50, 5756. Finally, nucleophilic substitution of compounds of formula IX with amines of formula VII gives compounds of formula II (where R, R, R, R 5a , and R 5b is as defined in formula I).

[0088] In yet another alternative process (Scheme 3), an alcohol of formula VIII is reacted with an alcohol of formula VIII Si The compound can be prepared from the silyl ether of the formula (I) by deprotection, for example, treatment with a fluoride, for example, tetrabutylammonium fluoride, in an inert solvent such as tetrahydrofuran. The reaction can be carried out at a temperature ranging from -10°C to 80°C, for example, from 0°C to 30°C. Such deprotection reactions are well known to those skilled in the art and are described in literature such as Protective Groups in Organic Synthesis, 3rd Edition, by Theodora W. Green (The Rowland Institute for Science) and Peter G.M.Wuts (Pharmacia and Upjohn Company), John Wiley & Sons, Inc., New York, NY, 1999, ISBN 0-471-16019-9.

[0089] Formula VIII Si The silyl ether of formula VIII A1 (where X A1is a halogen such as iodine or bromine), for example, by metallation by treatment with a turbo-Grignard reagent (iPrMgCl·LiCl) or butyllithium. Such metallation is well known to those skilled in the art and is described in literature, for example, Carey, Francis A. (2007). "Organometallic compounds of Group I and II metals". Advanced Organic Chemistry: Reaction and Synthesis Pt. B (Kindle ed.). Springer. ISBN 978-0-387-44899-2. The lithium or magnesium species thus produced can be, for example, transmetallated with a zinc halide, for example, zinc chloride, followed by conversion to a compound of formula VII in the presence of a palladium catalyst, for example, tris(dibenzylideneacetone)dipalladium(0), and a ligand, for example, a phosphine ligand, in an inert solvent such as tetrahydrofuran. A1 wherein R4 has the meaning given above in formula I and X C1 is a halogen, such as iodine or bromine. The reaction can be carried out at a temperature ranging from -100°C to 100°C, for example, from -78°C to 80°C. This transformation is known to those skilled in the art as, for example, Negishi cross-coupling, and is described in literature such as Jie Jack Li, Name Reactions, A Collection of Detailed Mechanisms and Synthetic Applications, Springer, ISBN: 978-3-030-50865-4.

[0090] Formula VIII A1 The compound of formula VIII B1 in an inert solvent such as tetrahydrofuran in the presence of a base such as an amine base such as imidazole to produce a compound of formula VII B1 (where (R A1 ) 3Si is trialkylsilyl, for example, dimethyl-tert-butylsilyl, and X B1Compound VII can be prepared by treatment of a silylating agent (wherein the silylating agent is a leaving group such as chloride, bromide, iodide, or triflate). B1 In R A1 is a straight-chain or branched C1-C4 alkyl, such as methyl or tert-butyl. The reaction can be carried out at a temperature ranging from 0°C to 100°C, for example, from 10°C to 80°C. Such silylation reactions are well known to those skilled in the art and are described in literature such as: Protective Groups in Organic Synthesis, 3rd Edition, Theodora W. Green (The Rowland Institute for Science) and Peter G.M.Wuts (Pharmacia and Upjohn Company), John Wiley & Sons, Inc., New York, NY, 1999, ISBN 0-471-16019-9.

[0091] Formula VIII B1 The compound of formula VIII C1 (where R 5a , R 5b and X A1 have the same meaning as above), after treatment with a base, for example a lithium amide base, for example lithium 2,2,6,6-tetramethylpyridine, to form a lithiated species and a compound of formula VII C1 (wherein R3 has the same meaning as defined above in formula I) can be prepared by reacting an aldehyde of the formula: embedded image The reaction can be carried out neat or in an organic solvent, for example, in tetrahydrofuran as a solvent The reaction can be carried out at a temperature range of -100°C to 100°C, for example, -80°C to 0°C, for example, at 0°C or -78°C.

[0092] Formula VII C1 and VIII C1 Compounds of the formula (I) are well known or commercially available.

[0093] A ketone of formula IV (wherein R3, R4, R 5a and R 5bis as defined in formula I, and X 05 where is as defined above) are commercially available or can be prepared as shown in Scheme 4. Scheme 4: [ka]

[0094] As shown in Scheme 4, a compound of formula XI (where R 5a and R 5b is as defined in Formula I, Z1 is C1-C4 alkyl, and X 05 is a leaving group as defined in formula IV) can be converted to a compound of formula XII (where R 5a , R 5b and Z1 as defined above in formula XI) can be converted to alkyl ketones of formula IV (where R3, X1 are as defined above) by methods known in the art (see, for example, WO 2011 / 143365, p. 138), activation of the carboxylic acid (see Scheme 1) and treatment with N-methoxy-N-methylamine (according to Weinreb et al. Tetrahedron Lett. 1981, 39, 3815). Treatment of compounds of formula XII (where R3 is as defined in formula I) with a Grignard reagent R3MgBr, e.g., MeMgBr, at lower temperatures, preferably 0-25°C, gives alkyl ketones of formula IV (where R3, X1 are as defined above) 05 , R 5a and R 5b is defined as above).

[0095] Compounds of formula IV can also be converted to compounds of formula XIII (Scheme 4) (where R, R, R) using a reagent of formula VII (where R is as defined in formula I) according to the reductive amination method described for the conversion of compounds of formula VI to compounds of formula II (see Scheme 2 above). 5a and R 5b is defined as in Formula I, and X05 can be used to prepare a leaving group, preferably Cl or Br.

[0096] A compound of formula XIII (wherein R, R, R 5a and R 5b is as defined in Formula I) can then be used as a starting material for another series of syntheses to provide compounds of Formula I, as shown in Scheme 5. Scheme 5: [ka]

[0097] Compounds of formula XIII can be reacted with activated carboxylic acids of general formula IIIa to give amides of general formula XIV (where A, R, R 2a , R 2b , R3, R 5a and R 5b is defined as in Formula I, and X 05 is a leaving group such as a halogen: F, Br, Cl, I, or OTf, preferably Cl or Br. Methods for this transformation are described above in Scheme 1. Compounds of formula XIV can be converted to compounds of formula I by a C—C coupling reaction with compounds of formula Vm (substituents defined in Scheme 2) according to the methods described above for Scheme 2.

[0098] A particular subclass of compounds of general formula II, namely compounds IIa (where R3, R4, R 5a and R 5b is as defined for Formula II and R is hydrogen) or a salt thereof (e.g., a hydrohalide, preferably a hydrochloride or hydrobromide, or a trifluoroacetate, or any other equivalent salt) is outlined in Scheme 6. Scheme 6: [ka]

[0099] The compound of formula II with a protecting group (e.g., R1 is benzyl) is subjected to hydrogenolysis with hydrogen in the presence of a palladium catalyst, such as palladium on carbon, in a solvent such as MeOH or EtOH to give a compound of formula IIa (where R3, R4, R 5a , and R 5b is defined as in formula I) (see, for example, Synlett, 2010, (18), page 2708). Alternatively, a compound of formula II (where R is allyl and R, R, R 5a , and R 5b is as defined in formula I) can also be converted to a compound of formula IIa by reaction with N,N'-dimethylbarbituric acid in the presence of a Pd catalyst, preferably tetrakis(triphenylphosphine)palladium(0), in a suitable solvent, such as CH2Cl2, according to J. Org. Chem. 1993, 58, 6109, to give a compound of formula IIa.

[0100] Alternatively, a compound of formula IIa (wherein R3, R4, R 5a and R 5b are as defined in formula I), or a salt thereof (e.g., a hydrohalide, preferably a hydrochloride or hydrobromide, or a trifluoroacetate, or any other equivalent salt) can be represented by formula VIIIZ3 (wherein R3, R4, R 5a and R 5bis as defined in Formula I, and Z3 can be prepared from the intermediates -NPhth (N-phthalimido group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group) under deprotection conditions well known to those skilled in the art and described in the literature, for example, in Protective Groups in Organic Synthesis, 3rd Edition, Theodora W. Green (The Rowland Institute for Science) and Peter G.M.Wuts (Pharmacia and Upjohn Company), John Wiley & Sons, Inc., New York, NY. 1999, ISBN 0-471-16019-9, typically by treatment with either hydrazine (preferably hydrazine hydrate or hydrazine monohydrate) in an alcoholic solvent such as ethanol or isopropanol (Z3 is -NPhth), or an acid such as trifluoroacetic acid or hydrochloric acid in the presence of a suitable solvent such as dichloromethane, tetrahydrofuran, or dioxane (Z3 is -NBoc2) (Scheme 6a). Scheme 6a: [ka]

[0101] A compound of formula VIIIZ3 (wherein R3, R4, R 5a and R 5b is as described in Formula I, Z3 is -NPhth (N-phthalimido group) or -NBoc2 (N-bis(tert-butyloxycarbonyl) group), an alcohol compound of Formula VIII (wherein R3, R4, R 5a and R 5bcan be prepared from the alcohol of formula VIII (as defined in formula I) by the Mitsunobu reaction. Such a reaction involves treating an alcohol of formula VIII with an azodicarboxylate such as diethyl azodicarboxylate or diisopropyl azodicarboxylate in the presence of a phosphine such as triphenylphosphine or tributylphosphine, and an amine such as phthalimide (-NPhth) or bis(tert-butoxycarbonyl)amine (NBoc2). Mitsunobu reactions (and conditions for carrying them out) are well known to those skilled in the art and are described, for example, in Chem. Rev. 2009, 109, 2551-2651.

[0102] Carboxylic acids of formula III are known or can be prepared by the methods described in the schemes below. Scheme 7: [ka]

[0103] Thus, compounds of formula IIIb (Scheme 7), where R 2b and A are as defined in formula I) can be converted to a compound of formula XXI (where R 2b and A are as defined in formula I and Z1 is C1-C4 alkyl) with a suitable base such as sodium hydroxide or lithium hydroxide. Compounds of formula XXI are prepared by oxidation of compounds of formula XXa with, for example, mCPBA or NaIO4 / RuCl3 in a solvent, preferably CHCl3 or a mixture of H2O, MeCN and CCl4. Such transformations are known to those skilled in the art and are described, for example, in J. Med. Chem. 2008, 51, 6902 or WO 2004 / 9086, pp. 24-25. Finally, compounds of formula XXa (where R 2band A are as defined in formula I and Z1 is C1-C4 alkyl) can be prepared by reacting a compound of formula XVIIIa with a suitable trifluoromethylthiolated copper reagent of formula XIX (where R 2b and A are as defined in formula I, and X 08 is Br or Cl) (the ligand is, for example, 1,10-phenanthroline or 4,4'-di-tert-butylbipyridine). Such processes have been described, for example, in Angew. Chem. Int. Ed. 2013, 52, 1548-1552; Angew. Chem. Int. Ed. 2011, 50, 3793; Org. Lett. 2014, 16, 1744; J. Org. Chem. 2017, 82, 11915.

[0104] Further intermediates of formula XX (wherein R 2a , R 2b and A is as defined in Formula I, and Z1 is C1-C4 alkyl) are commonly known or can be readily prepared by one skilled in the art. A typical example of such a synthesis of a compound of Formula XX is shown in Scheme 8. Scheme 8: [ka]

[0105] For example, a compound of formula XX can be prepared by reacting a compound of formula XVIIIb (wherein R 2b and A are as defined for formula I, and X 05is chlorine, bromine, iodine, OMs, OTs or OTf) with a compound of formula XXIII, where R 2a can be prepared by reaction with (as defined in formula I). ​​Such a process has already been described, for example, in Tetrahedron Letters 2002, 43, 6987-6990.

[0106] Compounds of formula XX can also be prepared by the reaction of a compound of formula XXIV (wherein R 2b and A and Z1 are as defined in formula XX) with a compound of formula XXV (wherein R 2a is as defined in formula I, and X 05 is a leaving group such as bromine or iodine. Such a process has already been described, for example, in WO 12139775, page 73.

[0107] A compound of formula XXIV, where R 2b and A and Z1 are as defined in formula I) can be reacted with a compound of formula XVIIIb (wherein R 2b and A and Z1 are as defined in formula XXIV, and X 05is Cl, Br, I, OMs, OTs or OTf) with a compound of formula XXII, such as bis(pinacolato)diboron (Bpin)2. Such a process has been described, for example, in Bioorg. Med. Chem. Lett. 2015, 25, 1730 and WO 12139775, p. 67.

[0108] Carboxylic acids of formula III can be prepared from compounds of formula XXVIII as outlined in Scheme 7 by treatment with, for example, aqueous LiOH, NaOH or KOH in a suitable solvent which may include, for example, a THF / MeOH mixture, typically with heating at temperatures between room temperature and 100°C, preferably between 20°C and the boiling point of the reaction mixture (see also Scheme 9).

[0109] Compounds of formula XXVIII (Scheme 9), where R 2b and A are defined as in formula I and Z1 is C1-C4 alkyl) can be prepared by treating a compound of formula XXVII, which is commercially available or (as in Org. Lett. 2016, 18, 2471) with a compound of formula XXVI, such as (trifluoroethyl)-diphenyl-sulfonium triflate (PhS), in the presence of an Fe catalyst and a base, preferably CsF, at a temperature between 0 and 50°C, preferably 20°C, in DMA as a solvent. + CH2CF3 - OTf) by methods known to those skilled in the art (see, for example, Angew. Chem. Int. Ed. 2004, 43, 1132 and Pure Appl. Chem. 1985, 57, 1771). The compound of formula XXVIII is obtained as a mixture of stereoisomers, with the trans isomer being the predominant isomer.

[0110] Yet another method for preparing compounds of formula XXVIII uses trifluoroethylamine hydrochloride / NaNO / NaOAc in the presence of an Fe catalyst; the reaction is carried out in HO; or in a mixture of CHCl and HO at room temperature (see, for example, Angew. Chem. Int. Ed. 2010, 49, 938 and Chemm. Commun. 2018, 54, 5110).

[0111] Scheme 9: [ka] Carboxylic acids of formula IIIc, where R 2b and A is as defined in formula I) can be prepared in a manner quite similar to that already shown in Scheme 7.

[0112] A compound of formula XXIX, where R 2b and A are as defined in Formula I, and Z1 is C1-C4 alkyl, are prepared by reaction of compounds of Formula XXVII (synthesized analogously to ACS Med. Chem. Lett. 2013, 4,514 or Tetrahedron Lett. 2001, 42, 4083) with (bromodifluoromethyl)-trimethylsilane in the presence of NH4Br in a suitable solvent, preferably THF or toluene, at temperatures between 70 and 110° C. Subsequent saponification of the ester intermediate XXIX gives compounds of Formula IIId (Scheme 10). Scheme 10: [ka]

[0113] Carboxylic acids of formula IIIe, where R 2b and A are as defined in Formula I) can be prepared according to Reaction Scheme 11. Thus, compounds of Formula XVIIIa (where R 2b and A are defined as in Formula I, Z1 is C1-C4 alkyl, and X 08is bromine or iodine) is treated with iPrMgCl / LiCl complex; subsequent reaction with CuCN and quenching with cyclopropanecarbonyl chloride such as formula XXX gives compounds of formula XXXI (analogous to WO 2006 / 067445, p. 148). After fluorination with 2,2-difluoro-1,3-dimethylimidazoline in a solvent such as 1,2-dimethoxyethane or in the absence of a solvent (see Chem. Commun. 2002, (15), 1618), compounds of formula XXXII are obtained. Subsequent hydrolysis, for example with LiOH, as previously described, gives carboxylic acids of formula IIIe. Scheme 11: [ka]

[0114] A particular group of compounds III is the corresponding ester of type XXXVI (where A and R 2b is defined as in Formula I, and Z1 is C1-C4 alkyl) by hydrolysis. A synthetic method for obtaining compounds of Formula XXXVI is shown in Scheme 12 below.

[0115]

[0033] In the presence of zinc(II) fluoride (ZnF2) and a palladium(0) catalyst, such as tris(dibenzylideneacetone)di-palladium(0)-chloroform adduct (Pd2(dba)3CHCl3), with a ligand, for example, Xantphos or BINAP, in an inert solvent, such as N,N-dimethylformamide (DMF), at a temperature between 100 and 180 °C, optionally under microwave heating, trimethylsilyl acetonitrile (Me3SiCH2CN) is used to prepare a compound of formula XVIIIc (where R 2b and A are as defined in formula I, and X 09 is a leaving group such as a halogen or sulfonate, preferably chlorine, bromine, iodine or trifluoromethanesulfonate, and Z1 is C1-C4 alkyl to give a compound of formula XXXV, where R 2b, Z1, and A are as defined in formula XVIIIc). Such methods are described in the literature, for example, in Org. Lett. 16(24), 6314-6317, 2014. Alternatively, the compound of formula XVIIIc can be reacted with 4-isoxazoleboronic acid or 4-isoxazoleboronic acid pinacol ester in the presence of potassium fluoride (KF) and a palladium catalyst such as bis(triphenylphosphine)palladium(II) dichloride (Pd(PPh3)2Cl2) in an inert solvent such as dimethyl sulfoxide (DMSO), optionally in a mixture with water, at a temperature of 40-150°C, optionally under microwave heating, to give the compound of formula XXXVII (where R 2b , A is as defined in formula I, and Z1 is C1-C4 alkyl. Reaction of compounds of formula XXXVII with aqueous potassium fluoride (KF concentration of 0.5-3 M, preferably 1 M) in an inert solvent such as dimethyl sulfoxide (DMSO) or methanol at a temperature of 20-150° C., optionally under microwave heating, gives compounds of formula XXXV, where R 2b , Z1 and A are as defined in formula XVIIIc) to obtain. Such chemical reactions are described in the literature, for example, in J. Am. Chem. Soc. 2011, 133, 6948-6951. Scheme 12: [ka]

[0116] A compound of formula XXXV, where R 2b and A are as defined in formula I, and Z1 is C1-C4 alkyl) can be reacted with a compound of formula XXXIV (wherein X 10is further treated with a leaving group such as a halogen (preferably chlorine, bromine, or iodine) to give a compound of formula XXXVI, where R 2b and A is as defined in formula I above, and Z1 is C1-C4 alkyl).

[0117] Alternatively, compounds of formula XXXVI can be prepared directly from compounds of formula XVIIIc by treatment with compounds of formula XXXVIII in the presence of a catalyst such as Pd2(dba)3, a ligand such as BINAP, and a strong base such as lithium hexamethyldisilazane (LiHMDS), in an inert solvent such as tetrahydrofuran (THF) at temperatures between 30 and 80° C. Such chemical reactions are described, for example, in J. Am. Chem. Soc. 127(45), 15824-15832, 2005.

[0118] In yet another method for preparing a compound of formula XXXV, a compound of formula XVIIIc (wherein R 2b and A are as defined in formula I, Z1 is C1-C4 alkyl, and X 09 is a leaving group, for example a halogen or sulfonate, preferably chlorine, bromine, iodine or trifluoromethanesulfonate, is reacted with a reagent of formula XXXVIII (wherein Z2 is C1-C4 alkyl) 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 in the presence of a transition metal catalyst such as palladium (including, for example, Pd(PPh3)2Cl2) or copper (including, for example, CuI) catalysis, in a suitable solvent such as toluene, dioxane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP) or dimethyl sulfoxide (DMSO), optionally in the presence of a phase transfer catalyst PTC, for example tetrabutylammonium bromide or triethylbenzylammonium chloride TEBAC, at a temperature between room temperature and 180°C to give a compound of formula XXXIX (wherein R 2band A are as defined in Formula I, and Z1 and Z2 are each, independently of one another, C1-C4 alkyl. The compound of Formula XXXIX is decarboxylated using conditions such as heating in wet DMSO, optionally in the presence of lithium chloride or sodium chloride, at temperatures between 50°C and 180°C, to give the compound of Formula XXXV. Similar chemical reactions are described, for example, in Synthesis 2010, No. 19, 3332-3338.

[0119] Formula I'a [ka] The compound of formula IIb [ka] (where R1, R3, R4, R 5a and R 5b is as described in formula I), or a salt thereof (e.g., a hydrohalide, preferably a hydrochloride or hydrobromide, or a trifluoroacetate, or any other equivalent salt), with a compound of formula III [ka] (where A, X, R 2a and R 2b can be prepared by reaction with a carboxylic acid derivative of formula I (described above).

[0120] This chemistry is described in more detail in Scheme 14, where X is oxygen. Scheme 14: [ka]

[0121] A compound of formula IIIa, where A, R 2a , R 2band X0 are as described in Scheme 1) can be converted to a compound of formula IIb (where R1, R3, R4, R 5a , and R 5b is as described in Formula I), or a salt thereof (e.g., a hydrohalide, preferably a hydrochloride or hydrobromide, or a trifluoroacetate, or any other equivalent salt). The formation of a compound of Formula IIIa from a compound of Formula III is described in Scheme 1.

[0122] Alternatively, compounds of formula I'a can also be prepared by reacting compounds of formula XL (where A, R, R 2a , R 2b , R3, R 5a , and R 5b is defined in formula I, and X 05 can be prepared by coupling of a compound of formula V (described above in Scheme 2) where X is a leaving group such as chlorine, bromine, iodine, arylsulfonate, alkylsulfonate, or trifluoromethanesulfonate. Scheme 15: [ka]

[0123] Such CC coupling reactions can be achieved at temperatures between 20 and 180°C, preferably between 60 and 120°C, in an inert solvent such as DMF, acetonitrile, or dioxane, in the presence of a base such as cesium carbonate or sodium tert-butoxide, and optionally in the presence of a copper salt such as copper(I) iodide. Further methods, including transition metal catalyzed methods, can be found in the literature, for example, in J. Paradies in Metal-Catalyzed Cross-Coupling Reactions and More (Eds. A. de Meijere, S. Braese, and M. Oestreich), Wiely-VCH (Weinheim), 2014, Vol. 3, p. 995. Compounds of formula XL can be prepared by the conversion of amines of formula XIIIa (where R1, R3, R 5a , and R 5b is defined in formula I, and X 05 is a leaving group such as chlorine, bromine, iodine, arylsulfonate, alkylsulfonate or trifluoromethanesulfonate) and a compound of formula IIIa.

[0124] The formation of compounds of formula IIb is outlined in Scheme 16. Scheme 16: [ka]

[0125] Compounds of formula IIb can be prepared by reacting compounds of formula IIc (where R, R, R) with compounds of formula XLI (where R is as defined in formula I) in the presence of, for example, NaBH(OAc) or NaBHCN in a suitable solvent, preferably acetic acid, at room temperature, analogously to WO 2002 / 088073, p. 35. 5a , and R 5b can be prepared by treatment with Ti(i-OiPr)4 and NaBH4 (as defined in Formula I). ​​Alternatively, another reagent system for reductive amination uses a combination of Ti(i-OiPr)4 and NaBH4 (see Synthesis 2003(14), 2206).

[0126] Amines of formula IIc can be obtained by biocatalytic deracemization of amines of formula IIa. This can be carried out, for example, using lipases, such as Candida Antarctica lipase B or Pseudomonas fluorescens lipase, eventually in immobilized form (e.g., Novozym® 435), in the presence of an acyl donor, such as ethyl methoxyacetate or vinyl acetate, in a suitable solvent such as acetonitrile or methyl tert-butyl ether at temperatures between 20°C and 100°C. Such processes are described, for example, in J. Org. Chem. 2007, 72, 6918-6923 or Adv. Synth. Catal. 2007, 349, 1481-1488. The expected stereochemical outcome of such enzymatic deracemization is known to those skilled in the art and is documented in the literature, for example in J. Org. Chem. 1991, 56, 2656-2665 or J. Am. Chem. Soc. 2015, 137, 3996-4009.

[0127] In an alternative process, a compound of formula IIc, or a salt thereof (e.g., a hydrohalide, preferably a hydrochloride or hydrobromide, or a trifluoroacetate, or any other equivalent salt) can be converted to a compound of formula VIIIa (wherein R3, R4, R 5a and R 5b is as described in Formula I). Scheme 17: [ka]

[0128] Amines of formula IIc can be prepared by reacting intermediates of formula XLII (where R3, R4, R 5a , and R 5bis obtained from an alcohol of formula XIIa (described in formula I, where Z3 is NPhth or NBoc2). Such intermediates can be obtained from an alcohol of formula XIIa by the Mitsunobu reaction, which involves treating an alcohol of formula VIIIa with diisopropyl azodicarboxylate in the presence of a phosphine such as triphenylphosphine or tributylphosphine and an amine such as phthalimide or bis(tert-butoxycarbonyl)amine. The Mitsunobu reaction is known by those skilled in the art to proceed with inversion of the stereocenter, as described, for example, in Chem. Rev. 2009, 109, 2551-2651. The amine of formula XLII can then be converted to an amine of formula IIc by treatment with hydrazine if Z3=NPhth, or with TFA if Z3=NBoc2.

[0129] Alternatively, amines of formula IIc can be converted to azides of formula XLIII (where R3, R4, R5) by treatment with triphenylphosphine and water (Staudinger reaction) or by hydrogenation using a palladium catalyst in the presence of hydrogen, for example. 5a , and R 5b is described in formula I). ​​Azides of formula XLIII can be obtained by reduction of alcohols of formula VIIIa (where R3, R4, R5) with an azide reagent such as diphenylphosphoryl azide in the presence of a base such as DBU in a solvent such as toluene or THF. 5a , and R 5b is obtained by treating the compound (I) as described in formula I. Such processes, which lead to the inversion of the stereocenter, are known by those skilled in the art and are described in the literature, for example in Adv. Synth. Catal. 2018, 360, 2157-2165.

[0130] The alcohol of formula VIIIa can be obtained by enantioselective reduction of the ketone of formula VI. Such reduction can be carried out with a chiral ligand such as RuCl[(R,R)-TsDPEN] (mesitylene) or RuBF4[(R,R)-TsDPEN] (p-cymene) using a catalyst such as a ruthenium or rhodium catalyst in the presence of a hydrogen donor system such as HCOOH / Et3N or HCO2NH4. Such processes are described in the literature, for example, in J. Org. Chem. 2017, 82, 5607.

[0131] Alternatively, compounds of formula IIc can also be prepared as outlined in Scheme 18. Scheme 18: [ka]

[0132] An amine of formula IIc, or a salt thereof (e.g., a hydrohalide, preferably a hydrochloride or hydrobromide, or a trifluoroacetate, or any other equivalent salt) can be reacted with an amine of formula XLIX (wherein R3, R4, R 5a and R 5b Amines of formula XLIX can be prepared by deprotection of diamines of formula XLVIII (where R 5a , and R 5bcan be obtained by condensation of hydroxyketones of formula XLVII (where R3 and R4 are as described in formula I). ​​This condensation can be carried out in the presence of a suitable solvent such as ethanol or isopropanol, in the presence of air or an oxidizing agent such as DDQ. Diketones of formula XLVII can be formed by oxidation of hydroxyketones of formula XLVI (where R3 and R4 are as described in formula I). ​​This oxidation can involve, for example, SO3-pyridine in the presence of dichloromethane or dimethyl sulfoxide (DMSO), or a mixture thereof, and a base such as triethylamine or N,N-diisopropylethylamine, or alternatively, in the presence of a catalyst such as TEMPO / Bu4NHSO4 in the presence of sodium hypochlorite. Examples of such oxidations can be found in the literature, for example, Synlett, 2014, 25, 596 or J. Am. Chem. Soc. 1990, 112, 5290-5313. The hydroxyketone of formula XLVI can be synthesized by cross-benzoin condensation between an aldehyde of formula XLIV (wherein R4 is as described in formula I) and an aldehyde of formula XLV (wherein R3 is as described in formula I). ​​The aldehyde of formula XLIV is commercially available in chiral form, such as Boc-L-alaninal (CAS 79069-50-4) or tert-butyl N-[(1S)-1-(cyclopropylmethyl)-2-oxo-ethyl]carbamate (CAS 881902-36-9). The cross-benzoin condensation is carried out in the usual manner by using an organic catalyst such as a triazolium salt or a thiazolium salt in the presence of a base such as potassium tert-butoxide or N,N-diisopropylethylamine in a suitable solvent such as dichloromethane or tetrahydrofuran at a temperature from -20°C to the boiling point of the solvent. Examples of catalysts for such transformations are described in the literature, for example in J. Am. Chem. Soc. 2014, 136, 7539-7542 or Org. Lett. 2016, 18, 4518-4521.

[0133] Amines of formula XIIIa can be prepared, for example, by a deracemization procedure involving selective acylation of one enantiomer. Such an example is described in more detail in Scheme 19. Scheme 19: [ka]

[0134] Amines of formula XIIIa can be obtained by biocatalytic deracemization of amines of formula XIII. This can be carried out, for example, using a lipase, such as Candida Antarctica lipase B or Pseudomonas fluorescens lipase, finally in immobilized form (e.g., Novozym® 435), in the presence of an acyl donor, such as ethyl methoxyacetate or vinyl acetate, in a suitable solvent such as acetonitrile or methyl tert-butyl ether at temperatures between 20°C and 100°C. Such processes are described, for example, in J. Org. Chem. 2007, 72, 6918-6923 or Adv. Synth. Catal. 2007, 349, 1481-1488. The expected stereochemical outcome of such enzymatic deracemization is known to those skilled in the art and is documented in the literature, for example in J. Org. Chem. 1991, 56, 2656-2665 or J. Am. Chem. Soc. 2015, 137, 3996-4009.

[0135] Amines of formula XIII can be formed by reductive amination of ketone IV, which can occur, for example, by treating a ketone of formula IV with a nitrogen source, such as ammonium acetate or ammonia, in the presence of a hydride donor, such as NaBH(OAc) or NaBHCN.

[0136] Alternatively, an amine of formula XIIIb (where R, R 5a , and R 5b Resolution of (depicted in Formula I) can be achieved using a chiral auxiliary, as depicted in Scheme 20. Scheme 20: [ka]

[0137] An amine of formula XIIIc (wherein R, R 5a , and R 5b is depicted in Scheme 1, and X 05 is a leaving group such as bromine, chlorine, iodine, mesylate, tosylate, or triflate) can be converted to an intermediate of formula L (where R, R 5a , and R 5b is depicted in Scheme 1, and X 05 is a leaving group such as bromine, chlorine, iodine, mesylate, tosylate, or triflate, and X 12 * A chiral auxiliary of formula LI (where X is a chiral auxiliary) can be prepared from a chiral auxiliary of formula LI (where X is a chiral auxiliary). 11 * is a chiral auxiliary, and X is as described in Scheme 1) is, for example, mandelic acid or (1R)-menthyl chloroformate. Amines of formula L can be formed by coupling of a chiral auxiliary of formula LI with an amine of formula XIIIb according to the conditions detailed in Scheme 1. Examples of such deracemizations have been reported in the literature, for example in J. Org. Chem. 2007, 72, 485-493.

[0138] Alternatively, an amine of Formula XIIIc, or a salt thereof (e.g., a hydrohalide, preferably a hydrochloride or hydrobromide, or a trifluoroacetate, or any other equivalent salt) can be formed as described in Scheme 21. Scheme 21: [ka]

[0139] Amines of formula XIIIc can be prepared by reacting intermediates of formula LIII (where R3, R 5a , and R 5b is as described in formula I, and X 05is a leaving group as defined above, and Z3 is NPhth or NBoc2). Such intermediates can be obtained by the Mitsunobu reaction from alcohols of formula LII (where R3, R 5a , and R 5b is described in formula I, and X 05 The Mitsunobu reaction is obtained from Z3 = NPhth (where Z3 is a leaving group as described above) and involves treating an alcohol of formula LII with diisopropyl azodicarboxylate in the presence of a phosphine such as triphenylphosphine or tributylphosphine and an amine such as phthalimide or bis(tert-butoxycarbonyl)amine. The Mitsunobu reaction is known by those skilled in the art to proceed with the inversion of the stereocenter, as described, for example, in Chem. Rev. 2009, 109, 2551-2651. The amine of formula LIII can then be converted to an amine of formula XIIIc by treatment with hydrazine if Z3 = NPhth or with TFA if Z3 = NBoc2.

[0140] Alternatively, amines of formula XIIIc can be converted to azides of formula LIV (where R, R 5a , and R 5b is as described in formula I, and X 05 is a leaving group as described above). Azides of formula LIV can be obtained by treatment of alcohols of formula LII with an azide reagent such as diphenylphosphoryl azide in the presence of a base such as DBU in a solvent such as toluene or THF. Such processes, which promote the inversion of the stereocenter, are known by those skilled in the art and are described in the literature, for example in Adv. Synth. Catal. 2018, 360, 2157-2165.

[0141] The alcohol of formula LII can be obtained by enantioselective reduction of the ketone of formula IV. Such reduction can be carried out with a chiral ligand such as RuCl[(R,R)-TsDPEN] (mesitylene) or RuBF4[(R,R)-TsDPEN] (p-cymene) using a catalyst such as a ruthenium or rhodium catalyst in the presence of a hydrogen donor system such as HCOOH / Et3N or HCO2NH4. Such processes are described in the literature, for example, in J. Org. Chem. 2017, 82, 5607.

[0142] Alternatively, compounds of formula I (wherein R 1 is different from hydrogen and X is oxygen) can be prepared, for example, as shown in Scheme 22. Scheme 22: [ka]

[0143] A compound of formula Ia, where A, R 2a , R 2b , R3, R4, R 5a and R 5b is as defined in Formula I) with a compound of formula R1-X3 (where R1 is as defined in Formula I but is not hydrogen and X3 is a leaving group such as a halogen, e.g., chloride, bromide, iodide, or mesylate, or a sulfonate) to produce a compound of formula I (where A, R 2a , R 2b , R1, R3, R4, R 5a and R 5bis as described in Formula I), can be obtained. This reaction can be carried out neat or in a solvent, preferably an organic solvent, such as N,N-dimethylformamide (DMF) or N,N-dimethylacetamide (DMA), or a mixture thereof, at a temperature ranging from -100 to +300°C, preferably 0°C to 200°C, with or without the addition of a base, such as an inorganic base, for example, sodium, potassium, or cesium carbonate, or an organic base, for example, triethylamine, diisopropylethylamine, or pyridine. Methods for alkylating amines and various conditions for carrying them out are well known to those skilled in the art.

[0144] A compound of formula Ia, where A, R 2a , R 2b , R3, R4, R 5a and R 5b is as described in Formula I) can be converted to an amine of Formula IIa (where R3, R4, R 5a and R 5b is as described in formula I), or a salt thereof (e.g., a hydrohalide, preferably a hydrochloride or hydrobromide, or a trifluoroacetate, or any other equivalent salt) with a carboxylic acid derivative of formula IIIa (wherein A, R 2a and R 2b is as described in Formula I, and X0 is as defined in Scheme 1).

[0145] Similarly, compounds of formula I'a (wherein R1 is different from hydrogen and X is oxygen) can be prepared, for example, as shown in Scheme 23. Scheme 23: [ka]

[0146] A compound of formula I'aa, where A, R 2a , R 2b , R3, R4, R5a and R 5b is as defined in Formula I) with a compound of formula R1-X3 (where R1 is as defined in Formula I but is different from hydrogen and X3 is a leaving group such as a halogen, e.g., chloride, bromide, iodide or mesylate, or a sulfonate) under conditions detailed in Scheme 22 to give a compound of formula I'a (where A, R 2a , R 2b , R1, R3, R4, R 5a and R 5b is as described in Formula I).

[0147] A compound of formula I'aa, where A, R 2a , R 2b , R3, R4, R 5a and R 5b is as described in Formula I), can be converted to an amine of Formula IIc (where R3, R4, R 5a and R 5b is as described in formula I), or a salt thereof (e.g., a hydrohalide, preferably a hydrochloride or hydrobromide, or a trifluoroacetate, or any other equivalent salt) with a carboxylic acid derivative of formula IIIa (wherein A, R 2a and R 2b is as described in Formula I, and X0 is as defined in Scheme 1).

[0148] As shown in Scheme 24, compounds of formula Ia-CN can be prepared by reacting compounds of formula I (where X is oxygen, R is hydrogen, and R 4a is CN, A, R 2a , R 2b , R3, R 4b , R 4c , R 5a and R 5b is as defined in Formula I. Compounds of Formula Ia-CN can be prepared by reacting compounds of Formula Ia-X (where A, R 2a , R2b , R3, R 4b , R 4c , R 5a and R 5b is as described in Formula I, and X4 can be prepared from a halogen (or a pseudohalogen leaving group such as a triflate), preferably bromine or chlorine, more preferably chlorine, via a cyanation reaction. Scheme 24: [ka]

[0149] Such cyanation reactions can be carried out in the presence of sodium cyanide (NaCN), potassium cyanide (KCN), copper cyanide (CuCN), zinc cyanide (Zn(CN)), or potassium ferrocyanide (K4) [Fe(CN)6], among others, optionally with a palladium catalyst and ligand, and optionally under microwave irradiation. Examples of palladium catalysts include, inter alia, palladium(II) acetate (Pd(OAc)2) or tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3), and examples of ligands include 1,1'-bis(diphenylphosphino)ferrocene (dppf), dicyclohexyl[2',4',6'-tris(propan-2-yl)[1,1'-biphenyl)-2-yl]phosphane (XPhos), or (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane) (Xantphos), among other phosphine-based ligands. Other examples of catalyst / ligand combinations include tetrakis(triphenylphosphine)palladium(0) Pd(PPh3)4, [1,1'bis(diphenylphosphino)ferrocene]dichloropalladium (PdCl2(dppf)), second generation XPhos precatalyst XPhos Pd G2, or third generation XPhos precatalyst XPhos Pd G3. The reaction can be carried out in the presence of a solvent such as N,N-dimethylformamide (DMF), dioxane, toluene, xylene, or acetonitrile, among others, at temperatures ranging from room temperature to the boiling point of the reaction mixture.

[0150] Compounds of formula Ia-X, where A, R 2a , R 2b , R3, R 4b , R 4c , R 5a and R 5b is as defined in Formula I and X4 is a halogen (or pseudohalogen leaving group such as triflate), preferably bromine or chlorine, more preferably chlorine, can be converted to an amine of Formula IIa-X (where R3, R 4b , R 4c , R 5a and R 5b is as described in formula I, and X4 is a halogen (or pseudohalogen leaving group such as triflate), preferably bromine or chlorine, more preferably chlorine), or a salt thereof (e.g., a hydrohalide, preferably a hydrochloride or hydrobromide, or a trifluoroacetate, or any other equivalent salt) can be reacted with a carboxylic acid derivative of formula IIIa (wherein A, R 2a and R 2b is as described in Formula I, and X0 is as defined in Scheme 1).

[0151] Compounds of Formula IIa-X (wherein R, R 4b , R 4c , R 5a and R 5b is as defined in Formula I and X4 is a halogen, preferably bromine or chlorine, more preferably chlorine), or a salt thereof (e.g., a hydrohalide, preferably a hydrochloride or hydrobromide, or a trifluoroacetate, or any other equivalent salt), can be prepared by reacting a compound of Formula VIIIZ3-X (wherein R3, R 4b , R 4c , R 5a and R 5b can be prepared from -NPhth (N-phthalimido group) under the deprotection conditions already described in Scheme 6a), where X4 is as defined in Formula I, X4 is halogen, preferably bromine or chlorine, more preferably chlorine, and Z3 is -NPhth (N-phthalimido group). Scheme 25: [ka]

[0152] Compounds of formula VIIIZ3-X (wherein R3, R 4b , R 4c , R 5a and R 5b is as described in formula I, X4 is halogen, preferably bromine or chlorine, more preferably chlorine, and Z3 is -NPhth (N-phthalimido group) to prepare a compound of formula VIIIZ3-2 (wherein R3, R 4b , R 4c , R 5a and R 5b can be prepared from -NPhth (N-phthalimido group) by treatment with a phosphorus reagent such as, inter alia, phosphorus oxychloride or phosphorus pentachloride in an inert solvent such as toluene or chlorobenzene at a temperature ranging from room temperature to the boiling point of the reaction mixture.

[0153] A compound of formula VIIIZ3-2 (wherein R3, R 4b , R 4c , R 5a and R 5b is as described in Formula I and Z3 is -NPhth (N-phthalimido group)) can be prepared by combining a compound of Formula VIIIZ3-1 (wherein R3, R 4b , R 4c , R 5a and R 5b can be prepared from -NPhth (N-phthalimido group) optionally in the presence of a solvent such as tetrahydrofuran or dioxane, at a temperature ranging from room temperature to the boiling point of the reaction mixture, by a hydrolysis reaction involving an acid such as hydrochloric acid.

[0154] A compound of formula VIIIZ3-1 (wherein R3, R 4b , R 4c , R 5a and R5b is as described in Formula I and Z3 is -NPhth (N-phthalimido group) to prepare a compound of Formula VIIIZ3 (where R3, R 4b , R 4c , R 5a and R 5b is as described in Formula I, and R a defines a particular subgroup of compounds of formula VIII, where Z is C1-C3 alkoxy and Z is -NPhth (N-phthalimido group). These compounds can therefore be prepared from compounds of formula VIII, as detailed in Scheme 6a.

[0155] 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).

[0156] 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.

[0157] The reaction is advantageously carried out in the temperature range of about -80°C to about +140°C, preferably about -30°C to about +100°C, and in many cases in the range of ambient temperature to about +80°C.

[0158] 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.

[0159] 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.

[0160] 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.

[0161] 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.

[0162] 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.

[0163] The compounds of formula I and, where appropriate, their tautomers, in each free or salt form, can exist in the form of pure isomers, such as enantiomers and / or diastereomers, or as isomeric mixtures, such as enantiomeric mixtures, such as racemates, diastereomeric mixtures or racemic mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms occurring in the molecule and / or depending on the configuration of non-aromatic double bonds occurring in the molecule; the invention relates to the pure isomers and also to all possible isomeric mixtures, and is to be understood in this sense above and below, respectively, even if details of the stereochemistry are not specifically stated in each case.

[0164] 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.

[0165] 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.

[0166] 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.

[0167] 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.

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

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

[0170] The compounds of formula I according to the following Tables A-1 to A-126 can be prepared according to the above method. The following examples are intended to illustrate the present invention and to show preferred compounds of formula I in the form of compounds of formula Iaa. [ka]

[0171] Table A-1 provides five compounds A-1.001 to A-1.005 of formula Iaa, where A is CH, R is H, and R 2a is Cl and R 2b is Cl and R4 is as defined in Table Z. For example, A-1.002 is [ka] is.

[0172] [Table 1]

[0173] Table A-2 provides five compounds A-2.001 to A-2.005 of formula Iaa, where A is CH, R is H, and R 2a is Cl and R 2b is Br and R4 is as defined in Table Z.

[0174] Table A-3 provides five compounds A-3.001 to A-3.005 of formula Iaa, where A is CH, R is H, and R 2a is Cl and R 2b is CF3 and R4 is as defined in Table Z.

[0175] Table A-4 provides five compounds A-4.001 to A-4.005 of formula Iaa, where A is CH, R is H, and R 2a is Br and R 2b is Cl and R4 is as defined in Table Z.

[0176] Table A-5 provides five compounds of formula Iaa, A-5.001 to A-5.005, where A is CH, R is H, and R 2a is Br and R 2b is Br and R4 is as defined in Table Z.

[0177] Table A-6 provides five compounds of formula Iaa, A-6.001 to A-6.005, where A is CH, R is H, and R 2a is Br and R 2b is CF3 and R4 is as defined in Table Z.

[0178] Table A-7 provides five compounds of formula Iaa, A-7.001 to A-7.005, where A is CH, R is H, and R 2a is CF3 and R 2b is Cl and R4 is as defined in Table Z.

[0179] Table A-8 provides five compounds of formula Iaa, A-8.001 to A-8.005, where A is CH, R is H, and R 2a is CF3 and R 2b is Br and R4 is as defined in Table Z.

[0180] Table A-9 provides five compounds of formula Iaa, A-9.001 to A-9.005, where A is CH, R is H, and R 2a is CF3 and R 2b is CF3 and R4 is as defined in Table Z.

[0181] Table A-10 provides five compounds of formula Iaa, A-10.001 to A-10.005, where A is CH, R is H, and R 2a is O-CF3, and R 2b is Cl and R4 is as defined in Table Z.

[0182] Table A-11 provides five compounds of formula Iaa, A-11.001 to A-11.005, where A is CH, R is H, and R 2a is O-CF3, and R 2b is Br and R4 is as defined in Table Z.

[0183] Table A-12 provides five compounds of formula Iaa, A-12.001 to A-12.005, where A is CH, R is H, and R 2a is O-CF3, and R 2b is CF3 and R4 is as defined in Table Z.

[0184] Table A-13 provides five compounds of formula Iaa, A-13.001 to A-13.005, where A is CH, R is H, and R 2a is SO2-CF3, and R 2b is Cl and R4 is as defined in Table Z.

[0185] Table A-14 provides five compounds of formula Iaa, A-14.001 to A-14.005, where A is CH, R is H, and R 2a is SO2-CF3, and R 2b is Br and R4 is as defined in Table Z.

[0186] Table A-15 provides five compounds of formula Iaa, A-15.001 to A-15.005, where A is CH, R is H, and R 2a is SO2-CF3, and R 2b is CF3 and R4 is as defined in Table Z.

[0187] Table A-16 provides five compounds of formula Iaa, A-16.001 to A-16.005, where A is CH, R is H, and R 2a is 1-cyano-cyclopropyl, and R 2b is Cl and R4 is as defined in Table Z.

[0188] Table A-17 provides five compounds of formula Iaa, A-17.001 to A-17.005, where A is CH, R is H, and R 2a is 1-cyano-cyclopropyl, and R 2b is Br and R4 is as defined in Table Z.

[0189] Table A-18 provides five compounds of formula Iaa, A-18.001 to A-18.005, where A is CH, R is H, and R 2a is 1-cyano-cyclopropyl, and R 2b is CF3 and R4 is as defined in Table Z.

[0190] Table A-19 provides five compounds of formula Iaa, A-19.001 to A-19.005, where A is CH, R is CH, and R 2a is Cl and R 2b is Cl and R4 is as defined in Table Z.

[0191] Table A-20 provides five compounds of formula Iaa, A-20.001 to A-20.005, where A is CH, R is CH, and R 2a is Cl and R 2b is Br and R4 is as defined in Table Z.

[0192] Table A-21 provides five compounds of formula Iaa, A-21.001 to A-21.005, where A is CH, R is CH, and R 2a is Cl and R 2bis CF3 and R4 is as defined in Table Z.

[0193] Table A-22 provides five compounds of formula Iaa, A-22.001 to A-22.005, where A is CH, R is CH, and R 2a is Br and R 2b is Cl and R4 is as defined in Table Z.

[0194] Table A-23 provides five compounds of formula Iaa, A-23.001 to A-23.005, where A is CH, R is CH, and R 2a is Br and R 2b is Br and R4 is as defined in Table Z.

[0195] Table A-24 provides five compounds of formula Iaa, A-24.001 to A-24.005, where A is CH, R is CH, and R 2a is Br and R 2b is CF3 and R4 is as defined in Table Z.

[0196] Table A-25 provides five compounds of formula Iaa, A-25.001 to A-25.005, where A is CH, R is CH, and R 2a is CF3 and R 2b is Cl and R4 is as defined in Table Z.

[0197] Table A-26 provides five compounds of formula Iaa, A-26.001 to A-26.005, where A is CH, R is CH, and R 2a is CF3 and R 2b is Br and R4 is as defined in Table Z.

[0198] Table A-27 provides five compounds of formula Iaa, A-27.001 to A-27.005, where A is CH, R is CH, and R 2a is CF3 and R2b is CF3 and R4 is as defined in Table Z.

[0199] Table A-28 provides five compounds of formula Iaa, A-28.001 to A-28.005, where A is CH, R is CH, and R 2a is O-CF3, and R 2b is Cl and R4 is as defined in Table Z.

[0200] Table A-29 provides five compounds of formula Iaa, A-29.001 to A-29.005, where A is CH, R is CH, and R 2a is O-CF3, and R 2b is Br and R4 is as defined in Table Z.

[0201] Table A-30 provides five compounds of formula Iaa, A-30.001 to A-30.005, where A is CH, R is CH, and R 2a is O-CF3, and R 2b is CF3 and R4 is as defined in Table Z.

[0202] Table A-31 provides five compounds of formula Iaa, A-31.001 to A-31.005, where A is CH, R is CH, and R 2a is SO2-CF3, and R 2b is Cl and R4 is as defined in Table Z.

[0203] Table A-32 provides five compounds of formula Iaa, A-32.001 to A-32.005, where A is CH, R is CH, and R 2a is SO2-CF3, and R 2b is Br and R4 is as defined in Table Z.

[0204] Table A-33 provides five compounds of formula Iaa, A-33.001 to A-33.005, where A is CH, R is CH, and R2a is SO2-CF3, and R 2b is CF3 and R4 is as defined in Table Z.

[0205] Table A-34 provides five compounds of formula Iaa, A-34.001 to A-34.005, where A is CH, R is CH, and R 2a is 1-cyano-cyclopropyl, and R 2b is Cl and R4 is as defined in Table Z.

[0206] Table A-35 provides five compounds of formula Iaa, A-35.001 to A-35.005, where A is CH, R is CH, and R 2a is 1-cyano-cyclopropyl, and R 2b is Br and R4 is as defined in Table Z.

[0207] Table A-36 provides five compounds of formula Iaa, A-36.001 to A-36.005, where A is CH, R is CH, and R 2a is 1-cyano-cyclopropyl, and R 2b is CF3 and R4 is as defined in Table Z.

[0208] Table A-37 provides five compounds of formula Iaa, A-37.001 to A-37.005, where A is CH, R is CH-cyclopropyl, and R 2a is Cl and R 2b is Cl and R4 is as defined in Table Z.

[0209] Table A-38 provides five compounds of formula Iaa, A-38.001 to A-38.005, where A is CH, R is CH-cyclopropyl, and R 2a is Cl and R 2b is Br and R4 is as defined in Table Z.

[0210] Table A-39 provides five compounds of formula Iaa, A-39.001 to A-39.005, where A is CH, R is CH-cyclopropyl, and R 2a is Cl and R 2b is CF3 and R4 is as defined in Table Z.

[0211] Table A-40 provides five compounds of formula Iaa, A-40.001 to A-40.005, where A is CH, R is CH-cyclopropyl, and R 2a is Br and R 2b is Cl and R4 is as defined in Table Z.

[0212] Table A-41 provides five compounds of formula Iaa, A-41.001 to A-41.005, where A is CH, R is CH-cyclopropyl, and R 2a is Br and R 2b is Br and R4 is as defined in Table Z.

[0213] Table A-42 provides five compounds of formula Iaa, A-42.001 to A-42.005, where A is CH, R is CH-cyclopropyl, and R 2a is Br and R 2b is CF3 and R4 is as defined in Table Z.

[0214] Table A-43 provides five compounds of formula Iaa, A-43.001 to A-43.005, where A is CH, R is CH-cyclopropyl, and R 2a is CF3 and R 2b is Cl and R4 is as defined in Table Z.

[0215] Table A-44 provides five compounds of formula Iaa, A-44.001 to A-44.005, where A is CH, R is CH-cyclopropyl, and R 2a is CF3 and R 2bis Br and R4 is as defined in Table Z.

[0216] Table A-45 provides five compounds of formula Iaa, A-45.001 to A-45.005, where A is CH, R is CH-cyclopropyl, and R 2a is CF3 and R 2b is CF3 and R4 is as defined in Table Z.

[0217] Table A-46 provides five compounds of formula Iaa, A-46.001 to A-46.005, where A is CH, R is CH-cyclopropyl, and R 2a is O-CF3, and R 2b is Cl and R4 is as defined in Table Z.

[0218] Table A-47 provides five compounds of formula Iaa, A-47.001 to A-47.005, where A is CH, R is CH-cyclopropyl, and R 2a is O-CF3, and R 2b is Br and R4 is as defined in Table Z.

[0219] Table A-48 provides five compounds of formula Iaa, A-48.001 to A-48.005, where A is CH, R is CH-cyclopropyl, and R 2a is O-CF3, and R 2b is CF3 and R4 is as defined in Table Z.

[0220] Table A-49 provides five compounds of formula Iaa, A-49.001 to A-49.005, where A is CH, R is CH-cyclopropyl, and R 2a is SO2-CF3, and R 2b is Cl and R4 is as defined in Table Z.

[0221] Table A-50 provides five compounds of formula Iaa, A-50.001 to A-50.005, where A is CH, R is CH-cyclopropyl, and R 2a is SO2-CF3, and R 2b is Br and R4 is as defined in Table Z.

[0222] Table A-51 provides five compounds of formula Iaa, A-51.001 to A-51.005, where A is CH, R is CH-cyclopropyl, and R 2a is SO2-CF3, and R 2b is CF3 and R4 is as defined in Table Z.

[0223] Table A-52 provides five compounds of formula Iaa, A-52.001 to A-52.005, where A is CH, R is CH-cyclopropyl, and R 2a is 1-cyano-cyclopropyl, and R 2b is Cl and R4 is as defined in Table Z.

[0224] Table A-53 provides five compounds of formula Iaa, A-53.001 to A-53.005, where A is CH, R is CH-cyclopropyl, and R 2a is 1-cyano-cyclopropyl, and R 2b is Br and R4 is as defined in Table Z.

[0225] Table A-54 provides five compounds of formula Iaa, A-54.001 to A-54.005, where A is CH, R is CH-cyclopropyl, and R 2a is 1-cyano-cyclopropyl, and R 2b is CF3 and R4 is as defined in Table Z.

[0226] Table A-55 provides five compounds of formula Iaa, A-55.001 to A-55.005, where A is N, R is H, and R 2ais Cl and R 2b is Cl and R4 is as defined in Table Z.

[0227] Table A-56 provides five compounds of formula Iaa, A-56.001 to A-56.005, where A is N, R is H, and R 2a is Cl and R 2b is Br and R4 is as defined in Table Z.

[0228] Table A-57 provides five compounds of formula Iaa, A-57.001 to A-57.005, where A is N, R is H, and R 2a is Cl and R 2b is CF3 and R4 is as defined in Table Z.

[0229] Table A-58 provides five compounds of formula Iaa, A-58.001 to A-58.005, where A is N, R is H, and R 2a is Br and R 2b is Cl and R4 is as defined in Table Z.

[0230] Table A-59 provides five compounds of formula Iaa, A-59.001 to A-59.005, where A is N, R is H, and R 2a is Br and R 2b is Br and R4 is as defined in Table Z.

[0231] Table A-60 provides five compounds of formula Iaa, A-60.001 to A-60.005, where A is N, R is H, and R 2a is Br and R 2b is CF3 and R4 is as defined in Table Z.

[0232] Table A-61 provides five compounds of formula Iaa, A-61.001 to A-61.005, where A is N, R is H, and R 2a is CF3 and R2b is Cl and R4 is as defined in Table Z.

[0233] Table A-62 provides five compounds of formula Iaa, A-62.001 to A-62.005, where A is N, R is H, and R 2a is CF3 and R 2b is Br and R4 is as defined in Table Z.

[0234] Table A-63 provides five compounds of formula Iaa, A-63.001 to A-63.005, where A is N, R is H, and R 2a is CF3 and R 2b is CF3 and R4 is as defined in Table Z.

[0235] Table A-64 provides five compounds of formula Iaa, A-64.001 to A-64.005, where A is N, R is H, and R 2a is O-CF3, and R 2b is Cl and R4 is as defined in Table Z.

[0236] Table A-65 provides five compounds of formula Iaa, A-65.001 to A-65.005, where A is N, R is H, and R 2a is O-CF3, and R 2b is Br and R4 is as defined in Table Z.

[0237] Table A-66 provides five compounds of formula Iaa, A-66.001 to A-66.005, where A is N, R is H, and R 2a is O-CF3, and R 2b is CF3 and R4 is as defined in Table Z.

[0238] Table A-67 provides five compounds of formula Iaa, A-67.001 to A-67.005, where A is N, R is H, and R 2a is SO2-CF3, and R2b is Cl and R4 is as defined in Table Z.

[0239] Table A-68 provides five compounds of formula Iaa, A-68.001 to A-68.005, where A is N, R is H, and R 2a is SO2-CF3, and R 2b is Br and R4 is as defined in Table Z.

[0240] Table A-69 provides five compounds of formula Iaa, A-69.001 to A-69.005, where A is N, R is H, and R 2a is SO2-CF3, and R 2b is CF3 and R4 is as defined in Table Z.

[0241] Table A-70 provides five compounds of formula Iaa, A-70.001 to A-70.005, where A is N, R is H, and R 2a is 1-cyano-cyclopropyl, and R 2b is Cl and R4 is as defined in Table Z.

[0242] Table A-71 provides five compounds of formula Iaa, A-71.001 to A-71.005, where A is N, R is H, and R 2a is 1-cyano-cyclopropyl, and R 2b is Br and R4 is as defined in Table Z.

[0243] Table A-72 provides five compounds of formula Iaa, A-72.001 to A-72.005, where A is N, R is H, and R 2a is 1-cyano-cyclopropyl, and R 2b is CF3 and R4 is as defined in Table Z.

[0244] Table A-73 provides five compounds of formula Iaa, A-73.001 to A-73.005, where A is N, R is CH, and R 2a is Cl and R 2b is Cl and R4 is as defined in Table Z.

[0245] Table A-74 provides five compounds of formula Iaa, A-74.001 to A-74.005, where A is N, R is CH, and R 2a is Cl and R 2b is Br and R4 is as defined in Table Z.

[0246] Table A-75 provides five compounds of formula Iaa, A-75.001 to A-75.005, where A is N, R is CH, and R 2a is Cl and R 2b is CF3 and R4 is as defined in Table Z.

[0247] Table A-76 provides five compounds of formula Iaa, A-76.001 to A-76.005, where A is N, R is CH, and R 2a is Br and R 2b is Cl and R4 is as defined in Table Z.

[0248] Table A-77 provides five compounds of formula Iaa, A-77.001 to A-77.005, where A is N, R is CH, and R 2a is Br and R 2b is Br and R4 is as defined in Table Z.

[0249] Table A-78 provides five compounds of formula Iaa, A-78.001 to A-78.005, where A is N, R is CH, and R 2a is Br and R 2b is CF3 and R4 is as defined in Table Z.

[0250] Table A-79 provides five compounds of formula Iaa, A-79.001 to A-79.005, where A is N, R is CH, and R 2a is CF3 and R 2b is Cl and R4 is as defined in Table Z.

[0251] Table A-80 provides five compounds of formula Iaa, A-80.001 to A-80.005, where A is N, R is CH, and R 2a is CF3 and R 2b is Br and R4 is as defined in Table Z.

[0252] Table A-81 provides five compounds of formula Iaa, A-81.001 to A-81.005, where A is N, R is CH, and R 2a is CF3 and R 2b is CF3 and R4 is as defined in Table Z.

[0253] Table A-82 provides five compounds of formula Iaa, A-82.001 to A-82.005, where A is N, R is CH, and R 2a is O-CF3, and R 2b is Cl and R4 is as defined in Table Z.

[0254] Table A-83 provides five compounds of formula Iaa, A-83.001 to A-83.005, where A is N, R is CH, and R 2a is O-CF3, and R 2b is Br and R4 is as defined in Table Z.

[0255] Table A-84 provides five compounds of formula Iaa, A-84.001 to A-84.005, where A is N, R is CH, and R 2a is O-CF3, and R 2b is CF3 and R4 is as defined in Table Z.

[0256] Table A-85 provides five compounds of formula Iaa, A-85.001 to A-85.005, where A is N, R is CH, and R 2a is SO2-CF3, and R 2b is Cl and R4 is as defined in Table Z.

[0257] Table A-86 provides five compounds of formula Iaa, A-86.001 to A-86.005, where A is N, R is CH, and R 2a is SO2-CF3, and R 2b is Br and R4 is as defined in Table Z.

[0258] Table A-87 provides five compounds of formula Iaa, A-87.001 to A-87.005, where A is N, R is CH, and R 2a is SO2-CF3, and R 2b is CF3 and R4 is as defined in Table Z.

[0259] Table A-88 provides five compounds of formula Iaa, A-88.001 to A-88.005, where A is N, R is CH, and R 2a is 1-cyano-cyclopropyl, and R 2b is Cl and R4 is as defined in Table Z.

[0260] Table A-89 provides five compounds of formula Iaa, A-89.001 to A-89.005, where A is N, R is CH, and R 2a is 1-cyano-cyclopropyl, and R 2b is Br and R4 is as defined in Table Z.

[0261] Table A-90 provides five compounds of formula Iaa, A-90.001 to A-90.005, where A is N, R is CH, and R 2a is 1-cyano-cyclopropyl, and R 2bis CF3 and R4 is as defined in Table Z.

[0262] Table A-91 provides five compounds of formula Iaa, A-91.001 to A-91.005, where A is N, R is CH2-cyclopropyl, and R 2a is Cl and R 2b is Cl and R4 is as defined in Table Z.

[0263] Table A-92 provides five compounds of formula Iaa, A-92.001 to A-92.005, where A is N, R is CH-cyclopropyl, and R 2a is Cl and R 2b is Br and R4 is as defined in Table Z.

[0264] Table A-93 provides five compounds of formula Iaa, A-93.001 to A-93.005, where A is N, R is CH2-cyclopropyl, and R 2a is Cl and R 2b is CF3 and R4 is as defined in Table Z.

[0265] Table A-94 provides five compounds of formula Iaa, A-94.001 to A-94.005, where A is N, R is CH-cyclopropyl, and R 2a is Br and R 2b is Cl and R4 is as defined in Table Z.

[0266] Table A-95 provides five compounds of formula Iaa, A-95.001 to A-95.005, where A is N, R is CH2-cyclopropyl, and R 2a is Br and R 2b is Br and R4 is as defined in Table Z.

[0267] Table A-96 provides five compounds of formula Iaa, A-96.001 to A-96.005, where A is N, R is CH-cyclopropyl, and R 2a is Br and R 2b is CF3 and R4 is as defined in Table Z.

[0268] Table A-97 provides five compounds of formula Iaa, A-97.001 to A-97.005, where A is N, R is CH2-cyclopropyl, and R 2a is CF3 and R 2b is Cl and R4 is as defined in Table Z.

[0269] Table A-98 provides five compounds of formula Iaa, A-98.001 to A-98.005, where A is N, R is CH2-cyclopropyl, and R 2a is CF3 and R 2b is Br and R4 is as defined in Table Z.

[0270] Table A-99 provides five compounds of formula Iaa, A-99.001 to A-99.005, where A is N, R is CH2-cyclopropyl, and R 2a is CF3 and R 2b is CF3 and R4 is as defined in Table Z.

[0271] Table A-100 provides five compounds A-100.001 to A-100.005 of formula Iaa, where A is N, R is CH-cyclopropyl, and R 2a is O-CF3, and R 2b is Cl and R4 is as defined in Table Z.

[0272] Table A-101 provides five compounds of formula Iaa, A-101.001 to A-101.005, where A is N, R is CH2-cyclopropyl, and R 2a is O-CF3, and R 2bis Br and R4 is as defined in Table Z.

[0273] Table A-102 provides five compounds of formula Iaa, A-102.001 to A-102.005, where A is N, R is CH-cyclopropyl, and R 2a is O-CF3, and R 2b is CF3 and R4 is as defined in Table Z.

[0274] Table A-103 provides five compounds of formula Iaa, A-103.001 to A-103.005, where A is N, R is CH2-cyclopropyl, and R 2a is SO2-CF3, and R 2b is Cl and R4 is as defined in Table Z.

[0275] Table A-104 provides five compounds of formula Iaa, A-104.001 to A-104.005, where A is N, R is CH-cyclopropyl, and R 2a is SO2-CF3, and R 2b is Br and R4 is as defined in Table Z.

[0276] Table A-105 provides five compounds of formula Iaa, A-105.001 to A-105.005, where A is N, R is CH2-cyclopropyl, and R 2a is SO2-CF3, and R 2b is CF3 and R4 is as defined in Table Z.

[0277] Table A-106 provides five compounds of formula Iaa, A-106.001 to A-106.005, where A is N, R is CH2-cyclopropyl, and R 2a is 1-cyano-cyclopropyl, and R 2b is Cl and R4 is as defined in Table Z.

[0278] Table A-107 provides five compounds of formula Iaa, A-107.001 to A-107.005, where A is N, R is CH2-cyclopropyl, and R 2a is 1-cyano-cyclopropyl, and R 2b is Br and R4 is as defined in Table Z.

[0279] Table A-108 provides five compounds of formula Iaa, A-108.001 to A-108.005, where A is N, R is CH2-cyclopropyl, and R 2a is 1-cyano-cyclopropyl, and R 2b is CF3 and R4 is as defined in Table Z.

[0280] Table A-109 provides five compounds of formula Iaa, A-109.001 to A-109.005, where A is CH, R is H, and R 2a is CF3 and R 2b is CHF2 and R4 is as defined in Table Z.

[0281] Table A-110 provides five compounds of formula Iaa, A-110.001 to A-110.005, where A is CH, R is H, and R 2a is CF3 and R 2b is 1-cyano-1-methyl-ethyl, and R4 is as defined in Table Z.

[0282] Table A-111 provides five compounds of formula Iaa, A-111.001 to A-111.005, where A is CH, R is H, and R 2a is CF3 and R 2b is I and R4 is as defined in Table Z.

[0283] Table A-112 provides five compounds of formula Iaa, A-112.001 to A-112.005, where A is CH, R is H, and R 2a is CF3 and R 2bis SO2-CH3 and R4 is as defined in Table Z.

[0284] Table A-113 provides five compounds of formula Iaa, A-113.001 to A-113.005, where A is CH, R is H, and R 2a is CF3 and R 2b is OCHF2 and R4 is as defined in Table Z.

[0285] Table A-114 provides five compounds of formula Iaa, A-114.001 to A-114.005, where A is CH, R is H, and R 2a is OCHF2 and R 2b is OCHF2 and R4 is as defined in Table Z.

[0286] Table A-115 provides five compounds of formula Iaa, A-115.001 to A-115.005, where A is CH, R is H, and R 2a is I and R 2b is I and R4 is as defined in Table Z.

[0287] Table A-116 provides five compounds of formula Iaa, A-116.001 to A-116.005, where A is CH, R is H, and R 2a is I and R 2b is Br and R4 is as defined in Table Z.

[0288] Table A-117 provides five compounds of formula Iaa, A-117.001 to A-117.005, where A is CH, R is H, and R 2a is I and R 2b is I and R4 is as defined in Table Z.

[0289] Table A-118 provides five compounds of formula Iaa, A-118.001 to A-118.005, where A is CH, R is CH, and R 2ais CF3 and R 2b is CHF2 and R4 is as defined in Table Z.

[0290] Table A-119 provides five compounds of formula Iaa, A-119.001 to A-119.005, where A is CH, R is CH, and R 2a is CF3 and R 2b is 1-cyano-1-methyl-ethyl, and R4 is as defined in Table Z.

[0291] Table A-120 provides five compounds of formula Iaa, A-120.001 to A-120.005, where A is CH, R is CH, and R 2a is CF3 and R 2b is I and R4 is as defined in Table Z.

[0292] Table A-121 provides five compounds of formula Iaa, A-121.001 to A-121.005, where A is CH, R is CH, and R 2a is CF3 and R 2b is SO2-CH3 and R4 is as defined in Table Z.

[0293] Table A-122 provides five compounds of formula Iaa, A-122.001 to A-122.005, where A is CH, R is CH, and R 2a is CF3 and R 2b is OCHF2 and R4 is as defined in Table Z.

[0294] Table A-123 provides five compounds of formula Iaa, A-123.001 to A-123.005, where A is CH, R is CH, and R 2a is OCHF2 and R 2b is OCHF2 and R4 is as defined in Table Z.

[0295] Table A-124 provides five compounds of formula Iaa, A-124.001 to A-124.005, where A is CH, R is CH, and R 2a is I and R 2b is I and R4 is as defined in Table Z.

[0296] Table A-125 provides five compounds of formula Iaa, A-125.001 to A-125.005, where A is CH, R is CH, and R 2a is I and R 2b is Br and R4 is as defined in Table Z.

[0297] Table A-126 provides five compounds of formula Iaa, A-126.001 to A-126.005, where A is CH, R is CH, and R 2a is I and R 2b is Cl and R4 is as defined in Table Z.

[0298] Certain intermediate compounds of formula II and IIb are also available, some of which are novel. For example: R3 is methyl and R 5a and R 5b are each hydrogen, and R1 and R4 are as defined in Tables A-1, A-19, and A-37; for example, compounds of formula II where R1 is H, R3 is methyl, and R 4a is H or Cl, and R 4b , R 4c , R 5a and R 5b is H; or a salt thereof; and R3 is methyl and R 5a and R 5b are each hydrogen, and R1 and R4 are as defined in Tables A-1, A-19, and A-37; for example, compounds of formula IIb where R1 is H, R3 is methyl, and R 4a is H or Cl, and R 4b , R 4c , R 5a and R5b is H; or a salt thereof: [ka]

[0299] Also, the compounds of formulae VIIIa, VIIIa', and VIII Si Certain intermediate compounds, some of which are novel, are also available, for example: R3 is methyl and R 5a and R 5b are each hydrogen, and R1 and R4 are as defined in Tables A-1, A-19 and A-37; and R3 is methyl and R 5a and R 5b are each hydrogen, and R1 and R4 are as defined in Tables A-1, A-19 and A-37; and ·(R A1 )3Si is tri(C1-C4 alkyl)-silyl, for example, tert-butyl-dimethyl-silyl; R3 is methyl and R 5a and R 5b are each hydrogen, and R1 and R4 are as defined in Tables A-1, A-19 and A-37; Si Compound. [ka]

[0300] Furthermore, as shown above, the compounds of formulae VIIIa, VIIIa', and VIII Si Certain intermediate compounds are also available, where: R1 is H, R3 is methyl, and R 4a is H, Cl, or C1-C3 alkoxy, such as methoxy, and R 4b , R 4c , R 5a and R 5b and each are H; or a salt thereof; and R1 is H, R3 is methyl, and R 4a is H, Cl, or C1-C3 alkoxy, such as methoxy, and R 4b , R 4c , R 5a and R 5b are each H; and ·(R A1 )3Si is tri(C1-C4 alkyl)-silyl, for example, tert-butyl-dimethyl-silyl; R3 is methyl and R 4a is C1-C3 alkoxy, for example methoxy, and R 4b , R 4c , R 5a and R 5b Formula VIII where Si or a salt thereof.

[0301] Furthermore, certain intermediate compounds of formula XLII and XLII', some of which are novel, are also available, for example: R3 is methyl and R 5a and R 5b are each hydrogen, and R1 and R4 are as defined in Tables A-1, A-19 and A-37; and R3 is methyl and R 5a and R 5b are each hydrogen, and R1 and R4 are as defined in Tables A-1, A-19, and A-37. [ka]

[0302] Also available are certain intermediate compounds of formula XLII and XLII', as shown above: R1 is H, R3 is methyl, and R 4a is H, Cl, OH or C1-C3 alkoxy, such as methoxy, and R 4b , R 4c , R 5a and R 5bis H; or a salt thereof; and R1 is H, R3 is methyl, and R 4a is H, Cl, OH or C1-C3 alkoxy, such as methoxy, and R 4b , R 4c , R 5a and R 5b and R are each H; or a salt thereof.

[0303] Additionally, certain intermediate compounds of formula XLIX and XLIX' are also available, some of which are novel. For example: R3 is methyl and R 5a and R 5b are each hydrogen, and R1 and R4 are as defined in Tables A-1, A-19 and A-37; and R3 is methyl and R 5a and R 5b are each hydrogen, and R1 and R4 are as defined in Tables A-1, A-19 and A-37. [ka]

[0304] In another aspect, the present invention therefore makes available compounds of formula II and IIb, wherein R, R, R, R 5a and R 5b is as defined for formula I of the first aspect. Furthermore, the corresponding embodiments exemplified for formula I also apply to compounds of formula II and IIb.

[0305] In another aspect, the present invention therefore provides compounds of formula VIIIa, VIIIa', and VIIIa', as shown above. Si where (R A1 )3Si is a silyl-protecting group, for example tri(C1-C4 alkyl)-silyl; R3, R 4a , R 4b , R 4c , R 5aand R 5b are as defined for formula I of the first aspect. Furthermore, the corresponding embodiments exemplified for formula I also include formulas VIIIa, VIIIa', and VIII Si This applies to compounds of the formula:

[0306] In yet another aspect, the present invention therefore also makes available compounds of formula XLII and XLII′, as shown above, wherein R, R 4a , R 4b , R 4c , R 5a and R 5b is as defined for formula I of the first aspect. Furthermore, the corresponding embodiments exemplified for formula I also apply to compounds of formulae XLII and XLII'.

[0307] In yet another aspect, the present invention therefore also makes available compounds of formula XLIX and XLIX′, as shown above, wherein R, R 4a , R 4b , R 4c , R 5a and R 5b is as defined for formula I in the first aspect. Furthermore, the corresponding embodiments exemplified for formula I also apply to compounds of formulae XLIX and XLIX'.

[0308] The compounds of formula I according to the present invention are preventively and / or therapeutically useful active ingredients in the field of pest control, even at low application rates, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded animal species, fish, and plants.The active ingredients according to the present invention act not only against normally susceptible animal pests, such as 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 present invention can be manifested directly, i.e., immediately or only after some time has passed, as destruction of pests, for example, during molting, or indirectly, for example, as reduced egg production and / or hatching rate.

[0309] Examples of the above animal pests are: From the order Acarina, for example: Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp., Eotetranychus spp. spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus spp.), Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp., Tarsonemus spp. and Tetranychus spp.; From the order Anoplura, for example: Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; From the order Coleoptera, for example: Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotoma spp., Conoderus spp., Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp.), Dermestes spp., Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa ​​decemLineata, Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Maladera castanea, Megascelis spp. spp., Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp., Phlyctinus spp., Popillia spp.), Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabaeidae, Sitophilus spp., Sitotroga spp., Somaticus spp., Sphenophorus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp. and Trogoderma spp.;. From the order Diptera, for example: Aedes spp., Anopheles spp., Antherigona soccata, Bactrocea oleae, Bibio hortulanus, Bradysia spp., Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp., Drosophila melanogaster, Fannia spp. spp.), Gastrophilus spp., Geomyza tripunctata, Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp. spp.), Rhagoletis spp., Rivelia quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; From the order Hemiptera, for example: Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Aleurodes spp., Amblypelta nitida, Bathycoelia thalassina, Blissus spp., Cimex spp., Clavigrella tomentosicollis, Creontiades spp., Distantiella theobroma, Dichelops furcatus, Dysdercus spp., Edessa spp., Euchistus spp., Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp., Margarodes spp., Murgantia histrionic, Neomegalotomus spp., Nesidiocoris tenuis, Nezara spp., Nysius simulans, Oebalus insularis insularis, Piesma spp., Piezodorus spp., Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp.), Thyanta spp., Triatoma spp., Vatiga illudens;. Acyrthosium pisum, Adalges spp., Agalliana ensigera, Agonoscena targionii, Aleurodicus spp., Aleurocanthus spp., Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp. spp.), Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp., Brachycaudus spp., Brevicoryne brassicae, Cacopsylla spp., Cavariella aegopodii Scop., Ceroplaster spp.), Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp., Cofana spectra, Cryptomyzus spp., Cicadulina spp., Coccus hesperidum, Dalbulus maidis, Dialeurodes spp., Diaphorina citri, Diuraphis noxia, Dysaphis spp., Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae, Hyalopterus spp., Hyperomyzus pallidus, Idioscopus clypealis, Jacobiasca lybica, Laodelphax spp., Lecanium corni, Lepidosaphes spp., Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp., Mahanarva spp., Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp.), Neotoxoptera spp., Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter, Bayberry whitefly (Parabemisia myricae), Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Corn planthopper (Peregrinus maidis), Perkinsiella spp., Hop wart aphid (Phorodon humuli, Phylloxera spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp., Scaphoideus spp. spp.), Schizaphis spp., Sitobion spp.), Sogatella furcifera, Spisstilus festinus, Tarophagus Proserpina, Toxoptera spp., Trialeurodes spp., Tridiscus sporoboli, Trionymus spp., Trioza erytreae, Unaspis citri, Zygina flammigera, Zyginidia scutellaris; From the order Hymenoptera, for example: Acromyrmex ants, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis ants, Neodiprion spp., Pogonomyrmex spp., Slenopsis invicta, Solenopsis spp. and Vespa spp.; From the order Isoptera, for example: Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Solenopsis geminate From the order Lepidoptera, for example: Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp., Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydalima perspectalis perspectalis, Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea, Earias spp.), Elasmopalpus lignosellus, Eldana saccharina, Ephestia spp., Epinotia spp., Estigmene acrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltia jaculiferia, Grapholita spp., Hedya nubiferana, Heliothis spp. spp.), Hellula undalis, Herpetogramma spp., Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostege bifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta), Mythimna spp., Noctua spp., . Operophtera spp., Orniodes indica, European corn borer (Ostrinia nubilalis), Pammene spp., Pandemis spp., Pine pine 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. 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.

[0310] 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.;

[0311] The compounds of the present invention may also have activity against mollusks, such as, for example, species of the family Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. rufus); Nemoralis); Ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicelia (H. itala, H. obvia); Helicidae (Helicigona albustrum) arbustorum); Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Monoa These include the genera Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.

[0312] 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.

[0313] 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.

[0314] 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.

[0315] 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.

[0316] 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).

[0317] 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.

[0318] 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).

[0319] The compounds of formula I are particularly suitable for controlling: Hemiptera pests, such as one or more of the following: Bemisia tabaci, Aphis craccivora, Myzus persicae, Rhopalosiphum padi, Nilaparvata lugens and Euschistus heros (preferably on vegetables, soybeans and sugarcane) Lepidoptera pests, for example one or more of the species Spodoptera littoralis, Spodoptera frugiperda, Plutella xylostella, Cnaphalocrocis medinalis, Cydia pomonella, Chrysodeixis includes, Chilo suppressalis, Elasmopalpus lignosellus, Pseudoplusia includesns and Tuta absoluta (preferably on vegetables and corn). pests of the order Thysanoptera, such as Thripidae, for example Thrips tabaci and Frankliniella occidentalis (preferably on vegetables); Soil pests (such as those of the order Coleoptera), for example the species Diabrotica balteata, Agriotes spp. and Leptinotarsa ​​decemLineata (preferably on vegetables and corn)

[0320] 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.

[0321] 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.

[0322] 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).

[0323] 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.

[0324] 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.

[0325] 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).

[0326] 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®.

[0327] 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.

[0328] 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.

[0329] 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.

[0330] 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.

[0331] 5. IPC 531 cotton, registration number C / ES / 96 / 02, manufactured by Monsanto Europe SA (270-272 Avenue de Tervuren, B-1150 Brussels, Belgium).

[0332] 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.

[0333] 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.

[0334] 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).

[0335] 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.

[0336] 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.

[0337] Crops also include those that have a high resistance to nematodes, such as the soybean cyst nematode.

[0338] 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.

[0339] 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).

[0340] 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.

[0341] The present invention provides compounds of the first aspect for use in therapy. The present invention provides compounds of the first aspect for use in controlling parasites in or on animals. The present invention further provides compounds of the first aspect for use in controlling ectoparasites on animals. The present invention further provides compounds of the first aspect for use in the prevention and / or treatment of diseases transmitted by ectoparasites.

[0342] The present invention provides the use of a compound of the first aspect for the manufacture of a medicament for controlling parasites in or on an animal. The present invention further provides the use of a compound of the first aspect for the manufacture of a medicament for controlling ectoparasites on an animal. The present invention further provides the use of a compound of the first aspect for the manufacture of a medicament for preventing and / or treating diseases transmitted by ectoparasites.

[0343] The present invention provides the use of a compound of the first aspect in the control of parasites in or on an animal. The present invention further provides the use of a compound of the first aspect in the control of ectoparasites on an animal.

[0344] The term "controlling" when used in relation to parasites in or on animals refers to the reduction of pest or parasite numbers, the eradication of pests or parasites and / or the prevention of further pest or parasite infestation.

[0345] The term "treating" when used in reference to parasites in or on an animal refers to suppressing, slowing, arresting or reversing the progression or severity of an existing condition or disease.

[0346] When used in reference to parasites in or on an animal, the term "prevent" refers to the avoidance of symptoms or disease developing in the animal.

[0347] When used in reference to parasites in or on animals, the term "animal" can refer to mammals and non-mammals such as birds or fish. In the case of mammals, this can be a human or non-human mammal. Non-human mammals include, but are not limited to, livestock animals and companion animals. Livestock animals include, but are not limited to, cows, camels, pigs, sheep, goats, and horses. Companion animals include, but are not limited to, dogs, cats, and rabbits.

[0348] A "parasite" is a pest that lives in or on a host animal and benefits from nutrients provided at the expense of the host animal. An "endoparasite" is a parasite that lives inside the body of a host animal. An "ectoparasite" is a parasite that lives on a host animal. Ectoparasites include, but are not limited to, mites, insects, and crustaceans (e.g., sea lice). The subclass Acari (or Acarina) includes ticks and mites. Ticks include, but are not limited to, members of the following genera: Rhipicaphalus, such as Rhipicaphalus (Boophilus) microplus and Rhipicephalus sanguineus; Amblyomma; Dermacentor; Haemaphysalis; Hyalomma; Ixodes; Rhipicentor; Margaropus; Argas; Otobius; and Ornithodoros. Mites include, but are not limited to, members of the following genera: Chorioptes, such as Chorioptes bovis; Psoroptes, such as Psoroptes ovis; Cheyletiella; Dermanyssus, such as Dermanyssus gallinae; Ortnithonyssus; Demodex, such as Demodex canis; Sarcoptes, such as Sarcoptes scabiei; and Psorergates.Insects include, but are not limited to, members of the following orders: Siphonaptera, Diptera, Chelonia, Lepidoptera, Coleoptera, and Homoptera. Members of the Siphonaptera order include, but are not limited to, the cat flea (Ctenocephalides felis) and the dog flea (Ctenocephatides canis). Members of the order Diptera include, but are not limited to, Musca species; bot flies, such as Gasterophilus intestinalis and Oestrus ovis; stable flies; horse flies, such as Haematopota species and Tabunus species; haematobia, such as Haematobia irritans; Stomoxys; Lucilia; midges; and mosquitoes. Members of the order Chestnuti include, but are not limited to, sucking and biting lice, such as Bovicola ovis and Bovicola bovis.

[0349] When used in connection with parasites in or on animals, the term "effective amount" refers to the amount or dosage of a compound of the present invention or a salt thereof that, upon administration to the animal in one or more doses, produces the desired effect in or on the animal. An effective amount can be readily determined by the attending diagnostician, as one skilled in the art, by using known techniques and observing results obtained under analogous circumstances. In determining an effective amount, the attending diagnostician will take into account numerous factors, including, but not limited to, the species of mammal; its size, age, and general health; the parasite and level of infestation to be controlled; the particular disease or disorder involved; the extent or complications or severity of the disease or disorder; the individual's response; the particular compound administered; the mode of administration; the bioavailability characteristics of the administered preparation; the selected dosage regimen; the use of concomitant medications; and other relevant circumstances.

[0350] The compounds of the present invention can be administered to animals by any route that has the desired effect, including, but not limited to, topical, oral, parenteral, and subcutaneous administration. Topical administration is preferred. Formulations suitable for topical administration include, for example, solutions, emulsions, and suspensions, and can be in the form of pour-ons, spots, spray-ons, spray-laces, or dips. Alternatively, the compounds of the present invention can be administered by ear tag or collar.

[0351] Salt forms of the compounds of the present invention include both pharmaceutically and veterinarily acceptable salts, which may differ from agrochemically acceptable salts. Pharmaceutically and veterinarily acceptable salts and the general methodology for preparing them are well known in the art. See, for example, Gould, PL, "Salt selection for basic drugs," International Journal of Pharmaceutics, 33:201-217 (1986); Bastin, RJ, et al., "Salt Selection and Optimization Procedures for Pharmaceutical New Chemical Entities," Organic Process Research and Development, 4:427-435 (2000); and Berge, SM, et al., "Pharmaceutical Salts," Journal of Pharmaceutical Sciences, 66:1-19 (1977). Those skilled in the art of synthesis will understand that the compounds of the present invention can be easily converted to salts such as hydrochlorides and isolated as such salts using techniques and conditions well known to those skilled in the art. Additionally, those skilled in the art of synthesis will recognize that compounds of the present invention can be readily converted from a corresponding salt to the corresponding free base, and isolated as such a salt.

[0352] 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.

[0353] 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.

[0354] 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.

[0355] 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.

[0356] 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.

[0357] [Table 2]

[0358] [Table 3-1] [Table 3-2] [Table 3-3]

[0359] 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.

[0360] 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.

[0361] 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).

[0362] 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.

[0363] 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.

[0364] 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.

[0365] Examples of such parasites are: Among the Anoplurida, the genera Haematopinus, Linognathus, Pediculus, Phtirus, and Solenopotes are included.

[0366] From the order Mallophagida, the genera Trimenopon, Menopon, Trinoton, Bovicola, Werneckiella, Lepikentron, Damalina, Trichodectes and Felicola.

[0367] 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.).

[0368] 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.).

[0369] From the order Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp., and Panstrongylus spp.

[0370] 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.

[0371] 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.

[0372] 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.

[0373] 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.

[0374] 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 beetles such as Xyleborus species, Tryptodendron species, Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon species and Dinoderus minutus, as well as beetles such as Sirex juvencus, Urocerus gigas, Urocerus gigas Hymenopteran insects such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, and Urocerus augur, as well asindicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and Coptotermes formosanus, as well as silverfish such as Lepisma saccharina. The compounds of formula I and I'a or salts thereof are particularly suitable for controlling one or more pests selected from the families: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae and Heteroderidae. In a preferred embodiment of each aspect, compound TX (wherein the abbreviation "TX" means "one compound selected from the compounds defined in Tables A-1 to A-126, Table P, and Table E") controls one or more pests selected from the families: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae.

[0375] The compounds of formula I and I'a or salts thereof are effective against pests of the genera Spodoptera spp., Plutella spp., Frankliniella spp., Thrips spp., Euschistus spp., Cydia spp., Nilaparvata spp., Myzus spp., Aphis spp., Diabrotica spp., Rhopalosiphum spp., Pseudoplusia spp. and Chilo spp. spp. In a preferred embodiment of each aspect, the compound TX (here, the abbreviation "TX" means "one compound selected from the compounds defined in Tables A-1 to A-126, Table P, and Table E") is selected from the genera: Spodoptera spp., Plutella spp., Frankliniella spp., Thrips spp., Euschistus spp., Cydia spp., Nilaparvata spp., Myzus spp., Aphis spp., Diabrotica spp., Rhopalosiphum spp. The present invention controls one or more pests selected from Pseudoplusia spp., Pseudoplusia spp., and Chilo spp.

[0376] The compounds of formula I and I'a or salts thereof are particularly suitable for controlling one or more of Spodoptera littoralis, diamondback moth (Plutella xylostella), western flower thrips (Frankliniella occidentalis), onion thrips (Thrips tabaci), Euschistus heros, codling moth (Cydia pomonella), brown planthopper (Nilaparvata lugens), green peach aphid (Myzus persicae), Chrysodeixis includens, bean aphid (Aphis craccivora), Diabrotica balteata, Rhopalosiphum padi and rice stem borer (Chilo suppressalis).

[0377] In a preferred embodiment of each aspect, compound TX (wherein the abbreviation "TX" means "one compound selected from the compounds defined in Tables A-1 to A-126, Table P, and Table E") is effective against Egyptian armyworm (Spodoptera littoralis), diamondback moth (Plutella xylostella), western flower thrips (Frankliniella occidentalis), onion thrips (Thrips tabaci), Euschistus heros, codling moth (Cydia pomonella), brown planthopper (Nilaparvata lugens), green peach aphid (Myzus persicae), Chrysodeixis includens, bean aphid (Aphis craccivora), Diabrotica Rice stem borer (Chilo Suppressalis) such as Rhopalosiphum Padia and Egyptian armyworm (Spodoptera littoralis) + TX, diamondback moth (Plutella xylostella) + TX; western flower thrips (Frankliniella occidentalis) + TX, onion thrips (Thrips tabaci) + TX, Euschistus heros + TX, codling moth (Cydia pomonella) + TX, brown planthopper (Nilaparvata lugens) + TX, green peach aphid (Myzus persicae) + TX, Chrysodeixis includens + TX, bean aphid (Aphis craccivora) + TX, Diabrotica balteata It controls one or more of the following: Rhopalosiphum Padi + TX, Chilo suppressalis + TX, and Rice Stem Borer (Chilo suppressalis) + TX.

[0378] In one embodiment of each aspect, one compound from the compounds of Tables A-1 to A-126, Table P, and Table E is used to control Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis includens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum padiata, Rhopalosiphum nigricans, Rhopalosiphum padiata ... padia) and rice stem borer (Chilo suppressalis).

[0379] In one embodiment, one compound from the compounds of Tables A-1 to A-126, Table P and Table E is suitable for controlling Mamestra (preferably in vegetables), codling moth (Cydia pomonella) (preferably in apple), Empoasca (preferably in vegetables, vineyards), Leptinotarsa ​​(preferably in potato) and Chilo supressalis (preferably in rice).

[0380] The compounds of the present invention may have any number of benefits, including, inter alia, advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (e.g., high biological activity, advantageous spectrum of activity, high safety profile (e.g., improved physicochemical properties or high biodegradability against above- and below-ground non-target organisms such as fish, birds and bees)). In particular, it has surprisingly been found that certain compounds of formula (I) may exhibit advantageous safety profiles, especially against non-target arthropods, such as pollinators such as honeybees, solitary bees and bumblebees, most particularly the European honeybee (Apis mellifera).

[0381] 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.

[0382] 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.

[0383] 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.

[0384] The formulation auxiliaries suitable for preparing the compositions according to the invention are known per se. 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.

[0385] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kiesl lager, limestone, calcium carbonate, bentonite, calcium montmorillonite, cotton hulls, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin, and similar materials.

[0386] 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).

[0387] 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.

[0388] 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.

[0389] 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.

[0390] 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.

[0391] 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%

[0392] Powder: Active ingredient: 0.1 to 10%, preferably 0.1 to 5% Solid carrier: 99.9 to 90%, preferably 99.9 to 99%

[0393] 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%

[0394] 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%

[0395] Granules: Active ingredient: 0.1 to 30%, preferably 0.1 to 15% Solid carrier: 99.5 to 70%, preferably 97 to 85%

[0396] The following examples further illustrate, but do not limit, the present invention.

[0397] [Table 4]

[0398] The complex is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to give a wettable powder which can be diluted with water to give a suspension of the desired concentration.

[0399] [Table 5]

[0400] 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 diluted with water and used directly for seed treatment.

[0401] [Table 6]

[0402] Emulsions of any required dilution that can be used for plant protection can be obtained from this concentrate by dilution with water.

[0403] [Table 7]

[0404] Ready-to-use dusts can be 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.

[0405] [Table 8]

[0406] The composite 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.

[0407] [Table 9]

[0408] In a mixer, the finely ground compound is applied uniformly to kaolin moistened with polyethylene glycol, thus obtaining coated granules that do not generate dust.

[0409] [Table 10]

[0410] 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.

[0411] [Table 11]

[0412] 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.

[0413] 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.

[0414] 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]

[0415] Preparation example: "Mp" means melting point (°C). 1 H NMR measurements were recorded on a Brucker 400 MHz spectrometer, and chemical shifts are given in ppm relative to the TMS standard. Spectra measured in deuterated solvents are as indicated. The following abbreviations are used: s = singlet; br s = broad singlet; d = doublet; br d = broad doublet; dd = doublet doublet; dt = double triplet; t = triplet, tt = triplet triplet; q = quartet, quin = quintuplet, sept = septet; m = multiplet.

[0416] Compounds were characterized using one of the following LCMS methods: The characteristic LCMS values ​​obtained for each compound were the retention time ("Rt", recorded in minutes) and the observed molecular ion (M+H). + Or (MH).

[0417] LCMS method: Method 1: Spectra were recorded on a Waters mass spectrometer (SQD, SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ion), capillary: 0.8-3.00 kV, cone: 5-30 V, source temperature: 120-150 °C, desolvation temperature: 350-600 °C, cone gas flow: 50-150 l / h, desolvation gas flow: 650-1000 l / h, mass range: 50-900 Da, and a Waters Corporation Acquity UPLC: binary pump, heated column compartment, diode-array detector, and ELSD detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm; Temperature: 60 °C; DAD wavelength range (nm): 210–400; Run time: 1.5 min; Solvent: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; Flow rate (ml / min): 0.85; Gradient: 10% B isocratic in 0.2 min, then 10–100% B in 1.0 min, 100% B isocratic in 0.2 min, 100–10% B in 0.05 min, 10% B isocratic in 0.05 min.

[0418] Method 2: Spectra were recorded on a Waters Corporation ACQUITY mass spectrometer (SQD or SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative, capillary: 3.0 kV, cone: 30 V, extractor: 3.00 V, source temperature: 150 °C, desolvation temperature: 400 °C, cone gas flow: 60 L / hr, desolvation gas flow: 700 L / h, mass range: 140-800 Da) and a Waters Corporation ACQUITY UPLC equipped with a solvent degasser, binary pump, heated column compartment, and diode-array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm; Temperature: 60 °C; DAD wavelength range (nm): 210–400; Solvent gradient: A = water / methanol 9:1 + 0.1% formic acid, B = acetonitrile + 0.1% formic acid; Gradient: 0–100% B in 2.5 min; Flow rate (ml / min): 0.75.

[0419] Example PE1: Preparation of 2-chloro-6-(1-cyanocyclopropyl)-N-[1-(3-pyrazin-2-yl)ethyl]pyridine-4-carboxamide (compound P27) [ka] Step 1: Preparation of 1-(3-iodopyrazin-2-yl)ethanol [ka] Under an argon atmosphere, THF (35 mL) was cooled to 0 °C. Next, 2,2,6,6-tetramethylpiperidine (5.4 mL, 30.9 mmol, 1.34 equiv.) was added at 0 °C, followed by the dropwise addition of 2.5 M n-BuLi (12 mL, 29.98 mmol, 1.3 equiv.). The reaction mixture was cooled to -78 °C, and then a solution of 2-iodopyrazine (5.0 g, 23.06 mmol, 1.0 equiv.) in THF (5 mL) was added dropwise. After stirring for 1 h, acetaldehyde (12 mL, 210 mmol, 9.2 equiv.) was added dropwise at -78 °C. After the addition, the reaction mixture was allowed to warm to room temperature and then quenched with saturated aqueous ammonium chloride. The reaction mixture was diluted with water and a mixture of TBME and ethyl acetate. The aqueous layer was acidified to pH 1-2 with 1 M HCl. The phases were separated, and the organic layer was washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The crude extract was purified by flash chromatography (0-10% ethyl acetate in cyclohexane) to give 1-(3-iodopyrazin-2-yl)ethanol. LC-MS (method 1): retention time 0.54 min, m / z 251[M+H + ]. 1 H NMR(400MHz,CDCl3)δ ppm 8.47(d,1H)8.31(d,1H)5.10(dd,1H)3.66-3.73(m,1H)1.52(d,3H).

[0420] Step 2: Preparation of tert-butyl-[1-(3-iodopyrazin-2-yl)ethoxy]-dimethyl-silane [ka] To a solution of 1-(3-iodopyrazin-2-yl)ethanol (1.20 g, 4.80 mmol, 1.0 equiv.) in THF (10 mL) was added imidazole (660 mg, 9.60 mmol, 2.0 equiv.), followed by tert-butyldimethylchlorosilane (1.1 mL, 5.76 mmol, 1.2 equiv.). The resulting reaction mixture was heated to 50 °C and stirred at this temperature for 2 h, after which it was allowed to cool to room temperature. The reaction mixture was filtered. The filter cake was washed with TBME, and the filtrate was concentrated in vacuo. The crude extract was purified by flash chromatography (0–3% ethyl acetate in cyclohexane) to give tert-butyl-[1-(3-iodopyrazin-2-yl)ethoxy]-dimethyl-silane. LC-MS (method 1): retention time 1.30 min, m / z 365[M+H + ]. 1 H NMR(400MHz,CDCl3)δ ppm 0.05(s,3H)0.074(s,3H)0.88(s,9H)1.51(d,5H)8.24(d,4H)8.52(d,1H)

[0421] Step 3: Preparation of tert-butyl-dimethyl-[1-(3-pyrazin-2-yl)ethoxy]silane (compound I5) [ka] Under an argon atmosphere, tert-butyl-[1-(3-iodopyrazin-2-yl)ethoxy]-dimethylsilane (500 mg, 1.372 mmol, 1.0 equiv.) was dissolved in degassed THF (14 mL). The solution was cooled to -78 °C, and then 1.3 M Turbo Grignard in THF (1.7 mL, 2.1 mmol, 1.6 equiv.) was added dropwise (Turbo Grignard = 2-butylmagnesium chloride lithium complex). After aging for 30 min, zinc chloride (1.2 g, 2.2 mmol, 1.65 equiv.) was added at -78 °C, and the reaction mixture was warmed to 0 °C. After 40 min, a solution of tris(2-furyl)phosphine (40 mg, 0.16 mmol, 0.12 equiv.), Pd2(dba)3 (78 mg, 0.08 mmol, 0.06 equiv.), and 2-iodopyrazine (350 mg, 1.6 mmol, 1.2 equiv.) in degassed THF (14 mL) was added dropwise. The resulting reaction mixture was heated to 60 °C and stirred for 1 h before being diluted with water and saturated aqueous ammonium chloride. After separation of the layers, the aqueous layer was extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by flash chromatography (0–5% ethyl acetate in cyclohexane) to give tert-butyl-dimethyl-[1-(3-pyrazin-2-ylpyrazin-2-yl)ethoxy]silane. LC-MS (method 1): retention time 1.17 min, m / z 317[M+H + ]. 1 H NMR(400MHz,CDCl3)δ ppm -0.18(s,3H)-0.15(s,3H)0.73(s,10H)1.66(d,3H)5.67(d,1H)8.60(d,1H)8.64-8.69(m,2H)8.72(d,1H)9.22(d,1H)9.62(d,1H).

[0422] Step 4: Preparation of 1-(3-pyrazin-2-yl)ethanol (Compound 14) [ka] To a solution of tert-butyl-dimethyl-[1-(3-pyrazin-2-yl)ethoxy]silane (320 mg, 0.96 mmol, 1.0 equiv.) in THF (10 mL) was added tetrabutylammonium fluoride (1 M in THF, 1.4 mL, 1.4 mmol, 1.5 equiv.). The reaction mixture was stirred at room temperature. After 2 h, additional tetrabutylammonium fluoride (1 M in THF, 0.1 mL, 0.1 mmol, 0.1 equiv.) was added, and the reaction mixture was stirred at room temperature for 30 min before being diluted with brine and ethyl acetate. The phases were separated, and the aqueous layer was extracted once more with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. The crude extract was purified by flash chromatography (15% ethyl acetate / ethanol (3 / 1) in cyclohexane) to give 1-(3-pyrazin-2-ylpyrazin-2-yl)ethanol. LC-MS (Method): Retention time 0.36 min, m / z 203[M+H + ]. 1 H NMR(400MHz,CDCl3)δ ppm 0.92(t,1H)1.24-1.35(m,1H)1.38-1.47(m,1H)1.59(d,3H)1.73-1.77(m,1H)2.38-2.50(m,1H)5.02(br d,2H)5.37(quin,2H)8.63-8.69(m,5H)8.71(d,2H)9.47(d,1H).

[0423] Step 5: Preparation of 2-[1-(3-pyrazin-2-ylpyrazin-2-yl)ethyl]isoindoline-1,3-dione (compound 13) [ka] Under an argon atmosphere, 1-(3-pyrazin-2-ylpyrazin-2-yl)ethanol (179 mg, 0.79 mmol, 1.0 equiv) was dissolved in THF (2 mL). Phthalimide (130 mg, 0.88 mmol, 1.1 equiv) was added, followed by triphenylphosphine (253 mg, 0.96 mmol, 1.2 equiv). The resulting solution was cooled to 0 °C, and diisopropyl azodicarboxylate (0.20 mL, 0.96 mmol, 1.2 equiv) was added. The reaction mixture was allowed to warm to room temperature and stirred at this temperature for 1 h before being diluted with water and ethyl acetate. The layers were separated, and the aqueous layer was extracted once more with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by flash chromatography (0 to 35% ethyl acetate in cyclohexane) to give the desired product, 2-[1-(3-pyrazin-2-ylpyrazin-2-yl)ethyl]isoindoline-1,3-dione. LC-MS (Method 1): Retention time 0.82 min, m / z 332[M+H + ]. 1 H NMR(400MHz,CDCl3)δ ppm 1.91(d,3H)6.52(q,2H)7.63-7.69(m,2H)7.70-7.77(m,2H)8.52-8.56(m,1H)8.59-8.62(m,2H)8.62-8.65(m,1H)9.20(d,1H).

[0424] Step 6: Preparation of 1-(3-pyrazin-2-ylpyrazin-2-yl)ethanamine (Compound 11) [ka] To a solution of 2-[1-(3-pyrazin-2-yl)ethyl]isoindoline-1,3-dione (1.73 g, 5.22 mmol) in EtOH (52 mL) was added hydrazine monohydrate (0.30 mL, 6.27 mmol, 1.2 equiv.). The resulting suspension was heated to reflux and stirred at this temperature for 16 h. The reaction mixture was then cooled to 20 °C, diluted with HO, acidified with HCl 2N, and washed with EtOAc. The aqueous phase was then basified with NaOH 4N and extracted with EtOAc. The organic phase was washed with brine, dried over magnesium sulfate, filtered, and concentrated under reduced pressure to give 1-(3-pyrazin-2-ylpyrazin-2-yl)ethanamine, which was used without further purification. LC-MS (method 1): retention time 0.19 min, m / z 202[M+H + ]. 1 H NMR(400MHz, CDCl3)δ:9.30(d,1H),8.65-8.71(m,3H),8.59(d,1H),4.68-4.76(m,1H),1.50(d,3H).

[0425] Step 7: Preparation of 2-chloro-6-(1-cyanocyclopropyl)-N-[1-(3-pyrazin-2-yl)ethyl]pyridine-4-carboxamide (compound P27) [ka] To a solution of 1-(3-pyrazin-2-ylpyrazin-2-yl)ethanolamine (0.040 g, 0.20 mmol) and 2-chloro-6-(1-cyanocyclopropyl)pyridine-4-carboxylic acid (0.044 g, 0.20 mmol) in ethyl acetate (0.8 mL) was added T3P (0.18 mL, 0.30 mmol, 1.5 equiv.) and N-ethyl-N-isopropyl-propan-2-amine (0.14 mL, 0.79 mmol, 4.0 equiv.). The reaction mixture was stirred at 20 °C for 1 h, and then pyridine (0.10 mL, 0.98 mmol) and additional T3P (0.12 mL, 0.2 mmol) were added. The reaction mixture was aged at 20 °C for an additional 60 min. The reaction mixture was then diluted with water and EtOAc. The aqueous phase was extracted with EtOAc. The combined organic layers were then washed with NaHCO, dried over MgSO, filtered, and concentrated under reduced pressure. The residue was purified by flash chromatography (ethyl acetate in cyclohexane) to give the desired product: 2-chloro-6-(1-cyanocyclopropyl)-N-[1-(3-pyrazin-2-yl)ethyl]pyridine-4-carboxamide. LC-MS (method 1): retention time 0.91 min, m / z 406 / 408[M+H + ]. 1 H NMR(400MHz,CDCl3)δ:9.46(d,1H),8.78(dd,1H),8.67-8.74(m,3H),7.93(d,1H),7.85(br d,1H),7.57(d,1H),6.32(q,1H),1.87-1.92(m,2H),1.79-1.84(m,2H),1.67(d,3H).

[0426] Example PE2: Preparation of 2-chloro-6-(1-cyanocyclopropyl)-N-methyl-N-[1-(3-pyrazin-2-ylpyrazin-2-yl)ethyl]pyridine-4-carboxamide (Compound P29) [ka] To a suspension of 2-chloro-6-(1-cyanocyclopropyl)-N-[1-(3-pyrazin-2-yl)ethyl]pyridine-4-carboxamide (0.024 g, 0.059 mmol) and cesium carbonate (0.058 g, 0.177 mmol, 3.00 equiv.) in acetonitrile (0.4 mL) and DMA (0.3 mL), iodomethane (0.019 mL, 0.296 mmol, 5.00 equiv.) was added, and the reaction mixture was stirred at RT for 20 h. The reaction was then partitioned between HO and EtOAc. The organic phase was washed with saturated aqueous LiCl, dried over MgSO, filtered, and concentrated under reduced pressure. The crude product was purified by flash chromatography (ethyl acetate in cyclohexane) to give the desired product: 2-chloro-6-(1-cyanocyclopropyl)-N-methyl-N-[1-(3-pyrazin-2-ylpyrazin-2-yl)ethyl]pyridine-4-carboxamide. LC-MS (method 1): retention time 0.92 min, m / z 420 / 422[M+H + ]. 1 H NMR (400 MHz, CDCl3) shows two rotamers, chemical shifts assigned to the major rotamer δ: 9.33 (d, 1H), 8.66-8.72 (m, 3H), 8.56-8.60 (m, 1H), 7.45-7.50 (m, 1H), 6.99-7.03 (m, 1H), 6.40 (q, 1H), 2.98 (s, 3H), 1.65-1.88 (m, 7H).

[0427] Example PE3: Preparation of N-[1-[3-(5-chloropyrazin-2-yl)pyrazin-2-yl]ethyl]-3-(1-cyano-1-methyl-ethyl)-5-(trifluoromethyl)benzamide (Compound P37) [ka] Step 1: Preparation of 2-[1-[3-(5-methoxypyrazin-2-yl)pyrazin-2-yl]ethyl]isoindoline-1,3-dione (Compound I8) [ka] 2-[1-[3-(5-Methoxypyrazin-2-yl)pyrazin-2-yl]ethyl]isoindoline-1,3-dione (I8) was prepared in three steps from tert-butyl-[1-(3-iodopyrazin-2-yl)ethoxy]-dimethylsilane and 2-bromo-5-methoxypyrazine, similar to compound I3, as described in Example PE1. LC-MS (method 1): retention time 0.95 min, m / z 362[M+H + ]. 1 H NMR(400MHz,CDCl3)δ:8.75(d,1H),8.54-8.59(t,2H),8.23(d,1H),7.73-7 .80(m,2H),7.67-7.70(m,2H),6.46-6.52(q,1H),3.99(s,3H),1.91(d,3H).

[0428] Step 2: Preparation of 2-[1-[3-(5-hydroxypyrazin-2-yl)pyrazin-2-yl]ethyl]isoindoline-1,3-dione (Compound I7) [ka] To a suspension of 2-[1-[3-(5-methoxypyrazin-2-yl)pyrazin-2-yl]ethyl]isoindoline-1,3-dione (0.45 g, 1.25 mmol) in 1,4-dioxane (3 mL) was added HCl (4 N in dioxane, 2.5 mL, 9.96 mmol, 8 equiv.), and the reaction mixture was stirred at 80° C. for 40 hours. The reaction mixture was concentrated under reduced pressure, and the residual solid was triturated with toluene. The solid was then dried in vacuo to give 2-[1-[3-(5-hydroxypyrazin-2-yl)pyrazin-2-yl]ethyl]isoindoline-1,3-dione, which was used without further purification. LC-MS (method 1): retention time 0.72 min, m / z 348[M+H + ]. 1H NMR(400MHz,CDCl3)δ:11.07-11.61(br s,1H),8.54(d,1H),8.47(d,1H),8.25(d,1H),8.11(d,1H),7.76-7.85(m,2H),7.67-7.74(m,2H),6.52(q,1H),1.94(d,3H).

[0429] Step 3: Preparation of 2-[1-[3-(5-chloropyrazin-2-yl)pyrazin-2-yl]ethyl]isoindoline-1,3-dione (Compound I11) [ka] To a mixture of 2-[1-[3-(5-hydroxypyrazin-2-yl)pyrazin-2-yl]ethyl]isoindoline-1,3-dione (0.47 g, 1.08 mmol) in chlorobenzene (4 mL) was added phosphorus pentachloride (0.34 g, 1.62 mmol, 1.5 equiv.) in small portions at room temperature. The resulting mixture was heated to reflux and aged at this temperature for 2 h, then cooled back to RT. The reaction mixture was diluted with water and extracted with EtOAc. The organic phase was dried over MgSO4 and concentrated under reduced pressure. The residue was purified by flash chromatography (ethyl acetate in cyclohexane) to give 2-[1-[3-(5-chloropyrazin-2-yl)pyrazin-2-yl]ethyl]isoindoline-1,3-dione. LC-MS (Method 1): Retention time 1.00 min, m / z 366 / 368[M+H + ]. 1 H NMR(400MHz,CDCl3)δ=9.10-9.04(m,1H),8.66(d,1H),8.64-8.60(m,2H),7.79-7.74(m,2H),7.73-7.66(m,2H),6.49(q,1H),1.94(d,3H).

[0430] Step 4: Preparation of 1-[3-(5-chloropyrazin-2-yl)pyrazin-2-yl]ethanamine (Compound I12) [ka] To a suspension of 2-[1-[3-(5-chloropyrazin-2-yl)pyrazin-2-yl]ethyl]isoindoline-1,3-dione (0.357 g, 0.976 mmol) in ethanol (10 mL) was added hydrazine hydrate (0.047 mL, 0.976 mmol, 1 equiv.). The mixture was warmed to 80 °C and stirred at this temperature for 16 h. The reaction mixture was cooled to RT and diluted with EtOAc and water. HCl 2M (2.5 mL) was added to acidify the mixture, and the layers were separated. The aqueous layer was basified with 4 M NaOH (4 mL) and extracted with EtOAc. The organic layer was dried over MgSO4, filtered, and concentrated under reduced pressure to provide 1-[3-(5-chloropyrazin-2-yl)pyrazin-2-yl]ethanamine, which was used without further purification. LC-MS (method 1): retention time 0.39 min, m / z 236 / 238[M+H + ]. 1 H NMR(400MHz, CDCl3)δ=9.15-9.09(m,1H),8.68(dd,2H),8.58(d,1H),7.02-6.99(m,1H),4.74(q,1H),1.52-1.48(d,3H).

[0431] Step 5: Preparation of N-[1-[3-(5-chloropyrazin-2-yl)pyrazin-2-yl]ethyl]-3-(1-cyano-1-methyl-ethyl)-5-(trifluoromethyl)benzamide (Compound P37) [ka] To a solution of 1-[3-(5-chloropyrazin-2-yl)pyrazin-2-yl]ethanamine (0.063 g, 0.27 mmol), 3-(1-cyano-1-methyl-ethyl)-5-(trifluoromethyl)benzoic acid (0.068 g, 0.27 mmol), and DMAP (one small crystal) in pyridine (1 mL) was added T3P (0.236 mL, 0.4 mmol, 1.5 equiv). The reaction mixture was stirred at RT for 3 h and then partitioned between EtOAc and water. The organic phase was washed with NaHCO3, dried over MgSO4, filtered, and concentrated under reduced pressure. The residue was purified by flash chromatography (ethyl acetate in cyclohexane) to give N-[1-[3-(5-chloropyrazin-2-yl)pyrazin-2-yl]ethyl]-3-(1-cyano-1-methyl-ethyl)-5-(trifluoromethyl)benzamide. LC-MS (method 1): retention time 1.10 min, m / z 475 / 477[M+H + ]. 1 H NMR(400MHz,CDCl3)δ:9.26(d,1H),8.78(d,1H),8.68-8.71(m,2H),8.13(m,1H),7.97(s,1H),7.88(s,1H),7.66(br d,1H),6.25-6.32(m,1H),1.80(d,6H),1.69(d,3H). 19 F NMR(CDCl3) δ: -62.57(s,3F).

[0432] Example PE4: Preparation of N-[1-[3-(5-cyanopyrazin-2-yl)pyrazin-2-yl]ethyl]-3-methylsulfonyl-5-(trifluoromethyl)benzamide (Compound P39) [ka] Similar to Example PE3, Step 5, Zn(CN) (0.005 g, 0.042 mmol) was added to a solution of N-[1-[3-(5-chloropyrazin-2-yl)pyrazin-2-yl]ethyl]-3-methylsulfonyl-5-(trifluoromethyl)benzamide (0.020 g, 0.041 mmol), prepared from 1-[3-(5-chloropyrazin-2-yl)pyrazin-2-yl]ethanamine and 3-methylsulfonyl-5-(trifluoromethyl)benzoic acid, in N,N-dimethylacetamide (0.12 mL). After degassing the solution with argon, X-Phos Pd G (0.0015 g, 0.0019 mmol) was added, and the vial was placed in a microwave oven and stirred at 150 °C for 30 min. The resulting dark solution was cooled to room temperature and partitioned between ethyl acetate and aqueous NaHCO. The organic phase was washed with water, dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by flash chromatography (silica gel, cyclohexane / ethyl acetate eluent) to give N-[1-[3-(5-cyanopyrazin-2-yl)pyrazin-2-yl]ethyl]-3-methylsulfonyl-5-(trifluoromethyl)benzamide as a yellow solid. LC-MS (method 1): retention time 0.95 min, m / z 477[M+H + ]. 1 H NMR(400MHz,CDCl3)δ 9.68-9.61(m,1H),9.09(d,1H),8.75(s,2H),8.53-8.48(m,1H),8.40-8.3 3(m,2H),7.69-7.64(m,1H),6.42-6.27(m,1H),3.16(s,3H),1.74(s,3H). 19 F NMR(CDCl3)δ -62.81(s,3F).

[0433] Example PE5: Preparation of N-[(1S)-1-(3-pyrazin-2-ylpyrazin-2-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (Compound E3) [ka] Step 1: Preparation of tert-butyl N-[(1S)-2-hydroxy-1-methyl-3-oxo-3-pyrazin-2-yl-propyl]carbamate [ka] A 25 ml round-bottom flask was charged with tert-butyl N-[(1S)-1-methyl-2-oxo-ethyl]carbamate (0.725 g), 3-benzyl-5-(3-hydroxyethyl)-4-methylthiazol-3-ium bromide (0.210 g), pyrazine-2-carbaldehyde (1.13 g), and dichloromethane (12 ml). N,N-Diisopropylethylamine (1.46 ml) was then added, and the mixture was stirred at ambient temperature for 2 hours. The reaction was quenched by the addition of saturated aqueous ammonium chloride solution and extracted with dichloromethane. The combined organic phases were dried over MgSO4 and concentrated under reduced pressure. The residue was purified by preparative HPLC on a reverse-phase C18 column using water and acetonitrile as eluents. This afforded tert-butyl N-[(1S)-2-hydroxy-1-methyl-3-oxo-3-pyrazin-2-yl-propyl]carbamate as a mixture of diastereoisomers in a ratio of approximately 3:1, which was used in the next step without further separation. LC-MS (method 1): retention time 0.74 min, m / z 280[MH] - (Negative mode). 1 H NMR (400 MHz, CDCl3) δ / ppm, signals for the major diastereoisomer: 9.20 (d, 1H), 8.80 (d, 1H), 8.65 (t, 1H), 5.27 (d, 1H), 4.63 (d, broad, 1H), 4.42 (m, 1H), 3.64 (d, 1H), 1.41 (d, 3H), 1.32 (s, 9H).

[0434] Step 2: Preparation of tert-butyl N-[(1S)-1-methyl-2,3-dioxo-3-pyrazin-2-yl-propyl]carbamate [ka] tert-Butyl N-[(1S)-2-hydroxy-1-methyl-3-oxo-3-pyrazin-2-yl-propyl]carbamate (0.590 g) was dissolved in a mixture of dichloromethane (7 ml), dimethyl sulfoxide (1 ml), and N,N-diisopropylethylamine (1.08 ml). After cooling the mixture to 0°C, sulfur trioxide pyridine complex (688 mg) was added to the orange solution in one portion. After 30 minutes at 0°C, the reaction was quenched with water and diluted with dichloromethane and aqueous HCl (1N). The phases were separated, and the aqueous phase was extracted with dichloromethane. The combined organic phases were dried over MgSO4 and concentrated under reduced pressure to give crude tert-butyl N-[(1S)-1-methyl-2,3-dioxo-3-pyrazin-2-yl-propyl]carbamate as a brown oil. The crude product was used in the next step without further purification. 1 H NMR (400 MHz, CDCl3) δ / ppm 9.28 (d, 1H), 8.84 (d, 1H), 8.73 (s, 1H), 5.11 (s, broad, 1H), 4.88 (m, 1H), 1.50 (d, 3H), 1.36 (s, 9H).

[0435] Step 3: Preparation of tert-butyl N-[(1S)-1-(3-pyrazin-2-ylpyrazin-2-yl)ethyl]carbamate (Compound I2) [ka] (Compound I2) To a solution of crude tert-butyl N-[(1S)-1-methyl-2,3-dioxo-3-pyrazin-2-yl-propyl]carbamate (570 mg) in ethanol (8 ml) was added ethane-1,2-diamine (1.39 ml). The resulting brown solution was stirred at ambient temperature open to the atmosphere. After 48 hours, the orange solution was concentrated in vacuo, and the residue was purified by chromatography on silica gel using cyclohexane and ethyl acetate as eluents. This gave tert-butyl N-[(1S)-1-(3-pyrazin-2-ylpyrazin-2-yl)ethyl]carbamate as a yellow gum. LC-MS (Method 1): Retention time 0.86 min, m / z 302[M+H + ]. 1 H NMR(400MHz,CDCl3)δ / ppm:9.39(d,1H),8.70(m,1H),8.63(m,3H),5.78(m,2H),1.56(d,3H),1.40(s,9H).

[0436] Step 4: Preparation of [(1S)-1-(3-pyrazin-2-ylpyrazin-2-yl)ethyl]ammonium-2,2,2-trifluoroacetate [ka] A solution of tert-butyl N-[(1S)-1-(3-pyrazin-2-ylpyrazin-2-yl)ethyl]carbamate (282 mg) in dichloromethane (7 ml) was treated with trifluoroacetic acid (0.5 ml) and stirred at ambient temperature for 20 hours. All volatiles were then removed under reduced pressure to give crude [(1S)-1-(3-pyrazin-2-ylpyrazin-2-yl)ethyl]ammonium-2,2,2-trifluoroacetate as a thick oil, which was used in the next step without further purification. LC-MS (Method 1): retention time 0.18 min, m / z 202 of the amine as the free base [M+H + ]. 1 H NMR (400 MHz, CDCl) δ / ppm: 9.62 (s, 1H), 9.40 (s, broad, 3H), 8.88 (d, 1H), 8.83 (d, 1H), 8.78 (d, 1H), 8.71 (d, 1H), 7.88 (s, broad, 2H), 5.68 (m, broad, 1H), 1.80 (d, 3H).

[0437] Step 5: Preparation of N-[(1S)-1-(3-pyrazin-2-ylpyrazin-2-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (Compound E3) [ka] A solution of [(1S)-1-(3-pyrazin-2-ylpyrazin-2-yl)ethyl]ammonium-2,2,2-trifluoroacetate (150 mg) in ethyl acetate (2 ml) was treated with 3,5-bis(trifluoromethyl)benzoyl chloride (160 mg) and sodium bicarbonate (1N in water, 2 ml). The biphasic mixture was vigorously stirred at ambient temperature. After 1.5 hours, the phases were separated, the aqueous phase was extracted with ethyl acetate, and the combined organic phases were concentrated under reduced pressure. The residue was purified by chromatography on silica gel using cyclohexane and ethyl acetate as eluents. This gave N-[(1S)-1-(3-pyrazin-2-ylpyrazin-2-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide. LC-MS (method 1): retention time 1.05 min, m / z 442[M+H + ]. 1 H NMR(400MHz,CDCl3)δ / ppm:9.44(d,2H),8.76(d,1H),8.71(m,3H),8.28(s,2H),8.01(s,1H),7.82,(d,broad,1H),6.33(q,1H),1.69(d,3H). 19 F NMR(377MHz,CDCl3)δ / ppm:-62.87(s,6F).

[0438] [Table 12-1] [Table 12-2] [Table 12-3] [Table 12-4] [Table 12-5] [Table 12-6] [Table 12-7] [Table 12-8]

[0439] [Table 13-1] [Table 13-2]

[0440] [Table 14-1] [Table 14-2] [Table 14-3]

[0441] Abbreviations used in the synthetic schemes and preparations ACN Acetonitrile Boc t-butoxycarbonyl DBU 1,8-diazabicyclo[5.4.0]undec-7-ene DCM dichloromethane DDQ 2,3-dichloro-5,6-dicyano-1,4-benzoquinone DMA Dimethylacetamide DMAP 4-dimethylaminopyridine DMSO dimethyl sulfoxide DMSO-d6 Deuterated dimethyl sulfoxide DPEN Diphenylethylenediamine ET3N Triethylamine EtOAc ethyl acetate EtOH ethanol HCl Hydrochloric acid MeCN acetonitrile MeOH Methanol Ms methanesulfonyl (mesyl) MgSO4 Magnesium Sulfate NaHCO3 Sodium bicarbonate NaOH Sodium hydroxide n-Bu N-butyl n-BuLi n-butyllithium NHC N-heterocyclic carbene NH4OH Ammonium hydroxide NPhth phthalimide-1-yl OMs mesylate group OTf triflate group OTs tosylate group PdCl2dppf 1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride PD2(dba)3 Tris(dibenzylideneacetone)dipalladium(0) T3P Propanephosphonic Anhydride TBME tert-butyl methyl ether TEA Triethylamine TEMPO (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl TF Trifluoromethanesulfonyl (triflyl) TFA trifluoroacetic acid THF tetrahydrofuran Ts p-Toluenesulfonyl (tosyl) X-Phos 2-Dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl X-Phos Pd G2 Chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) Zn(CN)2 zinc cyanide aq. water-based °C degree Celsius temperature equiv. h time LC / MS or LC-MS Liquid Chromatography Mass Spectrometry M mole MHz Megahertz min mp or MP melting point NMR nuclear magnetic resonance ppm parts per million RT room temperature RT retention time RBF Round Bottom Flask

[0442] The activity of the composition of the present invention can be considerably broadened by adding other insecticidal, acaricidal and / or fungicidal active ingredients, and can be adapted to the general situation.The mixture of the compound of formula I with other insecticidal, acaricidal and / or fungicidal active ingredients can also have other unexpected advantages, which may be described in a broader sense as synergistic activity.For example, better tolerance by plants, reduced phytotoxicity, insects can be controlled at different stages of their development, or better behavior during their preparation, for example, during grinding or mixing, during their storage, or during their use.

[0443] Suitable additives to the active ingredients herein are, for example, exemplified by the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, urea, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.

[0444] The following mixtures of compounds of formula I with active substances are preferred (the abbreviation "TX" means "one compound selected from the compounds defined in Tables A-1 to A-126 and Tables P and E"): 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, Afoxaraner +TX, Alanycarb +TX, Allethrin +TX, α-Cypermethrin +TX, α-Methrin +TX, Amidoflumet +TX, Aminocarb +TX, Azocyclotine +TX, Bensultap +TX, Benzochimate +TX, Benzpyrimoxane +TX, β-Cyfluthrin +TX, β-Cypermethrin +TX, Bifenazate +TX, Bifenthrin +TX, Binapacryl + TX, Bioallethrin + TX, S-Bioallethrin + TX, Bioresmethrin + TX, Bistrifluron + TX, Brofuranilide + TX, Broflutrinate + TX, Bromophos-ethyl + TX, Buprofezin + TX, Butocarboxim + TX, Cadusafos + TX, Carbaryl + TX, Carbosulfan + TX, Cartap + TX, CAS Number: 1632218-00-8 + TX, CAS Number: 1808115-49-2 + TX, CAS Number: 2032403-97-5 + TX, CAS Number: 2044701-44-0 + TX, CAS Number: 2128 706-05-6+TX, CAS number:2095470-94-1+TX, CAS number:2377084-09-6+TX, CAS number:1445683-71-5+TX, CAS number:2408220-94-8+TX, CAS number:2408220-91-5+TX, CA S 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, CAS number: 1922957-48-9+TX, CAS number: 24 15706-16-8+TX, CAS number: 1594624-87-9+TX, CAS number: 1594637-65-6+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 number: 2719848-60-7 + TX, CAS number: 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, cyanofenfen thiamin + TX, cyantraniliprole + TX, cyclaniliprole + TX, cyclobutrifluram + TX, cycloprothrin + TX, cycloxapride + TX, cycloxapride + TX, cyenopyrafen + TX, cetoprafen (or etoprafen) + TX, cyflumetofen + TX, cyfluthrin + TX, cyhalodiamide + TX, cyhalothrin + TX, cypermethrin + TX, cyphenothrin + TX, cyprofanilide + TX, cyromazine + TX, deltamethrin Torin + TX, diafenthiuron + TX, dialifos + TX, dibrom + TX, dichloromezothiaz + TX, diflovidazin + TX, diflubenzuron + TX, dimepropyridaz + TX, dinactin + TX, dinocap + TX, dinotefuran + TX, dioxabenzophos + TX, emamectin (or emamectin benzoate) + TX, empenthrin + TX, ε-monfluorotrin + TX, ε-metofluthrin + TX, esfenvalerate + TX, ethio thion +TX, ethiprole +TX, etofenprox +TX, etoxazole +TX, fanfur +TX, fenazaquin +TX, fenfluthrin +TX, phenmezodithiaz +TX, fenitrothion +TX, fenobucarb +TX, fenothiocarb +TX, fenoxycarb +TX, fenpropathrin +TX, fenpyroximate +TX, fensulfothion +TX, fenthion +TX, fentin acetate +TX, fenvalerate +TX,Fipronil + TX, flometoquin + TX, flonicamid + TX, fluacrypyrim + TX, fluazaindolizine + TX, fluazuron + TX, flubendiamide + TX, flubenzimine + TX, 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, fluxametamide + TX, fosthiazate + TX, gamma-cyhalothrin + TX, guadipyr + TX, halofenozide + TX, halofenprox + TX, heptafluthrin + TX, hexythiazox + TX, Hydramethylnon + TX, Imicyaphos + TX, Imidacloprid + TX, Imiprothrin + TX, Indazapiroxameth + TX, Indoxacarb + TX, Iodomethane + TX, Iprodione + TX, Isocycloceram + TX, Isothioate + TX, Ivermectin + TX, κ-bifenthrin + TX, κ-tefluthrin + TX, λ-cyhalothrin + TX, Lepimectin + TX, Lotinanel + 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, pirimiphos-ethyl +TX, pirimiphos-methyl +TX, polyhedrovirus +TX, prallethrin +TX, profenofos +TX, prothrombin Lofluthrin +TX, Propargite +TX, Propetamfos +TX, Propoxur +TX, Prothiofos +TX, Protrifenbut +TX, Piflubumid +TX, Pymetrozine +TX, Pyraclofos +TX, Pyrafluprole +TX, Pyridaben +TX, Pyridalyl +TX, Pyrifluquinazone +TX, Pyrimidifen +TX, Pirimostrobin +TX, Pyriprole +TX, Pyriproxyfen +TX, Resmethrin +TX, Sarolaner +TX, Selamectin +TX, Silafluofen +TX, Spinetoram +TX, Spinosad +TX, Spirogyc Lofen + TX, spiromesifen + TX, spiropydione + TX, spirotetramat + TX, spidoxamate + TX, sulfoxaflor + TX, tebufenozide + TX, tebufenpyrad + TX, tebupirimiphos + TX, tefluthrin + TX, temephos + TX, tetrachloraniliprole + TX, tetradifon + TX, tetramethrin + TX, tetramethylfluthrin + TX, tetranactin + TX, tetraniliprole + TX, θ-cypermethrin + TX, thiacloprid + TX, thiamethoxam + TX, thiocyclam + TX, thiodicarb + TX,Thiofanox + TX, Thiometon + TX, Thiosultap + TX, Tigolaner + TX, Thiolantraniliprole + TX, Thioxazaphen + TX, Tolfenpyrad + TX, Toxaphene + TX, Tralomethrin + TX, Transfluthrin + TX, Triazamate + TX, Triazophos + TX, Trichlorfon + TX, Trichloronate + TX, Trichlorofon + TX, Trifluenfuronate + TX, Triflumezopyrin + TX, Cyclopyrazofurol + TX, Zeta -Cypermethrin +TX, seaweed extract and fermented product derived from Melasse +TX, seaweed extract and fermented product derived 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 (Bacillus aizawai + TX, Bacillus chitinosporus AQ746 (NRRL accession number B-21618) + TX, Bacillus firmus + TX, Bacillus kurstaki + TX, Bacillus mycoides AQ726 (NRRL accession number B-21664) + TX, Bacillus pumilus (NRRL accession number B-30087) + TX, Bacillus pumilus AQ717 (NRRL accession number B-21662) + TX, Bacillus sp. AQ178 (ATCC accession number 53522) + TX, Bacillus sp.) AQ175 (ATCC accession number 55608) + TX, Bacillus sp.) AQ177 (ATCC accession number 55609) + TX, unspecified Bacillus subtilis + TX, Bacillus subtilis AQ153 (ATCC accession number 55614) + TX,Bacillus subtilis AQ30002 (NRRL accession number B-50421) + TX, Bacillus subtilis AQ30004 (NRRL accession number B-50455) + TX, Bacillus subtilis AQ713 (NRRL accession number B-21661) + TX, Bacillus subtilis AQ743 (NRRL accession number B-21665) + TX, Bacillus thuringiensis AQ52 (NRRL accession number B-21619) + TX, Bacillus thuringiensis thuringiensis BD#32 (NRRL accession number B-21530) + TX, Bacillus thuringiensis subspec. kurstaki BMP 123 + TX, Beauveria bassiana + TX, D-limonene + TX, granulovirus + TX, harpin + TX, Helicoverpa armigera nucleopolyhedron virus + TX, Helicoverpa zea nucleopolyhedron virus + TX, Heliothis virescens nucleopolyhedron virus + TX, Heliothis punctigera nucleopolyhedron virus + TX, Metarhizium spp. + TX, Muscodor albus albus 620 (NRRL accession number 30547) + TX, Muscodor roseus A3-5 (NRRL accession number 30548) + TX, Neem tree-based products + TX, Paecilomyces fumosoroseus + TX, Paecilomyces lilacinus + TX, Pasteuria nishizawae + TX, Pasteuria penetrans + TX, Pasteuria ramosa + TX, Pasteuria thornei + TX, Pasteuria usgae + TX, P-cymene + TX, Plutella xylostella granulosis virus + TX, Plutella xylostella nucleopolyhedrovirus + TX, Polyhedrovirus + TX, Pyrethrum pyrethrum + TX, QRD 420 (Terpenoid Blend) + TX, QRD 452 (Terpenoid Blend) + TX, QRD 460 (terpenoid blend) + TX, Quillaja saponaria + TX, Rhodococcus globerulus AQ719 (NRRL accession number B-21663) + TX, Spodoptera frugiperda nucleopolyhedrovirus + TX, Streptomyces galbus (NRRL accession number 30232) + TX, Streptomyces sp. (NRRL accession number B-30145) + TX, terpenoid blend + TX, and Verticillium spp.; an algicide selected from the group of substances consisting of bethoxadin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, sibutrin [CCN] + TX, dichloron (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamide (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomate (1011) + TX, cyclobutrifluram + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX, an avian repellent selected from the group of substances consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX, 1-Hydroxy-1H-pyridine-2-thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodicine (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargafen (alternative name) [CCN] + TX a fungicide selected from the group of substances consisting of TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, tecloftalam (766) + TX and thiomersal (alternative name) [CCN] + TX, Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis (alternative name) (33) + TX, Aphidius colemani (alternative name) (34) + TX, Aphidoletes aphidimiza aphidimyza (alternative name) (35) + TX, Autographa 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 (scientific name) (51) + TX, Bacillus thuringiensis subsp. kurstaki (scientific name) (51) + TX, Bacillus thuringiensis subsp. tenebrionis (Bacillus thuringiensis subsp.tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alternate name) (53) + TX, Beauveria brongniartii (alternate name) (54) + TX, Chrysoperla carnea (alternate name) (151) + TX, Cryptolaemus montrouzieri (red ladybird beetle) (alternate name) (178) + TX, Cydia pomonella GV (alternate name) (191) + TX, Dacnusa sibirica (alternate name) (212) + TX, Diglyphus isaea (alternate name) (254) + TX, Encarsia formosa (scientific name) (293) + TX, Eretmocerus eremicus (alternate name) (300) + TX, Helicoverpa zea NPV (alternate name) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alternate name) (433) + TX, Hippodamia convergens (alternate name) (442) + TX, Leptomastix dactylopii (alternate name) (488) + TX, Macrolophus caliginosus (alternate name) (491) + TX, Mamestra brassicae) NPV (alternate name) (494) + TX, Metaphycus helvolus (alternate name) (522) + TX,. Metarhizium anisopliae var. acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. lecontei NPV (alternate name) (575) + TX, Orius spp. (alternate name) (596) + TX, Paecilomyces fumosoroseus (alternate name) (613) + TX, Phytoseiulus persimilis (alternate name) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741) + TX, Steinernema bibionis (alternate name) (742) + TX, Steinernema carpocapsae (alternate name) (742) + TX, Steinernema feltiae (alternate name) (742) + TX, Steinernema glaseri (alternate name) (742) + TX, Steinernema riobrave (alternate name) (742) + TX, Steinernema riobravis (alternate name) (742) + TX, Steinernema scapterisi a biological agent selected from the group of substances consisting of Steinernema spp. (alternative name) (742) + TX, Trichogramma spp. (alternative name) (826) + TX, Typhlodromus occidentalis (alternative name) (844) and 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; antisterilizing agents selected from the group of substances consisting of Afolate [CCN] + TX, Visadyl (alternative name) [CCN] + TX, Busulfan (alternative name) [CCN] + TX, Diflubenzuron (250) + TX, Zimatif (alternative name) [CCN] + TX, Hemel [CCN] + TX, Hempa [CCN] + TX, Metepa [CCN] + TX, Methiotepa [CCN] + TX, Methyl Afolate [CCN] + TX, Morzide [CCN] + TX, Penfluron (alternative name) [CCN] + TX, Tepa [CCN] + TX, Thiohempa (alternative name) [CCN] + TX, Thiotepa (alternative name) [CCN] + TX, Tretamine (alternative name) [CCN] and Uredepa (alternative name) [CCN] + TX; (E)-Deca-5-en-1-yl acetate and (E)-dec-5-en-1-ol (IUPAC name) (222) + TX, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, (E,Z)-tetradec-4,1 0-Dien-1-yl acetate (IUPAC name) (779) + TX, (Z)-Dodec-7-en-1-yl acetate (IUPAC name) (285) + TX, (Z)-Hexadec-11-enal (IUPAC name) (436) + TX, (Z)-Hexadec-11-en-1-yl acetate (IUPAC name) (437) + TX, (Z)-Hex Sadec-13-en-11-yn-1-yl acetate (IUPAC name) (438) + TX, (Z)-Icos-13-en-10-one (IUPAC name) (448) + TX, (Z)-tetradec-7-en-1-al (IUPAC name) (782) + TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783) + TX, ( Z)-Tetradeca-9-en-1-yl acetate (IUPAC name) (784) + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283) + TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780) + TX, (9Z,12E)-tetradeca-9,12-Dien-1-yl acetate (IUPAC name) (781) + TX, 14-methyloctadec-1-ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol and 4-methylnonan-5-one (IUPAC name) (544) + TX, α-multistriatin (alternative name) [CCN] + TX, Brevicomin (alternative name) [CCN] + TX, Codlerure (alternative name) [CCN] + TX, Codlemone (alternative name) (167) + TX, Cureure (alternative name) (179) + TX, De 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, Gossiplua® (alternative name; 1:1 mixture of the (Z,E) and (Z,Z) isomers of hexadeca-7,11-dien-1-yl acetate) (420) + TX, Grandlua (421) + TX, Grandlua I (alternative name) (421) + TX, Grandlua II (alternative name) (421) + TX, Grandlua III (alternative name) (421) + TX, Grandlua 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) (Plastic name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alternative name) (210) + TX, abamectin (1) + TX, acetoprole [CCN] + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxicarb (863) + TX, AZ60541 (compound code) + TX, benclotiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbosulfan (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, cloetocarb (999) + TX, cyclobutrifluram + TX, cytokinin (alternative name) (210) + T X, Dazomet (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, Diamidaphos (1044) + TX, Diclofenthion (1051) + TX, Dicrifos (alternative name) + TX, Dimethoate (262) + TX, Doramectin (alternative name) [CCN] + TX, Emamectin (291) + TX, Emamectin Benzoate (291) + TX, Eprinomectin (alternative name) [CCN] + TX, Ethoprophos (312) + TX, Ethyl Dibromide len (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, ebe Lumectin (alternative name) [CCN] + TX, Kinetin (alternative name) (210) + TX, Mecarfone (1258) + TX, Metam (519) + TX, Metam-potassium (alternative name) (519) + TX, Metam-sodium (519) + TX, Methyl bromide (537) + TX, Methyl isothiocyanate (543) + TX, Milbemycin oxime (alternative name) [CCN] + TX, Moxidectin (alternative name) [CCN] + TX, Myrotheciumverrucaria) Composition (alternative name) (565) + TX, NC-184 (compound code) + TX, Oxamyl (602) + TX, Phorate (636) + TX, Phosphamidon (639) + TX, Phosphocarb [CCN] + TX, Cebufos (alternative name) + TX, Selamectin (alternative name) [CCN] + TX, Spinosad (737) + TX, Terbam (alternative name) + TX, Terbufos (773) + TX, Tetrachlorothiophene (IU a nematicide selected from the group of substances consisting of PAC / Chemical Abstracts Name) (1422) + TX, Thiafenox (alternative name) + TX, Thionazine (1434) + TX, Triazophos (820) + TX, Triazuron (alternative name) + TX, Xylenol [CCN] + TX, YI-5302 (compound code) and Zeatin (alternative name) (210) + TX, Fluensulfone [318290-98-1] + TX, Fluopyram + TX, Nitrification inhibitors selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX: a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX; 2-Isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, α-chlorohydrin [CCN] + TX, aluminum phosphide (640) + TX, antu (880) + TX, arsenic trioxide (882) + TX, barium carbonate (891) + TX, bisthiosemi (912) + TX, brodifacoium (89) + TX, bromadiolone (including alpha-bromadiolone) (mu) + TX, Bromethalin (92) + TX, Calcium cyanide (444) + TX, Chloralose (127) + TX, Chlorophacinone (140) + TX, Cholecalciferol (alternative name) (850) + TX, Coumacrol (1004) + TX, Coumafuryl (1005) + TX, Coumatetralyl (175) + TX, Crimidine (1009) + TX, Difenacoum (246) + TX, Difethialone (249) + TX, Diphacinone (273) + TX, Ergocalciferol (301) + TX, Flocoumafen (357) + TX, Fluoroacetamide (379) + TX, Flupropaline (1183) + TX, Flupropaline Hydrochloride (1183) + TX, γ-HCH (430) + TX, HCH (430) + TX, Hydrogen Cyanide (444) + TX, Iodomethane (IUPAC name) (542) + TX, Lindane (430) + TX, Magnesium Phosphide (IUPAC name) (640) + TX, Methyl Bromide (537) + TX, Norbormide (1318) + TX, Fosacetim (1336) + TX, Fosacetim a rodenticide selected from the group of substances consisting of sphingosine (IUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371) + TX, sciliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851) and zinc phosphide (640) + TX; a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934) + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol and nerolidol (alternative names) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piperotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesamolin (1394) and sulfoxide (1406) + TX; an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetate (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN], and ziram (856) + TX; a virucidal agent selected from the group of substances consisting of Imanin (alternative name) [CCN] and Ribavirin (alternative name) [CCN] + TX; a wound protectant selected from the group of substances consisting of mercuric oxide (512) + TX, octilinone (590) and thiophanate-methyl (802) + TX; 1,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX, 2,4-dichlorophenylbenzenesulfonate + TX, 2-fluoro-N-methyl-N-1-cinnamaldehyde + TX, 4-chlorophenyl phenyl sulfone + TX, acetoprole + TX, aldoxicarb + TX, amidithione + TX, amidothioate + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, alamite + TX, arsenic trioxide + TX, azobenzene + TX, azotoate + TX, benomyl + TX, benoxafos + TX, benzyl benzoate Oxalate +TX, Bixafen +TX, Brofenvalerate +TX, Bromocyclen +TX, Bromophos +TX, Bromopropylate +TX, Buprofezin +TX, Butocarboxim +TX, Butoxycarboxim +TX, Butylpyridaben +TX, Calcium polysulfate +TX, Camphechlor +TX, Carbanolate +TX, Carbophenothion +TX, Cimiazole +TX, Thiomethionate +TX, Chlorbeside +TX, Chlordimeform +TX, Chlordimeform hydrochloride +TX, Chlorphenetole +TX, Chlorfenson +TX , Chlorofensulfide +TX, Chlorobenzilate +TX, Chlormebform +TX, Chlormethiuron +TX, Chloropropylate +TX, Chlorthiophos +TX, Cinerin I +TX, Cinerin II +TX, Cinerins +TX, Closantel +TX, Coumaphos +TX, Crotamiton +TX, Crotoxyphos +TX, Kufraeb +TX, Cyanthoate +TX, DCPM +TX, DDT +TX, Demefion +TX, Demefion-O +TX, Demefion-S +TX, Demeton-methyl +TX, Demeton-O +TX, Demeton-O-methyl +TX , Demeton-S+TX, Demeton-S-methyl+TX, Demeton-S-methylsulfone+TX, Dichlofluanid+TX, Dichlorvos+TX, Dicrifos+TX, Dienochlor+TX, Dimefox+TX, Zinex+TX, Zinex-diclexin+TX, Dinocap-4+TX, Dinocap-6+TX, Dinocton+TX, Dinopenton+TX, Dinosulfone+TX, Dinotervone+TX, Dioxathion+TX, Diphenylsulfone+TX, Disulfiram+TX, DNOC+TX, Dofenapine+TX, Doramectin+TX, Endothion+TX,Epirinomectin +TX, Ethoate-methyl +TX, Etrimphos +TX, Fenazaflor +TX, Fenbutatin oxide +TX, Fenothiocarb +TX, Fenpyrad +TX, Fenpyroximate +TX, Fenpyrazamine +TX, Fenson +TX, Fentrifanil +TX, Flubenzimine +TX, Flucycloxuron +TX, Fluenethyl +TX, Fluorobenside +TX, FMC 1137 +TX, Formetanate +TX, Formetanate hydrochloride +TX, Formoparanate +TX, γ-HCH +TX, Gliodin +TX, Halfenprox +TX, Hexadecylcyclopropanecarboxylate +TX, Isocarbophos +TX, Jasmolin I +TX, Jasmolin II +TX, Jodofenphos +TX, Lindane +TX, Malonoben +TX, Mecarbam +TX, Mefosfolan +TX, Mesulfen +TX, Methacrifos +TX, methyl bromide +TX, metolcarb +TX, mexacarbate +TX, milbemycin oxime +TX, mipafox +TX, monocrotophos +TX, morphothion +TX, moxidectin +TX, naled +TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one +TX, nifururidide +TX, nikkomycin +TX, nitrilacarb +TX, nitrilacarb 1:1 chloride Zinc complex +TX, omethoate +TX, oxydeprophos +TX, oxydisulfoton +TX, pp'-DDT +TX, parathion +TX, permethrin +TX, fenkapton +TX, phosalone +TX, phospholan +TX, phosphamidon +TX, polychloroterpene +TX, polynactin +TX, proclonol +TX, promacyl +TX, propoxur +TX, protidathion +TX, prothoate +TX, pyrethrin I +TX, pyrethrin II + TX, pyrethrins + TX, pyridaphenthion + TX, pirimitate + TX, quinalphos + TX, quinthiofos + TX, R-1492 + TX, phosglycine + TX, rotenone + TX, shladan + TX, cevufos + TX, selamectin + TX, sofamid + TX, SSI-121 + TX, sulfiram + TX, sulfuramide + TX, sulfotep + TX, sulfur + TX, diflobidazin + TX, tau-fluvalinate + TX, TEPP + TX, terbam + TX,Tetrazifon + TX, Tetrasulfur + TX, Thiafenox + TX, Thiocarboxim + TX, Thiofanox + TX, Thiometon + TX, Thioquinox + TX, Thuringiensin + TX, Triamiphos + TX, Trialatin + 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, Streptavidin Quinine + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide + TX, 8-hydroxyquinoline sulfate + TX, bronopol + TX, copper hydroxide + TX, cresol + TX, dipyrithione + TX, doditin + TX, fenaminosulf + TX, formaldehyde + TX, hydralgafen + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel bis(dimethyldithiocarbamate) + TX, nitrapyrin + TX, octhilinone + TX, oxolinic acid + TX, oxytetracycline + TX, potassium hydroxyquinoline sulfate + TX, probenazole + TX, streptomycin + TX, streptomycin sesquisulfate + TX, tecloftalam + TX, thiomersal + TX, Adoxophyes orana GV+TX, Agrobacterium radiobacter+TX, Amblyseius spp.) + TX, Anagrapha falcifera NPV + TX, 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 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-ol + TX yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E,Z)-tetradec-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-icos-13-en-10-one + TX. (Z)-Tetradeca-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, α-multistriatin + TX, brevicomin + TX, codrellet + TX, codlemone + TX, querle + TX, disparle + TX, dodec-8-en-1-yl Acetate + TX, Dodec-9-en-1-yl acetate + TX, Dodec-8 + TX, 10-dien-1-yl acetate + TX, Dominicale + 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, Littlea + TX, Louplure + TX, Medulure + TX, Megatomoic acid + TX, Methyleugenol + TX, Muscale + TX, Octadeca-2,13-dien-1-yl acetate + TX, Octadeca-3,13-dien-1-yl acetate + TX, Olfural + 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, Butopyronoxyl + TX, Butoxy(polypropylene glycol) Cole) + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, diethyl toluamide + TX, dimethylcarbate + TX, dimethyl phthalate + 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-dichloro Isopropylpropene + TX, 1-bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)acetic acid ethyl ester + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + 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-xylyl) Xylyl)ethanol + TX, 2-chlorovinyldiethyl phosphate + TX, 2-imidazolidone + TX, 2-isovalerylindan-1,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate + TX, 2-thiocyanatoethyl laurate + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-methyl-1-phenylpyrazol-5-yldimethylcarbamate + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate + TX, 5,5-Dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate + 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) δ-endotoxin +TX, barium hexafluorosilicate +TX, barium polysulfide +TX, bartholin +TX, Bayer 22 / 190 +TX, Bayer 22408 +TX, β-cyfluthrin +TX, β-cypermethrin +TX, bioethanomethrin +TX, biopermethrin +TX, bis(2-chloroethyl) ether +TX, 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, chlor Ludecon + 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, Sithioate + TX, d-Tetramethrin + TX, DAEP + TX, Dazomet + TX, Decarbofuran + TX, Diamidaphos + TX, Dikapton + TX, Dichlorophenthion + TX, Dicresyl + TX, Dicyclanil + TX, Dieldrin + TX, Diethyl 5-methylpyrazol-3-yl phosphate + TX, Dilol + TX, Dimefluthrin + TX, Dimethane + TX, Dimethryn + TX, Dimethylvinphos + TX, Dimethylan + TX, Dinoprop + TX, Dinosam + TX, Dinoseb + TX, Diofenolan + TX, Dioxabenzophos + TX, Dicyclophos + TX, DSP + TX, Ecdysterone + TX, EI 1642 + TX, EMPC + TX, EPBP + TX, Ethyl Formate + TX, Ethylene Dibromide + TX, Ethylene Dichloride + TX, Ethylene Oxide + TX, EXD + TX, Fenchlorphos + TX, Fenetacarb + TX, Fenitrothion + TX, Fenoxacrim + TX, Fenpyrithrin + TX, Fensulfothion + TX, Fenthion-ethyl + TX, Flucofuron + TX, Fosmetyllan + TX, Fospirate + TX, Fostyl Ethane + TX, Furathiocarb + TX, Frethrin + TX, Guazatine + TX, Guazatine acetate + TX, Sodium tetrathiocarbonate + TX, Halfenprox + TX, HCH + TX, HEOD + TX, Heptachlor + TX, Heterofos + TX, HHDN + TX, Hydrogen cyanide + TX, Hikincarb + TX, IPSP + TX, Isazophos + TX, Isobenzane + TX, Isodrin + TX, Isofenphos + TX, Isolane + TX, Isoprothiolane + TX, Isoxa Thione + TX, larval hormone I + TX, larval hormone II + TX, larval 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, methane sulfonate Phonyl + 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-ethylethylphosphonothioate + 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'-Tetrapropyldithiopyrophosphate + TX, Oleic acid + TX, para-dichlorobenzene + TX, parathion-methyl + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH 60-38 + TX, Fenkapton + TX, Fosnichlor + TX, Phosphine + TX, Phoxim-methyl + TX, Pyrimetaphos + TX, Polychlorodicyclopentadiene Isomers + TX, Potassium Arsenite + TX, Potassium Thiocyanate + TX, Precocene I + TX, Precocene II + TX, Precocene III + TX, Pyrimidophos + TX, Profluthrin + TX, Promecarb + TX, Prothiofos + TX, Pyrazophos + TX, Pyrethmetry lan+TX, cassia+TX, quinalphos-methyl+TX, quinothione+TX, rafoxanide+TX, resmethrin+TX, rotenone+TX, kadetrin+TX, ryania+TX, ryanodine+TX, sabadila+TX, shradan+TX, cevufos+TX, SI-0009+TX, tiapronil+TX, sodium arsenite+TX, sodium cyanide+TX, sodium fluoride+TX, sodium hexafluorosilicate+TX, pentachloro Phenoxide sodium salt +TX, sodium selenate +TX, sodium thiocyanate +TX, sulcofuron +TX, sulcofuron-sodium +TX, sulfuryl fluoride +TX, sulprofos +TX, tar oil +TX, tazimcarb +TX, TDE +TX, tebupirimfos +TX, temephos +TX, telallethrin +TX, tetrachloroethane +TX, cyclofos +TX, thiocyclam +TX, thiocyclam hydrogen oxalate +TX, thicyclam Onadine + TX, Thiosultap + TX, Thiosultap-sodium + TX, Tralomethrin + TX, Transpermethrin + TX, Triazamate + TX, Trichlormethaphos-3 + TX, Trichloronat + 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, Anicifluprine + TX, Benclotiaz + TX, Cytokinin + TX, DCIP + TX, Furfural + TX, Isamidophos + TX, Kinetin + TX, Myrothecium verrucaria composition + TX, Tetrachlorothiophene + TX, Xylenol + TX, Zeatin + TX, Potassium ethylxanthogenate + TX, Acibenzolar + TX, Acibenzolar-S-methyl + TX, Reynoutria sachalinensis) extract +TX, α-chlorohydrin +TX, Anz +TX, barium carbonate +TX, bisthiosemi +TX, brodifacoum +TX, bromadiolone +TX, bromethalin +TX, chlorophacinone +TX, cholecalciferol +TX, coumachlor +TX, coumafuryl +TX, coumatetralyl +TX, crimidine +TX, difenacoum +TX, difethialone +TX, diphacinone +TX, ergocalciferol +TX, flocoumafen +TX, fluoroacetamide +TX, flupropazine +TX, flupropazine hydrochloride +TX, norbormide +TX, fosacetim +TX, phosphorus +TX, pindone +TX, pyrinuron +TX, sciliroside +TX, sodium fluoroacetate +TX, thallium sulfate +TX, warfarin +TX, 2-(2-butoxyethoxy)ethyl piperonylate +TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone +TX, farnesol and nerolidol +TX, berubutin +TX, MGK 264 + TX, piperonyl butoxide + TX, piprotal + TX, propyl 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, 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, Ancymidon flucloxil + TX, fenarimol + TX, nuarimol + TX, bupirimate + TX, dimethirimol + TX, ethirimol + TX, dodemorph + TX, fenpropizin + TX, fenpropimorph + TX, spiroxamine + TX, tridemorph + TX, cyprodinil + TX, mepanipyrim + TX, pyrimethanil + TX, fenpiclonil + TX, fludioxonil + TX, benalaxyl + TX, furalaxyl + TX, metalaxyl + TX, R-metalaxyl + TX, oflace + TX, oxadixyl + TX, carbendazim + TX, debacarb + TX, fuberi Dazole + TX, Thiabendazole + TX, Chlozolinate + TX, Dichlozolin + TX, Mycrozolin + TX, Procymidone + TX, Vinclozolin + TX, Boscalid + TX, Carboxin + TX, Fenfuram + TX, Flutolanil + TX, Mepronil + TX, Oxycarboxin + TX, Penthiopyrad + TX, Thifluzamide + TX, Dodine + TX, Iminoctadine + TX, Azoxystrobin + TX, Dimoxystrobin + TX, Enestrobulin + TX, Phenaminestrobin + TX, Flufenoxystrobin + TX, Fluxastro Bin + TX, Kresoxim-methyl + TX, Metominostrobin + TX, Trifloxystrobin + TX, Oryzastrobin + TX, Picoxystrobin + TX, Pyraclostrobin + TX, Pyrametstrobin + TX, Pyraoxystrobin + TX, Ferbam + TX, Mancozeb + TX, Maneb + ​​TX, Metiram + TX, Propineb + ​​TX, Zineb + ​​TX, Captafol + TX, Captan + TX, Fluorimide + TX, Folpet + TX, Tolylfluanid + TX, Bordeaux mixture + TX, Copper oxide + TX, Mancopper + TX, Oxine copper + TX,Nitrothal-isopropyl +TX, Edifenphos +TX, Iprobenfos +TX, Fosdifen +TX, Tolclofos-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, Flumethylflufolim +TX, Fluopicolide +TX, Fluoxythioconazole + TX, flusulfamide + TX, fluxapyroxad + TX, fenhexamid + TX, fosetyl-aluminum + TX, hymexazole + TX, iprovalicarb + TX, cyazofamid + TX, methasulfocarb + TX, metrafenone + TX, pencycuron + TX, phthalide + TX, polyoxin + TX, propamocarb + TX, pyribencarb + TX, proquinazid + TX, pyroquilon + TX, pyriophenone + TX, quinoxyfen + TX, quintozene + TX, tiadinil + TX, triazoxide + TX, tricyclazole + TX, triforine + TX, validamycin + TX, valifenalate + TX, zoxamide + TX, mandipropamid + TX, fluveneteram + TX, isopyrazam + TX, sedaxane + TX, Benzovindiflupyr + TX, pydiflumetofen + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, isoflucipram + TX, isotianil + TX, dipimethitrone + TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile + TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 4 -(2,6-Difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine + T X, fluindapyr + TX, methoxystrobin (jiaxiangjunzhi) + TX, rubenmixianan + TX, diclobenthiazox + TX, mandestrobin + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol + TX, oxathiapiproline + TX, 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]methanesulfonate + TX, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]o methyl]-2-pyridyl]carbamate + TX, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, pyridaclomethyl + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 1-[2-[[1-(4-chlorophenyl (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX, aminopyrifen + TX, ametoctrazine + TX, amisulbrom + TX, penflufen + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino- N,3-dimethyl-pent-3-enamide + TX, florylpicoxamide + TX, fenpicoxamide + TX, tebufloquine + TX, ipulfenoquine + TX, quinofumelin + TX, isofetamide + TX, ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate + TX (which can be prepared by the method described in WO 2020 / 056090), ...(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enoxy]phenyl]methyl]pyrazole-3-carboxylate + TX (which can be prepared by 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 can be prepared by 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 can be prepared by 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 can be prepared by 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 can be prepared by 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 can be prepared by the method described in WO 2020 / 109391), N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, benzothiostrobin + TX, fenamacryl + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, fluopyram + TX, fluofenoxadiazam + TX, flutianil + TX, fluopimomide + TX, pyrapropoin + TX, picarbutrazox + 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)triazole-2-yl]phenoxy]prop-2-enoate + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-(4-propyltriazole-2-yl)phenoxy]prop-2-enoate + TX, methyl (Z)-2-[5-(3- methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]-3-methoxy-prop-2-enoate + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]-3-methoxy-prop-2-enoate + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]-prop-2-enoate + TX (these compounds are disclosed in WO 2020 / 079111 No. 1,202,499), methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate + TX, methyl (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate + TX (these compounds can be prepared by the methods described in WO 2020 / 193387), 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxyphenyl]-4-hydroxy-2-methyl ... 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, trinexapac + TX, cumoxystrobin + TX, zhongshengmycin + TX, copper thiodiazole + TX, zinc thiazole + TX, amethotractin + TX, iprodione + TX, seboxylamine + TX; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy]benzonitrile + TX, trinexapac + TX, cumoxystrobin + TX, zhongshengmycin + TX, copper thiodiazole + TX, zinc thiazole + TX, amethotractin + TX, iprodione + TX, seboxylamine + 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-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX (fluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine + TX (these compounds can be prepared by the method described in WO 2019 / 110427); N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-fluoro-N-[(1S)- 1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX (these compounds can be prepared by the methods described in WO 2017 / 153380);1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX (these compounds were prepared by the method described in WO 2017 / 025510). 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline + TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole + TX (these compounds can be prepared by the methods described in WO 2016 / 156085);N-Methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N,2-Dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N-Ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX phenyl]phenyl]methyl]propanamide + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2 ,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate + TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine + TX. The compounds in this paragraph can be prepared by the methods described in WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 093348 and WO 2017 / 118689;2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound can be prepared by the method described in WO 2017 / 029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound can be prepared by the method described in WO 2017 / 029179); 3 -[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); (4-phenoxyphen N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzene (N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzene) with TX (this compound can be prepared by the method described in WO 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone with TX (this compound can be prepared by the method described in WO 2011 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzene Carbothioamide + TX; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX (this compound can be prepared by the method described in WO 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX;N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared by the method described in WO 2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX (this compound can be prepared by the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX (these compounds can be prepared by the method described in WO 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX (this compound can be prepared by the method described in WO 2018 / 065 414); ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate + TX (this compound can be prepared by the method described in WO 2018 / 158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX biologically active substances 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 NRRL 21882 (Aflaguard®) + TX, Aspergillus spp.) + TX, Aureobasidium pullulans + TX, Azospirillum + TX, (MicroAZ® + TX, TAZO B®) + TX, Azotobacter + TX, Azotobacter chroocuccum (Azotomeal®) + TX, Azotobacter cysts (Bionatural Blooming Blossoms®) + TX, Bacillus amyloliquefaciens + TX, Bacillus cereus + TX, Bacillus chitinosporus strain CM-1 + TX, Bacillus chitinosporus strain AQ746+TX, Bacillus licheniformis strain HB-2 (Biostart™ Rhizoboost®)+TX, Bacillus licheniformis strain 3086 (EcoGuard®+TX, Green Releaf®)+TX, Bacillus circulans+TX, Bacillus firmus (BioSafe®+TX, BioNem-WP®+TX, VOTiVO®)+TX, Bacillus firmus strain I-1582+TX, Bacillus macerans+TX, Bacillus 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. amyloliquefaciens (Bacillus subtilis amyloliquefaciens strain FZB24 (Taegro® +TX, Rhizopro®) +TX, Bacillus thuringiensis Cry 2Ae +TX, Bacillus thuringiensis Cry1Ab +TX, Bacillus thuringiensis aizawai GC 91 (Agree®) + TX, Bacillus thuringiensis israelensis (BMP123® + TX, Aquabac® + TX, VectoBac®) + TX, Bacillus thuringiensis 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 thuringiensis kurstaki BMP 123 (Baritone®) + TX, Bacillus thuringiensis kurstaki HD-1 (Bioprotec-CAF / 3P®) + TX, Bacillus thuringiensis strain BD#32 + TX, Bacillus thuringiensis strain AQ52 + TX, Bacillus thuringiensis var. aizawai (XenTari® + TX, DiPel®) + TX, bacterial spp.) (GROWMEND® +TX, GROWSWEET® +TX, Shootup®) +TX, Clavipacter michiganensis bacteriophage (AgriPhage®) +TX, Bakflor® +TX, Beauveria bassiana (Beaugenic® +TX, Brocaril WP®) +TX, Beauveria bassiana GHA (Mycotrol ES® +TX, Mycotrol O® +TX, BotaniGuard®) +TX, Beauveria brongniartii (Engerlingspilz® +TX, Schweizer Beauveria® +TX, Melocont®) +TX, Beauveria species (Beauveria spp.) + TX, Botrytis cineria + TX, Bradyrhizobium japonicum (TerraMax®) + TX, Brevibacillus brevis + TX, Bacillus thuringiensis tenebrionis (Novodor®) + TX, BtBooster + TX, Burkholderia cepacia (Deny® + TX, Intercept® + TX, Blue Circle®) + TX, Burkholderia gladii + TX, Burkholderia gladioli + TX, Burkholderia spp.) + TX, Canadian thistle fungus (CBH Canadian Bioherbicide®) + TX, Candida butyri + TX, Candida famata + TX, Candida fructus + TX, Candida glabrata + TX, Candida guilliermondii + TX, Candida melibiosica + TX, Candida oleophila strain O + TX, Candida parapsilosis + TX, Candida pelliculosa + TX, Candida pulcherrima 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 (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, Enterobacter iacae (Enterobacteriaceae) + TX, Entomophtora virulenta (Vektor®) + TX, Epicoccum nigrum + TX, Epicoccum purpurascens + TX, Epicoccum spp. + TX, Filobasidium floriforme + TX, Fusarium acuminatum + TX, Fusarium chlamydosporum 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 + TX, Gliocladium spp. (SoilGard®) + TX, Gliocladium virens virens (Soilgard®) + TX, Granulovirus (Granupom®) + TX, Halobacillus halophilus + TX, Halobacillus litoralis + TX, Halobacillus trueperi + TX, Halomonas spp.) + TX, Halomonas subglaciescola + TX, Halovibrio variabilis + TX, Hanseniaspora uvarum + TX, Helicoverpa armigera nuclear polyhedrosis virus (Helicovex®) + TX, Helicoverpa zea nuclear polyhedrosis virus (Gemstar®) + TX, isoflavone-formononetin (Myconate®) + TX, Kloeckera apiculata + TX, Kloeckera spp.) + TX, Lagenidium giganteum (Laginex®) + TX, Greenhouse whitefly (Lecanicillium longisporum) (Vertiblast®) + TX, Lecanicillium muscarium (Vertikil®) + TX, Gypsy moth (Lymantria dispar) nuclear polyhedrosis virus (Disparvirus®) + TX, Marinococcus halophilus + TX, Meira geulakonigii + TX, Metarhizium anisopliae (Met52®) + TX, Metarhizium anisopliae (Destruxin®) + TX, WP®) + TX, Metschnikowia fruticola (Shemer®) + TX, Metschnikowia pulcherrima + TX, Microdochium dimerum (Antibot®) + TX, Micromonospora coerulea + TX, Microsphaeropsis ochracea + TX, Muscodor albus 620 (Muscudor®) + TX, Muscodor roseus strain A3-5 + TX, Mycorrhizae spp.) (AMykor® +TX, Root Maximizer®) +TX, Myrothecium verrucaria strain AARC-0255 (DiTera®) +TX, BROS PLUS® +TX, Ophiostoma piliferum strain D97 (Sylvanex®) +TX, Paecilomyces farinosus +TX, Paecilomyces fumosoroseus (PFR-97® +TX, PreFeRal®) +TX, Paecilomyces linacinus (Biostat WP®) +TX, Paecilomyces lilacinus strain 251 (MeloCon WG®) + TX, Paenibacillus polymyxa + TX, Pantoea agglomerans (BlightBan C9-1®) + TX, Pantoea spp. + TX, Pasteuria spp. (Econem®) + TX, Pasteuria nishizawae + TX, Penicillium aurantiogriseum + TX, Penicillium billai (Jumpstart® + TX, TagTeam®) + TX, Penicillium brevicompactum brevicompactum + TX, Penicillium frequentans + TX, Penicillium griseofulvum + TX, Penicillium purpurogenum + TX, Penicillium spp.) + TX, Penicillium viridicatum + TX, Phlebiopsis gigantean (Rotstop®) + TX, Phospholysin (Phosphomeal®) + TX,. Phytophthora cryptogea + TX, Phytophthora palmivora (Devine®) + TX, Pichia anomala + TX, Pichia guilermondii + TX, Pichia membranaefaciens + TX, Pichia onychis + TX, Pichia stipites + TX, Pseudomonas aeruginosa + TX, Pseudomonas aureofaciens (Spot-Less Biofungicide®) + TX, Pseudomonas cepacia cepacia + TX, Pseudomonas chlororaphis (AtEze®) + TX, Pseudomonas corrugate + TX, Pseudomonas fluorescens strain A506 (BlightBan A506®) + TX, Pseudomonas putida + TX, Pseudomonas reactans + TX, Pseudomonas spp.) + TX, Pseudomonas syringae (Bio-Save®) + TX, Pseudomonas viridiflava + TX, Pseudomonas fluorescens (Zequanox®) + TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex L®) + TX, Puccinia canaliculata + TX, Puccinia thlaspeos (Wood Warrior®) + TX, Pythium paroecandrum + TX, Pythium oligandrum oligandrum (Polygandron® + TX, Polyversum®) + TX, Pythium periplocum + TX, Rhanella aquatilis + TX, Rhanella spp. + TX, Rhuzobia (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 nuclear polyhedrosis virus (Spod-X® + TX, Spexit®) + TX, Serratia marcescens + TX, Serratia plymuthica + TX, Serratia spp.) + TX, Sordaria fimicola + TX, Spodoptera littoralis nuclear polyhedrosis virus (Littovir®) + TX, Sporobolomyces roseus + TX, Stenotrophomonas maltophilia + TX, Streptomyces ahygroscopicus + TX, Streptomyces 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 IGR (Neemazad® +TX, Neemix®) +TX, canola oil (Lilly Miller Vegol®) +TX, American ant-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, oil of the sesame family (Pedaliaceae) (Nematon®) + TX, pyrethrum (pyrethrum) + TX, soapberry (Quillaja saponaria) (NemaQ®) + TX, Japanese knotweed (Reynoutria sachalinensis) (Regalia® + TX, Sakalia®) + TX, rotenone (Eco Roten®) + TX, Rutaceae plant extract (Soleo®) + TX, soybean oil (Ortho ecosense®) + TX, tea tree oil (Timorex Gold®) + TX, thyme oil + TX, AGNIQUE® MMF + TX, BugOil® + TX, a mixture of rosemary, sesame, peppermint, thyme and cinnamon extracts (EF300®) + TX, a mixture of clove rosemary and peppermint extracts (EF 400®) + TX, a mixture of clove peppermint garlic oil and mint (Soil Shot®) + TX, kaolin (Screen®) + TX, storage glucan from brown algae (Laminarin®); Pheromones, including: blackheaded fireworm pheromone (3M Sprayable Blackheaded Fireworm Pheromone®) + TX, codling moth pheromone (Paramount dispenser-(CM) / Isomate C-Plus®) + TX, grape berry moth pheromone (3M MEC-GBM Sprayable Pheromone®) + TX, leafroller pheromone (3M MEC-LR Sprayable Pheromone®) + TX, muscamone (Snip7 Fly Bait® + TX, Starbar Premium Fly Bait®) + TX, oriental fruit moth pheromone (3M oriental fruit moth sprayable pheromone®) + TX, peachtree Borer pheromone (Isomate-P®) + TX, Tomato Pinworm pheromone (3M Sprayable pheromone®) + TX, Entostat powder (palm tree extract) (Exosex CM®) + TX, (E+TX,Z+TX,Z)-3+TX, 8+TX, 11-tetradecatrienyl acetate + TX, (Z+TX,Z+TX,E)-7+TX, 11+TX, 13-hexadecatrienal + TX, (E+TX,Z)-7+TX, 9-dodecadien-1-yl acetate + TX, 2-methyl-1-butanol + TX, calcium acetate + TX, Scenturion® + TX, Biolure® + TX, Check-Mate® + TX, lavandulyl senecioate; Macrobials including: Aphelinus abdominalis + TX, Aphidius ervi (Aphelinus-System®) + TX, Acerophagus papaya + TX, Adalia bipunctata (Adalia-System®) + TX, Adalia bipunctata (Adaline®) + TX, Adalia bipunctata (Aphidalia®) + TX, Ageniaspis citricola + TX, Ageniaspis fuscicollis + TX, Amblyseius andersonii andersoni (Anderline® + TX, Andersoni-System®) + TX, Amblyseius californicus (Amblyline® + TX, Spical®) + TX, Amblyseius cucumeris (Thripex® + TX, Bugline cucumeris®) + TX, Amblyseius fallacis (Fallacis®) + TX, Amblyseius swirskii (Bugline swirskii® + TX, Swirskii-Mite®) + TX, Amblyseius womersleyi (WomerMite®) + TX, Amitus hesperidin hesperidum + TX, Anagyrus atomus + TX, Anagyrus fusciventris + TX, Anagyrus kamali + TX, Anagyrus loecki + TX, Anagyrus pseudococcuspseudococci (Citripar®) + TX, Anicetus benefices + TX, Anisopteromalus calandrae + TX, Anthocoris nemoralis (Anthocoris-System®) + TX, Aphelinus abdominalis (Apheline® + TX, Aphiline®) + TX, Aphelinus asychis + TX, Aphidius colemani (Aphipar®) + TX, Aphidius ervi (Ervipar®) + TX, Aphidius gifuensis + TX, Aphidius matricariae matricariae (Aphipar-M®) + TX, Aphidoletes aphidimyza (Aphidend®) + TX, Aphidoletes aphidimyza (Aphidoline®) + TX, Aphytis lingnanensis + TX, Aphytis melinus + TX, Aprostocetus hagenowii + TX, Atheta coriaria (Staphyline®) + TX, Bombus spp. + TX, Bombus terrestris (Natupol Beehive® + TX, Bombus terrestris (Beeline® + TX, Tripol®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus + TX, Chrysoperlacarnea (Chrysoline®) + TX, Chrysoperla carnea (Chrysopa®) + TX, Chrysoperla rufilabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichus phyllocnistoides + TX, Closterocerus chamaeleon + TX, Closterocerus spp. + TX, Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi) + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug® + TX, Cryptoline®) + TX, Cybocephalus nipponicus (Kimnetamakisut) + TX, Dacnusa sibirica (Leaf-grating cone wasp) + TX, Dacnusa sibirica (Leaf-grating cone wasp) (Minusa®) + TX, Diglyphus isaea (Diminex®) + TX, Delphastus catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsis jucunda + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea + TX, Diglyphus isaea (Miglyphus® + TX, Digline®) + TX, Dacnusa sibirica (DacDigline® + TX, Minex®) + TX, Diversinervus spp. + TX, Encarsia citrina + TX, Encarsia formosa (Encarsia max® + TX, Encarline® + TX, En-Strip®) + TX, Eretmocerus eremicus (Enermix®) + TX, Encarsia guadeloupae + TX, Encarsia haitiensis + TX, Episyrphus balteatus (Syrphidend®) + TX, Eretmoceris siphonini siphonini) + TX, Eretmocerus californicus + TX, Eretmocerus eremicus (Ercal® + TX, Eretline e®) + TX, Eretmocerus eremicus (Bemimix®) + TX, Eretmocerus hayachi (Eretmocerushayati + 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, Exhibitlinehm® + TX, Larvanem-M® + TX, Hippodamia convergens + TX, Hypoaspis aculeifer (Aculeifer-System® + TX, Entomite-A®) + TX, Hypoaspis miles (Hypoline m® + TX, Entomite-M®) + TX, Lbalia leucospoides + TX, Lecanoideus floccissimus + TX, Lemophagus errabundus + TX, Leptomastidea abnormis + TX, Leptomastix dactylopi 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 longusbrii lounsburyi + TX, Micromus angulatus (Milacewing®) + TX, Microterys flavus + TX, Muscidifurax lapotrerusraptorellus and Spalangia cameroni (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 (Pauesia juniperorum), Pediobius hobeoletus (Pediobius foveolatus + TX, Phasmarhabditis hermaphrodita (Nemaslug®) + TX, Phymastichus coffea + TX, Phytoseiulus macropilus + TX, Phytoseiulus persimilis (Spidex® + TX, Phytoline p®) + TX, Podisus maculiventris (Podisus®) + TX, Pseudacteon curvatus + TX, Pseudacteon obtusus + TX, Pseudacteon tricuspis + TX, Pseudaphycus maculipennis + TX, Pseudleptomastix mexicana + 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, Millenium® + 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 (BioVector® + TX, BioVektor®) + TX, Steinernema scapterisci (Nematac S®) + TX, Steinernema spp. + TX, Steinernema spp. spp.) (Guardian Nematodes®) + TX, Stethorus punctillum (Stethorus®) + TX, Tamarixia radiate + TX, Tetrastichus setifer + TX, Thripobius semiluteus + TX, Torymus sinensis + TX, Trichogramma brassicae (Tricholine b®) + TX, Trichogramma brassicae (Tricho-Strip®) + TX, Trichogramma evanescens + TX, Trichogramma minutum + TX, Trichogramma ostriniae + TX, Trichogramma platneri + TX, Trichogramma pretiosum + TX, Xanthopimpla stemmator;. Other biological products include: abscisic acid +TX, bioSea® +TX, Chondrostereum purpureum (Chontrol Paste®) +TX, Colletotrichum gloeosporioides (Collego®) +TX, copper octanoate (Cueva®) +TX, Delta Trap (Trapline d®) +TX, Erwinia amylovora (Harpin) (ProAct® +TX, Ni-HIBIT Gold CST®) +TX, fatty acids derived from natural by-products of extra virgin olive oil (FLIPPER®) +TX, ferric phosphate (Ferri-phosphate) (Ferramol®) +TX, Funnel Trap (Trapline d®) +TX 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 OrganicGrasshopper Control®) + TX, sticky traps (Trapline YF® + TX, Rebell Amarillo®) + TX and traps (Takitrapline y+b®) + TX; (1) An antibacterial agent selected from the following group: (1.1) Bacteria, examples of which include: Bacillus mojavensis strain R3B (accession number NCAIM(P)B001389) from Certis USA LLC, a subsidiary of Mitsui & Co. (WO 2013 / 034938) + TX; Bacillus pumilus, in particular the strain BU F-33 with NRRL accession number 50185 (available as part of the CARTISSA® product from BASF, EPA Reg. No. 71840-19) + TX; Bacillus subtilis, in particular the strain QST713 / AQ713 (SERENADE OPTI or SERENADE from Bayer CropScience LP, US); ASO, having NRRL accession number B21661 and described in U.S. Pat. No. 6,060,051) +TX; Bacillus subtilis strain BU1814, (available from BASF SE as VELONDIS® PLUS, VELONDIS® FLEX, and VELONDIS® EXTRA) +TX; Bacillus subtilis var. amyloliquefaciens strain FZB24, having accession number DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA Registration No. 70127-5)) +TX; Bacillus subtilis CX-9060 +TX from Certis USA LLC, a subsidiary of Mitsui & Co.; Bacillus spp. sp.), particularly strain D747 (Kumiai Chemical Industry Co., Ltd.) as DOUBLE NICKEL®, having accession number FERM BP-8234 and described in U.S. Pat. No. 7,094,592 +TX; Paenibacillus sp. strains having accession number NRRL B-50972 or accession number NRRL B-67129, WO 2016 / 154297 +TX; Paenibacillus polymyxa, particularly strain AC-1 (available, for example, as TOPSEED® from Green Biotech Company Ltd.) +TX; Pantoea agglomerans, particularly strain E325 (accession number NRRL B-21856) (available as BLOOMTIME BIOLOGICAL® FD from Northwest Agri Products) +TX. Pseudomonas proradix (e.g., PRORADIX® from Sourcon Padena) + TX; and (1.2) fungi, examples of which include 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 (as disclosed in WO 2011 / 151819 by Yissum Research Development Company, Hebrew University of Jerusalem) + TX; Saccharomyces cerevisiae, in particular Lesaffre et al. Strains from Compagnie, FR: CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938 or CNCM No. 1-3939 (WO 2010 / 086790); (2) A biological fungicide selected from the group consisting of: (2.1) Bacteria, examples of which include Agrobacterium radiobacter strain K84 (e.g., GALLTROL-A® from AgBioChem, CA) + TX; Agrobacterium radiobacter strain K1026 (e.g., NOGAL® from BASF SE) + TX; Bacillus subtilis var. amyloliquefaciens strain FZB24 with accession number DSM 10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA registration number 70127-5)) + TX; Bacillus amyloliquefaciens, in particular strain D747 (accession number FERM BP-8234, available from Kumiai Chemical Industry Co., Ltd. as Double Nickel™, 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 from ABiTEP, DE as RHIZOVITAL®) +TX; Bacillus amyloliquefaciens isolate B246 (available, for example, from the University of Pretoria) +TX; AVOGREEN™)+TX from Pretoria;Bacillus licheniformis, in particular strain SB3086 having accession number ATCC 55406, WO 2003 / 000051 (available from Novozymes as ECOGUARD® Biofungicide and GREEN RELEAF®) +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 mojavensis strain R3B (accession number NCAIM(P)B001389) (WO 2013 / 034938) (from Certis USA LLC, a subsidiary of Mitsui & Co.) +TX; Bacillus mycoides, an isolate having accession number B-30890 (available as BMJ TGAI® or WG and LifeGard® from Certis USA LLC, a subsidiary of Mitsui & Co.) +TX; Bacillus pumilus, particularly strain QST2808 (available as SONATA® from Bayer CropScience LP, LP, with accession number NRRL B-30087 and described in U.S. Pat. No. 6,245,551) +TX; Bacillus pumilus, particularly strain GB34 (Yield from Bayer AG, DE) Available as Shield® +TX;Bacillus pumilus, in particular the BU F-33 strain having NRRL accession number 50185 (available from BASF as part of its CARTISSA products, EPA Reg. No. 71840-19) + TX; Bacillus subtilis, in particular the QST713 / AQ713 strain (available from Bayer CropScience LP LP, US as SERENADE OPTI or SERENADE ASO, having NRRL accession number B21661 and 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 disinfectant under registration numbers 4764, 5454, 5096, and 5277) + TX; Bacillus Bacillus subtilis strain MBI 600 (available from BASF SE as SUBTILEX) (having accession number NRRL B-50595 and described in 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 VELONDIS® PLUS, VELONDIS® FLEX, VELONDIS® EXTRA) +TX; Bacillus subtilis CX-9060 +TX from Certis USA LLC, a subsidiary of Mitsui & Co.; Bacillus subtilis from Certis USA LLC, a subsidiary of Mitsui & Co. 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 from BioNTech, Taiwan as BIOBAC® WP, registered in Taiwan as a biological fungicide 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 spp. with accession number NRRL B-50972 or accession number NRRL B-67129 sp. strain, WO 2016 / 154297+TX; Pseudomonas chlororaphis strain AFS009, WO 2017 / 019448, having accession number NRRL B-50897 (e.g., HOWLER™ and ZIO®+TX from AgBiome Innovations, US); Pseudomonas chlororaphis, In particular, strain MA342 (CEDOMON®, CERALL®, CEDRESS®, etc. from Bioagri and Koppert) +TX; Pseudomonas fluorescens strain A506 (e.g., BLIGHTBAN® A506 from NuFarm) +TX; Pseudomonas proradix (e.g., PRORADIX® from Sourcon Padena) +TX; Streptomyces griseoviridis strain K61 (also known as Streptomyces galbus strain K61) (accession number DSM 7206) (MYCOSTOP® from Verdera, PREFENCE® from BioWorks, Crop Protection 2006, 25, 468-475) +TX; Streptomyces lydicus strain WYEC108 (also known as Streptomyces lydicus strain WYCD108US) (ACTINO-IRON® and ACTINOVATE® +TX from Novozymes); and (2.2) Fungi, examples of which include: Ampelomyces quisqualis, in particular the strain AQ 10 (for example AQ 10® from IntrachemBio Italia) + TX; Ampelomyces quisqualis AQ 10 strain with accession number CNCM 1-807 (for example AQ 10® from IntrachemBio Italia) + TX; Aspergillus flavus NRRL 21882 strain (product known as AFLA-GUARD® from Syngenta / ChemChina) + TX; Aureobasidium pullulans, in particular blastospores of the strain DSM 14940 + TX; Aureobasidium pullulans pullulans, in particular blastospores of the strain DSM 14941 + TX; Aureobasidium pullulans, in particular a mixture of blastospores of the 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 CBS 122244, U.S. Patent Application Publication No. 2010 / 0291039 A1) (Stichting Dienst 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) f. catenulate) strain J1446 (e.g., Prestop® by Lallemand) + TX; Gliocladium roseum (also known as Clonostachys rosea f rosea), in particular strain 321U from Adjuvants Plus, strain ACM941 disclosed in Xue (Efficacy of Clonostachys rosea strain ACM941 and fungicide seed treatments for controlling the root tot 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', Australas Plant Pathol. 2007, 36:95-101) + TX;Conidia of Lecanicillium lecanii (formerly Verticillium lecanii) 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 steckii from BASF SE (DSM 27859, 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® from Plant Products Co, CA) +TX; Saccharomyces cerevisiae, particularly strain LASO2 (Agro-Levures et Derives), strain LAS117 cell wall (CEREVISANE® from Lesaffre, ROMEO® from BASF SE), strains from Lesaffre et Compagnie, FR: CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938, CNCM No. 1-3939 (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 kd strain (e.g., T-Gro from Andermatt Biocontrol) + TX; Trichoderma asperellum, in particular the SKT-1 strain with accession number FERM P-16510 (e.g., ECO-HOPE® from Kumiai Chemical Industry), the T34 strain (e.g., T34 Biocontrol, ES from Biocontrol Technologies SL) or the ICC 012 strain from Isagro + TX; Trichoderma atroviride, in particular the SC1 strain (accession number CBS 122089 and described in WO 2009 / 116106 and U.S. Pat. No. 8,431,120 (from 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, NMI strain number V08 / 002388 +TX; Trichoderma atroviride, strain number V08 / 002389, and described in WO 2009 / 116106 and U.S. Pat. No. 8,431,120 (from Bi-PA)), strain 77B (T77 from Andermatt Biocontrol) or strain LU132 (e.g., Sentinel from Agrimm Technologies Limited) +TX; Trichoderma atroviride, strain number V08 / 002387 +TX; Trichoderma atroviride, strain number V08 / 002388 +TX; atroviride), NMI strain number V08 / 002389+TX; Trichoderma atroviride, NMI strain number V08 / 002390+TX; Trichoderma atroviride, strain LC52 (e.g., Tenet by Agrimm Technologies Limited)+TX;Trichoderma atroviride, ATCC 20476 strain (IMI 206040) + TX; Trichoderma atroviride, T11 strain (IMI352941 / CECT20498) + TX; Trichoderma atroviride, SKT-1 strain (FERM P-16510), JP 11-253151 A + TX; Trichoderma atroviride; SKT-2 strain (FERM P-16511), JP 11-253151 A + TX; Trichoderma atroviride, SKT-3 strain (FERM P-17021), JP 11-253151 A + TX; Trichoderma fertile (e.g., TrichoPlus, a product from BASF) + TX; Trichoderma gamsii (formerly known as T. viride), ICC080 strain (IMI CC 392151 CABI, e.g., BioDerma by AGROBIOSOL DE MEXICO, SADE CV) + TX; Trichoderma gamsii (formerly known as T. viride), ICC strain 080 (IMI CC 392151 CABI) (available under the trademark BIODERMA® by 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 Cepa SimbT5 ...

Claims

1. Formula I 【Chemical 1】 wherein X is O or S; R 1 is H, C 1 ~C 6 alkyl, C 1 ~C 6 cyanoalkyl, aminocarbonyl C 1 ~C 6 alkyl, hydroxycarbonyl C 1 ~C 6 alkyl, trimethylsilyl C 1 ~C 6 alkyl, C 1 ~C 6 haloalkyl, C 2 ~C 6 alkenyl, C 2 ~C 6 haloalkenyl, C 2 ~C 6 alkynyl, C 2 ~C 6 haloalkynyl, C 3 ~C 4 cycloalkyl C 1 ~C 2 alkyl, C 3 ~C 4 cycloalkyl C 1 ~C 2 alkyl (wherein the C 3 ~C 4 cycloalkyl group is substituted with one or two halo atoms), oxetan-3-yl-CH 2 -, benzyl or benzyl substituted with halogen; R 2a is H, halogen, C 1 to C 3 alkyl, C 1 to C 3 haloalkyl, C 1 to C 3 haloalkylthio, C 1 to C 3 alkoxy, C 1 to C 3 haloalkoxy, SF 5 , CN, C 3 to C 6 cycloalkyl; C 1 to C 3 alkyl, C 1 to C 3 haloalkyl, cyano, C 1 to C 3 alkoxy and from 1 to 3 substituents independently selected from halogen substituted C 3 to C 6 cycloalkyl; C 3 to C 6 cycloalkyl C 1 to C 4 alkyl; C 1 to C 3 alkyl, C 1 to C 3 haloalkyl, cyano, and from 1 to 5 substituents independently selected from halogen substituted C 3 to C 6 cycloalkyl C 1 to C 4 alkyl; C 1 to C 5 cyanoalkyl, C 1 to C 4 alkylsulfonyl, C 1 to C 4 haloalkylsulfonyl, C 1 to C 4 alkylsulfinyl, C 1 to C 4 haloalkylsulfinyl, C 3 to C 6 cycloalkylsulfanyl, C 3 to C 6 cycloalkylsulfinyl, or C 3 to C 6 which is cycloalkylsulfonyl; R 2b is H, halogen, C 1 to C 3 alkyl, C 1 to C 3 haloalkyl, C 1 to C 3 haloalkylthio, C 1 to C 3 alkoxy, C 1 to C 3 haloalkoxy, SF 5 , or CN; A is N or C—R 2c wherein; R 2c is H, halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, or C 1 -C 3 haloalkoxy; R 3 is C 1 to C 3 alkyl or C 1 to C 3 haloalkyl; R 4 is 【Chemical 2】 and Here, R 4a is hydrogen, halogen, CN, C 1 to C 3 alkyl, C 1 to C 3 haloalkyl, C 3 to C 4 cycloalkyl, C 1 to C 3 alkoxy, C 1 to C 3 haloalkoxy and C(=O)NR 4aa R 4ab wherein R 4aa and R 4ab are independently of each other hydrogen, C 1 to C 3 alkyl, C 3 to C 5 cycloalkyl, or R 4aa and R 4ab together with the nitrogen atom to which they are attached may further contain a heteroatom selected from oxygen and sulfur and form a 3- to 12-membered saturated or partially unsaturated heterocyclyl, and the above heterocyclyl may be substituted with 1 to 3 substituents) selected from R 4b is hydrogen, halogen, CN, C 1 to C 3 alkyl, C 1 to C 3 haloalkyl, C 3 to C 4 cycloalkyl, C 1 to C 3 alkoxy, C 1 to C 3 haloalkoxy and C(=O)NR 4aa R 4ab wherein R 4aa and R 4ab are each independently hydrogen, C 1 to C 3 alkyl, C 3 to C 5 cycloalkyl, or R 4aa and R 4ab together with the nitrogen atom to which they are attached may further contain a heteroatom selected from oxygen and sulfur and form a 3- to 12-membered saturated or partially unsaturated heterocyclyl, and the heterocyclyl may be substituted with 1 to 3 substituents) selected from R 4c is selected from hydrogen, halogen, CN, C 1 to C 3 alkyl, C 1 to C 3 haloalkyl, C 3 to C 4 cycloalkyl, C 1 to C 3 alkoxy, and C 1 to C 3 haloalkoxy, or R 4a , and R 4c is selected from; R 5a and R 5b are, independently of each other, hydrogen, halogen, CN, C 1 to C 3 alkyl, C 1 to C 3 haloalkyl, C 3 to C 4 cycloalkyl, C 1 to C 3 alkoxy, and C 1 to C 3 selected from haloalkoxy) a compound of formula I; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer and N-oxide of the compound of formula I.

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

3. The compound according to claim 1 or claim 2, wherein A is N.

4. A is C-R 2c wherein R 2c is hydrogen or halogen, preferably hydrogen, the compound according to claim 1 or claim 2.

5. R 1 is hydrogen, methyl, ethyl, n-propyl, isobutyl, cyclopropylmethyl or HCH≡CCH 2 -, the compound according to claim 1.

6. R 2a is halogen, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, C 1 -C 3 -haloalkylthio, C 1 -C 3 -alkoxy, C 1 -C 3 -haloalkoxy, CN, C 3 -C 6 -cycloalkyl, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, cyano, C 1 -C 3 -cycloalkyl which is substituted with 1 to 3 substituents independently selected from alkoxy and halogen, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkyl C 1 -C 4 -alkyl, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, cyano, and C which is substituted with 1 to 5 substituents independently selected from halogen, C 3 -C 6 -cycloalkyl C 1 -C 4 -alkyl, C 1 -C 5 -cyanoalkyl, C 1 -C 4 -alkylsulfonyl, C 1 -C 4 -haloalkylsulfonyl, C 1 -C 4 -alkylsulfinyl, C 1 -C 4 -haloalkylsulfinyl, C 3 -C 6 -cycloalkylsulfanyl, C 3 -C 6 -cycloalkylsulfinyl, or C 3 -C 6 The compound according to claim 1, which is cycloalkylsulfonyl.

7. R 2b is halogen, C 1 ~C 3 haloalkyl, C 1 ~C 3 haloalkylthio, C 1 ~C 3 alkoxy, C 1 ~C 3 haloalkoxy, or CN, and the compound according to claim 1.

8. R 4a 、 R 4b 、 and R 4c are, independently of one another, hydrogen, halogen, CN, C 1 ~C 3 haloalkyl and C 1 ~C 3 haloalkoxy, and the compound according to claim 1.

9. R 4b and R 4c are each hydrogen, and R 4a is hydrogen, halogen, CN, C 1 to C 3 haloalkyl or C 1 to C 3 haloalkoxy, the compound according to claim 1.

10. R 5a and R 5b are, independently of one another, hydrogen, halogen C 1 -C 3 alkyl, C 1 -C 3 alkoxy, and C 1 -C 3 haloalkoxy, and the compound according to claim 1

11. A composition comprising the compound according to claim 1, one or more auxiliaries and diluents, and optionally one or more other active ingredients.

12. (i) A method for controlling and preventing insects, mites, nematodes or mollusks, which comprises applying an insecticidally, acaricidally, nematocidally or molluscicidally effective amount of the compound according to claim 1 to a pest, the habitat of the pest, or a plant susceptible to attack by the pest, or (ii) A method for protecting plant propagation materials from attack by insects, mites, nematodes or mollusks, which comprises treating the propagation materials or the place where the propagation materials are planted with an effective amount of the compound according to claim 1, or (iii) A method for controlling parasites in or on the body surface of an animal in need thereof, which comprises administering an effective amount of the compound according to claim 1.

13. Plant propagation materials such as seeds, which comprise or are treated with or adhered to the compound according to claim 1 or the composition according to claim 11.

14. A compound of formula II or IIb [Chemical Formula 3] (wherein R 1 , R 3 , R 4a , R 4b , R 4c , R 5a and R 5b are each independently as defined in formula I according to any one of claims 1, 2, 5, 8 and 9))

15. Formula VIIIa, VIIIa' or VIII Si : 【Chemical 4】 (wherein, (R A1 ) 3 Si is tri(C 1 -C 4 alkyl)-silyl; R 3 、R 4a 、R 4b 、R 4c 、R 5a and R 5b are, independently of one another, as defined in any one of claims 1, 2, 5, 8 and 9 in formula I; or R 3 is methyl and R 4a is hydrogen, Cl, or C 1 to C 3 alkoxy, for example, H, Cl, or methoxy, and R 4b , R 4c , R 5a and R 5b are each hydrogen)

16. A compound of formula XLII or XLII': [Chemical Formula 5] (wherein R 3 , R 4a , R 4b , R 4c , R 5a , and R 5b are each independently as defined in formula I according to any one of claims 1, 2, 5, 8, and 9; or R 3 is methyl and R 4a is hydrogen, Cl, OH or C 1 to C 3 alkoxy, for example H, Cl, OH, or methoxy, and R 4b , R 4c , R 5a and R 5b are each hydrogen)

17. A compound of formula XLIX or XLIX': [Chemical Formula 6] (wherein R 3 , R 4a , R 4b , R 4c , R 5a , and R 5b are each independently as defined in formula I according to any one of claims 1, 2, 5, 8, and 9; or R 3 is methyl, and R 4a is hydrogen or Cl, and R 4b , R 4c , R 5a and R 5b are each hydrogen)

18. (i) A method for controlling and preventing insects, mites, nematodes or mollusks, which comprises applying an insecticidally, acaricidally, nematocidally or molluscicidally effective amount of the composition according to claim 11 to a pest, the habitat of the pest, or a plant susceptible to attack by the pest, or (ii) A method for protecting plant propagation materials from attack by insects, mites, nematodes or mollusks, which comprises treating the propagation materials or the place where the propagation materials are planted with an effective amount of the composition according to claim 11, or (iii) A method for controlling parasites in or on the body surface of an animal in need thereof, which comprises administering an effective amount of the composition according to claim 11.

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