Microbiocidal pyrazole derivatives

Abstract

A compound of formula (I) wherein the substituents are as defined in claim 1, as well as agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds, which can be used as fungicides. # imgabs0 #

Description

[0001] The present invention relates to microbicidal pyrazole derivatives, for example as active ingredients, which have microbicidal activity, in particular fungicidal activity. The present invention also relates to the preparation of these pyrazole derivatives, to intermediates useful in the preparation of these pyrazole derivatives, to the preparation of these intermediates, to agrochemical compositions comprising at least one of these pyrazole derivatives, to the preparation of these compositions and to the use of these pyrazole derivatives or compositions in agriculture or horticulture for controlling or preventing infection of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi.

[0002] According to a first aspect of the present invention, there is provided a compound having formula (I):

[0003]

[0004] in

[0005] R 1 is selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or C3-C6 cycloalkyl;

[0006] R 2 is selected from hydrogen, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimide, N-hydroxy-C-C1-C4 alkyl-carbonimide, or C1-C4 alkoxycarbonyl;

[0007] R 3 Selected from hydrogen, halogen, or C1-C4 alkyl;

[0008] R 4 is selected from hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, or di(C1-C4 alkylamino)carbonyl;

[0009] R 5 and R 6 Independently selected from hydrogen, or C1-C4 alkyl;

[0010] A 1 Selected from CR 7 or N,

[0011] A 2 Selected from CR 8 or N;

[0012] A 3 Selected from CR 9 or N;

[0013] R 7 , R 8 and R 9 independently selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or C1-C4 haloalkyl;

[0014] Q is selected from Q1, Q2, Q3, Q4, or Q5;

[0015]

[0016] in;

[0017] R 10 , R 11 , R 12 and R 13 independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, NC 1-4 Alkylamino, N,N-diC 1-4 Alkylamino, C1-C6 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimido, N-hydroxy-C1-C4 alkyl-carbonimido, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxyl, amino, phenyl, 5-membered or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5-membered or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S; and wherein any of the phenyl, 5-membered or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy;

[0018] Z 1 is selected from C1-C4 alkyl, phenyl, 5-membered or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein any of the 5-membered or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S; and wherein any of the phenyl, 5-membered or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, or C2-C4 alkynyl;

[0019] or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.

[0020] Surprisingly, it has been found that, for practical purposes, the compounds of formula (I) have a very advantageous level of biological activity for protecting plants against diseases caused by fungi.

[0021] According to a second aspect of the present invention, there is provided an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) according to the present invention. Such an agricultural composition may further comprise at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

[0022] According to a third aspect of the present invention, there is provided a method for controlling or preventing infection of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I) according to the present invention, or a composition comprising the compound of formula (I), is applied to these plants, their parts or their loci.

[0023] According to a fourth aspect of the present invention, there is provided the use of a compound of formula (I) according to the present invention as a fungicide. According to this particular aspect of the present invention, the use may not include methods of treating the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body.

[0024] Compounds of formula (I) with at least one basic center can form acid addition salts, for example, with strong inorganic acids, such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrohalic acids, strong organic carboxylic acids, such as unsubstituted or, for example, halogen-substituted C1-C4-alkanecarboxylic acids, for example acetic acid, 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 benzoic acid, or organic sulfonic acids, such as unsubstituted or, for example, halogen-substituted C1-C4-alkanesulfonic acids or arylsulfonic acids, for example methanesulfonic acid or p-toluenesulfonic acid. Compounds of formula (I) having at least one acidic group can, for example, form salts with bases, for example mineral salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts; or with ammonia or organic amines (such as morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, for example ethylamine, diethylamine, triethylamine or dimethylpropylamine, or mono-, di- or tri-hydroxy lower alkylamines, for example monoethanolamine, diethanolamine or triethanolamine).

[0025] In each case, the compounds of formula (I) according to the invention are in free form, oxidized form (such as N-oxide), or salt form (eg, agronomically usable salt form).

[0026] N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen-containing heteroaromatic compounds. They are described, for example, in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.

[0027] The compounds of formula (I) according to the invention also include hydrates which may be formed during salt formation.

[0028] When substituents are indicated as "optionally substituted", this means that they may or may not carry one or more identical or different substituents, for example, one, two or three R x Substituents. For example, C1-C6 alkyl substituted with 1, 2 or 3 halogens may include, but are not limited to -CH2Cl, -CHCl2, -CCl3, -CH2F, -CHF2, -CF3, -CH2CF3 or -CF2CH3 groups. As another example, C1-C6 alkoxy substituted with 1, 2 or 3 halogens may include, but are not limited to CH2ClO-, CHCl2O-, CCl3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O- or CH3CF2O- groups. Further, as used herein, the term "optionally substituted" means that the group mentioned is unsubstituted or substituted.

[0029] As used herein, the term "halogen" or "halo" refers to fluorine (fluorine, fluoro), chlorine (chlorine, chloro), bromine (bromine, bromo) or iodine (iodine, iodo), preferably fluorine, chlorine or bromine. This also applies accordingly to halogen in combination with other meanings, such as haloalkyl, haloalkenyl, haloalkynyl, haloalkoxy and halocycloalkyl.

[0030] As used herein, amino refers to a -NH2 group.

[0031] As used herein, cyano refers to a -CN group.

[0032] As used herein, the term "hydroxyl" or "hydroxy" refers to an -OH group.

[0033] As used herein, the term "carboxylic acid" refers to a -COOH group.

[0034] As used herein, the term "C1-C n"-alkyl" refers to a saturated straight or branched hydrocarbon group having 1 to n carbon atoms, attached via any carbon atom, such as any of the following groups: methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n-pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, or 1-ethyl-2-methylpropyl.

[0035] As used herein, the term "C2-C n "-Alkenyl" refers to a straight or branched alkenyl chain moiety having from two to n carbon atoms and one or two double bonds, for example vinyl, prop-1-enyl, but-2-enyl.

[0036] As used herein, the term "C2-C n "-alkynyl" refers to a straight or branched alkynyl chain moiety having from two to n carbon atoms and one triple bond, for example ethynyl, prop-2-ynyl, but-3-ynyl,

[0037] As used herein, the term "C3-C n "-cycloalkyl" refers to a tri(3) to n-membered cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0038] As used herein, the term "C1-C n "-alkoxy" refers to a straight or branched saturated alkyl group having one (1) to n carbon atoms attached via an oxygen atom (as mentioned above), i.e., for example, any of the following groups: methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy. As used herein, the term "C2-C n "-Alkenyloxy" refers to a straight or branched alkenyl chain (as mentioned above) having two (2) to n carbon atoms attached via an oxygen atom.

[0039] As used herein, the term "C1-C n"-haloalkyl" refers to a straight-chain or branched saturated alkyl group (as mentioned above) having 1 to n carbon atoms, attached via any carbon atom, wherein some or all of the hydrogen atoms in these groups may be replaced by fluorine, chlorine, bromine and / or iodine, i.e., for example, any of the following: chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl. Accordingly, the term "C1-C2 fluoroalkyl" will refer to a C1-C2 alkyl group with 1, 2, 3, 4, or 5 fluorine atoms, such as any of the following: difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl or pentafluoroethyl. Similarly, as used herein, the term "C2-C n -haloalkenyl" or "C2-C n "-haloalkynyl" refers to a C2-C4 substituted by one or more halogen atoms which may be the same or different. n -alkenyl or C2-C n -alkynyl. Similarly, as used herein, the term "C3-C n -halogenated cycloalkyl" or "C1-C n "-haloalkoxy" refers to a C3-C4 substituted by one or more halogen atoms which may be the same or different. n -cycloalkyl or C1-C n -alkoxy.

[0040] As used herein, the term "C1-C n -alkylthio" or "C1-C n -alkenylsulfanyl" refers to a C1-C n -alkyl.

[0041] As used herein, the term "C1-C n "-alkylsulfinyl" refers to a C1-C2-alkyl group attached through the sulfur atom of a sulfinyl (or S(=O)-) group. n alkyl.

[0042] As used herein, the term "C1-C n "-alkylsulfonyl" refers to a C1-C2- alkyl group attached through the sulfur atom of a sulfonyl (or S(=O)2-) group. n alkyl.

[0043] As used herein, the term "C1-C n "-alkylcarbonyl" refers to a C1-C2-alkyl group attached through the carbon atom of a carbonyl (C=O) group. n -alkyl.

[0044] As used herein, the term "C1-C n "-alkoxycarbonyl" refers to a C1-C2-alkyl group attached through the carbon atom of a carbonyl (or C=O) group. n -alkoxy moiety.

[0045] As used herein, the term "C1-C n -alkoxycarbonyl-C1-C6-alkyl" refers to a "C1-C n -alkoxycarbonyl substituted C1-C n -alkyl.

[0046] As used herein, the term "benzoyl" refers to a phenyl group attached through the carbon atom of a carbonyl (C=O) group.

[0047] As used herein, the term "C1-C n "-alkylaminocarbonyl" refers to a C1-C2-alkylaminocarbonyl group attached through the carbon atom of a carbonyl (C=O) group. n -alkylamino (or R a NHC(=O)-, where R a It is C1-C n -alkyl).

[0048] As used herein, the term "N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimido" refers to a a )=NO(R b ) group, wherein R a is C1-C4 alkyl as generally defined above, and R b is C1-C4 alkyl as generally defined above.

[0049] As used herein, the term "N-hydroxy-C-C1-C4 alkyl-carbonyl imide group" refers to a group having the formula -C(R a )=NOH group, wherein R a is C1-C4 alkyl as generally defined above.

[0050] As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic group containing 1, 2, 3 or 4 heteroatoms independently selected from N, O or S. Examples of heteroaryl include, but are not limited to, furanyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidinyl, or pyridinyl. The term "heteroaryl-C1-C1 n -alkyl" or "heteroaryl-C3-C n -cycloalkyl" refers to a C1-C n -alkyl or C3-C n -cycloalkyl. Heteroaryl-C1-C n -alkyl or heteroaryl-C3-C n -Cycloalkyl may, as the case may be, be substituted on heteroaryl, alkyl and / or cycloalkyl.

[0051] As used herein, the term "control" means reducing the number of pests, eliminating pests, and / or preventing further pest damage so that damage to plants or to plant-derived products is reduced.

[0052] As used herein, the term "pest" refers to insects and molluscs present in agriculture, horticulture, forestry, storage of products of plant origin (such as fruits, grains and wood); and those pests associated with damage to man-made structures. The term pest covers all stages of the life cycle of the pest.

[0053] As used herein, the term "effective amount" refers to an amount of a compound or a salt thereof, which provides the desired effect upon single or multiple administrations.

[0054] The effective amount is readily determined by one skilled in the art using known techniques and by observing the results obtained under similar circumstances. In determining the effective amount, many factors are considered, including, but not limited to, the type of plant or derived product to be applied; the pest to be controlled and its life cycle; the specific compound being applied; the type of application; and other relevant circumstances.

[0055] As used herein, the term "room temperature" or "RT" or "rt" refers to a temperature of about 15° C. to about 35° C. For example, rt may refer to a temperature of about 20° C. to about 30° C.

[0056] The following list provides substituents R for compounds of formula (I) of the present invention: 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R8 , R 9 , R 10 , R 11 , R 12 , R 13 , A 1 , A 2 , A 3 , Q (Q1, Q2, Q3, Q4 and Q5) and Z 1 For any of these substituents, any definition given below may be combined with any definition of any other substituent given below or elsewhere in this document.

[0057] In the embodiment of the present invention, R 1 is selected from C1-C4 alkyl. 1 is methyl, ethyl or isopropyl. More preferably, R 1 It's methyl.

[0058] In the embodiment of the present invention, R 2 is selected from hydrogen, halogen, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C2 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C2 alkyl-carbonylimide, or N-hydroxy-C-C1-C2 alkyl-carbonylimide. Preferably, R 2 is selected from hydrogen, halogen, methyl, ethyl, cyclopropyl, C1-C2-alkylcarbonyl, N-C1-C2alkoxy-C1-C2alkyl-carbonylimide, or N-hydroxy-C1-C2alkyl-carbonylimide. More preferably, R 2 is selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, cyclopropyl, acetyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, or -C(CH3)=NOH. Even more preferably, R 2 is selected from hydrogen, fluorine, chlorine, or methyl.

[0059] In the embodiment of the present invention, R 3 is selected from hydrogen, halogen, or C1-C2 alkyl. 3 is hydrogen, fluorine, chlorine, or methyl. More preferably, R 3 is hydrogen or methyl. Even more preferably, R 3 It's hydrogen.

[0060] In the embodiment of the present invention, R 4 is hydrogen, halogen, C1-C4 alkyl, cyano, C1-C4-alkylcarbonyl, or C1-C4-alkoxycarbonyl. 4 is hydrogen, chlorine, fluorine, C1-C3-alkyl, cyano, or CO2Me. More preferably, R 4is hydrogen, methyl, ethyl, isopropyl, or cyano. Even more preferably, R 4 is hydrogen or methyl. In one embodiment, R 4 is hydrogen. In another embodiment, R 4 It's methyl.

[0061] In the embodiment of the present invention, R 5 and R 6 are independently selected from hydrogen or C1-C2-alkyl. 5 and R 6 is independently selected from hydrogen or methyl. More preferably, R 5 and R 6 It's hydrogen.

[0062] In an embodiment of the present invention, Q is selected from Q1, Q2, Q3 or Q4:

[0063]

[0064] Where R 10 , R 11 , R 12 and R 13 is as defined above.

[0065] Preferably, Q is selected from Q1, Q2, or Q3:

[0066]

[0067] Where R 10 , R 11 , R 12 and R 13 is as defined above.

[0068] More preferably, Q is Q1:

[0069]

[0070] Where R 10 , R 11 , R 12 and R 13 is as defined above.

[0071] In the embodiment of the present invention, R 12 and R 13 is independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy. 12 and R 13 are independently selected from hydrogen, chlorine, bromine, fluorine, or methyl. More preferably, R 12 and R 13 It's hydrogen.

[0072] In the embodiment of the present invention, R 10 and R 11 independently selected from hydrogen, halogen, hydroxy, cyano, amino, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, NC 1-4 Alkylamino, N,N-diC 1-4 Alkylamino, C1-C6 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimidyl, N-hydroxy-C1-C4 alkyl-carbonimidyl, trifluoromethylsulfonyloxy, carboxyl, phenyl, 5-membered or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5-membered or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S; and wherein any of the phenyl, 5-membered or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy.

[0073] In another embodiment of the present invention, R 10 and R 11 independently selected from hydrogen, halogen, cyano, amino, C1-C3 alkyl, C1-C2 haloalkyl, C1-C3 haloalkoxy, C1-C4 alkoxy, C2-C3 alkenyloxy, C2-C3 alkynyloxy, C1-C2 alkylsulfanyl, C1-C2 alkylsulfinyl, C1-C2 alkylsulfonyl, C1-C2 alkoxy-C1-C2 alkyl, C1-C3 alkoxycarbonyl, C1-C2 alkylcarbonyl, N-C1-C2 alkoxy-C1-C2 alkyl-carbonimide, N-hydroxy -C1-C2 alkyl-carbonimido, hydroxy, C1-C2 alkylaminocarbonyl, di(C1-C2 alkylamino)carbonyl, trifluoromethylsulfonyloxy, carboxyl, phenyl, 5-membered or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5-membered or 6-membered heteroaryl contains 1 or 2 heteroatoms independently selected from N and O, and wherein any of the phenyl, 5-membered or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, or methyl.

[0074] In a preferred embodiment, R 10 and R 11independently selected from hydrogen, halogen, cyano, amino, C1-C3 alkyl, C1-C2 haloalkyl, C1-C3 haloalkoxy, C1-C4 alkoxy, C2-C3 alkenyloxy, C2-C3 alkynyloxy, C1-C2 alkylsulfanyl, C1-C2 alkylsulfinyl, C1-C2 alkylsulfonyl, C1-C2 alkoxy-C1-C2 alkyl, C1-C3 alkoxycarbonyl, C1-C2 alkylcarbonyl, N-C1-C2 alkoxy-C-C1-C2 alkyl-carbonimide, N-hydroxy-C1-C2 alkyl-carbonimide, hydroxy, C1-C2 alkylaminocarbonyl, di(C1-C2 alkylamino)carbonyl, trifluoromethylsulfonyloxy, carboxyl, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, [4-(trifluoromethyl)pyrazol-1-yl], [3-(trifluoromethyl)pyrazol-1-yl], (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), (5-chloropyrazol-1-yl), (4-chloropyrazol-1-yl), (3-chloropyrazol-1-yl), (5-fluoropyrazol-1-yl), (4-fluoropyrazol-1-yl), (3-fluoropyrazol-1-yl), (3,5-dimethylpyrazol-1-yl), (5-methylpyrazol-1-yl), (4-methylpyrazol-1-yl), (3-methylpyrazol-1-yl), pyrazol-1-yl, cyclopropyl, or 1-cyanocyclopropyl.

[0075] More preferably, R 10 and R 11independently selected from hydrogen, chlorine, fluorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, difluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, methoxy, ethoxy, propoxy, allyloxy, prop-2-ynyloxy, methylsulfanyl, methylsulfinyl, methyl-sulfonyl, methoxymethyl, ethoxymethyl, 2-methoxy-ethoxymethyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, acetyl, propionyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methyl-aminocarbonyl, di(methylamino)carbonyl, trifluoromethylsulfonyloxy, cyano, carboxyl, phenyl, 2-cyanophenyl, 3-

[0013] In some embodiments, R is 1-cyanophenyl, ... 10 and R 11 independently selected from hydrogen, chlorine, fluorine, bromine, methyl, trifluoromethyl, difluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, methoxy, propoxy, allyloxy, prop-2-ynyloxy, methylsulfanyl, methylsulfinyl, methylsulfonyl, methoxymethyl, 2-methoxyethoxymethyl, methoxycarbonyl, acetyl, propionyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methylaminocarbonyl, di(methylamino)carbonyl, trifluoromethyl-sulfonyloxy, cyano, carboxyl, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, [4-(trifluoromethyl)pyrazol-1-yl], [3-(trifluoromethyl)pyrazol-1-yl], (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), (5-chloropyrazol-1-yl), (4-chloropyrazol-1-yl), (3-chloropyrazol-1-yl), (5-fluoropyrazol-1-yl), (4-fluoropyrazol-1-yl), (3-fluoropyrazol-1-yl), (3,5-dimethylpyrazol-1-yl), (5-methylpyrazol-1-yl), (4-methylpyrazol-1-yl), (3-methylpyrazol-1-yl), pyrazol-1-yl, cyclopropyl, or 1-cyanocyclopropyl. Even more preferably, R 10 and R 11are independently selected from hydrogen, chlorine, fluorine, bromine, methoxy, cyano, amino, carboxyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), (5-chloropyrazol-1-yl), (4-chloropyrazol-1-yl), (3-chloropyrazol-1-yl), (5-fluoropyrazol-1-yl), (4-fluoropyrazol-1-yl), (3-fluoropyrazol-1-yl), (3,5-dimethylpyrazol-1-yl), (5-methylpyrazol-1-yl), (4-methylpyrazol-1-yl), (3-methylpyrazol-1-yl), pyrazol-1-yl, cyclopropyl, and 1-cyanocyclopropyl.

[0076] In yet another embodiment of the present invention, R 10 and R 11 R is independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5-membered or 6-membered heteroaryl or C3-C6 cycloalkyl, wherein the 5-membered or 6-membered heteroaryl contains 1 heteroatom selected from N, and wherein any one of the phenyl, 5-membered or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl. More preferably, R 10 and R 11 R is independently selected from hydrogen, chlorine, bromine, methoxy, cyano, amino, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), (3,5-dimethylpyrazol-1-yl), (5-methylpyrazol-1-yl), (4-methylpyrazol-1-yl), (3-methylpyrazol-1-yl), pyrazol-1-yl, cyclopropyl, and 1-cyanocyclopropyl. Even more preferably, R 10 and R 11 are independently selected from hydrogen, chlorine, bromine, cyano, or amino.

[0077] In an embodiment of the present invention, Q is selected from Q1, Q2, Q3, or Q4:

[0078]

[0079] in

[0080] R 10 and R 11 R is independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5-membered or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5-membered or 6-membered heteroaryl contains 1 heteroatom selected from N, and wherein any one of the phenyl, 5-membered or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl; and R 12 and R 13 It's hydrogen.

[0081] In another embodiment of the present invention, Q is selected from Q1, Q2, Q3, or Q4; wherein R 10 and R 11 are independently selected from hydrogen, halogen, cyano, or amino; and R 12 and R 13 It's hydrogen.

[0082] Preferably, Q is selected from Q1, Q2, or Q3:

[0083]

[0084] in

[0085] R 10 and R 11 independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N, and wherein any of the phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl; and

[0086] R 12 and R 13 It's hydrogen.

[0087] In another embodiment of the present invention, Q is selected from Q1, Q2, or Q3; wherein R 10 and R 11 are independently selected from hydrogen, halogen, cyano, or amino; and R 12 and R 13 It's hydrogen.

[0088] More preferably, Q is Q1

[0089]

[0090] in

[0091] R 10 and R 11 independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N, and wherein any of the phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl; and

[0092] R 12 and R 13 It's hydrogen.

[0093] In another embodiment of the present invention, Q is Q1; wherein R 10 and R 11 are independently selected from hydrogen, halogen, cyano, or amino; and R 12 and R 13 It's hydrogen.

[0094] In an embodiment of the present invention, A 1 Selected from CR 7 or N; A 2 Selected from CR 8 or N; A 3 Selected from CR 9 or N; where A 1 , A 2 and A 3 At least two of are selected from N. Preferably, in one embodiment of the present invention, A 1 Selected from CR 7 ; and A 2 and A 3 is N. Preferably, in another embodiment, A 1 and A 2 is N; and A 3 Selected from CR 9 Preferably, in another embodiment, A 1 Yes N; A 2 Yes CR 8 , and A 3 is N. More preferably, A 1 , A 2 and A 3 It is N.

[0095] In another embodiment of the present invention, A 1 and A 2 is N, and A 3 Yes CR 9 In yet another embodiment of the present invention, A 1 Yes CR 7 ; A 2 Yes CR 8 , and A 3 is N. In yet another embodiment of the present invention, A 1 Yes N; A 2 Yes CR 8 , and A 3 Yes CR 9 In yet another embodiment of the present invention, A 1 Yes CR 7 ; A 2 is N; and A 3 Yes CR 9 .

[0096] In the embodiment of the present invention, R 7 , R 8 and R 9 R is independently selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, or C2-C4 alkynyl. 7 , R 8 and R 9 is independently selected from hydrogen, halogen, methyl, or trifluoromethyl. More preferably, R 7 , R 8 and R 9 It's hydrogen.

[0097] In the embodiment of the present invention, Z 1 wherein the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, and wherein any of the phenyl and the 5- to 6-membered heteroaryl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from the group consisting of halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C2-C4-alkynyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, or C1-C4 alkylsulfonyl, and wherein the C3-C6-cycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from the group consisting of halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy.

[0098] In another embodiment, Z 1 is selected from C1-C3 alkyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- or 6-membered heteroaryl contains 1, 2 or 3 heteroatoms independently selected from N, O or S, and wherein any of the phenyl and the 5- to 6-membered heteroaryl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from fluorine, chlorine, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and wherein the C3-C6-cycloalkyl is unsubstituted or substituted with 1 or 2 substituents selected from methyl.

[0099] In another embodiment, Z 1is selected from C1-C3 alkyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N, O or S, and wherein any one of the phenyl and the 5- to 6-membered heteroaryl is unsubstituted or substituted by 1 or 2 substituents independently selected from fluorine, chlorine, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and wherein the C3-C6-cycloalkyl is unsubstituted or substituted by 1 or 2 substituents selected from methyl.

[0100] Preferably, Z 1 Selected from 1-methylpyrazol-4-yl, 2,3,4-trifluorophenyl, 2,3-difluorophenyl, 3,4-difluorophenyl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2-pyridyl, 2-fluoro-4-methoxy-phenyl, 2-fluoro-4-methylsulfonyl-phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3,5-difluoro-2-furanyl , 3-fluoro-2-furanyl, 5-fluoro-2-furanyl, 3,5-difluoro-2-thienyl, 3-fluoro-2-thienyl, 5-fluoro-2-thienyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3-methoxyphenyl, 4-ethynyl-2-fluoro-phenyl, 4-fluoro-2-methoxy-phenyl, cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, n-propyl, or phenyl. More preferably, Z 1 is selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2-chlorophenyl, 2-fluorophenyl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-fluorophenyl, 3-methylphenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, 4-methylphenyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, or phenyl. Even more preferably, Z 1 is selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 3,5-difluoro-2-pyridyl, 2,4-difluorophenyl, 2-fluorophenyl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, cyclobutyl, cyclohexyl, cyclopentyl, or phenyl. Still even more preferably, Z 1 Selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, 4-fluorophenyl, or phenyl.

[0101] In another embodiment of the present invention, Z 1is selected from C1-C4 alkyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- or 6-membered heteroaryl contains 1, 2 or 3 heteroatoms independently selected from N, O or S, and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from the following items: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy, and wherein the C3-C6-cycloalkyl is unsubstituted or substituted by 1 substituent selected from halogen or C1-C4 alkyl. Preferably, Z 1 is selected from phenyl or 5- to 6-membered heteroaryl; wherein the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N or S, and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from fluorine, chlorine, C1-C4 alkyl, or C1-C4 alkoxy. More preferably, Z 1 is selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2-pyridyl, 2-fluorophenyl, 3,5-difluoro-2-furyl, 3-fluoro-2-furyl, 5-fluoro-2-furyl, 3,5-difluoro-2-thienyl, 3-fluoro-2-thienyl, 5-fluoro-2-thienyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, cyclobutyl, cyclohexyl, cyclopentyl, or methyl. Still more preferably, Z 1 Selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2-pyridyl, 3,5-difluoro-2-furyl, 3-fluoro-2-furyl, 5-fluoro-2-furyl, 3,5-difluoro-2-thienyl, 3-fluoro-2-thienyl, 5-fluoro-2-thienyl, 2-fluorophenyl, 4-fluorophenyl, or phenyl.

[0102] In another embodiment of the present invention, Z 1 is selected from phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N or S, and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy, and wherein the C3-C6-cycloalkyl is unsubstituted or substituted by 1 substituent selected from halogen or C1-C4 alkyl. Preferably, Z 1wherein the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N or S, and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from fluorine, chlorine, C1-C4 alkyl, or C1-C4 alkoxy.

[0103] The present invention thus makes available compounds of formula (I) having R as defined above with respect to (I) in all combinations / permutations. 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , A 1 , A 2 , A 3 , Q (Q-1, Q2, Q3, Q4 and Q5) and Z 1 .

[0104] Embodiments according to the present invention are provided as listed below.

[0105] In one embodiment, a compound having formula (I) is provided, wherein

[0106] R 1 is selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, or C3-C6 cycloalkyl;

[0107] R 2 is selected from hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimide, N-hydroxy-C-C1-C4 alkyl-carbonimide, or C1-C6 alkoxycarbonyl;

[0108] R 3 is selected from hydrogen, halogen or C1-C4 alkyl;

[0109] R 4 is selected from hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, or di(C1-C4 alkylamino)carbonyl;

[0110] R 5 and R 6Independently selected from hydrogen or C1-C4 alkyl;

[0111] A 1 Selected from CR 7 or N,

[0112] A 2 Selected from CR 8 or N;

[0113] A 3 Selected from CR 9 or N;

[0114] R 7 , R 8 and R 9 independently selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or C1-C4 haloalkyl;

[0115] Q is selected from Q1, Q2, Q3, Q4, or Q5;

[0116]

[0117] in;

[0118] R 10 , R 11 , R 12 and R 13 independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, NC 1-4 Alkylamino, N,N-diC 1-4 alkylamino, C1-C6 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimido, N-hydroxy-C1-C4 alkyl-carbonimido, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxyl, amino, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, and wherein any of the phenyl, 5- to 6-membered heteroaryl or C3-C6-cycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy; and

[0119] Z 1is selected from C1-C4 alkyl, phenyl, 5-membered or 6-membered heteroaryl, or C3-C6-cycloalkyl, wherein the 5-membered or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, and wherein any of the phenyl, 5-membered or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, or C2-C4 alkynyl;

[0120] or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.

[0121] In an embodiment of the present invention, the compound having formula (I) may be a compound having formula (Ia):

[0122]

[0123] Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q (Q1, Q2, Q3, Q4 and Q5), R 10 , R 11 , R 12 , R 13 and Z 1 is as defined for the compounds of formula (I) according to the invention, and

[0124] A is selected from the group consisting of:

[0125]

[0126] in The bond to the C(=O) group is indicated and the arrow indicates the bond to Z 1 The bond of the group, and R 7 , R 8 and R 9 Independently selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or C1-C4 haloalkyl.

[0127] Preferably, in the compound having formula (Ia), R 1 , R 2 , R 3 , R 4 , R 5 , R 6, Q (Q1, Q2, Q3, Q4 and Q5), R 10 , R 11 , R 12 , R 13 and Z 1 is as defined for the compounds of formula (I) according to the present invention, A is selected from A1, A2, A3, A4, A5, A6, A7, or A9, and R 7 , R 8 and R 9 is hydrogen, halogen, methyl, or trifluoromethyl.

[0128] More preferably, in the compound having formula (Ia), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q (Q1, Q2, Q3, Q4 and Q5), R 10 , R 11 , R 12 , R 13 and Z 1 is as defined for the compounds of formula (I) according to the present invention, A is selected from A1, A2, A3, A4, A5, A6, A7, or A9, and R 7 , R 8 and R 9 It's hydrogen.

[0129] In an embodiment of the present invention, in the compound having formula (Ia), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q (Q1, Q2, Q3, Q4 and Q5), R 10 , R 11 , R 12 , R 13 and Z 1 is as defined for the compounds of formula (I) according to the invention, A is selected from

[0130]

[0131] in The bond to the C(=O) group is indicated and the arrow indicates the bond to Z 1 The bond of the group, and R 7 is selected from hydrogen, C1-C4 alkyl, C1-C4 alkenyl, C1-C4 alkynyl, or C1-C4 haloalkyl.

[0132] Preferably, in the compound having formula (Ia), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q (Q1, Q2, Q3, Q4 and Q5), R 10 , R 11 , R 12 , R 13 and Z 1 is as defined for the compounds of formula (I) according to the present invention, A is selected from A1, A2, or A3, and R 7 is hydrogen, halogen, methyl, or trifluoromethyl.

[0133] More preferably, in the compound having formula (Ia), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q (Q1, Q2, Q3, Q4 and Q5), R 10 , R 11 , R 12 , R 13 and Z 1 is as defined for the compounds of formula (I) according to the present invention, A is selected from A1, A2, or A3, and R 7 It's hydrogen.

[0134] In another embodiment of the present invention, in the compound having formula (Ia), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q (Q1, Q2, Q3, Q4 and Q5), R 10 , R 11 , R 12 , R 13 and Z 1 is as defined for the compounds of formula (I) according to the invention, A is selected from

[0135]

[0136] in The bond to the C(=O) group is indicated and the arrow indicates the bond to Z 1 The bond of the group.

[0137] Preferably, in the compound having formula (Ia), R 1 , R2 , R 3 , R 4 , R 5 , R 6 , Q (Q1, Q2, Q3, Q4 and Q5), R 10 , R 11 , R 12 , R 13 and Z 1 As defined for the compounds of formula (I) according to the invention, A is selected from A1 or A2.

[0138] More preferably, in the compound having formula (Ia), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q (Q1, Q2, Q3, Q4 and Q5), R 10 , R 11 , R 12 , R 13 and Z 1 As defined for the compounds of formula (I) according to the invention, A is selected from A1 or A2.

[0139] In yet another embodiment of the present invention, in the compound having formula (Ia), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , R 13 , and Z 1 is as defined for the compounds of formula (I) according to the invention,

[0140] A is selected from A1 or A2;

[0141] R 7 is hydrogen; and

[0142] Q is selected from Q1, Q2, Q3, or Q4.

[0143] In yet another embodiment of the present invention, in the compound having formula (Ia), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R12 , R 13 and Z 1 is as defined for the compounds of formula (I) according to the invention,

[0144] A is selected from A1 or A2;

[0145] R 7 is hydrogen; and

[0146] Q is selected from Q1, Q2, or Q3.

[0147] In yet another embodiment of the present invention, in the compound having formula (Ia), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , R 13 and Z 1 is as defined for the compounds of formula (I) according to the invention,

[0148] A is selected from A1 or A2;

[0149] R 7 is hydrogen; and

[0150] Q is Q1.

[0151] In an embodiment of the present invention, in the compound having formula (Ia), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q (Q1, Q2, Q3, Q4 and Q5), R 10 , R 11 , R 12 , R 13 and Z 1 is as defined for the compounds of formula (I) according to the invention, A is selected from

[0152]

[0153] in The bond to the C(=O) group is indicated and the arrow indicates the bond to Z 1 The bond of the group.

[0154] In another embodiment of the present invention, in the compound having formula (Ia), wherein R 1 , R2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , R 13 and Z 1 is as defined for the compounds of formula (I) according to the present invention, A is selected from A1, and Q is selected from Q1, Q2, Q3, or Q4.

[0155] In yet another embodiment of the present invention, in the compound having formula (Ia), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , R 13 and Z 1 is as defined for the compounds of formula (I) according to the present invention, A is selected from A1, and Q is selected from Q1, Q2, or Q3.

[0156] In yet another embodiment of the present invention, in the compound having formula (Ia), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , R 13 and Z 1 is as defined for the compounds of formula (I) according to the invention, A is selected from A1, and Q is Q1.

[0157] Preferably, in the compound of the present invention having formula (Ia)

[0158] R 1 is a C1-C4-alkyl group,

[0159] R 2 is hydrogen, fluorine, chlorine, or methyl;

[0160] R 3 is hydrogen or methyl,

[0161] R 4 is hydrogen or methyl;

[0162] R 5 and R6 independently selected from hydrogen or methyl;

[0163] A is A1 or A2;

[0164] R 7 It is hydrogen;

[0165] Q is Q1, Q2 or Q3;

[0166] R 10 and R 11 independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5-membered or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5-membered or 6-membered heteroaryl contains 1 heteroatom selected from N, and wherein any of the phenyl, 5-membered or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl;

[0167] R 12 and R 13 are independently selected from hydrogen; and

[0168] Z 1 wherein the 5- to 6-membered heteroaryl contains 1 heteroatom selected from N or S, and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy, and wherein the C3-C6-cycloalkyl is unsubstituted or substituted by 1 substituent selected from halogen or C1-C4 alkyl.

[0169] Preferably, in the compound of the present invention having formula (Ia)

[0170] R 1 is a C1-C4-alkyl group,

[0171] R 2 is hydrogen, fluorine, chlorine, or methyl;

[0172] R 3 is hydrogen or methyl,

[0173] R 4 is hydrogen or methyl;

[0174] R 5 and R 6 independently selected from hydrogen or methyl;

[0175] A is A1 or A2;

[0176] R 7 It is hydrogen;

[0177] Q is Q1;

[0178] R 10 and R 11 independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5-membered or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5-membered or 6-membered heteroaryl contains 1 heteroatom selected from N, and wherein any of the phenyl, 5-membered or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano or methyl;

[0179] R 12 and R 13 is selected from hydrogen; and

[0180] Z 1 wherein the 5- to 6-membered heteroaryl contains 1 heteroatom selected from N or S, and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy, and wherein the C3-C6-cycloalkyl is unsubstituted or substituted by 1 substituent selected from halogen or C1-C4 alkyl.

[0181] In an embodiment of the present invention, the compound having formula (Ia) may be a compound having formula (Ia-A), wherein A is A1:

[0182]

[0183] Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q (Q1, Q2, Q3, Q4 and Q5), R 10 , R 11 , R 12 , R 13 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0184] Preferably, in the compounds of the present invention having formula (Ia-A),

[0185] R 1 is a C1-C4-alkyl group,

[0186] R 2 is hydrogen, fluorine, chlorine, or methyl;

[0187] R 3 is hydrogen or methyl,

[0188] R 4 is hydrogen or methyl;

[0189] R 5 and R 6 are independently selected from hydrogen or methyl; and

[0190] Q, R 10 , R 11 , R 12 , R 13 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0191] In another embodiment, in the compound of the present invention having formula (Ia-A),

[0192] R 1 is a C1-C4-alkyl group,

[0193] R 2 is hydrogen, fluorine, chlorine, or methyl;

[0194] R 3 is hydrogen or methyl,

[0195] R 4 is hydrogen or methyl;

[0196] R 5 and R 6 independently selected from hydrogen or methyl;

[0197] Q is Q1, Q2, or Q3,

[0198] R 10 and R 11 independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5-membered or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5-membered or 6-membered heteroaryl contains 1 heteroatom selected from N, and wherein any of the phenyl, 5-membered or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl;

[0199] R 12 and R 13 are independently selected from hydrogen; and

[0200] Z 1wherein the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N or S, and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from fluorine, chlorine, C1-C4 alkyl, or C1-C4 alkoxy.

[0201] In yet another embodiment, in the compounds of the present invention having formula (Ia-A), R 1 is a C1-C4-alkyl group,

[0202] R 2 is hydrogen, fluorine, chlorine, or methyl;

[0203] R 3 is hydrogen or methyl,

[0204] R 4 is hydrogen or methyl;

[0205] R 5 and R 6 independently selected from hydrogen or methyl;

[0206] Q is Q1,

[0207] R 10 and R 11 independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5-membered or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5-membered or 6-membered heteroaryl contains 1 heteroatom selected from N, and wherein any of the phenyl, 5-membered or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano or methyl;

[0208] R 12 and R 13 are independently selected from hydrogen; and

[0209] Z 1 wherein the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N or S, and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from fluorine, chlorine, C1-C4 alkyl, or C1-C4 alkoxy.

[0210] In an embodiment of the present invention, the compound having formula (Ia) may be a compound having formula (Ia-B), wherein A is A2:

[0211]

[0212] Where R 1 , R 2 , R 3 , R4 , R 5 , R 6 , Q(Q 1 , Q 2 , Q 3 , Q 4 and Q 5 ), R 10 , R 11 , R 12 , R 13 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0213] Preferably, in the compounds of the present invention having formula (Ia-B),

[0214] R 1 is a C1-C4-alkyl group,

[0215] R 2 is hydrogen, fluorine, chlorine, or methyl;

[0216] R 3 is hydrogen or methyl,

[0217] R 4 is hydrogen or methyl;

[0218] R 5 and R 6 are independently selected from hydrogen or methyl; and

[0219] Q, R 10 , R 11 , R 12 , R 13 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0220] In another embodiment, in the compound of the present invention having formula (Ia-B),

[0221] R 1 is a C1-C4-alkyl group,

[0222] R 2 is hydrogen, fluorine, chlorine, or methyl;

[0223] R 3 is hydrogen or methyl,

[0224] R 4 is hydrogen or methyl;

[0225] R 5 and R 6 independently selected from hydrogen or methyl;

[0226] Q is Q1, Q2, or Q3,

[0227] R 10 and R 11 independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5-membered or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5-membered or 6-membered heteroaryl contains 1 heteroatom selected from N, and wherein any of the phenyl, 5-membered or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl;

[0228] R 12 and R 13 is hydrogen; and

[0229] Z 1 wherein the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N or S, and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from fluorine, chlorine, C1-C4 alkyl, or C1-C4 alkoxy.

[0230] In yet another embodiment, in the compounds of the present invention having formula (Ia-B),

[0231] R 1 is a C1-C4-alkyl group,

[0232] R 2 is hydrogen, fluorine, chlorine, or methyl;

[0233] R 3 is hydrogen or methyl,

[0234] R 4 is hydrogen or methyl;

[0235] R 5 and R 6 independently selected from hydrogen or methyl;

[0236] Q is Q1;

[0237] R 10 and R 11 independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5-membered or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5-membered or 6-membered heteroaryl contains 1 heteroatom selected from N, and wherein any of the phenyl, 5-membered or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl;

[0238] R 12 and R 13 is hydrogen; and

[0239] Z 1 wherein the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N or S, and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from fluorine, chlorine, C1-C4 alkyl, or C1-C4 alkoxy.

[0240] In an embodiment of the present invention, the compound having formula (Ia) may be a compound having formula (Ia-C), wherein A is A3, and wherein R 7 It is hydrogen:

[0241]

[0242] Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q (Q1, Q2, Q3, Q4 and Q5), R 10 , R 11 , R 12 , R 13 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0243] Preferably, in the compounds of the present invention having formula (Ia-C),

[0244] R 1 is a C1-C4-alkyl group,

[0245] R 2 is hydrogen, fluorine, chlorine, or methyl;

[0246] R 3 is hydrogen or methyl,

[0247] R 4 is hydrogen or methyl;

[0248] R 5 and R 6 are independently selected from hydrogen or methyl; and

[0249] Q, R 10 , R 11 , R 12 , R 13 and Z 1 is as defined for the compounds of formula (II) according to the invention.

[0250] In another embodiment, in the compounds of the present invention having formula (Ia-C),

[0251] R 1 Is C1-C4-alkyl

[0252] R 2 is hydrogen, fluorine, chlorine, or methyl;

[0253] R 3 is hydrogen or methyl

[0254] R 4 is hydrogen or methyl;

[0255] R 5 and R 6 independently selected from hydrogen or methyl;

[0256] Q is Q1, Q2 or Q3;

[0257] R 10 and R 11 independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5-membered or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5-membered or 6-membered heteroaryl contains 1 heteroatom selected from N, and wherein any of the phenyl, 5-membered or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl;

[0258] R 12 and R 13 is hydrogen; and

[0259] Z 1 wherein the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N or S, and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from fluorine, chlorine, C1-C4 alkyl, or C1-C4 alkoxy.

[0260] In yet another embodiment, in the compounds of the present invention having formula (Ia-C), R 1 is a C1-C4-alkyl group,

[0261] R 2 is hydrogen, fluorine, chlorine, or methyl;

[0262] R 3 is hydrogen or methyl,

[0263] R 4 is hydrogen or methyl;

[0264] R 5 and R 6 independently selected from hydrogen or methyl;

[0265] Q is Q1;

[0266] R 10 and R 11 independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5-membered or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5-membered or 6-membered heteroaryl contains 1 heteroatom selected from N, and wherein any of the phenyl, 5-membered or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, or methyl;

[0267] R 12 and R 13 is hydrogen; and

[0268] Z 1 wherein the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N or S, and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from fluorine, chlorine, C1-C4 alkyl, or C1-C4 alkoxy.

[0269] The presence of one or more possible asymmetric carbon atoms in any of the compounds of formula (I), (Ia), (Ia-A), (Ia-B) and (Ia-C) according to the present invention means that these compounds may exist in the form of chiral isomers, i.e. in the form of enantiomers or diastereoisomers.

[0270] Preferably, the compound of formula (I) according to the present invention is selected from the compounds listed in any one of Tables C-1 to C-21 or the compounds listed in Table P.

[0271] More preferably, the compounds of formula (I) according to the invention are chosen from the compounds listed in Table P.

[0272] In one embodiment of the present invention, the compound having formula (I) is selected from

[0273] N-[2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)triazole-4-carboxamide,

[0274] N-[2-(6-cyano-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)triazole-4-carboxamide,

[0275] N-[2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)triazole-4-carboxamide,

[0276] N-[2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)-1,2,4-triazole-3-carboxamide,

[0277] N-[2-(6-cyano-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)tetrazole-5-carboxamide,

[0278] N-[2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)tetrazole-5-carboxamide,

[0279] N-[2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(3,5-difluoro-2-pyridinyl)triazole-4-carboxamide,

[0280] N-[2-(6-bromo-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)triazole-4-carboxamide, or

[0281] N-[2-(6-cyano-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)triazole-4-carboxamide.

[0282] In one embodiment of the present invention, the compound having formula (I) is selected from

[0283] N-[2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)triazole-4-carboxamide,

[0284] N-[2-(6-cyano-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)triazole-4-carboxamide,

[0285] N-[2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)triazole-4-carboxamide,

[0286] N-[2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)-1,2,4-triazole-3-carboxamide,

[0287] N-[2-(6-cyano-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)tetrazole-5-carboxamide, or

[0288] N-[2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)tetrazole-5-carboxamide.

[0289] The following intermediates are novel and themselves form a further aspect of the invention.

[0290] According to a fifth aspect of the present invention, there is provided an intermediate compound having formula (III) or a salt thereof:

[0291]

[0292] Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and Q correspond to the same definitions as for the compounds of formula (I) according to the invention.

[0293] The intermediate compounds of formula (III) have R corresponding to the compounds of formula (I) according to the present invention and their corresponding preferred embodiments. 1 , R 2 , R 3 , R 4 , R 5 , R 6 Same definition as Q.

[0294] According to a sixth aspect of the present invention, there is provided an intermediate compound having formula (IIb) or a salt thereof:

[0295]

[0296] Where R 0 is a C1-C6 alkyl group and wherein A 1 , A 2 , A 3 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0297] The intermediate compounds of formula (IIb) have the same A as for the compounds of formula (I) according to the present invention and their corresponding preferred embodiments. 1 , A 2 , A 3 and Z 1 The same definition.

[0298] In one embodiment, the compound having formula (IIb) may be a compound having formula (IIba), wherein R 7 is hydrogen, R 0is a C1-C6 alkyl group, A 1 , A 2 , A 3 is N, and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0299]

[0300] The presence of one or more possible asymmetric carbon atoms in the compounds of formula (III) according to the invention means that these compounds may exist in the form of chiral isomers, ie in the form of enantiomers or diastereomers.

[0301] Compounds of formula (I) as defined in any embodiment of the invention may be prepared as shown in the following Schemes 1 to 15, wherein (unless otherwise stated) the definition of each variable is as defined above for any embodiment according to the invention.

[0302] In any of the following Schemes 1 to 15, the presence of one or more possible asymmetric carbon atoms in the compounds of formula (I) according to the invention means that these compounds can exist in the form of chiral isomers, ie in the form of enantiomers or diastereomers.

[0303] More specifically, the compound of formula (I) can be prepared from a compound of formula (III) or a salt thereof (wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , R 13 and Q is as defined above for compounds of formula (I)) by reacting with a compound of formula (II) (wherein A 1 , A 2 , A 3 and Z 1 is prepared by reaction of (as defined above for compounds of formula (I)). This reaction is shown in Scheme 1.

[0304]

[0305] In Scheme 1, a compound of formula (II) (wherein A 1 , A 2 , A 3and Z 1 is as defined above for compounds of formula (I)) activated to compounds of formula (IIa). For example, a compound of formula (IIa) wherein G 0 is halogen) is formed by treating a compound of formula (II) with, for example, oxalyl chloride or thionyl chloride in an inert solvent such as dichloromethane (CH2Cl2) or tetrahydrofuran (THF) in the presence of a catalytic amount of N,N-dimethylformamide (DMF) at a temperature between 20°C and 100°C (preferably 25°C). 1 , R 2 , R 3 , R 4 , R 5 , R 6 and Q is as defined above for compounds of formula (I)) treating a compound of formula (IIa), optionally in the presence of a base (e.g. triethylamine or pyridine), to obtain a compound of formula (I). Alternatively, a compound of formula (I) may be prepared by treating a compound of formula (II) with dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) or 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU) at a temperature between 30°C and 180°C in an inert solvent (e.g. pyridine, DMF, acetonitrile, CH2Cl2 or THF), optionally in the presence of a base (e.g. triethylamine) to obtain an activated compound of formula (IIa) (wherein G 0 is G as described below 01 , G 02 or G 03 (Scheme 2)). Finally, compounds of formula (II) can also be prepared by reacting with a coupling agent such as propanephosphonic anhydride (T3P) to provide compounds of formula (IIa) (wherein G 0 is G as described below 04 ) for activation, as described, for example, in Synthesis 2013, 45, 1569. Further reaction with an amine (or a salt thereof) of a compound of formula (III) gives a compound of formula (I).

[0306]

[0307] The compound of formula (II) can be prepared from a compound of formula (IIb) (wherein A 1 , A 2 , A 3 is N and Z 1 is as described in formula (I), and R0 C1-C4 alkyl) is prepared by ester hydrolysis. Various conditions can be used, such as sodium hydroxide or lithium hydroxide aqueous solution and organic water miscible solvents such as THF or dimethoxyethane or methanol or ethanol. Such ester hydrolysis is well known to those skilled in the art. Compounds with formula (IIb) can also be directly converted into compounds with formula (I) by reacting compounds with formula (IIb) with compounds with formula (III) in an inert solvent (such as toluene or dichloromethane) in the presence of trimethylaluminum or trimethylaluminum-DABCO complex. Such reactions have been reported in the literature (see Tetrahedron Lett. [tetrahedron communication] 1977, 4171-4174 and Tetrahedron Lett. [tetrahedron communication] 2006, 5767-5769, and references cited therein).

[0308] Compounds of formula (II) and (IIb) are commercially available or can be synthesized as described hereinafter.

[0309] A compound having the formula (III) or a salt thereof (wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , R 13 and Q is as defined above for compounds of formula (I)) can be prepared by one skilled in the art by reacting a nitrile of formula (IV) (wherein R 1 , R 2 , R 3 , R 4 , R 10 , R 11 , R 12 , R 13 and Q are as defined above for compounds of formula (I)) and a suitable nucleophile such as (dimethyl sulfide) dihydrogen borate (BMS), for example as described in J. Org. Chem. 1981, 47, 3153. Alternatively, the Grignard reagent R 5 MgBr or R 6 MgBr (where R 5 and R 6(as defined above for compounds of formula (I)) can be added sequentially or simultaneously as nucleophiles to compounds of formula (IV) to allow the preparation of more highly substituted amines of formula (III). i Such Grignard addition to nitrile is carried out in the presence of Pr)4) in an inert solvent such as diethyl ether, tert-butyl methyl ether and cyclopentyl methyl ether (see Synlett [Synthesis Express] 2007, (4), 652-654). This reaction is shown in Scheme 3.

[0310]

[0311] A compound having formula (IV) (wherein R 1 , R 2 , R 3 , R 4 , R 10 , R 11 , R 12 , R 13 and Q is as defined above for compounds of formula (I)) can be prepared by those skilled in the art according to known methods. More specifically, compounds of formula (IV) and intermediates thereof can be prepared from compounds of formula (V), as shown in Scheme 4.

[0312]

[0313] For example, a compound having formula (IV) (wherein R 1 , R 2 , R 3 , R 4 , R 10 , R 11 , R 12 , R 13 and Q are as defined above for compounds of formula (I), and R 4 Instead of hydrogen, the alkylation agent R can be prepared by one skilled in the art by using a strong base (such as n-butyl lithium or sodium hydride) in an inert solvent (such as tetrahydrofuran) at low temperature, followed by the addition of a suitable alkylating agent R 4 -X 0 (Where X 0 is halogen) (eg iodomethane) and a compound having formula (IVa) (wherein R 4 is hydrogen, and R 1 , R 2 , R 3 and Q is as defined above for compounds of formula (I)). Compounds of formula (IVa) (wherein R 4 is hydrogen, and R 1 , R2 , R 3 , R 10 , R 11 , R 12 , R 13 and Q is as defined above for compounds of formula (I)) can be prepared from an alcohol of formula (V) by treatment with cyanotrimethylsilane (TMSCN) in the presence of a base (such as lithium carbonate) in a nonpolar solvent (such as dichloromethane) at a temperature between 0°C and the boiling point of the reaction mixture. Such transformations are well known in the literature under various conditions, for example as described in Org. Lett. [Organic Chemistry Communications] 2008, 10, 4570 and references therein. This reaction is shown in Scheme 4.

[0314] Compounds of formula (V) can be prepared from compounds of formula (VI), prepared from any of compounds of formula (VIa), (VIb), (VIc), (VId) or (VIe), respectively, as shown in Scheme 5.

[0315]

[0316]

[0317] As shown in Scheme 5, a compound having formula (VII) (wherein R 1 , R 2 , R 3 , R 10 , R 11 , R 12 , R 13 is as defined above for compounds of formula (I), and X 01 is bromine or iodine) is metallated with a suitable reagent such as turbo Grignard reagent (isopropylmagnesium chloride-lithium chloride complex) or alkyl lithium (such as n-butyl lithium) to obtain an intermediate Grignard reagent or alkyl lithium reagent (M is MgX 01 or lithium). Such metals are inserted into CX 01 The reaction of the metallated substance (VIIa) with the compound of formula (VI) is well known to those skilled in the art and is usually carried out at a temperature between -78 ° C and rt in an inert solvent such as an ether (e.g., tert-butyl methyl ether or tetrahydrofuran, etc.). The solution of the metallated substance (VIIa) is then treated with (VIa), (VIb), (VIc), (VId) or (VIe) to obtain a compound of formula (V). Similar reactions of this type have been described, for example, in WO 2012 / 102297 and Bio.Med.Chem.Lett. [Bioorganic Chemistry and Medicinal Chemistry Communications] 2017, 27 (17), 4044-4050 (X 01is Br, n-butyllithium) and Angew.Chem.Int.Ed. [Applied Chemistry International Edition] 2016, 55(17), 5332-5336, US2014 / 0349990, WO 2002 / 004424, WO 2021 / 009068 (X 01 It is iodine, turbo Grignard reagent (isopropylmagnesium chloride-lithium chloride complex)).

[0318] Compounds of formula (VI) and (VII) are commercially available or readily prepared by methods known to those skilled in the art.

[0319] A further synthesis of compounds of formula (I) comprises treating a compound of formula (VIII) with a base such as sodium hydride or n-butyl lithium in an inert solvent such as tetrahydrofuran and subsequently reacting with a compound of formula (IX) wherein R 4 is as described in formula (I), and X 02 is a leaving group such as halogen, mesylate or tosylate) to produce a compound of formula (X). This reaction is shown in Scheme 6.

[0320]

[0321] The compound of formula (X) (wherein R is) is then treated with a strong base (such as sodium hydride) or an alkyl lithium base (such as n-butyl lithium) in an inert solvent (such as tetrahydrofuran or tert-butyl methyl ether) at a temperature between -78°C and room temperature. 1 , R 2 , R 3 and R 4 is as defined above for the compound of formula (I), followed by the addition of a compound of formula (XI), any one of the compounds of formula (XIa), (XIb), (XIc), (XId) or (XIe), respectively (where R 9 , R 10 , R 11 and R 12 is as defined above for compounds of formula (I), and X 03 is a leaving group such as halogen, preferably F, Cl or Br) to give a compound having formula (IV). This reaction is shown in Scheme 7.

[0322]

[0323] As previously described in Schemes 1, 2 and 3, a compound of formula (IV) is converted to a compound of formula (I). One skilled in the art will recognize that the conversion of compound (VIII) to a compound of formula (IV) can be performed sequentially or in the same reaction vessel, allowing the compound of formula (VIII) to be streamlined for conversion to a compound of formula (IV). This is described in more detail in the Preparation Examples.

[0324] A compound having formula (Ia) (wherein R 1 , R 2 , R 3 , R 5 ,Q,R 10 , R 11 , R 12 , R 13 , A 1 , A 2 , A 3 and Z 1 is as described above for compounds of formula (I), and R 4 and R 6 is hydrogen) can also be prepared by reacting a compound of formula (XII) (wherein R 5 The compound of formula (VI) is treated as described above for the compound of formula (I), any one of the compounds of formula (VIa), (VIb), (VIc), (VId) or (VIe), respectively, to obtain a compound of formula (XIII). These compounds can be separated and converted into compounds of formula (XIV) by treatment with anhydrides (such as trifluoroacetic anhydride) in an inert solvent (such as dichloromethane) in the presence of a base (such as triethylamine). This reaction is shown in Scheme 8.

[0325]

[0326] Those skilled in the art will appreciate that compounds of formula (VI) can be converted to compounds of formula (XIV) without the need to isolate intermediates of formula (XIII). Such reactions, known as Henry reactions, are well described in the literature, as demonstrated in Tetrahedron. 2001, 57(6), 915-945 and references cited therein. Compounds of formula (XIV) can be converted to compounds of formula (XV) by treatment with compounds of formula (VIIa) in an inert solvent such as tetrahydrofuran (see Scheme 5), known to those skilled in the art as the Michael reaction of organometallic compounds with nitroolefins. This reaction is shown in Scheme 9.

[0327]

[0328] Similar Michael additions of organometallic compounds to nitroolefins have been reported, for example, in Org. Lett. [Organic Chemistry Communications] 2007, 9, 85-87. The nitro group in the compound of formula (XV) is reduced to an amine to give a compound of formula (IIIa) (wherein R 1 , R 2 , R 3 , R 5 , R 10 , R 11 , R 12 , R 13 and Q are as defined above for compounds of formula (I), and R 4 and R 6 is hydrogen) can be achieved by various methods generally known to those skilled in the art, such as Bechamp reduction, or reduction with hydrogen in the presence of a metal catalyst. This reaction is shown in Scheme 10.

[0329]

[0330] Compounds of formula (IIIa) are converted to compounds of formula (Ia) by the methods described in Schemes 1 and 2.

[0331] Compounds of formula II are commercially available or can be synthesized as described hereinafter.

[0332] A compound having formula (IIb) wherein A 1 , A 2 , A 3 is N and Z 1 is as described in formula (I), i.e. a compound having formula (IIba)

[0333]

[0334] It can be obtained by reacting the following: a diazonium salt having the formula (XVI)

[0335]

[0336] Where Z 1 is as defined above in Formula I and Y - is the counterion, depending on the conditions under which the diazotization step is performed, e.g. Cl - or BF4 - , and a compound having formula (XVII),

[0337]

[0338] Where R0 It is a C1-C6 alkyl group. This reaction can be catalyzed by various silver salts, preferably silver acetate, and is carried out in various solvents (such as THF, DMF or toluene or mixtures thereof), usually at a temperature between 0°C and 25°C, in the presence of at least one equivalent of a base (such as sodium carbonate). These dipolar [3+2] cycloadditions are highly regioselective and are described in, for example, Tetrahedron [tetrahedron] 2020, 76 (14), 131063. Compounds of formula (XVI) as defined just before can be prepared by reacting a primary amine of formula (XVIII) with a diazotizing agent (such as a salt of nitrous acid, such as sodium nitrite). The solvent can be an aqueous solution of an acid, such as dilute hydrochloric acid or tetrafluoroboric acid. The counterion Y - Defined by the acid used. Diazotization reactions are commonly used in organic syntheses, even on an industrial scale, and are known to the person skilled in the art.

[0339] In order to reduce the risk of decomposition of the intermediate of formula (XVI), the diazotization step and the cycloaddition step can be carried out sequentially without the need to isolate (XVI). This variant is also described in Tetrahedron [Tetrahedron] 2020, 76 (14), 131063. The chemical process is summarized in Scheme 11:

[0340]

[0341] Compounds of formula (XVII) are commercially available, and compounds of formula (XVII) (e.g., R 0 It is methyl, CAS [6832-16-2]).

[0342] Very similarly, compounds of formula (IIba) (wherein A 1 , A 2 , A 3 is N and Z 1 is as described in formula (I)) can be obtained by making a compound having formula (XIX):

[0343]

[0344] Where R 0 is a C1-C6 alkyl group and Ar 1is phenyl or p-tolyl, reacted with a compound of formula (XVI) in the presence of a base (e.g. pyridine) at a temperature of from -50°C to 50°C to produce a compound of formula (IIba). Such reactions have good precedents in the literature, such as Chem. Comm. [Chemical Communications] 2017, 53 (69), 9620-9623, Angew. Chem. Int. Ed. [Applied Chemistry International Edition] 2017, 56 (47), 15044-15048 and J. Am. Chem. Soc. [American Chemical Society] 2016, 138 (44), 14609-14615. The compound of formula (XXVIII) is prepared as described in the literature cited above and exemplified in the preparation examples of the present application.

[0345] Alternatively, a compound of formula (IIba) wherein A 1 , A 2 and A 3 is N and Z 1 is as defined in formula (I), can be obtained by coupling a compound having formula (XX),

[0346]

[0347] Among them A 1 , A 2 and A 3 is N, and R 0 is as described above, with a boronic acid derivative of formula (XXI),

[0348]

[0349] Where Z 1 is as defined in formula I. This Chan-Lam type coupling reaction is usually carried out in a solvent (such as dichloromethane) in the presence of a catalytic amount of a copper-based catalyst, at a mild reaction temperature, in the presence of a base (such as potassium carbonate), in the atmosphere or under oxygen. It should be noted that compounds of formula (XX) (wherein A 1 , A 2 and A 3 N) exists in tautomeric forms.

[0350]

[0351] Those skilled in the art will envision that the coupling product of this reaction may be one of the regioisomers or a mixture thereof, but when the reaction conditions are selected as described in J. Org. Chem. 2014, 79, 6703-6707, the reaction shows excellent regioselectivity for compounds of formula (IIba). Those skilled in the art will recognize that this Chan-Lam coupling is a general method for preparing compounds of formula (IIb). Examples have been shown in the literature for compounds of formula (IIbb)

[0352]

[0353] Where Z 1 , R 12a and R 0 As previously defined (see J. Med. Chem. 2018, 61, 8, 3370-3388 and WO 14 / 041106), compounds of formula (IIbc) and (IIbd)

[0354]

[0355] Where Z 1 , R 12a , R 13a , R 14a and R 0 is defined as in formula (I) (see WO 15 / 155626, EP 2390252) and a compound of formula (IIbe)

[0356]

[0357] Where Z 1 , R 12a , R 13a , R 14a and R 0 is as defined in formula (I) (see J. Med. Chem. 2017, 60(14), 6166-6190, Org. Lett. 2008, 10(8), 1653-1655 and Bio. Med. Chem. Lett. 2009, 19(5), 1451-1456), as representative examples.

[0358] For preparing a compound having formula (IIba) (wherein A 1 , A 2 and A 3 is N and Z 1Another method wherein (I) is as defined in formula (I) is shown in Scheme 12.

[0359]

[0360] As shown in Scheme 12, the sequence begins with diazotization of a compound of formula (XVIII) as described previously above and then with a compound of formula (XXII) (wherein R 0 is C1-C6 alkyl) to produce a compound of formula (XXIII). 1 and R 0 is as defined previously) and then treated with aqueous ammonia in a miscible organic solvent (e.g. tetrahydrofuran or 2-methyltetrahydrofuran) at a temperature between 0°C and 30°C to obtain a compound of formula (XXIV). Finally, the compound of formula (XXIV) is diazotized with a salt of nitrous acid (e.g. sodium nitrite) at a temperature between -20°C and 0°C in a slightly acidic medium (e.g. acetic acid or aqueous hydrochloric acid) resulting in spontaneous cyclization of the diazonium salt formed to a tetrazole compound of formula (IIba). The sequence of reactions has previously been described in WO 13 / 087805.

[0361] The compound of formula (IIb) can also be prepared by: reacting a compound of formula (XX)

[0362]

[0363] Alkylation with a compound of formula (XXIV)

[0364] z 1 -x 0 (XXIV)

[0365] Where Z 1 is as previously described under Formula I and X 0 is a halogen, preferably chlorine, bromine or iodine, in the presence of a base (for example) and an alkaline earth metal base (such as NaOH, KOH, LiOH, Cs2CO3, K2CO3, etc.), in an inert aprotic or protic solvent. Such alkylations are well known to those skilled in the art and have been used in this context to prepare compounds of formula (IIb), as described, for example, in WO 14 / 168221; WO 10 / 043000; and WO 14 / 32498. Those skilled in the art will recognize that this can result in mixtures of regioisomeric compounds that can be separated by chromatographic techniques, or that pure isomers can be obtained by judicious choice of conditions and additives (for example palladium catalysts for the so-called Buchwald amination). For compounds wherein Z1 In the case of heteroaryl or aryl, the SnAr reaction (with or without copper catalysis) can be used to prepare compounds having formula (IIb) (see, for example, Polyhedron 2019, 165, 22-30; US 2018 / 0170909; Org. Lett. 2022, 24 (20), 3620-3625, J. Org. Chem. 2017, 82 (14), 7420-7427, Chem. Comm. 2021, 57 (57), 7047-7050, ACS Catalysis [ACS Catalysis] 2019, 9 (12), 10674-10679, Synthesis [Synthesis] 2017, 49 (23), 5120-5130, J. Org. Chem. [Journal of Organic Chemistry] 2019, 84 (12), 8160-8167, and references cited therein).

[0366] Additional compounds according to the invention may be prepared by derivatization using a key central intermediate at a later stage of the synthesis. For example, a compound of formula (I) wherein Q is Q1 and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , A 1 , A 2 , A 3 and Z 1 is as defined above for compounds of formula (I), and X 04 is halogen, preferably bromine or chlorine, for example, a compound of formula (Ia):

[0367]

[0368] This allows for further chemical reactions such as palladium-catalyzed carbonylations, Suzuki reactions, Stiller couplings, copper-catalyzed introduction of sulfonyl, haloalkyl, and cyano moieties, and SnAr reactions with various nucleophiles.

[0369] An example of such a reaction is shown in Scheme 13.

[0370]

[0371] As shown in Scheme 13, a compound having formula (I) wherein Q is Q1 and R 1 , R 2, R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , A 1 , A 2 , A 3 and Z 1 is as defined above for compounds of formula (I), and R 9 is a cyano group, i.e. a compound of formula (Ib)) can be obtained from a compound of formula (Ia) by treatment with an inorganic cyanide source, such as CuCN, in an inert solvent, such as dimethylformamide (DMF) or N-methyl-2-pyrrolidone, at a temperature between 0°C and 150°C. Such reactions are well known in the literature, for example, in J. Het. Chem. [Journal of Heterocyclic Chemistry] 1987, 24 (2), 373-6, Liebigs Ann. Chem. [Liebig Chemical Yearbook] 1994, (10), 1049-53, and Org. Prep. Proc. Int. [International Organic Preparation and Procedure] 1985, 17 (6), 391-9. Other methods for introducing a cyano group by replacing a halogen atom are known in the art. See, for example, Science of Synthesis [Synthesis Science] 2004, 19, 173-195.

[0372] A compound of formula (I) wherein Q is Q1 and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , A 1 , A 2 , A 3 and Z 1 is as defined above for compounds of formula (I), and R 9a is a C1-C4 haloalkyl group, i.e. a compound of formula (Ic)) can be prepared by reacting a compound of formula (XXV) (wherein R 9a is C1-C4 haloalkyl) to treat a compound having formula (Ia) (wherein Q is Q1, and R 1 , R 2 , R 3 , R 4 , R5 , R 6 , R 10 , R 11 , R 12 , A 1 , A 2 , A 3 and Z 1 is as defined above for compounds of formula (I), and X 04 is halogen, preferably bromine). Such reactions are known in the literature (Org. Lett. [Organic Chemistry Communications] 2014, 16 (6), 1744-1747). A compound of formula (I) (wherein Q is Q1, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , A 1 , A 2 , A 3 and Z 1 is as defined above for compounds of formula (I), and R 9b is phenyl, 5-membered or 6-membered heteroaryl or C3-C6 cycloalkyl, wherein the 5-membered or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, and wherein any of the phenyl, 5-membered or 6-membered heteroaryl and C3-C6 cycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkoxy, i.e., a compound of formula (Id)) can be prepared by Suzuki reaction (as shown in Scheme 13), which comprises, for example, reacting a compound of formula (Ia) (wherein X 04 is a leaving group, such as, for example, chlorine, bromine or iodine) and a compound of formula (XXVIa) wherein Y b1 It may be a boron-derived functional group such as, for example, B(OH)2 or B(OR b1 )2, where R b1 Can be C1-C4 alkyl or two groups OR b1The reaction is carried out by a palladium-based catalyst (e.g., tetrakis(triphenylphosphine)-palladium or (1,1'-bis(diphenylphosphino)-ferrocene) palladium dichloride-dichloromethane (1:1 complex)) in the presence of a base (e.g., sodium carbonate or cesium fluoride) in a solvent or solvent mixture (e.g., a mixture of 1,2-dimethoxyethane and water, or dioxane and water, or methyltetrahydrofuran and water), preferably under an inert atmosphere. The reaction temperature may preferably range from room temperature to the boiling point of the reaction mixture. Such Suzuki reactions are well known to those skilled in the art and have been reviewed in, for example, J. Organomet. Chem. 1999, 576, 147-168.

[0373] Alternatively, the compound of formula (Ic) can be prepared by reacting a compound of formula (XXVIb) (wherein Y b2 The invention relates to a method for preparing the present invention by the Stiehler reaction of a compound of formula (Ia) and a trialkyltin derivative, preferably tri-n-butyltin. Such a Stiehler reaction is carried out in the presence of a palladium catalyst (e.g., tetrakis(triphenylphosphine)palladium(0) or (1,1'-bis(diphenylphosphino)-ferrocene)palladium dichloride-dichloromethane (1:1 complex)), in an inert solvent (e.g., DMF, acetonitrile, or dioxane), optionally in the presence of an additive (e.g., cesium fluoride, or lithium chloride), and optionally in the presence of another catalyst (e.g., copper(I) iodide). Such Stiller couplings are also well known to those skilled in the art and have been described, for example, in J. Org. Chem. 2005, 70, 8601-8604, J. Org. Chem. 2009, 74, 5599-5602, and Angew. Chem. Int. Ed. 2004, 43, 1132-1136. A large number of compounds of formula (XXVIa) and (XXVIb) are commercially available or can be prepared by those skilled in the art.

[0374] Additional compounds obtainable from compounds of formula (Ia) are shown in Scheme 14.

[0375]

[0376] As shown in Scheme 14, a compound having formula (I) wherein Q is Q1 and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R12 , A 1 , A 2 , A 3 and Z 1 is as defined above for compounds of formula (I), and X 04 is a leaving group such as chlorine, bromine or iodine, i.e. a compound of formula (Ia)) can be treated with a compound of formula (XXVII) under Stiller reaction conditions to obtain a compound of formula (Ie). The compound of formula (Ie) can be isolated or directly hydrolyzed under aqueous acidic conditions to obtain a compound of formula (If). Such reactions are known in the literature and have been described, for example, in Synthesis 2001, (10), 1551-1555 and Tetrahedron 2001, 57 (13), 2507-2514. By reacting a compound (or a salt thereof) (wherein R is a leaving group such as chlorine, bromine or iodine) in an inert solvent (such as methanol, ethanol, tetrahydrofuran, methyl), optionally in the presence of an inorganic base (such as sodium carbonate or potassium carbonate) or an organic base (such as triethylamine, etc.) with a compound of formula (XXVIII) (or a salt thereof) 13 The compound having the formula (If) can be converted into a compound having the formula (Ig) (wherein Q is Q1, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , A 1 , A 2 , A 3 and Z 1 is as defined above for compounds of formula (I), and R 13 is hydrogen or C1-C4 alkyl). Many examples for the preparation of such oximes are known in the literature (see, for example, Molecules [molecules] 2019, 24, 2470 and references cited therein) and are familiar to those skilled in the art.

[0377] It can be made from a compound having formula (I) (wherein Q is Q1, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , A 1 , A2 , A 3 and Z 1 is as defined above for compounds of formula (I), and X 04 Further compounds prepared by using a leaving group like for example chloro, bromo or iodo, ie compounds having formula (Ia), are shown in Scheme 15.

[0378]

[0379] As shown in Scheme 15, compounds of formula (Ia) can be carbonylated to give compounds of formula (I), i.e., having R 14 C1-C4 alkyl compounds of formula (Ih) wherein Q is Q1, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , A 1 , A 2 , A 3 and Z 1 is as defined above for compounds of formula (I). In such alkoxycarbonylation, a compound of formula (Ia) is reacted with carbon monoxide, typically under pressure, in the presence of a metal catalyst such as a palladium catalyst (e.g. palladium(II) acetate, [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) chloride (Pd(dppf)Cl2), bis(triphenylphosphine)palladium(II) chloride (PdCl2(PPh3)2) or bis(diphenylphosphino)propane]palladium(II) (PdCl2(dippp)), optionally in the presence of a phosphine ligand (e.g. triphenylphosphine or 1,1'-bis(diphenylphosphino)ferrocene), in the presence of an alcohol (R 14 OH) (typically methanol or ethanol) (where R 14is C1-C4 alkyl), optionally in the presence of a cosolvent such as toluene, dioxane or N,N-dimethylformamide, and preferably in the presence of a base such as, for example, trimethylamine, at temperatures between 20° C. and 200° C., preferably between 50° C. and 180° C. Such carbonylation reactions are well known to those skilled in the art and also in the literature (see J. Org. Chem. 2008, 73, 7102-7107, and references cited therein). Such compounds of formula (Ih) can be easily saponified to compounds of formula (Ii) under conditions known to those skilled in the art such as, for example, conditions of aqueous sodium hydroxide, potassium hydroxide or lithium hydroxide in methanol, ethanol, tetrahydrofuran or dioxane at room temperature or up to reflux. Alternatively, treatment of ester compounds of formula (Ih) with a halide anion, preferably chloride ions, for example derived from lithium chloride (or alternatively sodium chloride or potassium chloride) in a solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone, can also produce carboxylic acid compounds of formula (Ii). The reaction temperature for such O-demethylation preferably ranges from 20°C to the boiling point of the reaction mixture, or the reaction can be carried out under microwave irradiation. Compounds of formula (Ii) can be converted to amides of formula (I), i.e. compounds of formula (Ij), wherein R 15 and R 16 are independently hydrogen or C1-C4 alkyl, wherein Q is Q1, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , A 1 , A 2 , A 3 and Z 1 is as defined for compounds of formula (I). Such reactions generally involve activation of the carboxyl group followed by reaction with a compound R 15 R 16 NH treatment or use of coupling agents in the presence of a compound having formula R 15 R 16 Direct conversion of the acid to the amide is carried out by treatment of the NH compound. These methods have been discussed above in Schemes 1 and 2.

[0380] Further, the compound of formula (Ij) can be converted into the compound of formula (I) by the so-called Curtius rearrangement, i.e., R 9 The amino compound has the formula (Ik), wherein Q is Q 1, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , A 1 , A 2 , A 3 and Z 1 Is as defined above for compounds of formula (I). In the Curtius rearrangement, a compound of formula (Ij) is treated with an organic azide in the presence of a suitable base and optionally in the presence or absence of a Lewis acid in an inert solvent at a temperature between 50°C and 200°C. Examples of organic azides include TMSN3, sodium azide, diphenylphosphoryl azide or tosyl azide, and a suitable solvent may be toluene, xylene, THF or acetonitrile. Examples of suitable Lewis acids may include Zn(OTf)2 in particular. The isocyanate formed in the rearrangement reacts with water to form a carbamate, which is decarboxylated to the corresponding amine of formula (lk) under the reaction conditions. Alternatively, these reactions may be carried out in an alcohol (e.g., tert-butyl alcohol) to allow the separation of tert-butyl carbamate. These in turn may be cleaved in a separate step by methods known to those skilled in the art with an acid (e.g., trifluoroacetic acid) to produce a compound of formula (Ik). Examples of such Curtius reactions have been reported, for example, in Org. Lett. [Organic Chemistry Communications] 2005, 7, 4107-4110, J. Med. Chem. [Journal of Medicinal Chemistry] 2006, 49 (12), 3614-3627 and Tetrahedron [Tetrahedron] 1974, 30, 2151-2157. The compound of formula (Ik) thus obtained can be amidated to a compound of formula (Im) (wherein Q is Q1 and R is R2) by treatment with a compound of formula (XIX) according to the amidation method described above. 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , A 1 , A 2 , A 3 and Z 1 is as defined above for compounds of formula (I), and R 18Those skilled in the art will recognize that this chemical reaction can be applied to any compound of formula (I) wherein Q is Q1, Q2, Q3, Q4, or Q5, located at any position of the heterocycle of formula Q (i.e., R 9 , R 10 , R 11 or R 12 ), when the following group is a leaving group such as a halogen atom.

[0381] The compound of formula (I) as defined in any embodiment of the present invention can be converted into another compound as defined in any embodiment of the present invention in a manner known per se by replacing one or more substituents of the starting compound with another or other substituents according to the present invention in a conventional manner. It will also be appreciated by those skilled in the art that the compound of formula (I) can be further converted into another derivative of formula (I) by, for example, alkylation, nucleophilic substitution, elimination, C-C bond formation reaction in the presence of a metal catalyst, heteroatom-carbon bond formation in the presence of a metal catalyst, oxidation and reduction.

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

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

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

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

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

[0387] The compounds of formula (I) and, where appropriate, their tautomers (in each case in free form or in salt form) can be present in the form of one of the possible isomers or in the form of mixtures of these isomers, for example in the form of pure isomers (such as enantiomers and / or diastereomers) or in the form of isomer mixtures (such as enantiomeric mixtures, for example racemates; diastereomeric mixtures or racemic mixtures), depending on the number of asymmetric carbon atoms present in the molecule, the absolute and relative configuration and / or on the configuration of non-aromatic double bonds present in the molecule; the invention relates to the pure isomers and also to all possible isomer mixtures and is to be understood in this sense in each case above and below, even in each case without specific mention of stereochemical details.

[0388] The compounds of the present invention having formula (I) exhibit an asymmetric carbon atom at the bis-benzyl position:

[0389] The skilled artisan will well appreciate that both enantiomers are within the scope of the present invention.

[0390] Diastereomeric mixtures or racemic mixtures of compounds of formula (I) in free form or in salt form, which may be obtained depending on the starting materials and procedures chosen, can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and / or chromatography.

[0391] Enantiomeric mixtures that can be obtained in an analogous manner (such as racemates) can be resolved into the optical enantiomers by known methods, for example by recrystallization from optically active solvents; by chromatography on chiral adsorbents, such as high performance liquid chromatography (HPLC) on acetylcellulose; by cleavage with specific immobilized enzymes with the aid of suitable microorganisms; via the formation of containing compounds, for example using chiral crown ethers, in which only one enantiomer is complexed; or by conversion into diastereomeric salts, for example by reacting the basic end product racemate with an optically active acid (such as a carboxylic acid, such as camphoric acid, tartaric acid or malic acid, or a sulfonic acid, such as camphorsulfonic acid), and separating the diastereomeric mixtures that can be obtained in this way, for example by fractional crystallization based on their different solubility, thereby obtaining diastereomers, from which the desired enantiomer can be freed by the action of suitable reagents (such as basic reagents).

[0392] Pure diastereomers or enantiomers can be obtained according to the invention not only by separation of the appropriate isomer mixtures but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the method according to the invention with starting materials having the appropriate stereochemistry.

[0393] If the individual components have different biological activities, it is advantageous to separate or synthesize the biologically more effective isomers, such as enantiomers or diastereomers or isomer mixtures, such as enantiomeric mixtures or diastereomeric mixtures, in each case.

[0394] As an example, compounds with more than one asymmetric carbon atom may exist in diastereomeric forms, which may optionally be separated using, for example, supercritical fluid chromatography (SFC) chromatography with a chiral column. Such diastereomers may show different fungicidal activity profiles, but all isomers and diastereomers form part of the present invention.

[0395] The compounds of the present invention having the formula (I) exhibit two asymmetric carbon atoms. The relationship between the enantiomers and diastereomers of the compounds having the formula (I) is shown below.

[0396]

[0397] Those skilled in the art are well aware of the diastereomers and enantiomers of the above formula (I) (wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , A 1 , A 2 , A 3 ,Q,R 10 , R 11 , R 12 , R 13 and Z 1 are as defined for formula (I)) are within the scope of the present invention.

[0398] Further, those skilled in the art are well aware that the above-mentioned diastereomers and enantiomers apply to compounds of formula (Ia), (Ia-A), (Ia-B) and (Ia-C) (where R 1 , R 2 , R 3 , R 4 , R 5 , R6 , R 7 , R 8 , R 9 , A 1 , A 2 , A 3 ,Q,R 10 , R 11 , R 12 , R 13 and Z 1 is as defined for formula (I)) and is within the scope of the present invention.

[0399] The compounds of the formula (I) and, where appropriate, their tautomers (in each case in free form or in salt form) can, if appropriate, also be obtained in the form of hydrates and / or include further solvents, such as those which can be used for crystallization of compounds present in solid form.

[0400] As already indicated, surprisingly, it has now been found that the compounds of the invention having formula (I) have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases caused by fungi.

[0401] Compounds with formula (I) according to the present invention can be used as active ingredients such as for controlling plant pests in the agricultural sector and related fields of use, or for controlling spoilage microorganisms or potentially harmful organisms to people on non-living materials. The feature of these novel compounds is that they have excellent activity at low application rates, and plants tolerate well and are safe for the environment. They have very useful therapeutic, preventive and systemic characteristics and can be used to protect a lot of cultivated plants. Compounds with formula (I) can be used to suppress or destroy the harmful organisms that occur on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of different useful plant crops, while also protecting those plant parts that grow later from, for example, the infringement of phytopathogenic microorganisms.

[0402] The invention further relates to a method for controlling or preventing infection of plants or plant propagation materials and / or harvested food crops susceptible to attack by microorganisms by treating the plants or plant propagation materials and / or harvested food crops, wherein an effective amount of a compound of formula (I) according to the invention is applied to the plant, its part or its locus.

[0403] As used herein, the term "control" when used in the context of infestation of plants or plant propagation material and / or harvested food crops, means reducing the number of pests, eliminating pests and / or preventing further pest damage so that damage to plants or to plant-derived products is reduced.

[0404] The term "prevent" when used in the context of an infestation of plants or plant propagation material and / or harvested food crops refers to avoiding symptoms due to attack by microorganisms or fungal infection (fungal growth).

[0405] It is also possible to use the compounds of formula (I) according to the present invention as fungicides. As used herein, the term "fungicide" means a compound that controls, alters, or prevents fungal growth. The term "fungicide effective amount" when used means the amount of such a compound or a combination of such compounds that can have an effect on fungal growth. The effects of control or alteration include all deviations from natural development, such as killing, retardation, etc., and prevention includes forming a barrier or other defense in or on the plant to prevent fungal infection.

[0406] It is also possible to use the compound with formula (I) according to the present invention as a seed dressing for treating plant propagation materials (for example, seeds, such as fruits, tubers or grains) or plant cuttings, for protecting against fungal infections and against plant pathogenic fungi present in the soil. Propagation materials can be treated with a composition comprising a compound with formula (I) before planting: for example, seed dressing can be used before sowing. The active compound with formula (I) can also be applied to grains (coating) by dipping seeds in a liquid formulation or by coating them with a solid formulation. It is also possible to apply the composition to the planting site when planting propagation materials, for example, to the furrow of the seed during sowing. The invention further relates to such methods for treating plant propagation materials, and to the plant propagation materials so treated.

[0407] Furthermore, the compounds of formula (I) according to the invention can be used for controlling fungi in related fields, for example in the protection of industrial materials (including wood and wood-related technical products), in food storage, in hygiene management.

[0408] Additionally, the present invention can be used to protect non-living materials such as wood, siding and paint from fungal attack.

[0409] The compounds of formula (I) according to the invention are effective, for example, against fungi and fungal vectors of diseases and phytopathogenic bacteria and viruses. These fungi and fungal vectors of diseases and phytopathogenic bacteria and viruses are, for example: Psoralea corylifolia, Alternaria species, Aphanomyces species, Aspergillus species, Aspergillus species (including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terreus), A. pullulans species (including A. pullulans), Blastomyces dermatitidis, B. graminis, B. graminis, B. oleraceus ... lactucae), Botrytis species (including B. dothidea, B. obtusa), Botrytis species (including B. cinerea), Candida species (including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis), Cephaloascus fragrans, Cephaloascus species, Cercospora species (including C. arachidicola), Cercosporidium personatum), Cladosporium species, Claviceps, Coccidioides immitis, Coccidioidomyces species, Colletotrichum species (including C. musae), Cryptococcus neoformans, Diaporthe species, Subsporus species, Entomophthora species, Entomophthora species, Epidermophyton species, Erwinia amylovora, Powdery mildew species (including E. cichoracearum), Eutypa lata, Fusarium species (including Fusarium culmorum, Fusarium graminearum, Fusarium langsethiae, Fusarium moniliforme, Fusarium gloeosporium, Fusarium solani, Fusarium oxysporum, Fusarium laminarum), Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena), Gloeosporium musarum, Glomerella cingulate, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium species, H. capsulatum species, Histoplasma species (including H.capsulatum), red thread pathogen, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum species, Streptoceras species, Mucor species, Mycosphaeria species (including Mycosphaeria graminicola and M. pomi), tree blight pathogen, spruce pathogen, Paracoccidioides species, Penicillium species (including Penicillium digitatum and Penicillium italicum), True mold species, Peronospora species (including Peronospora maize, Peronospora philippinarum and Peronospora kaoliang), Peronospora species, Septoria glume, Puccinia pachyrhizi, Phellinus igniarus, Phyllinus species, Phomopsis species, Phomopsis graminicola viticola), Phytophthora species (including Phytophthora infestans), Plasmopara species (including P. hallii, P. viticola), Lachnosporium species, Pseudocercosporella species (including P. leucotricha), Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides), Pseudomonas species, Pseudoperonospora species (including Cucumis sativus and Pseudoperonospora spp.), Pseudopeziza tracheiphila, Peronospora species (including P. hordei, P. recondita, P. Striformis, P. triticina), Sclerotinia species, Pyricularia species, Pythium species (including P. oryzae), Pythium species (including Pythium ultimum), Pythium species, Rhizomucor species, Rhizomucor pusillus, Rhizopus arrhizus, Rhizosporium species, Trichosporon species (including Scedosporium apiosporum and Scedosporium prolificum), Schizothyrium species. pomi), Sclerotinia species, Sclerotium species, Septoria species (including S. nodorum, S.tritici), Sphaerotheca macularis, Sphaerotheca fusca, (Sphaerotheca fuliginea), Sporothorix species, Stagonospora nodorum, Stemphylium species, Stereum hirsutum, Thanatephorus cucumeris), Thielaviopsis basicola, Tilletia species, Trichoderma species (including Trichoderma harzianum, Trichoderma pseudokoningii, Trichoderma viride), Trichophyton species, Pseudomonas species, Uncinaria vitis, Urocystis species, Ustilago species, Venturia species (including V. inaequalis), Verticillium species, and Xanthomonas species.

[0410] The compounds of formula (I) according to the invention can be used, for example, for lawns, ornamental plants such as flowers, shrubs, broad-leaved trees or evergreen plants, such as conifers, as well as tree injection, pest management and the like.

[0411] In the context of the present invention, target crops and / or useful plants to be protected typically include perennial and annual crops, such as berry plants, for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals, for example barley, maize (corn), millet, oats, rice, rye, sorghum, triticale and wheat; fiber plants, for example cotton, flax, hemp, jute and sisal; field crops, for example sugar beets and fodder beets, coffee beans, hops, mustard, rapeseed (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees, for example apples, apricots, avocados, bananas, cherries, citrus, nectarines, peaches, pears and plums; grasses, for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, rye, etc. Augustine grass and zoysia grass; herbs such as basil, borage, chives, cilantro, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes such as beans, lentils, peas and soybeans; nuts such as almonds, cashews, groundnuts, hazelnuts, peanuts, pecans, pistachios and walnuts; palm plants such as oil palms; ornamental plants such as flowers, shrubs and trees; other trees such as cocoa, coconut, olive and rubber trees; vegetables such as asparagus, eggplant, broccoli, cabbage, carrots, cucumbers, garlic, lettuce, zucchini, melon, okra, onions, peppers, potatoes, squash, rhubarb, spinach and tomatoes; and vines such as grapes.

[0412] The term "useful plants" is to be understood as also including useful plants which have been rendered tolerant to herbicides such as bromoxynil or classes of herbicides such as, for example, HPPD inhibitors, ALS inhibitors such as primisulfuron, primisulfuron and trifloxysulfuron, EPSPS (5-enol-pyruvate-shikimate-3-phosphate-synthetase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen oxidase) inhibitors as a result of conventional breeding methods or genetic engineering. Examples of crops which have been rendered tolerant to imidazolinones such as imazamox by conventional breeding methods (mutagenesis) are Summer rapeseed (canola). Examples of crops that have been rendered tolerant to herbicides or herbicides by genetic engineering methods include glyphosate-resistant and glufosinate-resistant maize varieties, which are based on Herculex and Commercially available under the trade name ANTIQUID®.

[0413] The term "useful plants" is to be understood as also including useful plants which have been transformed by the use of recombinant DNA techniques in such a way that they are able to synthesize one or more selectively acting toxins, as are known, for example, from toxigenic bacteria, in particular those of the genus Bacillus.

[0414] Examples of such plants are: (corn variety expressing CryIA(b) toxin); YieldGard (corn variety expressing CryIIIB(b1) toxin); YieldGard (maize varieties expressing CryIA(b) and CryIIIB(b1) toxins); (corn variety expressing Cry9(c) toxin); Herculex (a corn variety expressing the CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) that confers tolerance to the herbicide glufosinate ammonium); NuCOTN (cotton variety expressing CryIA(c) toxin); Bollgard (cotton variety expressing CryIA(c) toxin); Bollgard (cotton varieties expressing CryIA (c) and CryIIA (b) toxins); (cotton varieties expressing VIP toxin); (potato variety expressing CryIIIA toxin); Nature- GT Advantage (GA21 glyphosate tolerance trait), CBAdvantage (Bt11 corn borer (CB) trait), RW (corn rootworm trait) and

[0415] The term "crops" is to be understood as also including crop plants which have been transformed using recombinant DNA techniques in such a way that they are able to synthesize one or more selectively acting toxins, such as are known, for example, from toxigenic bacteria, in particular those of the genus Bacillus.

[0416] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus japonicus; or insecticidal proteins from Bacillus thuringiensis, such as □-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or vegetative insecticidal proteins (Vips), for example Vip1, Vip2, Vip3, or Vip3A; or insecticidal proteins of bacterial colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophila, or Xenorhabdus nematophila. nematophilus); toxins produced by animals, such as scorpion toxins, spider toxins, bee toxins and other insect-specific neurotoxins; toxins produced by fungi, such as streptomycin, plant lectins, such as pea lectin, barley lectin or snowdrop lectin; agglutinin; protease inhibitors, such as trypsin inhibitor, silk proteinase inhibitor, potato glycoprotein, cystatin, papain inhibitor; ribosome inactivating protein (RIP), such as ricin, maize-RIP, abrin, luffa seed toxin protein, saponin protein or bryophyllin; steroid metabolizing enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as sodium channel or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

[0417] Further, in the context of the present invention, delta-endotoxins (e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C) or vegetative insecticidal proteins (Vips) (e.g., Vip1, Vip2, Vip3 or Vip3A) are understood to include obviously also mixed toxins, truncated toxins and modified toxins. Mixed toxins are recombinantly produced by new combinations of different domains of those proteins (see, e.g., WO 2002 / 015701). Truncated toxins, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxins are replaced. In such amino acid replacements, it is preferred that non-naturally occurring protease recognition sequences are inserted into the toxins, such as, for example, in the case of Cry3A055, the cathepsin-G-recognition sequence is inserted into the Cry3A toxin (see WO 2003 / 018810).

[0418] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed in, for example, EP-A-0 374 753, WO 93 / 07278, WO 95 / 34656, EP-A-0 427 529, EP-A-451 878 and WO 2003 / 052073.

[0419] Methods for preparing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP-A-0 367474, EP-A-0 401 979 and WO 90 / 13651.

[0420] The toxins contained in the transgenic plants render the plants tolerant to harmful insects. Such insects can be found in any insect taxonomic group but are particularly common among beetles (Coleoptera), two-winged insects (Diptera), and moths (Lepidoptera).

[0421] Transgenic plants comprising 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 are: (corn variety expressing Cry1Ab toxin); YieldGard (corn variety expressing Cry3Bb1 toxin); YieldGard (corn varieties expressing Cry1Ab and Cry3Bb1 toxins); (corn variety expressing Cry9C toxin); Herculex (a corn variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) that confers tolerance to the herbicide glufosinate ammonium); NuCOTN (cotton variety expressing Cry1Ac toxin); Bollgard (cotton variety expressing Cry1Ac toxin); Bollgard (cotton varieties expressing Cry1Ac and Cry2Ab toxins); (cotton varieties expressing Vip3A and Cry1Ab toxins); (potato variety, expressing Cry3A toxin); GT Advantage (GA21 glyphosate tolerance trait), CB Advantage (Bt11 corn borer (CB) trait) and

[0422] Further examples of such genetically modified crops are:

[0423] 1. Bt11 corn, from Syngenta Seeds SAS, Chemin del'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified corn, which is resistant to attack by European corn borer (Ostrinia nubilalis and Sesamia inermis) by transgenic expression of a truncated Cry1Ab toxin. Bt11 corn also transgenic expression of the PAT enzyme to obtain tolerance to the herbicide glufosinate ammonium.

[0424] 2. Bt176 corn, from Syngenta Seeds, 27 Hobbit Road, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified corn, which is resistant to attack by European corn borer (Ostrinia nubilalis and Sesamia inermis) by transgenic expression of Cry1Ab toxin. Bt176 corn also transgenic expression of PAT enzyme to obtain tolerance to the herbicide glufosinate ammonium.

[0425] 3. MIR604 corn, from Syngenta Seeds, 27 Rue Hobbitt, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. Corn made insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic corn plants is described in WO 2003 / 018810.

[0426] 4. MON 863 maize, from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses the Cry3Bb1 toxin and is resistant to certain coleopteran insects.

[0427] 5. IPC 531 cotton, from Monsanto Europe AB, 270-272 Avenue Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0428] 6.1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Genetically modified maize expressing the protein Cry1F for resistance to certain lepidopteran insects and the protein PAT for tolerance to the herbicide glufosinate ammonium.

[0429] 7. NK603×MON 810 maize, from Monsanto Europe 270-272 Boulevard Tervuren, B 1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. Made from a conventionally bred hybrid maize variety by crossing the genetically modified varieties NK603 and MON 810. NK603×MON 810 maize transgenically expresses the protein CP4 EPSPS obtained from the Agrobacterium strain CP4, rendering it tolerant to herbicides (contains glyphosate), and also Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstakia, which confers resistance to certain lepidopteran insects, including the European corn borer.

[0430] The compounds of formula (I) according to the invention can be used for controlling or preventing phytopathogenic diseases, in particular phytopathogenic fungi, such as Alternaria on fruits, vegetables and potatoes; Botrytis cinerea on strawberries, tomatoes, sunflowers, legumes, vegetables and grapes; Rhizoctonia solani on potatoes and vegetables; Uncinaria vitis on grapes; Cladosporium, bryozoans, powdery mildew and chlorophyll on cucurbits; Cercospora spp. on cucurbits and solanaceous crops; Fusarium spp. on cereals; Leptosphaeria spp. on cereals; and Saccharomyces spp. on cereals.

[0431] As used herein, the term "locus" means a place where or on which plants grow, or where seeds of cultivated plants are sown, or where seeds are to be placed in the soil. It includes soil, seeds, and seedlings, together with established vegetation.

[0432] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves and fruits.

[0433] The term "plant propagation material" should be understood as meaning the reproductive parts of a plant, such as seeds, which can be used for the propagation of a plant, and vegetative materials, such as cuttings or tubers (e.g., potatoes). For example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants can be mentioned. Germinated plants and young plants that will be transplanted after germination or after emergence can also be mentioned. These young plants can be treated completely or partially by dipping and protected before transplanting. Preferably, "plant propagation material" should be understood as meaning seeds.

[0434] The compound with formula (I) according to the present invention can be used in unmodified form, or preferably, together with the adjuvant conventionally adopted in the preparation field.For this purpose, they can be conveniently formulated as emulsifiable concentrates, pastes that can be coated, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granules and also capsules, for example in polymeric substances, in a known manner.For the type of composition, according to the intended purpose and the environment at that time, application methods are selected, such as spraying, atomizing, dusting, sowing, smearing or watering.Composition can also contain other adjuvants, such as stabilizers, defoamers, viscosity modifiers, adhesives or tackifiers, together with fertilizers, micronutrient donors or other preparations for obtaining special effects.

[0435] Suitable carriers and adjuvants, for example, for agricultural use, can be solid or liquid and are substances useful in formulation technology, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, adhesives, or fertilizers. Such carriers are for example described in WO 97 / 33890.

[0436] Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations contain anti-settling agents and dispersants, and may further contain wetting agents to enhance activity, as well as defoamers and crystal growth inhibitors. When used, these concentrates are diluted in water and usually applied as a spray to the area to be treated. The amount of active ingredient can range from 0.5% to 95% of the concentrate.

[0437] Wettable powders are in the form of finely divided particles that disperse easily in water or other liquid carriers. These particles contain the active ingredient retained in a solid matrix. Typical solid matrices include Fuller's earth, kaolin, silica and other easily wetted organic or inorganic solids. Wettable powders usually contain from 5% to 95% of the active ingredient plus a small amount of a wetting agent, dispersant or emulsifier.

[0438] Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquids and may consist entirely of the active compound and a liquid or solid emulsifier, or may also contain a liquid carrier such as xylene, heavy aromatic naphtha, isophorone and other non-volatile organic solvents. When used, these concentrates are dispersed in water or other liquids and are usually applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

[0439] Granular formulations include both extrudates and coarser granules and are usually applied to the area to be treated without dilution. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite, montmorillonite, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, crushed corn cobs, crushed peanut shells, sugar, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesium oxide, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate and other organic or inorganic materials that absorb or can be coated with active compounds. Granular formulations usually contain 5% to 25% active ingredients, which may include surfactants such as heavy aromatic naphtha, kerosene and other petroleum fractions, or vegetable oils; and / or adhesives such as dextrins, glues or synthetic resins.

[0440] Dusts are free-flowing mixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.

[0441] Microcapsules are typically droplets or particles of active ingredients encapsulated in an inert porous shell that allows the encapsulated material to escape into the environment at a controlled rate. The diameter of the encapsulated droplets is typically 1 to 50 microns. The encapsulated liquid typically accounts for 50% to 95% of the weight of the capsule and can also contain solvents in addition to the active compound. The encapsulated particles are usually porous particles, in which the porous membrane seals the particle pores and retains the active species in the form of a liquid inside the particle pores. The diameter of the particles typically ranges from 1 mm to 1 cm and preferably 1 mm to 2 mm. The particles are formed by extrusion, coagulation or spheroidization, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and carbon fine particles. Shell or membrane materials include natural and synthetic rubbers, fiber materials, styrene-butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

[0442] Other useful formulations for agrochemical applications include simple solutions of the active ingredient in a solvent such as acetone, alkylated naphthalenes, xylene and other organic solvents in which the active ingredient is completely soluble at the desired concentration. Pressurized sprays may also be used in which the active ingredient is dispersed in finely divided form due to evaporation of a low boiling dispersant solvent carrier.

[0443] Suitable agricultural adjuvants and carriers useful for formulating the compositions of the present invention in the above-mentioned formulation types are well known to those skilled in the art.

[0444] Liquid carriers that can be used include, for example, water, toluene, xylene, naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol rosin acid ester, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl Formamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol (diproxitol), alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, α-pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glycerol diacetate, glycerol monoethyl Acid esters, triacetin, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, cumene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, dichloromethane, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, poly Ethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols (such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc.), ethylene glycol, propylene glycol, glycerol and N-methyl-2-pyrrolidone. Water is generally the carrier of choice for diluting concentrates.

[0445] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite, Fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.

[0446] A wide range of surfactants are advantageously employed in the liquid and solid compositions, especially those designed to be diluted with a carrier prior to application. These agents, when used, generally comprise from 0.1% to 15% by weight of the formulation. They may be anionic, cationic, nonionic or polymeric in nature and may be employed as emulsifiers, wetting agents, suspending agents or for other purposes. Typical surfactants include alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylaryl sulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub.18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecanol-C.sub.16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; salts of dialkyl sulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitan esters, such as sorbitan 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 dialkyl phosphates.

[0447] Other adjuvants commonly used in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, defoamers, opacifiers, compatibilizing agents, antifoaming agents, masking agents, neutralizing and buffering agents, corrosion inhibitors, dyes, flavor enhancers, spreading agents, penetration aids, micronutrients, emollients, lubricants, and fixatives.

[0448] In addition, further, other biocidal active ingredients or compositions can be combined with the composition of the present invention, and used in the method of the present invention and applied simultaneously or sequentially with the composition of the present invention. When applied simultaneously, these other active ingredients can be prepared or mixed in, for example, a spray tank together with the composition of the present invention. These other biocidal active ingredients can be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and / or plant growth regulators.

[0449] Pesticides referred to herein using their common names are known, for example, from “The Pesticide Manual”, 15th edition, British Crop Protection Council 2009.

[0450] In addition, the compositions of the invention may also be administered with one or more inducers of systemic acquired resistance ("SAR" inducers). SAR inducers are known and described, for example, in U.S. Pat. No. 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.

[0451] The compound with formula (I) according to the present invention is usually used in the form of an agrochemical composition and can be applied to a crop area or plant to be treated simultaneously or sequentially with other compounds. For example, these other compounds can be fertilizers or micronutrient donors or other preparations that affect plant growth. They can also be selective herbicides or non-selective herbicides, together with insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with other carriers, surfactants or adjuvants that are commonly used in the formulation field to promote application.

[0452] The compounds of formula (I) according to the invention can be used in the form of (fungicide) compositions for controlling or protecting against phytopathogenic microorganisms, these compositions comprising as active ingredients at least one compound of formula (I) or at least one preferred individual compound as defined herein (in free form or in the form of an agrochemically usable salt) and at least one of the above-mentioned adjuvants.

[0453] Therefore, the present invention provides a composition, preferably a fungicidal composition, comprising at least one compound according to the present invention having formula (I), an agriculturally acceptable carrier and optionally an adjuvant. An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural carriers are well known in the art. Preferably, in addition to the compound of formula (I), the composition may also comprise at least one or more pesticidal active compounds, such as additional fungicidal active ingredients.

[0454] The compound with formula (I) according to the present invention can be the sole active ingredient of composition, or it can be mixed with one or more other active ingredients (such as pesticide, fungicide, synergist, herbicide or plant growth regulator) when appropriate.In some cases, other active ingredients can produce unexpected synergistic activity.

[0455] Examples of suitable additional active ingredients include the following: acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, aniline fungicides, antibiotic fungicides, aromatic fungicides, arsenic-containing fungicides, arylphenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged biphenyl fungicides, carbamate fungicides, phenylcarbamate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine fungicides, organophosphorus fungicides, Organotin fungicides, oxathiin fungicides, oxazole fungicides, benzenesulfamide fungicides, polysulfide fungicides, pyrazole fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungicides, quinone fungicides, quinoxaline fungicides, strobilurin fungicides, sulfonanilide fungicides, thiadiazole fungicides, thiazole fungicides, thiazolidine fungicides, thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, valinamide fungicides, and zinc fungicides.

[0456] Examples of suitable additional active ingredients include the following: petroleum oil, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenylbenzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylacetamide, 4-chlorophenylphenyl sulfone, acetothionil, aldicarb, sirox, fosfos, fenamiphos, fenamiphos hydrogen oxalate, amitraz, cypermethrin, arsenic trioxide, azobenzene, azophos, benomyl, benoxafos, benzyl benzoate, Ester, bixafen, bromethrin, bromophenazone, bromothion, bromothion, bromopyralid, buprofezin, butanone, butanone sulfone, butyl pyridaben, calcium polysulfide, toxaphene, chlormethoxam, trithion, cypermethrin, chlorpyrifos, chlormethoxam, chlormethoxam hydrochloride, chlormethoxam, chlormethoxam, chlormethoxam hydrochloride, chlormethoxam, chlormethoxam, chlormethoxam, chlormethoxam, ethyl chlormethoxam, chlormethoxam (chloromebuform), chlormethoxam, propyl chlormethoxam, chlormethoxam, chlormethoxam I, chlormethoxam II, chlormethoxam, closantel, fly poison Phosphorus, crotamiton, baclofos, thiophanate, fruit insect phosphorus, DCPM, DDT, dinoxon, dinoxon-O, dinoxon-S, endotoxin-methyl, endotoxin-O, endotoxin-O-methyl, endotoxin-S, endotoxin-S-methyl, endotoxin-S-methyl sulfone, antifungal, dichlorvos, dicliphos, chloranil, methylphos, dinex, dinex-diclexine, diclofenac-4 , dimethoate-6, ortho-dimethoate, nitropentyl, nitrooctyl, nitrobutyl, dimethoate, sulfodiphenyl, disulfiram, DNOC, dofenapyn, doramectin, indophos, eprinomectin, thiophos, ethidium, anti-mite azole, fenbutatin, fenthiocarb, fenpyrad, fenpyrad, fenpyrad, fenpyrad-8, fentrifanil, fluazifop-butyl, flufenoxuron, fluazifop-butyl, flufenoxuron, flufenoxuron, flufenoxantrone, FMC 1137, fenthion, fenthion hydrochloride, formparanate, γ-HCH, chloranil, benzyl chloranil, hexadecyl cyclopropane carboxylate, isothiocarb, jasmonate I, jasmonate II, iodine, lindane, propanil, cypermethrin, dithiophos, methylthiophene, cypermethrin, methyl bromide, cypermethrin, chloranil, milbemid, propylamine, monocrotophos, malathion, moxidectin, naled, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3 -pyridyl)methoxy]pyridazine-3-one, fluazifop, nikkomycin, pentocyanamide, pentocyanamide 1:1 zinc chloride complex, omethoate, isothiocarb, sulfone, pp'-DDT, parathion, permethrin, fenthion, phosalone, thiocyanate, phosphamidon, polychloroterpenes, polynactins, chloranil, cypermethrin, propoxur, ethidium, thiophos, pyrethrin I, pyrethrin II, pyrethrin, pyridazithion, pyrimithiophos,Quinalphos, quintiofos, R-1492, glyphosate, rotenone, octamethrin, clomar, selamectin, thiothion, SSI-121, sulfluramid, sulfotep, sulfur, flumethoxam, τ-fluvalinate, TEPP, tert-butylcarb, tetrachlorothiazide, thiafenox, thiafenox, chlorpyrifos, methyl thiophos, chlorpyrifos, thiafenox ... Methomyl, vaniliprole, bethoxazin, copper dioctanoate, copper sulfate, cybutryne, dichloronaphthoquinone, dichlorophen, endoxan, triphenyltin, slaked lime, sodium mancozeb, quinone, quinone, simazine, triphenyltin acetate, triphenyltin hydroxide, fosfomycin, piperazine, thiophanate, chloralose, fenthion, pyridine-4-amine, strychnine, 1-hydroxy-1H-pyridine-2-thione, 4-(quinoxaline-2-ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, hydroxide Copper, cresol, disopyrtioxon, dodex, sodium sulfone, formaldehyde, mercurygafen, kasugamycin, kasugamycin hydrochloride hydrate, nickel di(dimethyldithiocarbamate), trichloromethylpyridine, octhiothione, oxolinic acid, oxytetracycline, potassium hydroxyquinoline sulfate, thiabendazole, streptomycin, streptomycin sesquisulfate, chlorothiazide, thimerosal, cotton brown banded moth GV, Agrobacterium radiobacterium, Amblyseius species, celery budworm NPV, original cherry-winged tassel wasp, short-spurred aphid wasp, cotton aphid parasitic wasp, aphid-eating gall midge, lucerne budworm NPV, spherical Bacillus, Beauveria bassiana, common lacewings, Cryptosporus monnieri Lip ladybug, GV of apple moth, Siberian jawed braconid, pea leafminer, beautiful aphid wasp, paddle-horned aphid wasp, bacteriotrophic Heterorhabditis and Heterorhabditis spp., spotted long-legged ladybug, parasitic wasp of citrus powdery scale, blind bug, cabbage armyworm NPV, yellow broad-stalked jumping wasp, yellow green Metarhizium anisopliae, Metarhizium anisopliae microspore variant, European new pine sawfly NPV and red-headed new pine sawfly NPV, species of the genus Microseudemys, Fumosodium roseum, Chilean small phytoseiid mite, hairy mosquito nematode, small rolling moth nematode, noctuid Steinernema, Gricea nematode, sharp-sided Steinernema, Steinernema reesei (Steinernema riobravis), Steinernema cricket, Steinernema species, Trichogramma species, western blind mite, Verticillium lecanii, oxazolidinone, bis(aziridine)methylaminophosphonium sulfide, busulfan, dimethivin, hexamethylmelamine, hexamethylphosphine, methyl tibacterium, methyl oxazolidinone, infertile chloranil, tibacterium, hexamethylphosphine thioate, thiothiazine, trothamide, urea imine, (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol, (E)-tridec-4-en-1-yl acetate, (E)-6-methylhept-2-en-4-ol,(E,Z)-tetradec-4,10-dien-1-yl acetate, (Z)-dodec-7-en-1-yl acetate, (Z)-hexadec-11-enal, (Z)-hexadec-11-en-1-yl acetate, (Z)-hexadec-13-en-11-yn-1-yl acetate, (Z)-eicos-13-en-10-one, (Z)-tetradec-7-en-1-al, (Z)-tetradec-9-en-1-ol, (Z)-tetradec-9-en-1-yl acetate, (7E,9Z)-dodec-7,9-dien-1-yl acetate, (9Z,11E)-tetradec-9,11-dien-1-yl acetate, (9Z,12E)-tetradec-9,12-dien-1-yl acetate. 1-methyl acetate, 14-methyloctadec-1-ene, 4-methylnon-5-ol and 4-methylnon-5-one, α-polystyrene, western pine beetle gathering pheromone, dodecadienol, codmon, fly attractant, epoxy nonadecane, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodec-8,10-dien-1-yl acetate, dominicalure, ethyl 4-methyloctanoate, eugenol, southern pine beetle gathering pheromone, trap-killing ene mixture, trap-killing ene mixture I, trap-killing ene mixture II, trap-killing ene mixture III, trap-killing ene mixture IV, hexane attractant, tooth beetle dienol, small stupid enol, scarab sex attractant, trimethyl dioxytricyclononane, moth attractant (lit lure), cabbage looper sex attractant, trap ester, megatomoic acid, trap ether, trap ene, octadec-2,13-diene-1-yl acetate, octadec-3,13-diene-1-yl acetate, Hekangbi, coconut rhinoceros beetle aggregation pheromone, non-Lekang, trap ring, sordidin, fungi-eating attractant, tetradec-11-ene-1-yl acetate, Mediterranean fruit fly attractant, Mediterranean fruit fly attractant A, Mediterranean fruit fly attractant B1, Mediterranean fruit fly attractant B2, Mediterranean fruit fly attractant C, Chuangteyi (Chuangteyi), 2-(octylthio)-ethanol, dimethoate, butoxy (polypropylene glycol), dibutyl adipate, dibutyl phthalate, butyrate dibutyl dicarboxylate, DEET, mosquito repellent, dimethyl phthalate, ethyl hexanediol, hexyl urea, mequindine, methyl neodecylamide, oxamate, picaridin, 1-dichloro-1-nitroethane, 1,1-dichloro-2,2-di(4-ethylphenyl)-ethane, 1,2-dichloropropane and 1,3-dichloropropylene, 1-bromo-2-chloroethane, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate, 2-(2-butoxyethoxy)ethyl thiocyanate, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate,2-(4-chloro-3,5-xylyloxy)ethanol, 2-chlorovinyl diethyl phosphate, 2-imidazolidinone, 2-isovaleryl indan-1,3-dione, 2-methyl (prop-2-ynyl) aminophenyl methylcarbamate, 2-thiocyanatoethyl laurate, 3-bromo-1-chloroprop-1-ene, 3-methyl-1-phenylpyrazol-5-yl dimethyl-carbamate, 4-methyl (prop-2-ynyl) amino -3,5-Dimethylphenylmethylcarbamate, 5,5-dimethyl-3-oxocyclohex-1-enyldimethylcarbamate, acethion, acrylonitrile, aldrin, alloamicin, chlorpyrifos, α-deceprin, aluminum phosphide, chlorpyrifos, neonicotinoids, ethylthiocarbamide (athidathion), methyl pyrifos, Bacillus thuringiensis delta-endotoxin, barium hexafluorosilicate, barium polysulfide, fumonisin, Bayer 22 / 1 90, Bayer 22408, β-cyfluthrin, β-cypermethrin, bioethanomethrin, biopermethrin, bis(2-chloroethyl) ether, borax, bromophenone, bromo-DDT, synthate, butathiofos, butathiofos, calcium arsenate, calcium cyanide, carbon disulfide, carbon tetrachloride, badan hydrochloride, cevadine, borneol, chlordane, chlordecone, chloroform, chloropicrin, chloraniloxime, chlorprazophos, cis-resmethrin, cismethrin, clocythrin, copper acetoarsenite, copper arsenate, copper oleate, coumithoate, cryolite, CS 708, benzonitrile, cypermethrin, cypermethrin, d-methrin, DAEP, dazomethane, decarbofuran, chloranil, isochlor, chloranil, dicresyl, cypermethrin, dieldrin, diethyl 5-methylpyrazol-3-yl phosphate, dilor, tetrafluthrin, demicarb, pyrethrin, methyl chlorpyrifos, difenocarb, propanol, pentotropol, dinofuranoside, fenthion, vegetable phosphorus, thiopyraphos, DSP, ecdysterone, EI 1642, EMPC, EPBP, etaphos, ethiobencarb, ethyl formate, ethylene dibromide, ethylene dichloride, ethylene oxide, EXD, pyrifos, ethiobencarb, fenoxacrim, cypermethrin, fenthion, ethylfenthion, flucofuron, butylfenthion, phosphodiesteril, butylfenthion, furathiocarb, pyrethroid, biguanide salt, biguanide acetate, sodium tetrathiocarbonate, benzyl chlorpyrifos, HCH, HEOD, heptachlor, thiothion, HHDN, hydrogen cyanide, quinoline carbendazim, IPSP, chlorfenapyr, carbochlorin, isothrin, isofenphos, transplanting spirit, rice blast spirit, oxathiophos, juvenile hormone I,Juvenile hormone II, juvenile hormone III, chlorpentyl, methoprene, lead arsenate, bromophenylphos, acetamiprid, thiathion, m-isopropyl methylcarbamate, magnesium phosphide, phosphorus azide, methyl aphid, chlorpyrifos, mercurous chloride, methyl sulfoxide, metamifop, metamifop potassium salt, metamifop sodium salt, methylsulfonyl fluoride, butenamidophos, methoprene, methylthiothrin, methoxychlor, methyl isothiocyanate, methyl chloroform, dichloromethane, chlorpyrifos, anticide, naphthiophos, naphthalene, NC-1 70. Nicotine, nicotine sulfate, nithiazine, orthonicotine, O-5-dichloro-4-iodophenyl O-ethylethyl phosphonothioate, O,O-diethyl O-4-methyl-2-oxo-2H-benzopyran-7-yl phosphonothioate, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphonothioate, O,O,O',O'-tetrapropyl dithiodipyrophosphate, oleic acid, p-dichlorobenzene, methyl parathion, pentachlorophenol, pentachlorophenyl laurate, PH 60-38, fenthion, parachlorothion, phosphine, methyl phoxim, methamidophos, polychlorinated dicyclopentadiene isomers, potassium arsenite, potassium thiocyanate, precocious I, precocious II, precocious III, amidothiophos, profluthrin, fenthiocarb, pyraclostrobin, anti-pyrethroids, quassia, quinalphos-methyl, fenthiocarb, iodophos, resmethrin, rotenone, thiamethoxam, ryanodine, sabadilla, octamethylenetetracycline , cloran, SI-0009, thiopropionitrile, sodium arsenite, sodium cyanide, sodium fluoride, sodium hexafluorosilicate, sodium pentachlorophenol, sodium selenate, sodium thiocyanate, sulcofuron, sulcofuron-sodium, sulfuryl fluoride, thiopromide, tar, thiocarb, TDE, butylpyrimidinphos, dimethoate, cyclopentylthrin, tetrachloroethane, thiochlorvos, cyclohexane, cyclohexane oxalate, cypermethrin, cypermethrin sodium, tralomethrin, anti-chloride Pyrethroids, trichlormetaphos-3, trichlormetaphos-3, chlorpyrifos, tolprocarb, chlorpyrifos-butyl, methoxythiocarb, veratridine, veratridine, XMC, zetamethrin, zinc phosphide, tolfenphos, and chlorfluanid, tetrafluanid, bis(tributyltin) oxide, bromoacetamide, iron phosphate, niclosamide-ethanolamine, tributyltin oxide, pyroximate, snail killer, 1, 2-dibromo-3-chloropropane, 1,3-dichloropropylene, 3,4-dichlorotetrahydrothiophene 1,1-dioxide, 3-(4-chlorophenyl)-5-methylrhodanine, 5-methyl-6-thioxo-1,3,5-thiadiazin-3-yl acetic acid, 6-isopentenylaminopurine, 2-fluoro-N-(3-methoxyphenyl)-9H-purine-6-amine, phenylchlorothiol, cytokinin, DCIP, furfural, isoamidophos, kinetin, verrucosporium mycorrhizal composition, tetrachlorothiophene, xylenol, zeatin,Potassium ethyl xanthate, acibenzolar, acibenzolar-S-methyl, Polygonum cuspidatum extract, α-chloroalcohol, antu, barium carbonate, bifenthrin, brodifacoum, bromadiolone, brofenthion, chlorfenthion, cholecalciferol, chlorfenthion, chlorfenthion, chlorfenthion, chlorfenthion, chlorfenthion, chlorfenthion, chlorfenthion, chlorfenthion, calciferol, flufenthion, fluoroacetamide, flufenthion, flufenthion hydrochloride, flufenthion, flufenthion, phosphorus, flufenthion, flufenthion, chlorfenthion, chlorfenthion, scilia glycoside, sodium fluoroacetate, thallium sulfate, flufenthion, 2-(2-butoxyethoxy)ethyl piperate, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, farnesol with nerolidol, synergistic acetylene ether, MGK 264, piperonyl butoxide, synergistic aldehyde, propyl isomer, S421, synergistic powder, sesame, sulfoxide, anthraquinone, copper cyclohexane, copper oxychloride, dicyclopentadiene, serene, zinc cyclohexane, zinc ziram, imanin, ribavirin, chloroindole hydrazide, mercuric oxide, thiophanate-methyl, azaconazole, bifenthrin, fuconazole, cyproconazole, difenoconazole, diniconazole, flufenoxazole, nitrobenzamide, fluquinconazole, flusilazole, flutriafol, furopyram, hexaconazole, imazalil, imipenem, cyproconazole, metconazole, myclobutrazol, paclobutrazol, rice blast ester, penconazole, prothioconazole, pyridoxine (py rifenox), prochloraz, propiconazole, pyraclostrobin, simeconazole, tebuconazole, fluconazole, triadimefon, triadimenol, triflumizole, trichlorfonazole, pyrimidine, chlorfenapyr, flufenapyr, bupirimate, dimethirimol, ethirimol, dodecacyclic morpholine, fenpropidin, fenbutamide, spiroxamorph, tridecamorph, cyprodinil, pyraclostrobin, pyrimethanil, fenpiclonil, fludioxonil, benzyl alcohol benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, furamide, oxadixyl, carbendazim, debacarb, thiabendazole, chlozolinate, dichlozoline, myclozoline, procymidone, vinclozoline, boscalid, carboxin , flutolanil, flutolanil, oxadiazine, oxadiazine, penthiopyrad, thiofuran, dodine, biguanide, azoxystrobin, etherstrychnine, enestroburin, enestroburin, flutolanil, fluoxastrobin, etherstrychnine, fenoxystrobin, trifloxystrobin, trifloxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, ferram, mancozeb, maneb, manam, methyl propineb, maneb, captan, captan, pyraclostrobin, folpet, tolylfluanid,Bordeaux mixture, copper oxide, mancozeb, quinoline copper, phthalocyanine, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil, chloranil fenamidone, fenamidone, fenoxanil, ferimzone, fluazinam, flumetylsulforim, fluopicolide, fluconazole, flusulfamide, flupyrosinamide, fenoxamidine, fosetylaluminium, hymexazol, propineb, cyazofamid, methasulfocarb, metrafenone, pencycuron, phthalide, polyoxins polyoxins, propamocarb, pyraclostrobin, proquinazid, pyroquilon, pyriofenone, quinoxyfen, pentachloronitrobenzene, thiazolamide, triazoxide, tricyclazole, triazine, validamycin, valeramide, zoxamide, mandipropamid, flubeneteram, isopyrazam, sedaxane, benzovintriazole, fluopyram, 3-difluoromethyl-1-methyl 1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide, pyrazole carboxamide fungicides (isoflucypram), isothiopyrad, dipymetitrone, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide,4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, fluindapyr, jiaxiangjunzhi, chlorophenyletheramide, dichlorobenzothiazole, mandestrobin, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol, oxathiazole apiprolin), N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamic acid tert-butyl ester, bifenthrin, succinate dehydrogenase inhibitor fungicides, carbamate fungicides, clofosconazole, ifen trifluconazole, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, [2-[3-[2-[1- [2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl] methanesulfonate, N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamic acid but-3-ynyl ester, N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine, phenylpyridazine fungicides, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole -4-formamide, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one, aminopyridine, pyraclostrobin, indazolesulfazoline, fluopicolide, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine, pyridine, fenpicoxamid, methylpyramid, isobutylethoxyquinoline, quinoline fungicides, quinoxaline, isopropylthiopyrad,1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylic acid ethyl ester (which can be prepared by the method described in WO 2020 / 056090), 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enyloxy]phenyl]methyl]pyrazole-3-carboxylic acid ethyl ester (which can be prepared by the method described in WO 2020 / 056090), 2020 / 056090), methyl N-[[4-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (can be prepared by the method described in WO2020 / 097012), methyl N-[[4-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (can be prepared by the method described in WO 2020 / 097012), methyl 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (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 (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 (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, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide, benzathiostrobin, cyanobacterium methyl, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1), fluopyram, flufenoxadiazam, fluthiazolin, fluopyram, pyrapropoyne , picarbutrazox, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, tetrazolylpyrazolone, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide,α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-diphenyl]-4-yl]-5-pyrimidinemethanol, piperidinylthiazoleisoxazoline fungicides (fluoxapiprolin), enoxastrobin, (Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop-2-enoic acid methyl ester, (Z)-3-methoxy-2-[2-methyl-5-(4-prop methyl (Z)-2-[5-(3-isopropylpyrazol-1-yl)-2-methyl-phenoxy]-3-methoxy-prop-2-enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-(3-propylpyrazol-1-yl)phenoxy]prop-2-enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]prop-2-enoate (these compounds can be prepared from WO 2020 / 079111), (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoic acid methyl ester, (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoic acid methyl ester (these compounds can be prepared by WO 2020 / 193387), 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, 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, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioalkyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, trinexapac-ethyl, syringostaryl, zhongshengmycin, thiophanate-methyl, thiophanate-copper Zinc azide, amitriptyline (amectotractin), isopyrim, cinclorac, N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine,N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-isopropyl-N-methyl-formamidine (these compounds can be prepared from WO 2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine (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, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine (these compounds can be prepared by the method described in WO 2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetane-2-yl]phenyl]-N-methyl-formamidine, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine (these compounds can be prepared by WO 2019 / 110427); N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, N-[(1S)- 1-Benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide,N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide (these compounds can be prepared from WO 2017 / 153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole (these compounds can be prepared by the method described in WO2017 / 025510); 2016 / 156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one,5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylic acid ethyl ester, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine (these compounds can be prepared from WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 093348 and WO 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (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 (this compound can be prepared by the method described in WO 2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound can be prepared by the method described in WO 2-Amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester (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)-tetraone (this compound can be prepared by the method described in WO 2011 / 138281),N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]thiobenzamide; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine (this compound can be prepared by the method described in WO2018 / 153707); N '-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine; N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared by the method described in WO2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (this compound can be prepared by the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone (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 (this compound can be prepared by the method described in WO 2018 / 065414); 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylic acid ethyl ester (this compound can be prepared by the method described in WO2018 / 158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, N-[ (E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[N-methoxy-methyl-carbonimido]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (these compounds can be prepared by the method described in WO 2018 / 202428). 、

[0457] The compounds of the present invention can also be used in combination with anthelmintics. Such anthelmintics include compounds selected from macrolide compounds, such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemaketin and milbemycin derivatives, as described in EP 0357460, EP 0444964 and EP0594291. Other anthelmintics include semisynthetic and biosynthetic avermectin / milbemycin derivatives, such as those described in US 5,015,630, WO 94 / 15944 and WO 95 / 22552. Other anthelmintics include benzimidazoles, such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxbendazole, parbendazole and other members of this category. Additional anthelmintics include imidazothiazoles and tetrahydropyrimidines, such as tetramisole, levamisole, pyrantel pamoate, octadalafil or morantel. Additional anthelmintics include flukeicides (such as triclabendazole and clorsulon) and tapewormicides (such as praziquantel and ethacistel).

[0458] The compounds of the present invention may be used in combination with derivatives and analogs of the paraherquamide / marcfortine class of anthelmintics and antiparasitic oxazolines such as those disclosed in US 5,478,855, US 4,639,771 and DE-19520936.

[0459] The compounds of the invention may be used in combination with derivatives and analogs of the general class of dioxomorpholine antiparasitic agents as described in WO 96 / 15121 and also with anthelmintic active cyclic depsipeptides such as those described in WO 96 / 11945, WO 93 / 19053, WO 93 / 25543, EP 0626375, EP 0382173, WO 94 / 19334, EP 0382173, and EP 0503538.

[0460] The compounds of the present invention can be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as chlorfenuron; ecdysone agonists such as tebufenozide; neonicotinoids such as imidacloprid, etc.

[0461] The compounds of the invention may be used in combination with terpene alkaloids, such as those described in WO 95 / 19363 or WO 04 / 72086, in particular the compounds disclosed therein.

[0462] Other examples of such biologically active compounds that can be used in combination with the compounds of the present invention include, but are not limited to, the following:

[0463] Organophosphates: acephate, methyl pyraclofos, ethyl azinphos-methyl, methyl azinphos-methyl, bromophos, ethyl bromophos, cadusin, chlorethoxyphos, chlorpyrifos, chlorfenapyr, chlormethylphos, demeton, demeton-S-methyl, demeton-S-methyl sulfone, chlormet, diazinon, dichlorvos, dicrotophos, dimethoate, ethion, ethion, ethion, oxamethoxam, fenamiphos, fenitrothion, fenthion, fenthion, fenthion, pyrifos, fenfothion, anchovy, thiamethoxam, heptylphos, chlorazophos, isopropylphos, isoxazophos, malathion Phosphorus, acaricide, methamidophos, methidathion, methyl parathion, mefenphos, monocrotophos, dibromophos, omethoate, methyl oxo-demeton, paraoxon, parathion, methyl parathion, fenthion, phosalone, thiocyanate, phosphine, phosmet, phosphamidon, phosphamidon, phosphamidon, phosphamidon, phosphamidon, phosphamidon, phosphamidon, phosphamidon-methyl, bromophos, propanphos, proetamphos, prothiophos, pyraclofos, pyridazinphos, quinalphos, thiocarb, thimeton, terbufos, butylpyrimidinphos, stirofosate, thimeton, triazophos, trichlorfon, and chlorpyrifos.

[0464] Carbamates: aldicarb, 2-sec-butylphenyl methyl carbamate, benfuracarb, carbaryl, chlorpyrifos, carbofuran, butylthiocarb, diflubenzuron, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801, isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-isopropylphenylbutynyl (methyl) carbamate, cypermethrin, pirimicarb, propoxur, thiodicarb, long-lasting carb, triazolam, UC-51717.

[0465] Pyrethroids: flumethrin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E)-(1R)-cis-2,2-dimethyl-3-(2-oxathiolane-3-ylidenemethyl) cyclopropanecarboxylate, bifenthrin, β-cypermethrin, flucythrin, alpha-cypermethrin, β-cypermethrin, bio-allethrin, bio-allethrin ((S)-cyclopentyl isomer), bio-resmethrin, bifenthrin, NCI-85193, Pyrethrins, cyhalothrin, cypermethrin, deltamethrin, d-cypermethrin, esfenvalerate, etherpermethrin, pentothrin, cypermethrin, cypermethrin, flucythrin, fluvalinate (D isomer), imiprothrin, cyhalothrin, lambda-cyhalothrin, permethrin, phenothrin, prallethrin, pyrethrin (natural product), resmethrin, tetramethrin, transfluthrin, theta-cypermethrin, silafluthrin, t-fluvalinate, tefluthrin, tralomethrin, ζ-cypermethrin.

[0466] Arthropod growth regulators: a) Chitin synthesis inhibitors: benzoyl ureas: chlorfenapyr, diflubenzuron, fluazifop, flufenoxuron, flubendiamide, hexaflumuron, chlorfenuron, isoflurane, diflubenzuron, diflubenzuron, thiocarb, buprofezin, benzylfen, hexathiapiprolin, etoxazole, chlorfentazine; b) Ecdysone antagonists: chlorfenapyr, methoxyfenapyr, fenpyroximate; c) Juvenile hormone analogs: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) Lipid biosynthesis inhibitor: spirodiclofen.

[0467] Other antiparasitic drugs: acequinoxaline, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, sulfamethoxazole, bifenazate, binacarb, bromocriptine, BTG-504, BTG-505, toxaphene, cartap, ethyl cypermethrin, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, clothianidin, cypermethrin, diacloden, cypermethrin, DBI-3204, diclofenac, dihydroxy methyl dihydroxypyrrolidine, dimethoate, dimethoate, endosulfan, ethiprole, fenpyroxen, flumite, MTI-800, fenpyroximate, pyrimidine, flumethrin, bromothrin, flumethoate, trifluroxyfen, halofenprox, hydrazone, IKI-220, sodium silicate, NC-196, neem guard), nidinorterfuran, nitenpyram, SD-35651, WL-108477, pyridalyl, propargite, protrifenbute, pymetrozine, pyridabenzane, pyrimidine, NC-1111, R-195, RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601, flutoxin, silomadine, spinosad, tebufenpyrad, trichloroacetic acid sulfone, tetracycline, thiacloprid, thiamethoxam, tolfenpyrad, triacetin, triacylglycerol, synergistic acetyl ether, vertalec, YI-5301.

[0468] Biological agents: Bacillus thuringiensis ssp. aizawai, Bacillus thuringiensis ssp. kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, insect pathogenic bacteria, viruses and fungi.

[0469] Bactericides: chlortetracycline, oxytetracycline, streptomycin.

[0470] Other biologics: enrofloxacin, febantel, pentoxacillin, meloxicam, cephalexin, kanamycin, pimobendan, clenbuterol, omeprazole, tiamulin, benazepril, pyriprole, cefquinome, florfenicol, buserelin, cefuroxime, tolamectin, ceftiofur, carprofen, mefluazione, praziquantel, triclabendazole.

[0471] The following mixtures of compounds of formula (I) with active ingredients are preferred. The abbreviation "TX" means a compound selected from the group consisting of compounds of formula (I), (Ia), (Ia-A), (Ia-B) or (Ia-C), or a compound selected from the group consisting of compounds as shown in Tables C-1 to C-21, or as listed in Table P (below):

[0472] A compound selected from the group consisting of: petroleum oil + TX, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX, 2,4-dichlorophenylbenzenesulfonate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 4-chlorophenylphenyl sulfone + TX, acetofenamide + TX, aldicarb + TX, sirox + TX, fomanphos + TX, amine oxalate + TX, amitraz + TX, cypermethrin + TX, arsenic trioxide + TX, azobenzene + TX, azophos + TX, benomyl + TX, benoxafos + TX, benzyl benzoate + TX, bixafen + TX, bromomethrin + TX , bromophenic acid + TX, bromothion + TX, bromopyralid + TX, buprofezin + TX, butanone + TX, butanone sulfone + TX, butylpyridaben + TX, calcium polysulfide + TX, octachlorocamphene + TX, chlormethoxam + TX, trithion + TX, cypermethrin + TX, chlormequat + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorfenapyr + TX, chlorfenapyr + TX, chlorfenapyr + TX, chlorfenapyr + TX, chlorfenapyr + TX, chlorfenapyr + TX, ethyl chlorfenapyr + TX, chlormebuform (chloromebuform) + TX, chlorfenapyr + TX, propyl chlorfenapyr + TX, chlorfenapyr + TX, chlorfenapyr I + TX, chlorfenapyr II + TX, chlorfenapyr + TX, closantel + TX, fly Toxophos + TX, crotamiton + TX, baclofos + TX, thiophos + TX, fruit insect phosphorus + TX, DCPM + TX, DDT + TX, dinafos + TX, dinafos-O + TX, dinafos-S + TX, methyl + TX, methyl + TX, methyl + TX, methyl + TX, methyl + TX, methyl + TX, methyl + TX, methyl sulfone + TX, antifungal + TX, dichlorvos + TX, dicliphos + TX, dichlorvos + TX, dichlorvos + TX, dichlorvos + TX, dinitrophos + TX, dinex + TX, dinex-diclexine + TX, dinitrophos-4 + T X, dimethoate-6+TX, ortho-dimethoate+TX, nitropentyl+TX, nitrooctyl+TX, nitrobutyl+TX, dimethoate+TX, sulfodiphenyl+TX, disulfiram+TX, DNOC+TX, dofenapyn+TX, doramectin+TX, indophos+TX, eprinomectin+TX, phosphosulfate+TX, ethiprox+TX, anti-mite+TX, fenbutatin+TX, fenthiocarb+TX, cypermethrin+TX, cyfluthrin+TX, fenpyraclostrobin+TX, fentrifanil+TX, fluazifop+TX, flufenoxuron+TX, fluazifop+TX, flufenoxam+TX, FMC 1137+TX, fenthiocarb+TX, fenthiocarb hydrochloride+TX, formparanate+TX, γ-HCH+TX, fenthiocarb+TX, benzylfen+TX,Hexadecyl cyclopropanecarboxylate + TX, isocarbophos + TX, jasmonate I + TX, jasmonate II + TX, iodine + TX, lindane + TX, propanil + TX, cypermethrin + TX, dithiophos + TX, methylthiophene + TX, cypermethrin + TX, methyl bromide + TX, cypermethrin + TX, milbemycin + TX, propylamine + TX, monocrotophos + TX, maoguo + TX, moxidectin + TX, naled + TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazine-3-one + TX, fluazifop + TX, nikkomycin + TX, pentamethylenetetramine + TX, pentamethylenetetramine 1:1 zinc chloride complex + TX, omethoate + TX, isothiocarb + TX, sulfone + TX, pp'-DDT + TX, parathion + TX, permethrin + TX, fenthion + TX, phosalone + TX, thiocarb + TX, phosphamidon + TX, polychloroterpenes + TX, polynactins + TX, chloranil + TX, cypermethrin + TX, propoxur + TX, ethidium + TX, thiophanate + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrin + TX, pyrimethoxam + TX, pyrimithiophos + TX, quinalphos + TX, quintiofos + TX, R-1492 + TX, glyphosate +TX, rotenone +TX, octamethrin +TX, clomiphene +TX, selamectin +TX, thiophos +TX, SSI-121 +TX, sulfilam +TX, flubendiamide +TX, sulfotep +TX, sulfur +TX, fluazifop +TX, τ-fluvalinate +TX, TEPP +TX, tert-butylcarb +TX, tetrachlorocarbamide +TX, carbendazim +TX, carbendazim +TX, thiophene +TX, thiophene +TX, thiophene +TX, thiophene +TX, methyl thiocarb +TX, carbendazim +TX, thiophene +TX, thiophene +TX, thiophene +TX, thiophene +TX, thiophene +TX, triazophos +TX, triazuron +TX, trichloropropoxyphos +TX, triamcinol +TX, aphidoxime +TX, vaniliprole e) + TX, bethoxazin + TX, copper dioctanoate + TX, copper sulfate + TX, cyclobutanenitrile + TX, dichloronaphthoquinone + TX, dichlorophen + TX, endoxan + TX, triphenyltin + TX, slaked lime + TX, mancozeb + TX, algaquinone + TX, quinone + TX, simazine + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, yuxu phosphorus + TX, piperazine + TX, thiophanate + TX, chloralose + TX, fenthion + TX, pyridine-4-amine + TX, strychnine + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 4-(quinoxaline-2-ylamino)benzenesulfonamide + TX, 8-hydroxyquinoline sulfate + TX, bronopol + TX, copper hydroxide + TX,Cresol + TX, dipyrithione + TX, dodixin + TX, sodium sulfone + TX, formaldehyde + TX, mercury plus phenanthene + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel di(dimethyldithiocarbamate) + TX, trichloromethylpyridine + TX, octhiothionine + TX, oxolinic acid + TX, oxytetracycline + TX, potassium hydroxyquinoline sulfate + TX, thiabendazole + TX, streptomycin + TX, streptomycin sesquisulfate + TX, chlorothiazide + TX, thimerosal + TX, cotton brown-banded moth GV + TX, radiobacterium + TX, blunt mite species + TX, celery armyworm NPV + TX, original cherry-winged tassel wasp + TX, short-spurred aphid wasp + TX, cotton aphid parasitic wasp + TX, aphid-eating gall midge + TX, alfalfa armyworm NPV + TX, spherical Bacillus + TX, Beauveria bassiana + TX, Common lacewings + TX, Meng's Cryptolip ladybird + TX, Apple moth GV + TX, Siberian jawed braconid wasp + TX, pea leafminer + TX, beautiful aphid wasp + TX, paddle-horned aphid wasp + TX, bacteriotrophic Heterorhabditis elegans and large Heterorhabditis elegans + TX, spotted long-legged ladybird + TX, citrus powdery scale parasitic wasp + TX, blind bug + TX, cabbage armyworm NPV + TX, yellow broad-handled jumping wasp + TX, yellow-green green Mushroom + TX, Metarhizium anisopliae microspore variant + TX, European new pine sawfly NPV and red-headed new pine sawfly NPV + TX, species of the genus Pseudomonas + TX, Paecilomyces fumosorum + TX, Chilean phytoseiid mite + TX, mosquito nematode + TX, small spiral moth nematode + TX, noctuid nematode + TX, Geer's nematode + TX, sharp-sided nematode + TX, Steinernema reesei (Steinernema riobravis)+TX, mole cricket Steinernema+TX, Steinernema species+TX, Trichogramma species+TX, western blind mite+TX, Lecanicillium lecanii+TX, oxazolidinone+TX, bis(aziridine)methylaminophosphonium sulfide+TX, busulfan+TX, dimethivin+TX, hexamethylmelamine+TX, hexamethylphosphonium+TX, methyl tibac+TX, methyl thiotibac+TX, methyl oxazolidinone+TX, infertile oxazolidinone+TX, fluoroquinolone+TX, tibac+TX, hexamethylphosphonium thioate+TX, thiotibac+TX, trothamide+TX, urethaneimide+TX, (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol +TX, (E)-1-tridec-4-en-1-yl acetate +TX, (E)-6-methylhept-2-en-4-ol +TX, (E,Z)-14dec-4,10-dien-1-yl acetate +TX, (Z)-1-dodec-7-en-1-yl acetate +TX, (Z)-11-hexadec-11-enal +TX, (Z)-11-hexadec-11-en-1-yl acetate +TX, (Z)-11-hexadec-13-en-11-yn-1-yl acetate +TX, (Z)-eicos-13-en-10-one +TX, (Z)-14dec-7-en-1-al +TX, (Z)-14dec-9-en-1-ol +TX,(Z)-tetradec-9-en-1-yl acetate + TX, (7E,9Z)-dodec-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-methylnon-5-ol and 4-methylnon-5-one + TX, α-polystyrene + TX, western pine beetle aggregation pheromone + TX, dodecadienol + TX, caldoxane + TX, fly attractant + TX, epoxide nonadecane + TX, dodec-8-en-1-yl acetate + TX, dodec-9- 1-ene acetate + TX, dodecan-8 + TX, 10-diene-1-yl acetate + TX, dominic lure + TX, 4-methyloctanoic acid ethyl ester + TX, eugenol + TX, southern pine beetle gathering pheromone + TX, trap ene mixture + TX, trap ene mixture I + TX, trap ene mixture II + TX, trap ene mixture III + TX, trap ene mixture IV + TX, hexane attractant + TX, tooth beetle dienol + TX, small stupid enol + TX, scarab sex attractant + TX, trimethyl dioxytricyclononane + TX, noctuid attractant (litlure) + TX, cabbage looper sex attractant + TX, trap ester + TX, megatomoic acid (megatomoic acid acid)+TX, insect trap ether+TX, insect trap ene+TX, octadec-2,13-diene-1-yl acetate+TX, octadec-3,13-diene-1-yl acetate+TX, Hekangbi+TX, coconut rhinoceros beetle aggregation pheromone+TX, Feilekang+TX, insect trap ring+TX, sordidin+TX, fungi-eating acetoin+TX, tetradec-11-ene-1-yl acetate+TX, Mediterranean fruit fly attractant+TX, Mediterranean fruit fly attractant A+TX, Mediterranean fruit fly attractant B1+TX, Mediterranean fruit fly attractant B2+TX, Mediterranean fruit fly attractant C+TX, Chuangte+TX, 2-(octylthio)-ethanol+TX, dimethoate+TX, butoxy(polypropylene glycol)+TX, dibutyl adipate+ TX, dibutyl phthalate + TX, dibutyl succinate + TX, DEET + TX, mosquito repellent + TX, dimethyl phthalate + TX, ethyl hexanediol + TX, hexyl urea + TX, mequindine + TX, methyl neodecylamide + TX, oxamate + TX, picaridin + TX, 1-dichloro-1-nitroethane + TX, 1,1-dichloro-2,2-di(4-ethylphenyl)-ethane + TX, 1,2-dichloropropane and 1,3-dichloropropylene + TX, 1-bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX,2-(2-Butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenylmethylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidinone + TX, 2-isovaleryl indan-1,3-dione + TX, 2-methyl (prop-2-ynyl) aminophenylmethylcarbamate + TX, 2-thiocyanatoethyl laurate + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-methyl-1-phenylpyrazol-5-yl dimethyl- Carbamate + TX, 4-methyl (prop-2-ynyl) amino-3,5-xylyl methyl carbamate + TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethyl carbamate + TX, acethion + TX, acrylonitrile + TX, aldrin + TX, alloamicin + TX, chloranil + TX, α-decandrin + TX, aluminum phosphide + TX, chloranil + TX, neonicotinoid + TX, ethylthiocarbamide (athidathion) + TX, methyl pyrifos + TX, Bacillus thuringiensis δ-endotoxin + TX, barium hexafluorosilicate + TX, barium polysulfide + T X, fumigantrin + TX, Bayer 22 / 190 + TX, Bayer 22408 + TX, β-cypermethrin + TX, β-cypermethrin + TX, bioethanomethrin + TX, biopermethrin + TX, bis(2-chloroethyl) ether + TX, borax + TX, bromophenoxyacetate + TX, bromo-DDT + TX, synchlorpyrifos + TX, cypermethrin + TX, butathiofos + TX, butyl ester + TX, calcium arsenate + TX, calcium cyanide + TX, carbon disulfide + TX, carbon tetrachloride + TX, badan hydrochloride + TX, cevadine + TX, borneol + TX, chlordane + TX, chlordecone + TX, chloroform + TX, chloropicrin + TX, chlornitroxime + TX, chlorprazophos + TX, cis-resmethrin + TX, cismethrin + TX, clocythrin + TX, copper acetoarsenite + TX, copper arsenate + TX, copper oleate + TX, coumithoate + TX, cryolite + TX, CS 708+TX, benzonitrile+TX, cypermethrin+TX, cypermethrin+TX, thiamethoxam+TX, d-carbofuran+TX, DAEP+TX, dazomethane+TX, decarbofuran+TX, chloranil+TX, isochlorophos+TX, chloranil+TX, dichlorvos+TX, cypermethrin+TX, dieldrin+TX, diethyl 5-methylpyrazol-3-yl phosphate+TX, dilor+TX, tetrafluoromethylthiocarb+TX, dimethoate+TX, pyrethrin+TX,Methyl chlorpyrifos + TX, dichlorvos + TX, propanol + TX, pentanophenol + TX, dinoseb + TX, benzylpyridin + TX, vegetable and fruit phosphorus + TX, thiopyraphos + TX, DSP + TX, ecdysterone + TX, EI 1642 + TX, EMPC + TX, EPBP + TX, ethiofencarb + TX, ethyl formate + TX, ethylene dibromide + TX, ethylene dichloride + TX, ethylene oxide + TX, EXD + TX, ethiofencarb + TX, fenitrothion + TX, fenoxacrim + TX, cypermethrin + TX, fenthion + TX, ethyl fenthion + TX, flucofuron + TX, butylfenthion + TX, phosphonium phosphate + TX, butyl cyclothion + TX, furathiocarb + TX, anti-insect pyrethrin + T X、Biguanide octyl salt + TX、Biguanide octyl acetate + TX、Sodium tetrathiocarbonate + TX、Benzyl chloramine + TX、HCH + TX、HEOD + TX、Heptachlor + TX、Thiothion + TX、HHDN + TX、Hydrogen cyanide + TX、Quinolincarb + TX、IPSP + TX、Chlorphenazone + TX、Carbochlorin + TX、Isoaldrin + TX、Isothiophos + TX、Transplanting + TX、Rice blast + TX、Oxazophos + TX、Juvenile hormone I + TX、Juvenile hormone II + TX、Juvenile hormone III + TX、Chlorpentyl + TX、Methoprene + TX、Lead arsenate + TX、Bromphenazone + T X, acetamiprid + TX, thiamethoxam + TX, m-isopropyl methyl carbamate + TX, magnesium phosphide + TX, phosphorus azide + TX, methyl aphidite + TX, aphidite + TX, mercurous chloride + TX, methyl sulfoxide + TX, metamifop + TX, metamifop potassium salt + TX, metamifop sodium salt + TX, methylsulfonyl fluoride + TX, butenamidophos + TX, methoprene + TX, methyl ether thiocyanate + TX, methoxychlor + TX, methyl isothiocyanate + TX, methyl chloroform + TX, dichloromethane + TX, chlorpyrifos + TX, anticide + TX, naphthiophos + TX, naphthalene + TX, NC-1 70+TX, Nicotine+TX, Nicotine sulfate+TX, Nithiothiazine+TX, Orthonicotine+TX, O-5-dichloro-4-iodophenyl O-ethylethylphosphonothioate+TX, O,O-diethyl O-4-methyl-2-oxo-2H-benzopyran-7-ylphosphonothioate+TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-ylphosphonothioate+TX, O,O,O',O'-tetrapropyl dithiodipyrophosphate+TX, Oleic acid+TX, p-dichlorobenzene+TX, Methyl parathion+TX, Pentachlorophenol+TX, Pentachlorophenyl laurate+TX, PH 60-38+TX, fenthion+TX, parachlorothion+TX, phosphine+TX, methyl phoxim+TX, methamidophos+TX, polychlorinated dicyclopentadiene isomers+TX, potassium arsenite+TX, potassium thiocyanate+TX, precocious element I+TX, precocious element II+TX, precocious element III+TX, amidophos+TX,Profluthrin + TX, fenvalerate + TX, pyraclostrobin + TX, pyrethroid + TX, quassia extract + TX, quinalphos-methyl + TX, fenvalerate + TX, iodophos + TX, resmethrin + TX, rotenone + TX, thiamethoxam + TX, ryanodine + TX, sabadilla + TX, octamethrin + TX, clostridium + TX, SI-0009 + TX, thiamethoxam + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium hexafluorosilicate + TX, sodium pentachlorophenol + TX, sodium selenate + TX, sodium thiocyanate + TX, sulcofuron + TX, sulcofuron sodium salt ( sulcofuron-sodium)+TX, sulfuryl fluoride+TX, thiopromide+TX, tar+TX, thiamethoxam+TX, TDE+TX, butylpyrimidinphos+TX, dimethophos+TX, cyclopentylthrin+TX, tetrachloroethane+TX, thiochlorvos+TX, cypermethrin+TX, cypermethrin oxalate+TX, cypermethrin+TX, cypermethrin+TX, cypermethrin sodium+TX, tralomethrin+TX, permethrin+TX, trichlormetaphos-3+TX, cypermethrin+TX, chlorpyrifos+TX, trichlormetaphos-3+TX, chlorpyrifos+TX, tolprocarb+TX, chlorpyrifos-butyl+TX, methoprene+TX, veratridine+TX, veratridine +TX, XMC+TX, ζ-cypermethrin+TX, zinc phosphide+TX, tolfenphos+TX, and chlorflumethrin+TX, tetraflumethrin+TX, bis(tributyltin)oxide+TX, bromoacetamide+TX, iron phosphate+TX, niclosamide-ethanolamine+TX, tributyltin oxide+TX, pyrifos+TX, snail killer+TX, 1,2-dibromo-3-chloropropane+TX, 1,3-dichloropropylene+TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide+TX, 3-(4-chlorophenyl)-5-methylrhodanine+TX, 5-methyl-6-thioxo-1,3,5-thiadiazin-3-yl acetic acid+TX, 6-isopentenylaminopurine+TX, 2-fluoro-N-(3-methoxyphenyl)- 9H-purine-6-amine + TX, benzothiol + TX, cytokinin + TX, DCIP + TX, furfural + TX, isoamidophos + TX, kinetin + TX, verrucospore mycorrhizal composition + TX, tetrachlorothiophene + TX, xylenol + TX, zeatin + TX, potassium ethyl xanthate + TX, acibenzolar + TX, acibenzolar-S-methyl + TX, Polygonum cuspidatum extract + TX, α-chlorohydrin + TX, antu + TX, barium carbonate + TX, bifenthrin + TX, brodifacoum + TX, brodifacoum + TX, brofenthion + TX, chlorfenapyr + TX, cholecalciferol + TX, chlorfenapyr + TX, rat-killing + TX, rat-killing naphthalene + TX, rat-killing pyrimidine + TX, rat-killing + TX, thiazolin + TX, difacoum + TX,Calcifenol + TX, fludioxaline + TX, fluoroacetamide + TX, fludioxaline + TX, fludioxaline hydrochloride + TX, fosfos + TX, phosphorus + TX, warfarin + TX, warfarin + TX, scillarin + TX, scutellarin + TX, sodium fluoroacetate + TX, thallium sulfate + TX, warfarin + TX, 2-(2-butoxyethoxy)ethyl piperate + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, farnesol with nerolidol + TX, synergistic acetylene ether + TX, MGK 264+TX, piperonyl butoxide+TX, synergistic aldehyde+TX, propyl isomer+TX, S421+TX, synergistic powder+TX, sesamelin+TX, sulfoxide+TX, anthraquinone+TX, copper cyclohexaneate+TX, copper oxychloride+TX, dicyclopentadiene+TX, salen+TX, zinc cyclohexaneate+TX, zinc thiram+TX, imanin+TX, ribavirin+TX, mercuric oxide+TX, thiophanate-methyl+TX, azaconazole+TX, bifenthrin+TX, oxadiazole+TX, cyproconazole+TX, difenoconazole+TX, diniconazole+TX, epoxiconazole+TX, fenbuconazole+TX TX, fluquinconazole + TX, flusilazole + TX, flutriafol + TX, furopyram + TX, hexaconazole + TX, imazalil + TX, imidazole + TX, picolinamide + TX, metconazole + TX, myclobutrazol + TX, paclobutrazol + TX, pyrifenox + TX, prochloraz + TX, prochloraz + TX, pyraclostrobin + TX, pyraconazole + TX, simeconazole + TX, tebuconazole + TX, fluconazole + TX, triadimefon + TX, triadimenol + TX, triflumizole + TX, sterilization azole + TX, pyrimidine alcohol + TX, chlorfenapyridine alcohol + TX, flufenapyridine alcohol + TX, bupirimate + TX, dimethirimol + TX, ethirimol + TX, dodecacyclic morpholine + TX, fenpropidin + TX, fenpropimorph + TX, spiroxafil + TX, tridecafil + TX, cyprodinil + TX, pyrimethanil + TX, fenpiclonil + TX, fludioxonil + TX, benalaxyl + TX, furanil Furalaxyl + TX, metalaxyl + TX, R-metalaxyl + TX, furamide + TX, oxadixyl + TX, carbendazim + TX, debacarb + TX, chloramphenicol + TX, thiabendazole + TX, chlozolinate + TX, dichlozoline + TX, myclozoline + TX, procymidone + TX, vinclozoline + TX,Boscalid + TX, carboxin + TX, furamide + TX, flutolanil + TX, oxamoxadone + TX, penthiopyrad + TX, thiofuran + TX, dodine + TX, biguanide + TX, azoxystrobin + TX, enestroburin + TX, enestroburin + TX, flutolanil + TX, fluoxastrobin + TX, enestroburin + TX, fenpyroximate + TX, fenpyroximate + TX, fenpyroximate + TX, fenpyroximate + TX, fenpyroximate + TX, fenpyroximate + TX, fenpyroximate + TX, fenpyroximate + TX, Manganese + TX, mancozeb + TX, methyl propineb + ​​TX, mancozeb + TX, captan + TX, azole + TX, folpet + TX, tolylfluanid + TX, Bordeaux mixture + TX, copper oxide + TX, mancozeb + TX, quinoline copper + TX, phthalocyanine + TX, kefansan + TX, isothiocyanate + TX, chlorpyrifos + TX, methyl tolclofos + TX, captan + TX, benthiopyrad + TX, blasticidin + TX, chloroneb + ​​TX, thiophanate-methyl + TX, cyfluanid + TX, cymoxanil + TX, triflupyridam + TX, diclocymet + TX, diclofenac mezine + TX, dicloran + TX, diethofencarb + TX, oxadiazine + TX, flumorph + TX, dithianon + TX, ethaboxam + TX, etridiazole + TX, oxadiazine + TX, fenamidone + TX, fenoxanil + TX, ferimzone + TX, fluazinam + TX, fluopicolide + TX, flusulfamide + TX, fluazole Bacteramide + TX, fenacet + TX, fosetyl-aluminium + TX, hymexazol + TX, propineb + ​​TX, cyazofamid + TX, methasulfocarb + TX, methacycline + TX, pencycuron + TX, phthalide + TX, polyoxins + TX, propamocarb + TX, pyraclostrobin + TX, proquinazid + TX, pyroquilon + TX, pyriofenone + TX,Quinoxyfen + TX, pentachloronitrobenzene + TX, thiazolamide + TX, triazoxide + TX, tricyclazole + TX, quinoxaline + TX, validamycin + TX, valeramide + TX, zoxamide + TX, mandipropamid + TX, flubeneteram + TX, isopyrazam + TX, sedaxane + TX, benzovintriazole + TX, fluopyram + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl) )-amide + TX, pyrazole carboxamide fungicides + TX, isothiopyrad + TX, dipymetitrone + 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+TX, fluindapyr+TX, jiaxiangjunzhi+TX, chlorophenyl ether amide+TX, dichlorobenzothiazole+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 1-(4-(2-( ...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-piperidinyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl] methanesulfonate + TX, N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamic acid but-3-ynyl ester + TX, N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester + TX, 3 -Chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, phenylpyridazine fungicides + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazolyl-5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazolyl-5-one + TX, aminopyrphen + TX, pyraclostrobin + TX, indazolesulfazoline + TX, fluopicolide + TX, (Z,2E)- 5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine + TX, pyridamole + TX, fenpicoxamid + TX, isobutylethoxyquinoline + TX, quinoline fungicides + TX, quinoline thiophene + TX, isopropylthiophene + TX, 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, benzathiostrobin + TX, cyproconazole + TX, 5-amino-1,3,4- Thiadiazole-2-thiol zinc salt (2:1) + TX, fluopyram + TX, fluthiazolin + TX, fluopyram + TX, pyrazole carboxamide fungicide + 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, tetrazobactam + TX,2-(Difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-diphenyl]-4-yl]-5-pyrimidinemethanol + TX, piperidinylthiazoleisoxazoline fungicides + TX, enoxastrobin + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)- )propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(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-ethyl + TX, syringoxystrobin + T X, Zhongshengmycin + TX, thiophanate-copper + TX, thiazole zinc + TX, amitriptyline + TX, isoprodinil + TX, N-octyl-N'-[2-(octylamino)ethyl]ethane-1,2-diamine + TX; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds can be prepared by WO 2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridinyl]-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)oxetane-2-yl]phenyl]-N-methyl-formamidine + TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[2-trifluoromethyl)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- Formamide + 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 + T X, 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 made from WO 2017 / 153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline+TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline+TX, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline+TX,4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline+TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline+TX (these compounds can be prepared from 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 WO 2016 / 156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, )-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 3-ethyl-1-methoxy-1-[[4-[ 5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]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, 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylic acid ethyl ester+TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine+TX. The compounds in this paragraph can be prepared from 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-hydroxy-propyl]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-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester + TX (this compound can be prepared by the method described in WO2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']bipyrrole-1,3,5,7(2H,6H)-tetraketone + TX (this compound can be prepared by the method described in WO 2011 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]thiobenzamide+TX; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine+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 2-(Difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX (this compound can be prepared by the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]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 / 065414); 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylic acid ethyl ester + TX (this compound can be prepared by the method described in WO 2018 / 158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide+TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzoyl Amine + TX, N-[N-methoxy-C-methyl-carbonimido]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX (these compounds can be prepared by the method described in WO2018 / 202428), chloroindole hydrazide + TX, pyrimidine fungicides + TX, fluconazole + TX, flufenoxadiazam + TX, metaylpicoxamid + TX. 、

[0473] Reference numbers in brackets after the active ingredients, e.g. [3878-19-1], refer to Chemical Abstracts Registry Numbers. The mixed compatibilities described above are known. In the case where the active ingredients are included in “The Pesticide Manual” [The Pesticide Manual—A World Compendium; 13th ed.; Editor: CDSTomLin; The British Crop Protection Council], they are described therein by the entry number given in brackets above for the specific compound; e.g. the compound “avermectin” is described by entry number (1). In the case where “[CCN]” is added above to a specific compound, the compound in question is included in the “Compendium of Pesticide Common Names”, which can be found on the Internet [A.Wood; Compendiumof PesticideCommon Names , 1995-2004]; for example, the compound "acetoprole" is described on the Internet at http: / / www.alanwood.net / pesticides / acetoprole.html.

[0474] Most of the above-mentioned active ingredients are referred to above by so-called "common names", in individual cases the corresponding "ISO common name" or another "common name" being used. If a name is not a "common name", the kind of name used is replaced by the name given in parentheses for the specific compound; in this case, the IUPAC name, IUPAC / Chemical Abstracts name, "Chemical Name", "Conventional Name", "Compound Name" or "Development Code" is used, or, if neither one of those names nor the "common name" is used, an "alternative name" is used. "CAS Registry Number" means the Chemical Abstracts Registry Number.

[0475] A compound selected from the group consisting of compounds of formula (I), (Ia), (Ia-A), (Ia-B) or (Ia-C), or a compound selected from the group consisting of compounds as shown in Tables C-1 to C-21, or an active ingredient mixture of compounds as listed in Table P (below): preferably in a mixing ratio of from 100:1 to 1:100, especially from 50:1 to 1:50, more especially from 20:1 to 1:20, even more especially from 10:1 to 1:10, and still more especially from 5:1 to 1:5. Those mixing ratios are by weight.

[0476] The mixtures as described above may be used in a method for controlling pests which comprises applying a composition comprising a mixture as described above to the pests or their environment, except for methods for treating the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body.

[0477] A mixture comprising a compound selected from a compound of formula (I), (Ia), (Ia-A), (Ia-B), (Ia-C), or a compound selected from the group consisting of compounds as shown in Tables C-1 to C-21, or a compound as listed in Table P (below), and one or more active ingredients as described above can be applied, for example, in a single "ready-to-use" form, in a combined spray mixture (the mixture consists of separate formulations of the single active ingredient components) (such as a "tank mix"), and when applied in a sequential manner (i.e., one after another within a reasonably short period of time, such as a few hours or days) these single active ingredients are used in combination. The order of applying a compound selected from a compound of formula (I), (Ia), (Ia-A), (Ia-B), (Ia-C), or a compound selected from the group consisting of compounds as shown in Tables C-1 to C-21, or a compound as listed in Table P (below): with one or more active ingredients as described above is not critical for practicing the present invention.

[0478] The compositions according to the invention may also contain further solid or liquid auxiliaries, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soybean oil), defoamers (for example silicone oils), preservatives, viscosity regulators, adhesives and / or tackifiers, fertilizers or other active ingredients for obtaining specific effects, such as bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0479] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries, for example by grinding, screening and / or compressing the solid active ingredient; and in the presence of at least one auxiliary, for example by intimately mixing the active ingredient with one or more auxiliary agents and / or grinding the active ingredient with one or more auxiliary agents. These methods for preparing the compositions and the use of compound (I) for preparing these compositions are also the subject matter of the present invention.

[0480] Another aspect of the invention relates to the use of a compound of formula (I) or preferably a compound as defined herein, a composition comprising at least one compound of formula (I) or at least one preferred compound as defined herein, or a fungicidal or insecticidal mixture comprising at least one compound of formula (I) or at least one preferred compound as defined herein (in admixture with other fungicides or insecticides as described above) according to the invention for controlling or preventing infestation of plants, such as useful plants (such as crop plants), their propagation materials (such as seeds), harvested crops (such as harvested food crops), or non-living materials by insects or phytopathogenic microorganisms, preferably fungal organisms.

[0481] Another aspect of the present invention relates to a method for controlling or preventing infestation of plants, for example useful plants (such as crop plants), their propagation materials (such as seeds), harvested crops (such as harvested food crops), or non-living materials by phytopathogenic microorganisms or spoilage microorganisms or organisms potentially harmful to humans (especially fungal organisms), which method comprises applying a compound of formula (I) according to the present invention or preferably various compounds as defined herein as active ingredients to these plants, parts of these plants or their loci, their propagation materials, or any parts of these non-living materials.

[0482] Control or prevention means the reduction of infestation by insects or phytopathogenic or spoilage microorganisms or organisms potentially harmful to humans, especially fungal organisms, to such a level that an improvement is demonstrated.

[0483] The preferred method of controlling or preventing crop plants from being infected by plant pathogenic microorganisms (especially fungal organisms) or insects is foliar application, which includes applying the compound of formula (I) according to the present invention or containing at least one agrochemical composition of the compound of formula (I). Frequency of application and application ratio will depend on the risk of infection by the corresponding pathogen or insect. However, the compound of formula (I) according to the present invention can also penetrate plants by roots (systemic action) through soil by soaking the place of plants with liquid formulations or by applying the compound in solid form, for example, in granular form to soil (soil application). In rice crops, such granules can be applied to the paddy field of irrigation. The compound of formula (I) can also be applied to seeds (coating) by dipping seeds or tubers with liquid formulations of fungicides or coating them with solid formulations.

[0484] Formulations (e.g. compositions containing a compound of formula (I) according to the invention and, if desired, solid or liquid adjuvants or monomers for encapsulating the compound of formula (I)) can be prepared in a known manner, typically by intimately mixing and / or grinding the compound with extenders (e.g. solvents, solid carriers and optionally surface-active compounds (surfactants)).

[0485] Advantageous application rates are generally from 5 g to 2 kg of active ingredient (ai) / hectare (ha), preferably from 10 g to 1 kg ai / ha, most preferably from 20 g to 600 g ai / ha. When used as a seed drench, a suitable dosage is from 10 mg to 1 g of active substance / kg seed.

[0486] As used herein, the term "gai / ha" refers to the application rate given in grams [g] of active ingredient [ai] per unit surface [ha]. The unit hectare (symbol ha) is equal to a square meter with a side length of 100 m (1 hm 2 ) or a square of 10,000 square meters. The hectare is a commonly used unit of area in the metric system.

[0487] When the combination according to the invention is used to treat seed, application rates of 0.001 to 50 g of compound of formula (I) per kg of seed, preferably from 0.01 to 10 g per kg of seed, are generally sufficient.

[0488] Suitably, the composition comprising a compound of formula (I) according to the invention is administered prophylactically (meaning before the disease develops) or therapeutically (meaning after the disease develops).

[0489] The composition of the present invention can be used in any conventional form, for example in the form of a twin pack, a dry powder for seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water-dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspoemulsion (SE), a capsule suspension (CS), a water-dispersible granule (WG), an emulsifiable granule (EG), an oil-in-water emulsion (EO), an oil-in-water emulsion (EW), a microemulsion (ME), a dispersible oil suspension (OD), an oil suspension (OF), an oil-soluble liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with an agriculturally acceptable adjuvant.

[0490] Such compositions can be produced in a conventional manner, for example by mixing the active ingredient with an appropriate formulation inert (diluent, solvent, filler and optionally other formulation ingredients, such as surfactants, biocides, antifreeze agents, adhesives, thickeners and compounds providing auxiliary effects). Conventional slow-release formulations intended to provide long-term sustained efficacy can also be used. In particular, formulations to be applied in a spray form, such as water-dispersible concentrates (e.g., EC, SC, DC, OD, SE, EW, EO, etc.), wettable powders and granules may contain surfactants such as wetting agents and dispersants and other compounds providing auxiliary effects, such as condensation products of formaldehyde with naphthalene sulfonates, alkylaryl sulfonates, lignin sulfonates, fatty alkyl sulfates and ethoxylated alkylphenols and ethoxylated fatty alcohols.

[0491] The seed dressing formulation is applied to the seed in a manner known per se using the combination of the invention and the diluent in the form of a suitable seed dressing formulation, for example an aqueous suspension or dry powder with good adhesion to the seed. Such seed dressing formulations are known in the art. The seed dressing formulation may contain a single active ingredient or a combination of active ingredients in encapsulated form, for example as a sustained-release capsule or microcapsule.

[0492] Typically, these formulations comprise by weight from 0.01% to 90% of an active agent, from 0% to 20% of an agriculturally acceptable surfactant and 10% to 99.99% of a solid or liquid formulation inert agent and one or more adjuvants, the active agent being optionally composed together with other active agents (particularly microbicides or preservatives, etc.) by a compound with formula (I) at least according to the present invention. The concentrated form of the composition typically contains by weight between about 2% and 80%, preferably between about 5% and 70% of an active agent. The application form of the formulation can for example contain by weight from 0.01% to 20%, preferably by weight from 0.01% to 5% of an active agent. However, commercial products will preferably be formulated as concentrates, and end users will typically use diluted formulations.

[0493] While it is preferred that commercial products be formulated as concentrates, the end user will generally employ a diluted formulation.

[0494] The application rate varies within a wide range and depends on the nature of the soil, the application method, the crop plants, the harmful organisms to be controlled, the prevailing climatic conditions, and other factors governed by the application method, the application time and the target crop. In general, the compound can be applied at a rate of from 1 to 2000 l / ha, especially from 10 to 1000 l / ha.

[0495] Preferred formulations may have the following composition (wt%):

[0496] Emulsifiable concentrates :

[0497] Active ingredient: 1% to 95%, preferably 60% to 90%

[0498] Surfactant: 1% to 30%, preferably 5% to 20%

[0499] Liquid carrier: 1% to 80%, preferably 1% to 35%

[0500] Dust powder :

[0501] Active ingredient: 0.1% to 10%, preferably 0.1% to 5%

[0502] Solid carrier: 99.9% to 90%, preferably 99.9% to 99%

[0503] Suspension concentrate:

[0504] Active ingredient: 5% to 75%, preferably 10% to 50%

[0505] Water: 94% to 24%, preferably 88% to 30%

[0506] Surfactant: 1% to 40%, preferably 2% to 30%

[0507] Wettable powder :

[0508] Active ingredient: 0.5% to 90%, preferably 1% to 80%

[0509] Surfactant: 0.5% to 20%, preferably 1% to 15%

[0510] Solid carrier: 5% to 95%, preferably 15% to 90%

[0511] Granules:

[0512] Active ingredient: 0.1% to 30%, preferably 0.1% to 15%

[0513] Solid carrier: 99.5% to 70%, preferably 97% to 85%

[0514] The disclosure of the present application enables every combination of the embodiments disclosed herein to be achieved.

[0515] Compounds according to the following tables C-1 to C-21 can be prepared according to the above method. These examples that follow are intended to illustrate the present invention and to show preferred compounds with formula (I). In any one of the following tables C-1 to C-21, the presence of one or more possible asymmetric carbon atoms in compounds with formula (I) according to the present invention means that these compounds can exist in chiral isomer form, i.e., enantiomer or diastereoisomer form.

[0516] The disclosure of the present application enables every combination of the embodiments disclosed herein to be achieved.

[0517] The compounds according to the following Tables C-1 to C-21 can be prepared according to the above methods. The examples which follow are intended to illustrate the invention and to show preferred compounds of formula (I).

[0518] Table A :

[0519] This table discloses 20 substituent definitions of formula (I)

[0520]

[0521] Where G has the formula defined as

[0522] Table B :

[0523] This table discloses 14 substituent definitions Q having formula (I)

[0524]

[0525] index Q index Q Q-1 2-Pyridyl Q-8 (6-Cyclopropyl-2-pyridyl) Q-2 (6-Chloro-2-pyridinyl) Q-9 (6-Chloro-4-methoxy-2-pyridinyl) Q-3 (6-Bromo-2-pyridyl) Q-10 (6-Chloro-5-methyl-2-pyridinyl) Q-4 (6-Methyl-2-pyridyl) Q-11 (6-Chloropyrazin-2-yl) Q-5 (6-Cyano-2-pyridyl) Q-12 (2-Chloropyrimidin-4-yl) Q-6 (6-vinyl-2-pyridyl) Q-13 (6-Chloropyridazin-3-yl) Q-7 [6-(Trifluoromethyl)-2-pyridinyl] Q-14 (6-cyanopyrazin-2-yl)

[0526] Tables C-1 to C-21 disclose specific compounds of the present invention having formula (I) wherein the Q and G substituents are as defined in Tables A and B.

[0527] Table C-1: This table provides 20 compounds C-1.01 to C-1.20 having formula (I), wherein R 2 , R 4 , R 5 and R 6 is H, Q is Q-1 as defined in Table B, and G is as defined in Table A.

[0528] For example, compound C-1.01 has the following structure:

[0529]

[0530] Table C-2: This table provides 20 compounds C-2.01 to C-2.20 having formula (I), wherein R 2 , R 5 , R 6 Yes H, R 4 is CH3, Q is Q-1 as defined in Table B, and G is as defined in Table A.

[0531] For example, compound C-2.05 has the following structure:

[0532]

[0533] Table C-3: This table provides 20 compounds C-3.01 to C-3.20 having formula (I), wherein R 2 , R 5 , R 6 Yes H, R 4is CH3, Q is Q-2 as defined in Table B, and G is as defined in Table A. For example, compound C-3.11 has the following structure;

[0534]

[0535] Table C-4: This table provides 20 compounds C-4.01 to C-4.20 having formula (I), wherein R 2 , R 5 , R 6 Yes H, R 4 is CH3, Q is Q-3 as defined in Table B, and G is as defined in Table A.

[0536] Table C-5: This table provides 20 compounds C-5.01 to C-5.20 having formula (I), wherein R 2 , R 5 , R 6 Yes H, R 4 is CH3, Q is Q-4 as defined in Table B, and G is as defined in Table A.

[0537] Table C-6: This table provides 20 compounds C-6.01 to C-6.20 having formula (I), wherein R 2 , R 5 , R 6 Yes H, R 4 is CH3, Q is Q-5 as defined in Table B, and G is as defined in Table A.

[0538] Table C-7: This table provides 20 compounds C7.01 to C-7.20 having formula (I), wherein R 2 , R 5 , R 6 Yes H, R 4 is CH3, Q is Q-6 as defined in Table B, and G is as defined in Table A.

[0539] Table C-8: This table provides 20 compounds C8.01 to C-8.20 having formula (I), wherein R 2 , R 5 , R 6 Yes H, R 4 is CH3, Q is Q-7 as defined in Table B, and G is as defined in Table A.

[0540] Table C-9: This table provides 12 compounds C-9.01 to C-9.20 having formula (I), wherein R2 , R 5 , R 6 Yes H, R 4 is CH3, Q is Q-8 as defined in Table B, and G is as defined in Table A. For example, compound C-9.03 has the following structure:

[0541]

[0542] Table C-10: This table provides 20 compounds C-10.01 to C-10.20 having formula (I), wherein R 2 , R 5 , R 6 Yes H, R 4 is CH3, Q is Q-9 as defined in Table B, and G is as defined in Table A.

[0543] Table C-11: This table provides 20 compounds C-11.01 to C-11.20 having formula (I), wherein R 2 , R 5 , R 6 Yes H, R 4 is CH3, Q is Q-10 as defined in Table B, and G is as defined in Table A.

[0544] Table C-12: This table provides 20 compounds C-12.01 to C-12.20 having formula (I), wherein R 2 , R 5 , R 6 Yes H, R 4 is CH3, Q is Q-11 as defined in Table B, and G is as defined in Table A.

[0545] Table C-13: This table provides 20 compounds C-13.01 to C-13.20 having formula (I), wherein R 2 , R 5 , R 6 Yes H, R 4 is CH3, Q is Q-12 as defined in Table B, and G is as defined in Table A.

[0546] Table C-14: This table provides 20 compounds C-14.01 to C-14.20 having formula (I), wherein R 2 , R 5 , R 6 Yes H, R 4 is CH3, Q is Q-13 as defined in Table B, and G is as defined in Table A.

[0547] Table C-15: This table provides 20 compounds C-15.01 to C-15.20 having formula (I), wherein R 2 , R 5 , R 6 Yes H, R 4 is CH3, Q is Q-14 as defined in Table B, and G is as defined in Table A. For example, compound C-15.12 has the following structure:

[0548]

[0549] Table C-16: This table provides 20 compounds C-16.01 to C-16.20 having formula (I), wherein R 5 , R 6 Yes H, R 2 and R 4 is CH3, Q is Q-2 as defined in Table B, and G is as defined in Table A.

[0550] Table C-17: This table provides 20 compounds C-17.01 to C-17.20 having formula (I), wherein R 5 , R 6 Yes H, R 2 and R 4 is CH3, Q is Q-3 as defined in Table B, and G is as defined in Table A.

[0551] Table C-18: This table provides 20 compounds C-18.01 to C-18.20 having formula (I), wherein R 5 , R 6 Yes H, R 2 and R 4 is CH3, Q is Q-5 as defined in Table B, and G is as defined in Table A. For example, compound C-18.01 has the following structure:

[0552] Table C-19: This table provides 20 compounds C-19.01 to C-19.20 having formula (I), wherein R 5 , R 6 Yes H, R 2 It is Cl, R 4 is CH3, Q is Q-2 as defined in Table B, and G is as defined in Table A.

[0553] Table C-20: This table provides 20 compounds C-20.01 to C-20.20 having formula (I), wherein R5 , R 6 Yes H, R 2 It is Cl, R 4 is CH3, Q is Q-3 as defined in Table B, and G is as defined in Table A.

[0554] Table C-21: This table provides 20 compounds C-21.01 to C-21.20 having formula (I), wherein R 5 , R 6 Yes H, R 2 It is Cl, R 4 is CH3, Q is Q-5 as defined in Table B, and G is as defined in Table A. For example, compound C-21.01 has the following structure:

[0555]

[0556] Examples

[0557] The following examples serve to illustrate the invention and are not meant to limit the invention in any way.

[0558] The compounds of the invention can be distinguished from known compounds by a greater efficacy at low application rates, which can be demonstrated by a person skilled in the art using the experimental procedures outlined in the examples, using lower application rates (if necessary), for example, 60 ppm, 20 ppm or 2 ppm.

[0559] Compounds of formula (I) may have a number of benefits, including, among others, favorable levels of biological activity for protecting plants against diseases caused by fungi or superior properties for use as active ingredients in agrochemicals (e.g., higher biological activity, favorable activity spectrum, increased safety (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).

[0560] Throughout this specification, temperatures are given in degrees Celsius (°C) and "mp" means melting point. LC / MS or LC-MS or LCMS means liquid chromatography mass spectrometry and a description of the apparatus and methods follows.

[0561] Recorded on a Bruker 400 MHz spectrometer 1 H NMR and 19 F NMR measurements, chemical shifts relative to TMS ( 1 H) and CFCl3( 19F) Standards are given in ppm. Spectra were measured in deuterated solvents as specified. The compounds were characterized using any of the following LCMS methods. The characteristic LCMS values ​​obtained for each compound are the retention time ("Rt", reported in minutes) and the measured molecular ion (M+H) + or (MH) - .

[0562] LCMS Method A: Spectra were recorded on a mass spectrometer from Waters Corp. (SQD, SQDII or QDA single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ions), capillary: 0.8-3.00 kV, cone: 5-30 V, source temperature: 120°C-150°C, desolvation temperature: 350°C-600°C, cone gas flow: 50-150 l / h, desolvation gas flow: 650-1000 l / h, mass range: 50 to 900 Da, and Acquity UPLC from Waters Corp.: binary pump, heated column compartment, diode array detector and ELSD. Column: Waters UPLC HSST3, 1.8 μm, 30 x 2.1 mm, temperature: 60°C, DAD wavelength range (nm): 210 to 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 for 0.2 min, then 10%-100% B in 1.0 min, 100% B isocratic for 0.2 min, 100%-10% B in 0.05 min, 10% B isocratic for 0.05 min.

[0563] LCMS Method B: Spectra were recorded on a mass spectrometer from Waters (SQD, SQDII or QDA single quadrupole mass spectrometer) equipped with an electrospray source.

[0564] Optimized mass parameters: ionization method: electrospray (ESI), polarity: positive and negative polarity switching, scan type: full scan, capillary (kV): 0.8, cone voltage (V): 23, source temperature (°C): 120, desolvation gas flow (L / Hr): 1000, desolvation temperature (°C): 600, cone gas flow (L / Hr): 50, mass range: 110 to 1200 Da;

[0565] Gradient conditions: Solvent A: water containing 0.1% formic acid: acetonitrile: 95:5 v / v, Solvent B: acetonitrile containing 0.05% formic acid

[0566]

[0567] PDA wavelength range: 200 to 400 nm

[0568] Column: Acquity UPLC HSS T3 C18, column length: 30 mm, column inner diameter: 2.1 mm, particle size: 1.8 μ, column oven temperature: 40 °C.

[0569] LCMS Method C: Spectra were recorded on a mass spectrometer from Waters (SQD, SQDII or QDA single quadrupole mass spectrometer) equipped with an electrospray source.

[0570] Optimized mass parameters: Ionization method: electrospray (ESI); Polarity: positive and negative polarity switching; Scan type: full scan; Capillary (kV): 3.00; Cone voltage (V): 41.00; Source temperature (°C): 150; Desolvation gas flow (L / Hr): 1000; Desolvation temperature (°C): 500; Cone gas flow (L / Hr): 50; Mass range: 110 to 1000 Da

[0571] Gradient conditions: Solvent A: water containing 0.1% formic acid: acetonitrile: 95:5 v / v; Solvent B: acetonitrile containing 0.05% formic acid

[0572]

[0573] PDA wavelength range: 200 to 400 nm;

[0574] Column: Acquity UPLC HSS T3 C18; column length: 30 mm; column inner diameter: 2.1 mm; particle size: 1.8 μ; column oven temperature: 40°C.

[0575] LCMS Method D: Spectra were recorded on a 6410 triple quadrupole mass spectrometer from Agilent Technologies (HPLC: Agilent 1200 Series HPLC)

[0576] Optimized mass parameters: ionization method: electrospray (ESI); polarity: positive and negative polarity switching; scan type: MS2 scan; capillary (kV): 4.00; fragmentor voltage (V): 100.00; gas temperature (°C): 350; gas flow (L / min): 11; nebulizer gas (psi): 40; mass range: 110 to 1000Da; detection (VWD): 254nm.

[0577] Gradient conditions: Solvent A: water containing 0.1% formic acid: acetonitrile: 95:5 v / v; Solvent B: acetonitrile containing 0.1% formic acid

[0578]

[0579]

[0580] Column: KINETEX EVO C18; Column length: 50 mm; Column inner diameter: 4.6 mm; Particle size: 2.6 μ; Column oven temperature: 40 °C

[0581] LCMS Method E: Spectra were recorded on a mass spectrometer from Waters (Acquity QDa mass spectrometer) equipped with an electrospray source (polarity: positive and negative switching), capillary: 0.8 kV, cone range: 25 V, extractor: V (Qda detector without extractor voltage), source temperature: 120°C, desolvation temperature: 600°C, cone gas flow: 50 L / h, desolvation gas flow: 1000 L / h, mass range: 110 to 850 Da) and Acquity UPLC from Waters: quaternary solvent manager, heated column compartment, diode array detector. Column: Acquity UPLC HSS T3 C18, 1.8 μm, 30x2.1 mm, temperature: 40°C, DAD wavelength range (nm): 200 to 400, solvent gradient: A = water + 5% acetonitrile + 0.1% HCOOH, B = acetonitrile + 0.05% HCOOH: Gradient: 0 min 10% B; 0.-0.2 min 10%-50% B; 0.2-0.6 min 50-100% B; 0.6-1.3 min 100% B; 1.3-1.4 min 100-10% B; 1.4-1.6 min 10% B; flow rate (mL / min) 0.6.

[0582] LCMS Method F:Spectra were recorded on an ACQUITY mass spectrometer from Waters (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 / hr, mass range: 140 to 800 Da) and an ACQUITY UPLC from Waters with a solvent degasser, binary pump, heated column compartment, and a diode array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30x2.1 mm, temperature: 60°C, DAD wavelength range (nm): 210 to 400, solvent gradient: A = water / methanol 9:1 + 0.1% formic acid, B = acetonitrile + 0.1% formic acid, gradient: 0%-100% B in 3.0 min; flow rate (ml / min) 0.75.

[0583] Preparation Examples

[0584] Wettable

[0585]

[0586] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain wettable powders which can be diluted with water to give a suspension of the desired concentration.

[0587] Dry seeds

[0588]

[0589] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a dust that can be used directly for seed treatment.

[0590] Emulsifiable concentrates

[0591]

[0592] Emulsions of any desired dilution which can be used in plant protection can be obtained from these concentrates by dilution with water.

[0593] dust

[0594]

[0595] Ready-to-use dusts are obtained by mixing the combination with a carrier and grinding the mixture in a suitable grinder. Such dusts can also be used for dry seed dressing of seeds.

[0596] Extruder Granules

[0597]

[0598] The combination is mixed with the auxiliaries and ground, and the mixture is moistened with water. The mixture is extruded and then dried in an air stream.

[0599] Coated granules

[0600] Active ingredient 8%

[0601] Polyethylene glycol (molecular weight 200) 3%

[0602] Kaolin 89%

[0603] The finely ground combination is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

[0604] Suspension concentrates

[0605]

[0606]

[0607] The finely ground combination is intimately mixed with the adjuvants to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants together with plant propagation materials can be treated and protected against microbial infestation by spraying, pouring or immersion.

[0608] Flowable concentrate for seed treatment

[0609]

[0610] The finely ground combination is intimately mixed with the adjuvants to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants together with plant propagation materials can be treated and protected against microbial infestation by spraying, pouring or immersion.

[0611] Extended-release capsule suspension

[0612] 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is reached. To this emulsion are added 2.8 parts of a 1,6-hexanediamine mixture in 5.3 parts of water. The mixture is stirred until the polymerization reaction is complete. The capsule suspension obtained is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% of active ingredient. The diameter of the medium capsules is 8-15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for this purpose.

[0613] 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 emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oil dispersions (OD), oil suspensions (OF), oil-soluble liquids (OL), soluble concentrates (SL), ultra low volume suspensions (SU), ultra low volume liquids (UL), master batches (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0614] abbreviation

[0615] CDCl3 deuterated chloroform

[0616] conc.

[0617] DABCO 1,4-diazabicyclo[2.2.2]octane, also known as triethylenediamine or TEDA

[0618] DCC Dicyclohexylcarbodiimide

[0619] DIPEA Diisopropylethylamine (N,N-diisopropylethylamine)

[0620] DMF Dimethylformamide (N,N-dimethylformamide)

[0621] DMSO Dimethyl sulfoxide

[0622] DMSO-d6 Deuterated dimethyl sulfoxide

[0623] equiv. Equivalent

[0624] EtOAc Ethyl acetate

[0625] HATU 1-[Bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate

[0626] HCl

[0627] h / hrs hour

[0628] LCMS liquid chromatography mass spectrometry

[0629] rh relative humidity

[0630] rt room temperature

[0631] RT retention time

[0632] ssp. subspecies

[0633] TBME tert-butyl methyl ether or tert-butyl methyl ether

[0634] THF Tetrahydrofuran

[0635] TLC Thin layer chromatography

[0636] TMS Tetramethylsilane

[0637] T3P Propylphosphonic anhydride, reactive n-propylphosphonic acid cyclic anhydride Preparation Example:

[0638] The compounds of formula (I) according to the present invention can be prepared using the synthetic techniques described above and below.

[0639] "Mp" means melting point in °C (degrees Celsius). Free radical means methyl group.

[0640] Recorded on a Bruker 400 MHz spectrometer 1 H NMR and 19 F NMR measurements, chemical shifts relative to TMS ( 1 H) and CFCl3( 19 F) Standards are given in ppm. Spectra were measured in deuterated solvents as specified. The compounds were characterized using any of the following LCMS methods. The characteristic LCMS values ​​obtained for each compound are the retention time ("Rt", reported in minutes) and the measured molecular ion (M+H) + or (MH) - .

[0641] Example 1: N-[2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl) Preparation of triazole-4-carboxamide (Compound P-1, Table P)

[0642]

[0643] Step 1: Preparation of 2-(1-methylpyrazol-4-yl)propionitrile

[0644]

[0645] 2-(1-methyl-1h-pyrazole-4-yl)acetonitrile (10.00g, 78.42mmol) is dissolved in THF (314mL) under argon, and the light yellow solution is cooled to -78 ° C. In this solution, n-butyl lithium (31mL, 78.42mmol) is added dropwise, and the light brown suspension of the obtained is stirred at this temperature for 25 minutes. After this time, iodomethane (11.24g, 4.93mL, 78.42mmol) is added dropwise. The brown solution of the obtained is stirred at -78 ° C for 5 minutes, warmed to room temperature (rt) and stirred under argon for 30 minutes at rt. The reaction mixture is poured into water, and then extracted twice with EtOAc. The combined organic layer is washed once with brine, dried over anhydrous sodium sulfate, filtered and concentrated in a vacuum to obtain 2-(1-methylpyrazole-4-yl) propionitrile as a light brown liquid.

[0646] LC / MS (Method A); 136 [M+H] + ; Retention time: 0.43min, 0.44min, 0.55min.

[0647] 1 H NMR (400MHz, CDCl3) δppm 1.64 (d, J = 6.90Hz, 3H) 3.86-3.93 (m, 4H) 7.40 (s, 1H) 7.46 (s, 1H).

[0648] Step 2: Preparation of 2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propionitrile

[0649]

[0650] Under argon, 2-(1-methylpyrazole-4-yl)propionitrile sample (2.00g, 14.80mmol) was dissolved in THF (59.18mL) to obtain a light yellow solution. The solution was cooled to -78 ° C, and then treated dropwise with n-butyl lithium (5.90mL, 14.80mmol). Before adding 2,6-dichloropyridine (2.23g, 14.80mmol) in batches, the resulting light brown suspension was stirred at this temperature for 10 minutes. The resulting brown suspension was stirred at -78 ° C for 5 minutes, brought to room temperature and stirred at rt for 30 minutes under argon to obtain a light brown solution. The reaction mixture was poured into water and extracted twice with ethyl acetate. The combined organic layer was washed once with brine, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo at 60 ° C to obtain 3.68g of dark brown liquid. The crude brown liquid was purified by flash chromatography using ethyl acetate in cyclohexane as eluent to give 2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propanenitrile (2.71 g, 74.2 yield) as a light yellow oil.

[0651] LC / MS (Method A); 247 [M+H] + ; Retention time: 0.82min.

[0652] 1 H NMR (400MHz, CDCl3) δppm 2.12 (s, 3H) 3.90 (s, 3H) 7.27-7.32 (m, 1H) 7.45 (s, 1H) 7.46-7.54 (m, 2H) 7.62-7.74 (m, 1H).

[0653] Step 3: Preparation of 2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propan-1-amine

[0654]

[0655] A solution of 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propionitrile (2.71 g, 11.0 mmol) in THF (33.0 mL) was treated dropwise with borane dimethyl sulfide complex (2.50 g, 3.13 mL, 33.0 mmol) at room temperature under argon, and the resulting pale yellow solution was stirred at 65° C. for 4 hours. The reaction mixture was cooled to 0° C. before concentrated hydrochloric acid (HCl) (7.36 mL, 44.2 mmol) was added dropwise. The reaction mixture was stirred at 50° C. for 1 hour. The reaction mixture was cooled to rt and water was added. To this reaction mixture was added an aqueous sodium hydroxide (6N NaOH) solution until the pH was 12, and the resulting reaction mixture was extracted three times with ethyl acetate. The combined organic layers were washed once with brine, dried over anhydrous sodium sulfate, and concentrated in vacuo to give 2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propan-1-amine as a light yellow oil, which was used in the next step without further purification.

[0656] 1 H NMR(400MHz,DMSO d6)δppm 1.57(s,3H)2.98(d,J=12.72Hz,1H)3.16(d,J=12.72Hz,1H)3.77(s,3H)7.20-7.35(m,3H)7.50(s,1H)7.75(t,J=7.81Hz,1H).

[0657] Step 4: Preparation of methyl 1-(2,4-difluorophenyl)triazole-4-carboxylate

[0658]

[0659] A solution of 1-azido-2,4-difluoro-benzene (0.30 g, 1.8 mmol) in methanol (3.6 mL) was treated with anhydrous copper sulfate (II) (0.053 g, 0.33 mmol), sodium ascorbate (0.46 g, 2.3 mmol) in water (3.6 mL), and then methyl prop-2-ynoate (0.14 g, 0.14 mL, 1.7 mmol). The reddish reaction mixture was stirred at rt for 2 days (monitored by LCMS). The reaction mixture was then concentrated in vacuo, and the residue was taken up in water and EtOAc. The organic layer was separated, washed with brine, and the separated organic layer was dried over MgSO4, filtered and concentrated in vacuo. The crude product was adsorbed onto The product was purified by column chromatography on silica gel (Rf 200) eluting with cyclohexane / EtOAc to give the title compound as a white solid.

[0660] LC / MS (Method A) m / z=240 [M+H] +; Retention time = 0.79min;

[0661] 1 H NMR (400MHz, CDCl3) δppm 4.02 (s, 3H) 7.09-7.17 (m, 2H) 7.96-8.05 (m, 1H) 8.59 (d, J = 2.57Hz, 1H)

[0662] Step 5: Preparation of 1-(2,4-difluorophenyl)triazole-4-carboxylic acid

[0663]

[0664] 1-(2,4-difluorophenyl)triazole-4-carboxylic acid methyl ester (0.31 g, 1.3 mmol) was dissolved in THF (6.5 mL) and water (3.2 mL) under argon to give a light brown solution. To this solution was added LiOH.HO (0.047 g, 1.9 mmol) and the mixture was stirred at rt. After 3 hours, LC / MS analysis (desired mass at rt = 0.63 min) showed complete consumption of the starting material. The sample was concentrated in vacuo and the residue was taken up in water and EtOAc, and the resulting mixture was acidified with 2N HCl. The organic layer was separated, dried over NaSO, filtered and concentrated in vacuo to give the title compound as a white solid.

[0665] LC / MS (Method A): m / z=226 [M+H] + ; Retention time = 0.63min;

[0666] 1 H NMR(400MHz,DMSO)δppm 7.27-7.52(m,1H)7.73(ddd,J=11.10,8.71,2.57Hz,1H)7.95(td,J=8.80,5.87Hz,1H)9.15(d,J=1.47Hz,1H)13.26-13.60(m,1H)

[0667] Step 6: N-[2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl) Preparation of triazole-4-carboxamide (Compound P-1, Table P)

[0668] 1-(2,4-difluorophenyl)triazole-4-carboxylic acid (0.225g, 1.0mmol) and 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazole-4-yl)propan-1-amine (0.25g, 1mmol) were suspended in EtOAc (6mL). Diisopropylethylamine (DIPEA) (0.65g, 5mmol) and 1-propanephosphonic anhydride (T3P, 50% by mass in EtOAc, 2mL) were added to this mixture at 0°C, and the reaction mixture was stirred at rt for 2 hours (LCMS analysis showed that the reaction was complete). The reaction mixture was diluted with water and the resulting mixture was extracted with EtOAc (2x20 mL). The combined organic layer was washed with brine, dried over Na2SO4 and concentrated in vacuo. The crude product was adsorbed onto silica gel and purified by combiflash chromatography eluting with 0-80% cyclohexane / EtOAc to give the title compound as a white solid.

[0669] 1 H NMR (400MHz, CDCl3) δppm 8.50 (d, J = 2.57Hz, 1H) 8.05 (br t,J=6.36Hz,1H)7.91(td,J=8.71,5.69Hz,1H)7.58(t,J=7.82Hz,1H)7.35(s,1H)7.29(s,1H)7.23(d,J=7.82H z,1H)7.12(dd,J=8.86,8.01Hz,2H)7.06-7.10(m,1H)4.11(dd,J=16.75,6.60Hz,2H)3.88(s,3H)1.74(s,3H);

[0670] LC / MS (Method B): m / z=458 [M+H] + ; Retention time = 1.09 min

[0671] Example 2: N-[2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)- Preparation of 1,2,4-triazole-3-carboxamide (Compound P-4, Table P).

[0672]

[0673] Step 1: Preparation of methyl 1-(2,4-difluorophenyl)-1,2,4-triazole-3-carboxylate

[0674]

[0675] Analogous to the preparation described in Org. Lett. [Organic Chemistry Communications] 2018, 20, 6930-6933. Therefore, a solution of 2,4-difluorobenzenediazonium tetrafluoroborate (prepared as described in J. Am. Chem. Soc. [American Chemical Society] (1956), 78, 2593-6, 500 mg, 0.5 g, 2.1939 mmol) in THF (8.8 mL) was cooled to 0 ° C, and lithium acetate dihydrate (0.44765 g, 4.3879 mmol), Cu (OAc) 2 (0.10 eq., 0.03985 g, 0.21939 mmol) and methyl 2-isocyanatoacetate (1.20 eq., 0.2609 g, 0.239 mL, 2.6327 mmol) were added at 0 ° C, and the mixture was stirred at this temperature for 4 hours. LCMS analysis showed that the reaction was complete after this time. The reaction mixture was poured into water (25 mL) and the resulting mixture was extracted with EtOAc (2 × 20 mL). The combined organic layers were washed with brine, dried over Na2SO4 and concentrated in vacuo. The crude material was purified by column chromatography (24 g SiO2 column, eluted with EtOAc / cyclohexane gradient) to obtain the title compound as an oil.

[0676] 1 H NMR (400MHz, CDCl3) δppm 8.68 (d, J = 2.81Hz, 1H) 7.93-8.00 (m, 1H) 7.08-7.14 (m, 2H) 4.08 (s, 3H) 1.27 (s, 1H)

[0677] Step 2: N-[2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)- Preparation of 1,2,4-triazole-3-carboxamide (Compound P-4, Table P)

[0678] 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazole-4-yl)propan-1-amine (0.031g, 0.12mmol) is added to a solution of 1-(2,4-difluorophenyl)-1,2,4-triazole-3-formic acid methyl ester (0.025g, 0.10mmol) in toluene (0.75mL) in a microwave vial. This reaction mixture is stirred for 5 minutes under an argon atmosphere and then bis(trimethylaluminum)-1,4-diazabicyclo[2.2.2]octane adduct (0.041g, 0.16mmol) is added, and the resulting reaction mixture is stirred in a microwave at 70°C. After the reaction is complete, the reaction mixture is diluted with water, extracted with EtOAc, and the organic layer is washed with brine, dried over Na2SO4 and concentrated in vacuo. The crude residue obtained was purified by silica gel chromatography using a cyclohexane / ethyl acetate eluent system to give N-[2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-1-(2,4-difluorophenyl)-1,2,4-triazole-3-carboxamide as a sticky mass.

[0679] LCMS (method C): 458 [M+H] + ; Retention time = 1.03min;

[0680] 1 H NMR(400MHz,CDCl3)δppm 8.52(d,1H),8.27(br t,1H),7.94(td,1H),7.51(t,1H),7.23-7.20(m,2H),7.14-7.18(m,1H),6.98-7.10(m,3H),4.01(dd,2H),3.80(s,3H),1.66(s,3H)

[0681] Example 3: N-[2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl) Preparation of tetrazole-5-carboxamide (Compound P-6, Table P)

[0682]

[0683] Step 1: Preparation of ethyl (2E)-2-(p-toluenesulfonylhydrazono)acetate

[0684]

[0685] At room temperature, a solution of 4-methylbenzenesulfonyl hydrazide (CAS [1576-35-8], 2 g, 10.73 mmol) in ethanol (40 mL) was treated with 2-oxoethyl acetate (2.63 g, 12.88 mmol). The reaction mixture was stirred for 1 hour and ethanol was removed by concentrating in a vacuum. The obtained residue was diluted with water and extracted with EtOAc. The organic phase was separated, and the solvent was evaporated in a vacuum to obtain (2E)-2-(tosylhydrazono)ethyl acetate, which was used as is in the next step (step 2).

[0686] LCMS (method C): 271 [M+H] + ; Retention time = 1.04min;

[0687] 1 H NMR (400MHz, CDCl3) δppm 9.31(s,1H)7.85(d,J=8.31Hz,2H)7.34(d,J=8.07Hz,2H)7.23(s,1H)4.27(q,J =7.09Hz,2H)4.14(q,J=7.09Hz,1H)2.44(s,3H)2.07(s,2H)1.23-1.37(m,7H).

[0688] Step 2: Preparation of ethyl 2-(2,4-difluorophenyl)tetrazolyl-5-carboxylate

[0689]

[0690] 2,4-difluoroaniline (1g, 7.74mmol) is dissolved in 6M aqueous hydrochloric acid solution (deionized water) (6mL, 36mmol) and ethanol (5mL) and is cooled to 0 DEG C. Sodium nitrite (0.64g, 9.29mmol) is added to the solution and the solution of gained is stirred at 0 DEG C for 1 hour, and then added dropwise at -20 DEG C to a solution of (2E)-2-(tosylhydrazono)ethyl acetate (2.3g, 8.51mmol) in pyridine (20mL). Allow the reaction mixture to slowly warm up to room temperature and then stir for 5 hours. The mixture of gained is diluted with 1N HCl and water layer is extracted with EtOAc (3x20 mL). The combined organic layers were dried over Na 2 SO 4 and concentrated in vacuo to give the crude product, which was purified by column chromatography eluting with 30% EtOAc in hexanes to give ethyl 2-(2,4-difluorophenyl)tetrazole-5-carboxylate as a reddish oil.

[0691] LCMS (Method B): [M+H+] not detected; retention time = 1.10 min;

[0692] 1H NMR (400MHz, CDCl3δppm 7.86-7.94(m,1H)7.11-7.21(m,2H)4.60(q,J=7.21Hz,2H)2.03(s,1H)1.51(t,J=7.13Hz,3H)

[0693] Step 3: Preparation of 2-(2,4-difluorophenyl)tetrazolyl-5-carboxylic acid

[0694]

[0695] Under rt, add LiOH.H to the solution of 5-methylisoxazole-3-methyl-formiate (300mg, 1.18mmol) in THF (3mL) and water (1.5mL) that stirs o (0.113mg, 4.72), and reactant mixture is stirred at room temperature for 30min.Organic solvent is removed by concentrating in a vacuum, and aqueous residue is diluted with 2N HCl, and then extracted with EtOAc (3x20 mL).By the organic phase merged through Na sO dry, filter and concentrate in a vacuum to obtain reddish solid 2-(2,4-difluorophenyl) tetrazole-5-formic acid.

[0696] LCMS (Method C): 227 [M+H] + ; Retention time = 0.87-1.11min;

[0697] 1 H NMR(400MHz,DMSO-d6)δppm 8.10(td,J=8.69,5.75Hz,1H)7.73-7.88(m,1H)7.40-7.50(m,1H)3.36-3.63(m,3H)3.07-3.35(m,3H)1.99(s,1H)1.91(s,1H)1.24(s,1H)

[0698] Step 4: N-[2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl) Preparation of tetrazole-5-carboxamide (Compound P-6, Table X).

[0699] A mixture of 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazole-4-yl)propan-1-amine (6.37 g, 22.9 mmol, prepared as previously described), 2-(2,4-difluorophenyl)tetrazole-5-carboxylic acid (6.32 g, 25.2 mmol), N,N-diisopropylethylamine (DIPEA) (9.33 g, 68.6 mmol) and T3P (50 mass % in EtOAc) (40 mL) was stirred in EtOAc (114 mL) at room temperature for 1 hour. LCMS showed that the reaction was complete after this time. The reaction mixture was diluted with water and EtOAc, the organic layer was separated and the water layer was stripped three times with EtOAc. The combined organic layer was dried over Na2SO4, filtered and evaporated in a vacuum. The crude product was purified by column chromatography eluting with EtOAc / cyclohexane to give N-[2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)tetrazole-5-carboxamide as an off-white solid.

[0700] LCMS (method B): 459 [M+H] + ; Retention time = 1.14min;

[0701] 1 H NMR(400MHz,DMSO-d6)δppm 8.75(t,J=6.38Hz,1H),8.07(td,J=8.76,5.75Hz,1H),7.76-7.83(m,2H),7.62(s,1H),7.45(t,J=8.38Hz,1H),7.38(d,J=7.38Hz,1H),7 .35(d,J=0.75Hz,1H),7.29(d,J=7.25Hz,1H),4.08(dd,J=13.26,6.25Hz,1H),3.91(dd,J=13.32,6.57Hz,1H),3.78(s,3H),1.66(s,3H)

[0702] Example 4: N-[2-(6-cyano-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorobenzene Preparation of 5-(4-(4-(4-nitro)tetrazole-5-carboxamide (Compound P-5, Table P).

[0703]

[0704] Under nitrogen atmosphere, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)tetrazole-5-carboxamide (2.40 g, 4.97 mmol, prepared as described in Example 3) and zinc cyanide (1.19 g, 9.94 mmol) were dissolved in N,N-dimethylformamide (25 mL). The resulting reaction mixture was degassed under nitrogen for 10 minutes. Then, tetrakis(triphenylphosphine)palladium(0) (0.58 g, 0.49 mmol) was added, and the resulting light brown suspension was stirred in a microwave at 120° C. for 2 hours. The reaction progress was monitored by LCMS. After completion of the reaction, the reaction mixture was diluted with water and extracted with EtOAc. The organic layer was dried over Na2SO4 and concentrated in vacuo. The crude compound was purified by combined flash chromatography using EtOAc / cyclohexane as eluent. The resulting compound was further purified by reverse phase column using acetonitrile in water as eluent to give N-[2-(6-cyano-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl)tetrazole-5-carboxamide as a white solid.

[0705] LCMS (method B): 450 [M+H] + ; Retention time = 0.95min;

[0706] 1 H NMR(400MHz,DMSO-d6)δppm 8.80(t,J=6.30Hz,1H),8.07(td,J=8.74,5.75Hz,1H),7.90-7.99(m,2H),7.80(ddd,J=11.10,8.83,2.69Hz,1H),7.64(s,1H),7.63(d,J=8.34 Hz,1H),7.42-7.48(m,1H),7.36(d,J=0.73Hz,1H),4.13(dd,J=13.33,6.24Hz,1H),3.94(dd,J=13.39,6.66Hz,1H),3.78(s,3H),1.69(s,3H).

[0707] Example 5: N-[2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl) Preparation of triazole-4-carboxamide (Compound P-3, Table P).

[0708]

[0709] Step 1: Preparation of ethyl 2-[(2,4-difluorophenyl)hydrazono]-3-oxo-propionate

[0710]

[0711] At room temperature, 2,4-difluoroaniline (4.00g, 30.9mmol) and concentrated HCl (12mL, 35%) in water (32mL) were added to a two-necked round-bottom flask equipped with a nitrogen inlet. The reaction mixture was cooled to 0°C and a cold solution of sodium nitrite (2.56g, 37.1mmol) in water (32mL) was added to this solution, and the resulting mixture was stirred at 0°C for 5min. In another round-bottom flask, a solution of 3-(dimethylamino)prop-2-enoic acid ethyl ester (12.0g, 23.4mmol) and potassium acetate (4.61g, 46.4mmol) in ethanol (40mL) was stirred and cooled to 0°C. At 0°C, the above-mentioned diazotization solution was added dropwise thereto, and the reaction mixture was allowed to warm to room temperature and stirred for 18 hours. LCMS showed that the desired product was formed. The reaction was diluted with water and extracted with EtOAc (3x50 mL). The combined organic layers were washed with brine, dried over Na 2 SO 4 and concentrated in vacuo to give crude 2-[(2,4-difluorophenyl)hydrazono]-3-oxo-propionic acid ethyl ester as a brown solid, which was used as such in the next step.

[0712] LCMS (method B): 257 [M+H] + ; Retention time = 1.09 min

[0713] Step 2: Preparation of ethyl 2-[(2,4-difluorophenyl)hydrazono]-3-oximino-propionate

[0714]

[0715] To a solution of 2-[(2,4-difluorophenyl)hydrazono]-3-oxo-propionic acid ethyl ester (3.00 g, 5.85 mmol) in ethanol (30 mL) was added potassium acetate (1.45 g, 14.6 mmol) and hydroxylamine hydrochloride (0.49 g, 7.02 mmol). The reaction mixture was stirred at 80 ° C for 2 h. LCMS showed complete conversion to the desired product. The reaction mixture was cooled to rt and diluted with water and extracted with EtOAc (3x50 mL). The combined organic layer was washed with brine, dried over Na2SO4, and concentrated in vacuo to give the title compound as a brown solid, which was used as is in the next step.

[0716] LCMS (method B): 272 [M+H] + ; Retention time = 1.16min;

[0717] Step 3: Preparation of ethyl 2-(2,4-difluorophenyl)triazole-4-carboxylate

[0718]

[0719] At room temperature, 2- [(2,4- difluorophenyl) hydrazono] -3- oximino-propionic acid ethyl ester (3.4g, 6.3mmol) is treated with acetic anhydride (34mL, 10mL / g). Then the reaction mixture is stirred at 140 ° C for 1h. The reaction is monitored by LC-MS and the reaction mixture is cooled and quenched with ice-cold brine after completion. The reaction mixture is extracted with EtOAc (3x25 mL), and the combined organic layer is dried over Na2SO4, and concentrated in vacuo to produce a crude product. It is purified by using EtOAc / cyclohexane as eluent (5:95) combined flash chromatography to obtain the title compound as a brown solid.

[0720] LCMS (method C): 254 [M+H] + ; Retention time = 1.19 min

[0721] Step 4: Preparation of lithium 2-(2,4-difluorophenyl)triazole-4-carboxylate

[0722]

[0723] To the stirred solution of 2-(2,4-difluorophenyl)triazole-4-ethyl formate (0.10g, 0.31mmol) in THF (0.4mL) and water (0.1mL), lithium hydroxide (11.0mg0.47mmol) was added, and the reaction was stirred at rt for 3 hours. After the reaction was completed, the reaction mixture was concentrated in a vacuum, and the residue was ground with TBME. This produced 2-(2,4-difluorophenyl)triazole-4-lithium formate, which was used in the next step as it was.

[0724] LCMS (method B): 224 [M+H] + ; Retention time = 0.29 min

[0725] Step 5: N-[2-(6-chloro-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorophenyl) Preparation of triazole-4-carboxamide (Compound P-3, Table P).

[0726] 2-(2,4-difluorophenyl) triazole-4-formate lithium (70.0mg, 0.30mmol) and 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazole-4-yl) propan-1-amine (91.0mg, 0.36mmol) are suspended in ethyl acetate (5mL) and treated with triethylamine (97.7 μL, 0.66mmol) and T3P (50 mass %) in EtOAc (2mL) at 0°C. The reaction is stirred at room temperature for 2 hours, after which TLC and LCMS show that the reaction is complete. The reaction mixture is diluted with water and extracted with EtOAc (2x25 mL). The combined organic layer is washed with brine, dried over Na2SO4 and concentrated in vacuo. The crude product is purified by combined flash chromatography using 0-70% EtOAc / cyclohexane as eluent to obtain a product in the form of a yellow viscous mass.

[0727] LCMS (method C): 458 [M+H] + ; Retention time = 1.19min;

[0728] 1 H NMR (400MHz, CDCl3) δppm 8.28(s,1H),8.13-8.23(m,1H),7.89-7.95(m,1H),7.58(t,J=7.82Hz,1H),7.32(s,1H) ,7.16-7.25(m,2H),6.97-7.10(m,3H),4.03(d,J=6.36Hz,2H),3.88(s,3H),1.72(s,3H)

[0729] Example 6: N-[2-(6-cyano-2-pyridinyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(2,4-difluorobenzene Preparation of 4-(4-(4-yl)triazole-4-carboxamide (Compound P-2, Table P).

[0730]

[0731] By N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazole-4-yl) propyl]-2-(2,4-difluorophenyl) tetrazole-5-carboxamide (0.1g, 0.20mmol) and zinc cyanide (0.049g, 0.41mmol) in anhydrous N, N-dimethylformamide (1mL) solution degassed under nitrogen for 10 minutes.Then tetrakis (triphenylphosphine) palladium (0) (0.024g, 0.020mmol) is added, and the light brown suspension of gained is stirred in microwave for 3 hours at 120 ℃.After the reaction is completed, the reaction mixture is diluted with ice-cold water and extracted with EtOAc (2x25 mL).The organic layer merged is washed with salt water, through Na2SO4 is dried and concentrated in vacuo. The crude product was absorbed on silica gel and purified by combined flash chromatography using 0-80% EtOAc / cyclohexane as eluent to give the product as a white sticky solid.

[0732] LCMS (method B): 449 [M+H] + ; Retention time = 1.07min;

[0733] 1 H NMR (400MHz, CDCl3) δppm 8.28(s,1H),8.07(brt,1H),7.90-7.94(m,1H),7.76(t,J=7.29Hz,1H),7.62(d,J=7.46Hz,1H),7.43(d ,J=8.07Hz,1H),7.23-7.32(m,2H),7.02-7.11(m,2H),4.07(d,J=6.48Hz,2H),3.89(s,3H),1.74(s,3H)

[0734] Further examples of synthesized compounds of formula (I) are shown in Table P.

[0735] Table P: Synthesized compounds with spectroscopic and physicochemical data.

[0736]

[0737]

[0738]

[0739] Biological Examples

[0740] Example B1: Alternaria solani / tomato / leaf disc (early blight)

[0741] Tomato leaf disks cultivar Baby were placed on agar in a multiwell plate (24-well format) and sprayed with the prepared test compound diluted in water. After 2 days of application, the leaf disks were inoculated with a spore suspension of fungi. In a climate chamber, under a light scheme of 12 / 12h (light / darkness), the leaf disks inoculated were incubated at 23°C / 21°C (day / night) and 80% rh, and the activity of the compound was assessed as the percentage of disease control compared to untreated when appropriate levels of disease damage occurred on untreated inspection leaf disks (after 5-7 days of application).

[0742] The following compounds at 200 ppm gave at least 80% control of Alternaria solani when compared to untreated controls which showed extensive disease development under the same conditions:

[0743] P-1, P-3, P-5, P-6, P-7, P-8

[0744] Example B2: Botryotiniafuckeliana (Botrytis cinerea (Botrytiscinerea)) / Liquid culture (Botrytis cinerea)

[0745] Fungal conidia from frozen storage were directly mixed into nutrient broth (Vogels broth). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 3-4 days after application.

[0746] The following compounds gave at least 80% control of Botrytis cinerea at 20 ppm when compared to untreated controls showing extensive disease development under the same conditions:

[0747] P-1, P-5, P-6, P-7, P-8

[0748] Example B3: Glomerell alagenarum (Cucurbitaceae) (Colletotrichum lagenarium)) / Liquid culture (Anthrax)

[0749] The fungal conidia from frozen storage were directly mixed into the nutrient broth (PDB-potato dextrose broth). After the (DMSO) solution of the test compound was placed in a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. The test plate was incubated at 24°C and the inhibition of growth was measured photometrically 3-4 days after application.

[0750] The following compounds at 20 ppm gave at least 80% control of Aspergillus niger when compared to untreated controls showing extensive disease development under the same conditions:

[0751] P-1, P-5, P-6, P-7, P-8

[0752] Example B4: Blumeria graminis f. sp. tritici (Wheat Powdery Mildew (Erysiphegraminis f.sp.tritici) / wheat / leaf disc preventive (powdery mildew on wheat)

[0753] Wheat leaf segments cv. Kanzler were placed on agar in multiwell plates (24-well format) and sprayed with formulated test compounds diluted in water. One day after application, leaf disks were inoculated by shaking powdery mildew infected plants over these test plates. Inoculated leaf disks were incubated at 20° C. and 60% rh in a climate chamber under a light regime of 24 h dark followed by 12 h light / 12 h dark, and the activity of the compounds was assessed as the percentage of disease control compared to the untreated when appropriate levels of disease damage appeared on untreated test leaf segments (6-8 days after application).

[0754] The following compounds gave at least 80% control of wheat powdery mildew at 200 ppm when compared to untreated controls showing extensive disease development under the same conditions:

[0755] P-1, P-2, P-5, P-6, P-7, P-8, P-9

[0756] Example B5: Fusarium culmorum / liquid culture (head blight)

[0757] Fungal conidia from frozen storage were mixed directly into nutrient broth (PDB-potato dextrose broth). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 3-4 days after application.

[0758] The following compounds gave at least 80% control of Fusarium oxysporum at 20 ppm when compared to untreated controls showing extensive disease development under the same conditions:

[0759] P-1, P-6, P-7, P-8

[0760] Example B6: Fusarium spp. / wheat / spikelet preventive (head blight)

[0761] Wheat spikelets cultivar Monsun were placed on agar in a multiwell plate (24-well format) and sprayed with the prepared test compound diluted in water. One day after application, the spikelets were inoculated with a spore suspension of the fungus. The spikelets were incubated at 20°C and 60% rh in a climate chamber under a light regime of 72 h semi-darkness followed by 12 h light / 12 h dark, and the activity of the compound was assessed as the percentage of disease control compared to the untreated spikelets when appropriate levels of disease damage occurred (6-8 days after application).

[0762] The following compounds gave at least 80% control of Fusarium oxysporum at 200 ppm when compared to untreated controls showing extensive disease development under the same conditions:

[0763] P-6

[0764] Example B7: Phaeosphaerianodorum, Septorianodorum / wheat / leaf disc Prevention (glume blight)

[0765] Wheat leaf segments cv. Kanzler were placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compounds diluted in water. 2 days after application, the leaf disks were inoculated with a spore suspension of the fungus. The inoculated test leaf disks were incubated at 20°C and 75% rh in a climate chamber under a light regime of 12 h light / 12 h dark, and the activity of the compound was assessed as the percentage of disease control compared to the untreated when the appropriate level of disease damage appeared on the untreated test leaf disks (5-7 days after application).

[0766] The following compounds at 200 ppm gave at least 80% control of Septoria nodosum when compared to untreated controls which showed extensive disease development under the same conditions:

[0767] P-1, P-5, P-6, P-7, P-8, P-9

[0768] Example B8: Monographella nivalis (Snow mold leaf blight) / liquid culture (cereal root rot sick)

[0769] The fungal conidia from frozen storage were directly mixed into the nutrient broth (PDB-potato dextrose broth). After the (DMSO) solution of the test compound was placed in a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. The test plate was incubated at 24°C and the inhibition of growth was determined photometrically 4-5 days after application.

[0770] The following compounds gave at least 80% control of Thielavia nivalis at 20 ppm when compared to untreated controls showing extensive disease development under the same conditions:

[0771] P-1, P-5, P-6, P-7, P-8, P-9

[0772] Example B9: Mycosphaerella arachidis (Mycosphaerella arachidis) (Cercosporaarachidicola)) / Liquid culture (early leaf spot)

[0773] The fungal conidia from frozen storage were directly mixed into the nutrient broth (PDB-potato dextrose broth). After the (DMSO) solution of the test compound was placed in a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. The test plate was incubated at 24°C and the inhibition of growth was determined photometrically 4-5 days after application.

[0774] The following compounds gave at least 80% control of Mycosphaeria arachidis at 20 ppm when compared to untreated controls which showed extensive disease development under the same conditions:

[0775] P-1, P-5, P-6, P-7, P-8

[0776] Example B10: Pyrenophorateres / barley / leaf disc preventive (net spot)

[0777] Barley leaf segments cv. Hasso are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. 2 days after application, the leaf segments are inoculated with a spore suspension of the fungus. The inoculated leaf segments are incubated at 20°C and 65% rh in a climate chamber under a light regime of 12h light / 12h dark, and the activity of the compound is assessed as disease control compared to the untreated when an appropriate level of disease damage appears on the untreated test leaf segments (5-7 days after application).

[0778] The following compounds at 200 ppm gave at least 80% control of Pyricularia terrestris when compared to untreated controls showing extensive disease development under the same conditions:

[0779] P-1, P-3, P-5, P-6, P-7, P-8, P-9

[0780] Example B11: Sclerotinia sclerotiorum / liquid culture (cotton rot)

[0781] Mycelial fragments of freshly grown liquid cultures of the fungus were mixed directly into nutrient broth (PDB-potato dextrose broth). After placing a (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal material was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 3-4 days after application.

[0782] The following compounds gave at least 80% control of Sclerotinia sclerotiorum at 20 ppm when compared to untreated controls showing extensive disease development under the same conditions:

[0783] P-5, P-6

[0784] Example B12: Mycosphaerella graminicola (Septoria graminicola) / liquid culture (leaf Septoriablotch

[0785] The fungal conidia from frozen storage were directly mixed into the nutrient broth (PDB-potato dextrose broth). After the (DMSO) solution of the test compound was placed in a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. The test plate was incubated at 24°C and the inhibition of growth was determined photometrically 4-5 days after application.

[0786] The following compounds gave at least 80% control of Mycosphaeria graminearum at 20 ppm when compared to untreated controls which showed extensive disease development under the same conditions:

[0787] P-1, P-5, P-6, P-8, P-7, P-9

[0788] Example B13: Gibberella zeae (Fusarium graminearum) / Wheat / Spikelet Preventive (Fusarium head blight)

[0789] Wheat spikelets cultivar Ambershang were placed on agar in a multiwell plate (24-well format) and sprayed with the prepared test compound diluted in water. One day after application, the spikelets were inoculated with a spore suspension of the fungus. In a climate chamber, the inoculated test leaf disks were incubated at 20°C and 60% rh under a light regime of 72h semi-darkness followed by 12h light / 12h darkness, and the activity of the compound was assessed as the percentage of disease control compared to the untreated when the appropriate level of disease damage appeared on the untreated test spikelets (6-8 days after application).

[0790] The following compounds gave at least 80% control of Gibberella zeae at 200 ppm when compared to untreated controls which showed extensive disease development under the same conditions:

[0791] P-7

[0792] Example B14: Phytophthora infestans / tomato / leaf disc preventive (late blight)

[0793] Tomato leaf discs were placed on water agar in multiwell plates (24-well format) and sprayed with formulated test compounds diluted in water. One day after application, the leaf discs were inoculated with a spore suspension of the fungus. The inoculated leaf discs were incubated at 16°C and 75% rh in a climate chamber under a light regime of 24 h dark followed by 12 h light / 12 h dark, and the activity of the compounds was assessed as the percentage of disease control compared to the untreated when appropriate levels of disease damage appeared in the untreated test leaf discs (5-7 days after application).

[0794] The following compounds gave at least 80% control of Phytophthora infestans at 200 ppm when compared to untreated controls which showed extensive disease development under the same conditions:

[0795] P-2

[0796] Example B15: Plasmoparaviticola / Grapes / Leaf disc preventive (late blight)

[0797] Grapevine leaf discs were placed on water agar in multiwell plates (24-well format) and sprayed with formulated test compounds diluted in water. One day after application, the leaf discs were inoculated with a spore suspension of the fungus. The inoculated leaf discs were incubated at 19°C and 80% rh in a climate chamber under a light regime of 12h light / 12h dark, and the activity of the compounds was assessed as the percentage of disease control compared to the untreated when appropriate levels of disease damage appeared in the untreated test leaf discs (6-8 days after application).

[0798] The following compounds gave at least 80% control of grape downy mildew at 200 ppm when compared to untreated controls which showed extensive disease development under the same conditions:

[0799] P-1, P-2

[0800] Example B16: Magnaporthe grisea (Pyricularia oryzae) / Liquid culture (Rice blast)

[0801] Fungal conidia from frozen storage were mixed directly into nutrient broth (PDB-potato dextrose broth). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 3-4 days after application.

[0802] The following compounds at 20 ppm gave at least 80% control of Magnaporthe oryzae when compared to untreated.

Claims

1. A compound having formula (I): in R 1 is selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or C3-C6 cycloalkyl; R 2 is selected from hydrogen, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimide, N-hydroxy-C-C1-C4 alkyl-carbonimide, or C1-C4 alkoxycarbonyl; R 3 Selected from hydrogen, halogen, or C1-C4 alkyl; R 4 is selected from hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, or di(C1-C4 alkylamino)carbonyl; R 5 and R 6 Independently selected from hydrogen, or C1-C4 alkyl; A 1 Selected from CR 7 or N, A 2 Selected from CR 8 or N; A 3 Selected from CR 9 or N; R 7 , R 8 and R 9 independently selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or C1-C4 haloalkyl; Q is selected from Q1, Q2, Q3, Q4, or Q5; in; R 10 , R 11 , R 12 and R 13 independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, NC 1-4 Alkylamino, N,N-diC 1-4 Alkylamino, C1-C6 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimido, N-hydroxy-C1-C4 alkyl-carbonimido, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxyl, amino, phenyl, 5-membered or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5-membered or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S; and wherein any of the phenyl, 5-membered or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy; Z 1 is selected from C1-C4 alkyl, phenyl, 5-membered or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein any of the 5-membered or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S; and wherein any of the phenyl, 5-membered or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, or C2-C4 alkynyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.

2. The compound of formula (I) according to claim 1, wherein A 1 Selected from CH or N; A 2 Selected from CH or N; A 3 is selected from CH or N; and wherein A 1 , A 2 and A 3 At least two of are selected from N.

3. A compound of formula (I) according to claim 1 or claim 2, wherein R 1 Selected from methyl, ethyl, or isopropyl.

4. A compound of formula (I) according to any one of claims 1 to 3, wherein R 2 is selected from hydrogen, fluorine, chlorine, or methyl.

5. A compound of formula (I) according to any one of claims 1 to 4, wherein R 3 is selected from hydrogen or methyl.

6. A compound of formula (I) according to any one of claims 1 to 5, wherein R 4 is selected from hydrogen or methyl.

7. A compound of formula (I) according to any one of claims 1 to 6, wherein R 5 and R 6 are independently selected from hydrogen or methyl.

8. A compound of formula (I) according to any one of claims 1 to 7, wherein Q is selected from Q1, Q2, or Q3.

9. A compound of formula (I) according to any one of claims 1 to 8, wherein R 10 and R 11 are independently selected from hydrogen, chloro, bromo, methoxy, cyano, amino, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), (3,5-dimethylpyrazol-1-yl), (5-methylpyrazol-1-yl), (4-methylpyrazol-1-yl), (3-methylpyrazol-1-yl), pyrazol-1-yl, cyclopropyl, or 1-cyanocyclopropyl; and R 12 and R 13 It's hydrogen.

10. The compound of formula (I) according to claim 9, wherein R 10 and R 11 are independently selected from hydrogen, chlorine, bromine, cyano, or amino.

11. A compound of formula (I) according to any one of claims 1 to 10, wherein Z 1 Selected from 1-methylpyrazol-4-yl, 2,3,4-trifluorophenyl, 2,3-difluorophenyl, 3,4-difluorophenyl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2-pyridyl, 2-fluoro-4-methoxy-phenyl, 2-fluoro-4-methylsulfonyl-phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3,5-difluoro-2-furanyl , 3-fluoro-2-furyl, 5-fluoro-2-furyl, 3,5-difluoro-2-thienyl, 3-fluoro-2-thienyl, 5-fluoro-2-thienyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3-methoxyphenyl, 4-ethynyl-2-fluoro-phenyl, 4-fluoro-2-methoxy-phenyl, cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, n-propyl, or phenyl.

12. A compound of formula (I) according to any one of claims 1 to 11, wherein Z 1 Selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 3,5-difluoro-2-pyridyl, 2,4-difluorophenyl, 2-fluorophenyl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, cyclobutyl, cyclohexyl, cyclopentyl, or phenyl.

13. An agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 12.

14. A method for controlling or preventing infection of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 12 or a composition comprising the compound of formula (I) is applied to the plants, parts thereof or the locus thereof.

15. Use of a compound according to any one of claims 1 to 12 as a fungicide.

Images