Microbicide pyrazole derivatives

Abstract

Compounds of formula (I): [Formula 1] JPEG2026505027000125.jpg38160, wherein the substituents are as defined in claim 1, and the agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of these compounds may be used as fungicides.

Description

[Technical Field]

[0001] The present invention relates to microbicidal pyrazole derivatives as active ingredients having, for example, microbicidal, particularly fungicidal, activity. The present invention also relates to the preparation of these pyrazole derivatives, intermediates useful in the preparation of these pyrazole derivatives, the preparation of these intermediates, agrochemical compositions comprising at least one pyrazole derivative, the preparation of these compositions, and the use of the pyrazole derivatives or compositions in agriculture or horticulture to control or prevent infection of plants, harvested food crops, seeds, or non-living materials by phytopathogenic microorganisms, particularly fungi. Summary of the Invention [Means for solving the problem]

[0002] According to a first aspect of the present invention, there is provided a compound of formula (I): [ka] (In the formula, 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, C1-C4 alkoxy, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C1-C2 alkyl-C1-C4 alkoxy, C1-C2 alkyl-C1-C4 alkoxy-C1-C2 alkoxy, C1-C4 alkylcarbonyl, N—C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C1-C4 alkyl-carbonimidoyl, or C1-C4 alkoxycarbonyl; R 3 is selected from hydrogen, halogen, or C1-C4 alkyl; R 4is selected from hydrogen, halogen, C1-C4 alkyl, cyano, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, or di(C1-C4 alkylamino)carbonyl; R 5 and R 6 are independently selected from hydrogen or C1-C4 alkyl; A 1 , A 2 and A 3 is CR 7 , N, NR 8 , O, or S, with the proviso that A 1 , A 2 and A 3 is selected from N, O, or S, and 1 , A 2 and A 3 at most one of is O or S; R 7 and R 8 are independently selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl; B 1 is CR 9 or N and B 2 is CR 10 or N and B 3 is CR 11 or N and B 4 is CR 12 or N, provided that B 1 , B 2 , B 3 , and B 4 Only one of is N; R 10 , R 11 , R 12 and R 13is hydrogen, halogen, amino, hydroxy, carboxylic acid, cyano, 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, N-C1-C4 alkylamino, N,N-di(C1-C4 alkyl)amino, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C1-C4 alkyl-carbonimidoyl, C1-C4 alkylaminocarbonyl, di( wherein said 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms independently selected from N, O, or S, provided that not more than one is O or S; and wherein any of said phenyl, 5- 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 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrazin-2-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, or pyrimidin-5-yl; wherein any of the pyridyl-, pyrazine-pyridazine, and pyrimidine moieties is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, cyano, C1-C4 alkyl, C3-C6 cycloalkyl, C2-C4 alkynyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, or C1-C4 alkylsulfonyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof is provided.

[0003] Surprisingly, it has now been found that the compounds of formula (I) exhibit a level of biological activity which is highly advantageous in practice for protecting plants against diseases caused by fungi.

[0004] According to a second aspect of the present invention there is provided an agricultural composition comprising a fungicidally effective amount of a compound of formula (I) according to the present invention. Such agricultural compositions may further comprise at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

[0005] 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, which comprises applying to the plant, part of it or its habitat a fungicidally effective amount of a compound of formula (I) according to the present invention, or a composition comprising a compound of formula (I).

[0006] 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, methods for treating the human or animal body by surgery or therapy and diagnostic methods carried out on the human or animal body may be excluded from this use.

[0007] The compounds of formula (I) having at least one basic centre 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, or with strong organic carboxylic acids, for example C1-C4 alkanecarboxylic acids which are unsubstituted or substituted, for example, by halogens, such as acetic acid, for example saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, for example hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid or for example benzoic acid, or with organic sulfonic acids, for example C1-C4 alkane or arylsulfonic acids which are unsubstituted or substituted, for example, by halogens, such as methane- or p-toluenesulfonic acid. Compounds of formula (I) having at least one acidic group can, for example, form salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or with ammonia or organic amines, for example morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or mono-, di- or trihydroxy-lower alkylamines, for example mono-, di- or triethanolamine.

[0008] In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form as N-oxides or in salt form, for example in agriculturally acceptable salt form.

[0009] N-oxides are the oxidized forms of tertiary amines or nitrogen-containing heteroaromatic compounds, as described, for example, in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.

[0010] The compounds of formula (I) according to the invention also include the hydrates which may be formed during salt formation.

[0011] When substituents are indicated as "optionally substituted," this means that they may be substituted with one or more of the same or different substituents, for example, one, two, or three R x It means that it may or may not have a substituent. For example, C1-C6 alkyl substituted with 1, 2 or 3 halogens includes -CH2Cl, -CHCl2, -CCl 3、 Examples include, but are not limited to, -CHF, -CHF, -CF, -CHCF, or -CFCH groups. As another example, C1-C6 alkoxy substituted with 1, 2, or 3 halogens includes, but is not limited to, CH2ClO-, CHCl2O-, CCl3O-, CH2FO-, CHF2O-, CF3O-, CF3CHO-, or CH3CF2O- groups. Furthermore, the term "optionally substituted" as used herein can be used interchangeably with the term "unsubstituted or substituted."

[0012] The term "halogen" or "halo" as used herein means fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine. Likewise, this applies to halogen in combination with other meanings, such as haloalkyl, haloalkenyl, haloalkynyl, haloalkoxy and halocycloalkyl.

[0013] As used herein, "amino" refers to the group --NH.sub.2.

[0014] As used herein, "cyano" refers to a -CN group.

[0015] The term "hydroxyl" or "hydroxy" as used herein means an --OH group.

[0016] As used herein, the term "carboxylic acid" refers to a -COOH group.

[0017] As used herein, "C1-C nThe term "-alkyl" refers to a saturated linear or branched hydrocarbon group having 1 to n carbon atoms and bonded via any carbon atom, such as any one of 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.

[0018] As used herein, "C2-C n The term "-alkenyl" refers to a straight or branched alkenyl chain moiety having 2 to n carbon atoms and one or two double bonds, for example ethenyl, prop-1-enyl, but-2-enyl.

[0019] As used herein, "C2-C n The term "-alkynyl" refers to a straight or branched alkynyl chain moiety having 2 to n carbon atoms and one triple bond, for example ethynyl, prop-2-ynyl, but-3-ynyl.

[0020] As used herein, "C3-C n The term "cycloalkyl" refers to 3 to n-membered cycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0021] As used herein, "C1-C nThe term "C2-C alkoxy" refers to any one of the linear or branched saturated alkyl groups (as described above) having 1 to n carbon atoms attached through an oxygen atom, i.e., for example, methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy, and 1,1-dimethylethoxy. n The term "-alkenyloxy" refers to a straight or branched alkenyl chain (as described above) having 2 to n carbon atoms attached through an oxygen atom.

[0022] As used herein, "C2-C n The term "alkynyloxy" refers to the R a However, as generally defined above, C2~C n an alkynyl group of the formula -OR a Refers to the group of

[0023] As used herein, "C1-C n -Alkoxy-C1~C n The term "-alkyl" refers to C1-C n -refers to an alkyl group (as defined above) substituted with an alkoxy group. Examples are methoxymethyl, methoxyethyl, ethoxymethyl and propoxymethyl.

[0024] As used herein, "C1-C n -Alkyl-C1-C n The term "-alkoxy" refers to a group of groups of the formula -CR a -OR b where R a are C1 to C as defined above n is an alkyl group, and R b are C1 to C as defined above n Refers to an alkyl group.

[0025] As used herein, "C1-C n -Alkyl-C1-C n -Alkoxy-C1~C n The term "-alkoxy" refers to a group of groups of the formula -CRa -OR b -OR c where R a are C1 to C as defined above n is an alkyl group, and R b and R c are C1 to C as defined above n Refers to an alkyl group.

[0026] As used herein, "C3-C n -Cycloalkyl-C1-C n The term "-alkyl" refers to C3 to C n -refers to an alkyl group (as described above) substituted with a cycloalkyl group. Examples are cyclopropylmethyl, cyclopropylethyl. Similarly, "C3-C n -Halocycloalkyl-C1-C n The term "-alkyl" refers to an alkyl group substituted with a cycloalkyl group, where the cycloalkyl group is substituted with one or more of the same or different halogen atoms. Examples are 3,3-difluorobutylmethyl and 1-chlorocyclopropylmethyl.

[0027] As used herein, "C1-C nThe term "haloalkyl" refers to a linear or branched saturated alkyl group having 1 to n carbon atoms (as defined above) bonded via any of the carbon atoms, in which some or all of the hydrogen atoms of the group may be replaced by fluorine, chlorine, bromine and / or iodine, i.e., for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 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. Thus, the term "C1-C2 fluoroalkyl" refers to any one of a C1-C2 alkyl group having 1, 2, 3, 4 or 5 fluorine atoms, such as difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl or pentafluoroethyl. Similarly, as used herein, "C2-C n -haloalkenyl" or "C2-C n The term "haloalkynyl" refers to a C-C alkyl group substituted with one or more halogen atoms, each of which may be the same or different. n -alkenyl or C2-C nSimilarly, as used herein, "C3-C" refers to an -alkynyl group. n -halocycloalkyl" or "C1-C n The term "haloalkoxy" refers to a C3-C alkyl group substituted with one or more halogen atoms, each of which may be the same or different. n -cycloalkyl group or C1-C n -refers to an alkoxyl group.

[0028] As used herein, "C1-C n -alkylthio" or "C1-C n The term "-alkylsulfanyl" refers to a C1-C alkyl group linked through a sulfur atom. n Refers to an alkyl group.

[0029] As used herein, "C1-C n -haloalkylthio" or "C1-C n The term "haloalkylsulfanyl" refers to a C-C alkyl group linked through a sulfur atom. n -refers to a haloalkyl group.

[0030] As used herein, "C1-C n The term "-alkylsulfinyl" refers to a C1-C alkylsulfinyl group linked through the sulfur atom of the sulfinyl (or S(=O)-) group. n Refers to an alkyl group.

[0031] As used herein, "C1-C n The term "alkylsulfonyl" refers to a C1-C alkyl group linked through the sulfur atom of the sulfonyl (or S(=O)2-) group. n Refers to an alkyl group.

[0032] As used herein, "C1-C n -Alkylsulfonyl-C1-C n The term "-alkyl" refers to C1-C n C1-C substituted with alkylsulfonyl groups n Refers to an alkyl group.

[0033] As used herein, "C1-Cn The term "-alkylcarbonyl" refers to a C1-C alkyl group linked through the carbon atom of a carbonyl (C=O) group. n Refers to an alkyl group.

[0034] As used herein, "C1-C n The term "-alkoxycarbonyl" refers to a C1-C alkoxycarbonyl group linked through the carbon atom of the carbonyl (or C=O) group. n -refers to the alkoxy moiety.

[0035] As used herein, "C1-C n -Alkoxycarbonyl-C1-C n The term "-alkyl" refers to C1-C n -C1-C substituted with alkoxycarbonyl group n -refers to alkyl groups.

[0036] The term "benzoyl," as used herein, refers to a phenyl group attached through the carbon atom of a carbonyl (C=O) group.

[0037] As used herein, "C1-C n The term "haloalkoxycarbonyl" refers to a C1-C alkoxy group linked through the carbon atom of a carbonyl (C=O) group. n -refers to a haloalkoxy group.

[0038] As used herein, "C2-C n The term "-alkenyloxycarbonyl" refers to a C-C alkyl group linked through the carbon atom of a carbonyl (C=O) group. n -refers to an alkenyloxycarbonyl group.

[0039] As used herein, "C1-C n The term "-alkylaminocarbonyl" refers to a C1-C aryl group linked through the carbon atom of a carbonyl (C=O) group. n -Alkylamino group (or R a NHC(=O)-, where R a However, C1~C n-alkyl groups).

[0040] As used herein, "aminocarbonyl-C1-C n The term "-alkyl" refers to a C1-C alkyl group substituted with an aminocarbonyl (or NHC(=O)-) group. n -refers to alkyl groups.

[0041] As used herein, "C1-C n -Alkylaminocarbonyl-C1-C n The term "-alkyl" refers to C1-C n -alkylaminocarbonyl (or R a NHC(=O)-) group (wherein R a However, C1~C n -C substituted with alkyl n -Alkyl groups: C1-C linked to nitrogen n The alkyl group may be substituted.

[0042] As used herein, "N-C1 to C n The term "-alkylamino" refers to a group of amino acids having the formula -NH-R a where R a are C1 to C as defined above. n It is an alkyl group.

[0043] As used herein, "N,N-di(C1-C n The term "amino" refers to a group of the formula -N(R a )R a In the formula, each R a is a C1-n alkyl group which may be the same or different as defined above.

[0044] As used herein, "C1-C n -Alkylcarbonyloxy-C1~C n The term "-alkyl" refers to C1-C n -alkylcarbonyloxy (or R a C(=O)O-) group (in the formula, R a However, C1~Cn -C substituted with haloalkyl group n -refers to alkyl groups.

[0045] As used herein, "C1-C n -Alkoxycarbonyloxy-C1~C n The term "-alkyl" refers to C1-C n -alkoxycarbonyloxy (or R c C(=O)O-) group (in the formula, R c However, C1~C n -C substituted with an alkoxy group n -refers to alkyl groups. C1-Cn-alkoxy groups linked to nitrogen may be substituted.

[0046] As used herein, the term “N—C1-C4 alkoxy-C—C1-C4 alkyl-carbonimidoyl” refers to a group of the formula —C(R a )=NO(R b )(wherein, R a is a C1-C4 alkyl group as generally defined above, and R b is a C1-C4 alkyl group as generally defined above).

[0047] As used herein, the term “N-hydroxy-C—Ci-C4 alkyl-carbonimidoyl” refers to a group of the formula —C(R a )=NOH(where R a is a C1-C4 alkyl group as generally defined above).

[0048] As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic ring 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, pyrimidyl, or pyridyl. "Heteroaryl-C1-C n-alkyl" or "heteroaryl-C3-C n The term "-cycloalkyl" refers to any C1-C4 alkyl group substituted with a heteroaryl group. n Alkyl or C3-C n Refers to cycloalkyl groups. Heteroaryl-C1-C n -Alkyl or heteroaryl-C3-C n -Cycloalkyl groups may be optionally substituted on the heteroaryl, alkyl and / or cycloalkyl group.

[0049] As used herein, the term "control" refers to reducing the number of pests, eradicating pests and / or preventing further pest damage, such that damage to plants or plant-derived products is reduced.

[0050] As used herein, the term "pest" refers to insects and mollusks found in agriculture, horticulture, forestry, and storage of plant-based products (such as fruit, grain, and lumber); pests associated with damage to man-made structures. The term pest encompasses all stages in the life cycle of a pest.

[0051] As used herein, the term "effective amount" refers to an amount of a compound or a salt thereof that produces a desired effect upon single or multiple applications.

[0052] An effective amount is readily determined by one skilled in the art using known techniques and by observing results obtained under analogous circumstances. In determining an effective amount, several factors are taken into consideration, including, but not limited to, the type of plant or derived product to which it is applied; the pest to be controlled and its life cycle; the particular compound applied; the type of application; and other relevant circumstances.

[0053] As used herein, the term "room temperature" or "RT" or "rt" or "ambient temperature" refers to a temperature of about 15° C. to about 35° C. For example, rt can refer to a temperature of about 20° C. to about 30° C.

[0054] The following list refers to compounds of formula (I) of the present invention and defines substituent R 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 , B 1 , B 2 , B 3 , B 4 , A 1 , A 2 , A 3 and Z 1 For any one of these substituents, any definition given below can be combined with any definition of any other substituent given below or elsewhere in this specification. DETAILED DESCRIPTION OF THE INVENTION

[0055] In one embodiment of the present invention, R 1 is hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or C3-C6 cycloalkyl. 1 is C1-C4 alkyl. Preferably, R 1 is C1-C3 alkyl. More preferably, R 1 is methyl, ethyl, or isopropyl. Even more preferably, R 1 is methyl.

[0056] In one embodiment of the present invention, R 2is selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 alkoxy, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C1-C2 alkyl-C1-C4 alkoxy, C1-C2 alkyl-C1-C4 alkoxy-C1-C2 alkoxy, C1-C4 alkylcarbonyl, N—C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C1-C4 alkyl-carbonimidoyl, or C1-C4 alkoxycarbonyl. Preferably, R 2 is hydrogen, halogen, C1-C3 alkyl, C1-C3 alkoxy, C3-C6 cycloalkyl, C1-C2 alkyl-C1-C2 alkoxy, C1-C2 alkyl-C1-C4 alkoxy-C1-C2 alkoxy, C1-C2 alkylcarbonyl, N-C1-C2 alkoxy-C-C1-C2 alkyl-carbonimidoyl, or N-hydroxy-C-C1-C2 alkyl-carbonimidoyl. Even more preferably, R 2 is hydrogen, halogen, C1-C3 alkyl, C1-C3 alkoxy, C3-C6 cycloalkyl, or C1-C2 alkyl-C1-C2 alkoxy. Even more preferably, R 2 is hydrogen, halogen, C1-C3 alkyl, C1-C3 alkoxy, or C1-C2 alkyl-C1-C2 alkoxy.

[0057] In one embodiment of the present invention, 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-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimidoyl, or C1-C4 alkoxycarbonyl. 2 is hydrogen, halogen, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl, or N-hydroxy-C1-C4 alkyl-carbonimidoyl.2 is hydrogen, halogen, C1-C3 alkyl, cyclopropyl, C1-C2 alkylcarbonyl, N-C1-C2 alkoxy-C-C1-C2 alkyl-carbonimidoyl, or N-hydroxy-C-C1-C2 alkyl-carbonimidoyl. 2 is hydrogen, halogen, C1-C3 alkyl, cyclopropyl, acetyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, or -C(CH3)=NOH. Even more preferably, R 2 is selected from hydrogen, halogen, or C1-C4 alkyl. 2 is selected from hydrogen, halogen, or C1-C3 alkyl. Most preferably, R 2 is hydrogen, chlorine, or methyl. In one preferred embodiment, R 2 is hydrogen. In another preferred embodiment, R 2 is methyl. In yet another preferred embodiment, R 2 is chlorine. In another preferred embodiment, R 2 is cyclopropyl.

[0058] In another embodiment of the present invention, R 2 is selected from hydrogen, halogen, C1-C4 alkyl, or C3-C6 cycloalkyl. 2 is hydrogen, halogen, C1-C3 alkyl, or C3-C6 cycloalkyl. More preferably, R 2 is hydrogen, chlorine, methyl, or cyclopropyl.

[0059] In another embodiment of the present invention, R 2 is selected from C1-C4 alkoxy, C1-C2 alkyl-C1-C4 alkoxy, or C1-C2 alkyl-C1-C4 alkoxy-C1-C2 alkoxy. Preferably, R 2 is C1-C3 alkoxy, C1-C2 alkyl-C1-C3 alkoxy, or C1-C2 alkyl-C1-C3 alkoxy-C1-C2 alkoxy. More preferably, R2 is methoxy, ethoxy, methoxymethyl, or ethoxymethyl.

[0060] In one embodiment of the present invention, R 3 is selected from hydrogen, halogen, or C1-C4 alkyl. 3 is hydrogen, fluorine, chlorine, or methyl. More preferably, R 3 is hydrogen or methyl. Even more preferably, R 3 is hydrogen.

[0061] In one embodiment of the present invention, R 4 is selected from hydrogen, halogen, C1-C4 alkyl, cyano, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, or di(C1-C4 alkyl)aminocarbonyl. 4 is hydrogen, halogen, cyano, C1-C4 alkyl, C1-C4 alkylcarbonyl, or C1-C4 alkoxycarbonyl. 4 is hydrogen, chlorine, fluorine, C1-C3-alkyl, cyano, or CO2Me. More preferably, R 4 is hydrogen, methyl, ethyl, isopropyl, or cyano. Even more preferably, R 4 is hydrogen or methyl. In one embodiment, R 4 is hydrogen. 4 is methyl.

[0062] In one embodiment of the present invention, R 5 and R 6 are independently selected from hydrogen or C1-C4 alkyl. Preferably, R 5 and R 6 are independently selected from hydrogen or C1-C2 alkyl. More preferably, R 5 and R 6 are independently selected from hydrogen or methyl. Even more preferably, R 5 and R 6is hydrogen.

[0063] In one embodiment of the present invention, A 1 , A 2 and A 3 independently, CR 7 , N, NR 8 , O or S, with the proviso that A 1 , A 2 and A 3 is selected from N, O, or S, and 1 , A 2 and A 3 At most one of is O or S.

[0064] In another embodiment of the present invention, A 1 , A 2 and A 3 is CR 7 , N, O, or S, with the proviso that A 1 , A 2 and A 3 is selected from N, O, or S, and 1 , A 2 and A 3 At most one of is O or S.

[0065] In one embodiment of the present invention, R 7 and R 8 are independently selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl. Preferably, R 7 and R 8 are independently selected from hydrogen or C1-C4 alkyl. More preferably, R 7 and R 8 are independently selected from hydrogen or methyl. More preferably, R 7 and R 8 is hydrogen.

[0066] In one embodiment of the present invention, B 1 is CR 9 or N and B 2 is CR 10 or N and B 3is CR 11 or N and B 4 is CR 12 or N, provided that B 1 , B 2 , B 3 , and B 4 Only one of them is N.

[0067] In another embodiment of the present invention, B 1 is CR 9 and B 2 is CR 10 and B 3 is CR 11 and B 4 is CR 12 or B 1 is N and B 2 is CR 10 and B 3 is CR 11 and B 4 is CR 12 or B 1 is CR 9 and B 2 is N and B 3 is CR 11 and B 4 is CR 12 or B 1 is CR 9 and B 2 is CR 10 and B 3 is N and B 4 is CR 12 or B 1 is CR 9 and B 2 is CR 10 and B 3 is CR 11 and B 4 is N. Preferably, B 1 is CR 9 and B 2 is CR 10 and B 3 is CR 11 and B 4 is CR 12 or B 1 is N and B2 is CR 10 and B 3 is CR 11 and B 4 is CR 12 or B 1 is CR 9 and B 2 is N and B 3 is CR 11 and B 4 is CR 12 More preferably, B 1 is CR 9 and B 2 is CR 10 and B 3 is CR 11 and B 4 is CR 12 is.

[0068] In one embodiment of the present invention, R 9 , R 10 , R 11 and R 12are independently hydrogen, halogen, amino, hydroxy, carboxylic acid, cyano, 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, N-C1-C4 alkylamino, N,N-di(C1-C4 alkyl)amino, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C1-C4 alkyl-carbonimidoyl, C1-C4 alkylaminocarbonyl, di (C1-C4 alkylamino)carbonyl), C1-C4 alkylcarbonylamino, C1-C4 alkylsulfonylamino, trifluoromethylsulfonyloxy, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl; wherein said 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms independently selected from N, O, or S, provided that not more than one is O or S; and wherein any of said phenyl, 5- 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.

[0069] In another embodiment of the present invention, R 9 and R 10are independently 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, N-C1-C4 alkylamino, N,N-di(C1-C4 alkyl)amino, C1-C6 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxyC1-C4 alkyl-carbonimidoyl, N-hydroxyC1 wherein said 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms independently selected from N, O, or S; and wherein any of said phenyl, 5- 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.

[0070] In another embodiment of the present invention, R 9 and R 10is 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-carbonimidoyl, N-hydroxy-C1-C2 alkyl-carbonimidoyl, hydroxy, C1-C2 alkyl wherein said 5- or 6-membered heteroaryl contains 1 or 2 heteroatoms independently selected from N and O; and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6 cycloalkyl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, or methyl.

[0071] In a preferred embodiment, R 9 and R 10is 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-carbonimidoyl, N-hydroxy-C1-C2 alkyl-carbonimidoyl, hydroxy, C1-C2 alkylaminocarbonyl, di(C1-C2 alkylamino)carbonyl, trifluoromethylsulfonyloxy, carboxy, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyano and independently selected from phenyl, 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.

[0072] More preferably, R9 and R10 are selected from the group consisting of hydrogen, chloro, fluoro, bromo, methyl, ethyl, trifluoromethyl, difluoromethyl, difluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, methoxy, ethoxy, propoxy, allyloxy, prop-2-ynoxy, methylsulfanyl, methylsulfinyl, methylsulfonyl, methoxymethyl, ethoxymethyl, 2-methoxy-ethoxymethyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, acetyl, propanoyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methyl-aminocarbonyl, di(methylamino)carbonyl, trifluoromethylsulfonyloxy, cyano, carboxy, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 5-cyanophenyl, 6-cyanophenyl, 7-cyanophenyl, 8-cyanophenyl, 9-cyanophenyl, 10-cyanophenyl, 11-cyanophenyl, 12-cyanophenyl, 13-cyanophenyl, 14-cyanophenyl, 15-cyanophenyl, 16-cyanophenyl, 17-cyanophenyl, 18-cyanophenyl, 19-cyanophenyl, 20-cyanophenyl, 21-cyanophenyl, 22-cyanophenyl, 23-cyanophenyl, 24-cyanophenyl, 25-cyanophenyl, 26-cyanophenyl, 27-cyanophenyl, 28-cyanophenyl, 29-cyanophenyl, 29-cyanophenyl, 21-cyanophenyl, 22-cyanophenyl, 23-cyanophenyl, 24-cyanophenyl, 25-cyanophenyl, 26-cyanophenyl, 27-cyanophenyl, 28-cyanophenyl, and independently selected from phenyl, 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.

[0073] Even more preferably, R 9 and R 10is hydrogen, chloro, fluoro, bromo, methyl, trifluoromethyl, difluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, methoxy, propoxy, allyloxy, prop-2-ynoxy, methylsulfanyl, methylsulfinyl, methylsulfonyl, methoxymethyl, 2-, methoxyethoxymethyl, methoxycarbonyl, acetyl, propanoyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methylaminocarbonyl, di(methylamino)carbonyl, trifluoromethylsulfonyloxy, cyano, carboxy, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, [4-(

[0039] Independently selected from (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.

[0074] Even more preferably, R9 and R10 are independently selected from hydrogen, chloro, fluoro, bromo, methoxy, cyano, amino, carboxy, 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.

[0075] In yet another embodiment of the present invention, R 9 and R 10 are independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkoxy, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl; wherein said 5- or 6-membered heteroaryl contains one heteroatom selected from N; and wherein any of said phenyl, 5- or 6-membered heteroaryl, and C3-C6 cycloalkyl is unsubstituted or substituted with one or two substituents independently selected from halogen, cyano, or methyl.

[0076] More preferably, R9 and R10 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. Even more preferably, R 10 and R 11are independently selected from hydrogen, chloro, bromo, cyano, or amino.

[0077] In another embodiment of the present invention, R9 and R10 are independently selected from hydrogen, halogen, or cyano. More preferably, R 10 and R 11 is independently selected from hydrogen, chloro, bromo, or cyano.

[0078] In another embodiment of the present invention, R 11 and R 12 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy. Preferably, R 11 and R 12 are independently selected from hydrogen, chlorine, bromine, fluorine, or methyl. More preferably, R 11 and R 12 is hydrogen.

[0079] In one embodiment, Z 1 is selected from 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrazin-2-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, or pyrimidin-5-yl; wherein any of the pyridyl, pyrazine, pyridazine, or pyrimidine moieties is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, cyano, C1-C4 alkyl, C3-C6 cycloalkyl, C2-C4 alkynyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, or C1-C4 alkylsulfonyl. Preferably, Z 1is selected from 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrazin-2-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, or pyrimidin-5-yl, wherein any of the pyridyl, pyrazine, pyridazine, or pyrimidine moieties is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, or C1-C4 alkyl. More preferably, Z 1 is selected from 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrazin-2-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, or pyrimidin-5-yl, wherein any of the pyridyl, pyrazine, pyridazine, or pyrimidine moieties is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from fluorine, trifluoromethyl, difluoromethyl, or methyl. More preferably, Z 1 is selected from 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrazin-2-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, or pyrimidin-5-yl, and any of the pyridyl moiety, pyrazine moiety, pyridazine, or pyrimidine moiety is unsubstituted or substituted with 1 to 2 substituents selected from fluorine.

[0080] In another more preferred embodiment of the present invention, Z 1are 5-fluoropyrimidin-4-yl, 3,6-difluoro-2-pyridyl, 4,6-difluoro-2-pyridyl, 4,5-difluoro-2-pyridyl, 5,6-difluoro-2-pyridyl, 3-fluoro-4-pyridyl, 2-fluoro-4-pyridyl, 2,3-difluoro-4-pyridyl, 2,5-difluoro-4-pyridyl, 2,6-difluoro-4-pyridyl, 3,5-difluoro-4-pyridyl, 2,5-difluoro-4-pyridyl, 2-fluoro-3-pyridyl, 6-fluoro-3-pyridyl, 5 -fluoro-3-pyridyl, 4-fluoro-3-pyridyl, 2,6-difluoro-3-pyridyl, 2,5-difluoro-3-pyridyl, 2,4-difluoro-3-pyridyl, 4,6-difluoro-3-pyridyl, 5,6-difluoro-3-pyridyl, 6-fluoropyrimidin-4-yl, 2-fluoropyrimidin-4-yl, 2,5-difluoropyrimidin-4-yl, 2,6-difluoropyrimidin-4-yl, 5,6-difluoropyrimidin-4-yl, 4-fluoropyrimidin-5-yl, 2-fluoropyrimidin-4-yl, Rimidin-5-yl, 2,4-difluoropyrimidin-5-yl, 4-fluoropyrimidin-2-yl, 5-fluoropyrimidin-2-yl, 4,5-difluoropyrimidin-2-yl, 4,6-difluoropyrimidin-2-yl, 4-fluoropyridazin-3-yl, 5-fluoropyridazin-3-yl, 6-fluoropyridazin-3-yl, 4,5-difluoropyridazin-3-yl, 4,6-difluoropyridazin-3-yl, 5,6-difluoropyridazin-3-yl, 3-fluoropyridazin-4- Preferably, Z is selected from Z-yl, 6-fluoropyridazin-4-yl, 5-fluoropyridazin-4-yl, 3,6-difluoropyridazin-4-yl, 5,6-difluoropyridazin-4-yl, 3,5-difluoropyridazin-4-yl, 3,5-difluoro-2-pyridyl, 3,4-difluoro-2-pyridyl, 6-fluoro-2-pyridyl, 4-fluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2-pyridyl, 4,5-difluoro-3-pyridyl, and 4-fluoropyrimidin-5-yl. 1is selected from 3-fluoro-2-pyridyl, 5-fluoro-2-pyridyl, 6-fluoro-2-pyridyl, 3,4-difluoro-2-pyridyl, 3,5-difluoro-2-pyridyl, 2-fluoro-4-pyridyl, 5-fluoropyrimidin-4-yl, 5-fluoropyrimidin-2-yl, 4-fluoropyridazin-3-yl, 5-fluoropyridazin-3-yl, 4,5-difluoropyridazin-3-yl, or 5-fluoropyridazin-4-yl. 1 is selected from 3-fluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3,4-difluoro-2-pyridyl, 3,5-difluoro-2-pyridyl, 2,6-difluoro-3-pyridyl, 4-fluoropyridazin-3-yl, 4,5-difluoropyridazin-3-yl, or 5-fluoropyridazin-4-yl. Even more preferably, Z 1 is selected from 3-fluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3,4-difluoro-2-pyridyl, 2,6-difluoro-3-pyridyl, or 3,5-difluoro-2-pyridyl. 1 is selected from 3-fluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3,4-difluoro-2-pyridyl, 2,6-difluoro-3-pyridyl, or 3,5-difluoro-2-pyridyl.

[0081] In another preferred embodiment, Z 1 is 2-pyridyl, 3-pyridyl, or 4-pyridyl; wherein any of said pyridyl moieties is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C3-C6 cycloalkyl, C2-C4 alkynyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, or C1-C4 alkylsulfonyl. Preferably, Z 1is 2-pyridyl, 3-pyridyl, or 4-pyridyl; wherein any of said pyridyl moieties is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, or C1-C4 alkyl. More preferably, Z 1 is 2-pyridyl, 3-pyridyl, or 4-pyridyl; wherein any of said pyridyl moieties is unsubstituted or substituted with 1 to 2 substituents selected from fluorine. Even more preferably, Z 1 is 3-fluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3,4-difluoro-2-pyridyl, 3,5-difluoro-2-pyridyl, or 2,6-difluoro-3-pyridyl. Even more preferably, Z 1 is 3-fluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3,4-difluoro-2-pyridyl, 2,6-difluoro-3-pyridyl, or 3,5-difluoro-2-pyridyl. 1 is 2,6-difluoro-3-pyridyl or 3,5-difluoro-2-pyridyl. 1 is 2,6-difluoro-3-pyridyl. 1 is 3,5-difluoro-2-pyridyl.

[0082] In another embodiment of the present invention, Z 1 is selected from 6-membered heteroaryl; wherein said heteroaryl contains 1 or 2 heteroatoms selected from N; and wherein said 6-membered heteroaryl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C2-C4 alkynyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, or C1-C4 alkylsulfonyl. In one embodiment of the present invention, Z 1is selected from 6-membered heteroaryl; wherein said heteroaryl contains 1 or 2 heteroatoms selected from N; and wherein said 6-membered heteroaryl is unsubstituted or substituted with 1 to 2 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy. Preferably, Z 1 is selected from 6-membered heteroaryl; wherein said heteroaryl contains 1 or 2 heteroatoms selected from N; and wherein said 6-membered heteroaryl is unsubstituted or substituted with 1 to 2 substituents independently selected from halogen or C1-C4 haloalkyl. More preferably, Z 1 is selected from 6-membered heteroaryl; wherein said heteroaryl contains 1 or 2 heteroatoms selected from N; and wherein said 6-membered heteroaryl is unsubstituted or substituted with 1 to 2 substituents selected from fluorine.

[0083] In yet another embodiment of the present invention, Z 1 is selected from 6-membered heteroaryl; wherein said heteroaryl contains one heteroatom selected from N; and wherein said 6-membered heteroaryl is unsubstituted or substituted with 1 to 2 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy. Preferably, Z 1 is selected from 6-membered heteroaryl; wherein said heteroaryl contains one heteroatom selected from N; and wherein said 6-membered heteroaryl is unsubstituted or substituted with 1 to 2 substituents independently selected from halogen or C1-C4 haloalkyl. More preferably, Z 1 is selected from 6-membered heteroaryl; wherein said heteroaryl contains 1 heteroatom selected from N; and wherein said 6-membered heteroaryl is unsubstituted or substituted with 1 to 2 substituents selected from fluorine.

[0084] In the present invention, therefore, R as defined above 1 , R 2 , R 3 , R 4 , R 5 , R 6 , A 1 , A 2 , A 3 , R 7 , R 8 , B 1 , B 2 , B 3 , B 4 , R 9 , R 10 , R 11 , R 12 and Z 1 Compounds of formula (I) having all combinations / sequences of:

[0085] Embodiments according to the present invention are provided as follows.

[0086] In one embodiment of the present invention, a compound of formula (I): [ka] (In the formula, 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-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C1-C4 alkyl-carbonimidoyl or C1-C4 alkoxycarbonyl; R 3 is selected from hydrogen, halogen, or C1-C4 alkyl; R 4is selected from hydrogen, halogen, C1-C4 alkyl, cyano, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, or di(C1-C4 alkylamino)carbonyl; R 5 and R 6 are independently selected from hydrogen or C1-C4 alkyl; A 1 , A 2 and A 3 is CR 7 , N, NR 8 , O, or S, with the proviso that A 1 , A 2 and A 3 is selected from N, O, or S, and 1 , A 2 and A 3 at most one of is O or S; R 7 and R 8 are independently selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl; B 1 is CR 9 or N and B 2 is CR 10 or N and B 3 is CR 11 or N and B 4 is CR 12 or N, provided that B 1 , B 2 , B 3 , and B 4 Only one of is N; R 10 , R 11 , R 12 and R 13is hydrogen, halogen, amino, hydroxy, carboxylic acid, cyano, 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, N-C1-C4 alkylamino, N,N-di(C1-C4 alkyl)amino, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C1-C4 alkyl-carbonimidoyl, C1-C4 alkylaminocarbonyl, di( wherein said 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms independently selected from N, O, or S, provided that not more than one is O or S; and wherein any of said phenyl, 5- 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 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrazin-2-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, or pyrimidin-5-yl; wherein any of the pyridyl-, pyrazine-pyridazine, and pyrimidine moieties is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, cyano, C1-C4 alkyl, C3-C6 cycloalkyl, C2-C4 alkynyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, or C1-C4 alkylsulfonyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof is provided.

[0087] In another embodiment of the present invention, the compound of formula (I): [ka] (In the formula, R 1 is selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or C3-C6 cycloalkyl; R 2 is selected from C1-C4 alkoxy, C1-C2 alkyl-C1-C4 alkoxy, or C1-C2 alkyl-C1-C4 alkoxy-C1-C2 alkoxy; R 3 is selected from hydrogen, halogen, or C1-C4 alkyl; R 4 is selected from hydrogen, halogen, C1-C4 alkyl, cyano, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, or di(C1-C4 alkylamino)carbonyl; R 5 and R 6 are independently selected from hydrogen or C1-C4 alkyl; A 1 , A 2 and A 3 is CR 7 , N, NR 8 , O, or S, with the proviso that A 1 , A 2 and A 3 is selected from N, O, or S, and 1 , A 2 and A 3 at most one of is O or S; R 7 and R 8 are independently selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl; B 1 is CR9 or N and B 2 is CR 10 or N and B 3 is CR 11 or N and B 4 is CR 12 or N, provided that B 1 , B 2 , B 3 , and B 4 Only one of is N; R 10 , R 11 , R 12 and R 13 is hydrogen, halogen, amino, hydroxy, carboxylic acid, cyano, 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, N-C1-C4 alkylamino, N,N-di(C1-C4 alkyl)amino, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C1-C4 alkyl-carbonimidoyl, C1-C4 alkylaminocarbonyl, di( wherein said 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms independently selected from N, O, or S, provided that not more than one is O or S; and wherein any of said phenyl, 5- 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 1is selected from 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrazin-2-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, or pyrimidin-5-yl; wherein any of the pyridyl-, pyrazine-pyridazine, and pyrimidine moieties is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, cyano, C1-C4 alkyl, C3-C6 cycloalkyl, C2-C4 alkynyl, C1-C4 haloalkoxy, C1-C4 alkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, or C1-C4 alkylsulfonyl; or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof is provided.

[0088] In an embodiment of the invention, the compound of formula (I) may be a compound of formula (IA): [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , B 1 , B 2 , B 3 , B 4 , R 9 , R 10 , R 11 , R 12 and Z 1 is as defined for the compounds of formula (I) according to the invention, and A is A1 to A36 [ka] is selected from the group consisting of [ka] indicates the position of bonding to the C(=O) group, and the arrow indicates Z 1 indicates the position of attachment to the R 1, R 2 , R 3 , R 4 , R 5 , R 6 , B 1 , B 2 , B 3 , B 4 , R 9 , R 10 , R 11 , R 12 and Z 1 is as defined for the compounds of formula (I) according to the invention, and R 8 may be selected from hydrogen or C1-C4 alkyl).

[0089] Preferably, the compound of formula (I) is a compound of formula (IA) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , B 1 , B 2 , B 3 , B 4 , R 9 , R 10 , R 11 , R 12 and Z 1 is as defined for the compounds of formula (I) according to the invention, A is selected from one of A1 to A36, R 8 is selected from methyl).

[0090] In one embodiment of the present invention, in compounds of formula (IA), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , B 1 , B 2 , B 3 , B 4 , R 9 , R 10 , R 11 , R 12 and Z 1is as defined for the compounds of formula (I) according to the invention, and A is A1, A4, A6, A7, A9, A10, A13, or A15 [ka] is selected from: [ka] indicates the position of bonding to the C(=O) group, and the arrow indicates Z 1 indicates the position of attachment to the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , B 1 , B 2 , B 3 , B 4 , R 9 , R 10 , R 11 , R 12 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0091] In another embodiment of the present invention, in the compound of formula (IA), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , B 1 , B 2 , B 3 , B 4 , R 9 , R 10 , R 11 , R 12 and Z 1 is as defined for the compounds of formula (I) according to the invention, and A is A4, A6, A7, A9 or A10 [ka] is selected from: [ka] indicates the position of bonding to the C(=O) group, and the arrow indicates Z 1 The position of attachment to the group is indicated.

[0092] In another embodiment of the present invention, in the compound of formula (IA), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , B 1 , B 2 , B 3 , B 4 , R 9 , R 10 , R 11 , R 12 and Z 1 is as defined for the compounds of formula (I) according to the invention, and A is A4, A7, A9 or A10 [ka] is selected from: [ka] indicates the position of bonding to the C(=O) group, and the arrow indicates Z 1 The position of attachment to the group is indicated.

[0093] In another preferred embodiment of the present invention, in the compound of formula (IA), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , B 1 , B 2 , B 3 , B 4 , R 9 , R 10 , R 11 , R 12 and Z 1 is as defined for the compounds of formula (I) according to the invention, and A is A4 or A9 [ka] is selected from: [ka] indicates the position of bonding to the C(=O) group, and the arrow indicates Z 1 The position of attachment to the group is indicated.

[0094] In yet another embodiment of the present invention, in compounds of formula (IA), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , B 1 , B 2 , B 3 , B 4 , R 9 , R 10 , R 11 , R 12 and Z 1 is as defined for the compounds of formula (I) according to the invention, and A is selected from A4.

[0095] In yet another embodiment of the present invention, in compounds of formula (IA), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , B 1 , B 2 , B 3 , B 4 , R 9 , R 10 , R 11 , R 12 and Z 1 is as defined for the compounds of formula (I) according to the invention, and A is selected from A9.

[0096] In one embodiment of the present invention, the compound of formula (I) is B 1 is CR 9 and B 2 is CR 10 and B 3 is CR 11and B 4 is CR 12 and A is as defined for compounds of formula (IA): [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and Z 1 are as defined for the compounds of formula (I) according to the present invention).

[0097] Preferably, in the compound of formula (I-A1), R 1 is C1-C3 alkyl; R 2 is hydrogen, halogen, C1-C3 alkyl, or C3-C6 cyclopropyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is as defined for compounds of formula (IA), and R 9 , R 10 , R 11 , R 12 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0098] Preferably, in the compound of formula (I-A1), R 1 is C1-C3 alkyl; R 2 is hydrogen, halogen, C1-C3 alkyl, or C3-C6 cyclopropyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6is hydrogen; A is A4, A6, A7, A9, or A10; R 9 , R 10 are independently selected from hydrogen, halogen, or cyano; R 11 , R 12 is hydrogen; Z 1 is as defined for the compounds of formula (I) according to the invention.

[0099] Preferably, in the compound of formula (I-A1), R 1 is C1-C3 alkyl; R 2 is hydrogen, halogen, C1-C3 alkyl, or C3-C6 cyclopropyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is A4, A6, A7, A9, or A10; R 9 , R 10 are independently selected from hydrogen, halogen, or cyano; R 11 , R 12 is hydrogen; Z 1 is 2-pyridyl, 3-pyridyl, or 4-pyridyl; wherein any of said pyridyl moieties is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, or C1-C4 alkyl.

[0100] Preferably, in the compound of formula (I-A1), R 1 is methyl; R 2 is hydrogen, chlorine, methyl, or cyclopropyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is A4, A6, A7, A9, or A10; R 9 , R 10 are independently selected from hydrogen, halogen, or cyano; R 11 , R 12 is hydrogen; Z 1is 2-pyridyl, 3-pyridyl, or 4-pyridyl; wherein any of said pyridyl moieties is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, or C1-C4 alkyl.

[0101] Preferably, in the compound of formula (I-A1), R 1 is C1-C3 alkyl; R 2 is hydrogen, halogen, or C1-C3 alkyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is A4, A6, A7, A9, or A10; R 9 , R 10 are independently selected from hydrogen, halogen, or cyano; R 11 , R 12 is hydrogen; Z 1 is 2-pyridyl, 3-pyridyl, or 4-pyridyl; wherein any of said pyridyl moieties is unsubstituted or substituted with 1 to 2 substituents selected from fluorine.

[0102] Preferably, in the compound of formula (I-A1), R 1 is C1-C3 alkyl; R 2 is hydrogen, halogen, C1-C3 alkyl, or C3-C6 cyclopropyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is A4 or A9; R 9 , R 10 are independently selected from hydrogen, halogen, or cyano; R 11 , R 12 is hydrogen; Z 1 is 2-pyridyl, 3-pyridyl, or 4-pyridyl; wherein any of said pyridyl moieties is unsubstituted or substituted with 1 to 2 substituents selected from fluorine.

[0103] In another preferred embodiment, in the compound of formula (I-A1), R 1 is C1-C3 alkyl; R 2 is C1-C3 alkoxy, C1-C2 alkyl-C1-C3 alkoxy, or C1-C2 alkyl-C1-C3 alkoxy-C1-C2 alkoxy; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is as defined for compounds of formula (IA), and R 9 , R 10 , R 11 , R 12 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0104] Preferably, in the compound of formula (I-A1), R 1 is C1-C3 alkyl; R 2 is C1-C3 alkoxy, C1-C2 alkyl-C1-C3 alkoxy, or C1-C2 alkyl-C1-C3 alkoxy-C1-C2 alkoxy; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is A4, A6, A7, A9, or A10; R 9 , R 10 are independently selected from hydrogen, halogen, or cyano; R 11 , R 12 is hydrogen; Z 1 is as defined for the compounds of formula (I) according to the invention.

[0105] Preferably, in the compound of formula (I-A1), R 1 is C1-C3 alkyl; R 2 is C1-C3 alkoxy, C1-C2 alkyl-C1-C3 alkoxy, or C1-C2 alkyl-C1-C3 alkoxy-C1-C2 alkoxy; R 3is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is A4, A7, A9, or A10; R 9 , R 10 are independently selected from hydrogen, halogen, or cyano; R 11 , R 12 is hydrogen; Z 1 is 2-pyridyl, 3-pyridyl, or 4-pyridyl; wherein any of said pyridyl moieties is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, or C1-C4 alkyl.

[0106] Preferably, in the compound of formula (I-A1), R 1 is methyl; R 2 is C1-C3 alkoxy or C1-C2 alkyl-C1-C3 alkoxy; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is A4, A7, A9, or A10; R 9 , R 10 are independently selected from hydrogen, halogen, or cyano; R 11 , R 12 is hydrogen; Z 1 is 2-pyridyl, 3-pyridyl, or 4-pyridyl; wherein any of said pyridyl moieties is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, or C1-C4 alkyl.

[0107] Preferably, in the compound of formula (I-A1), R 1 is C1-C3 alkyl; R 2 is C1-C3 alkoxy or C1-C2 alkyl-C1-C3 alkoxy; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5and R 6 is hydrogen; A is A4, A7, A9, or A10; R 9 , R 10 are independently selected from hydrogen, halogen, or cyano; R 11 , R 12 is hydrogen; Z 1 is 2-pyridyl, 3-pyridyl, or 4-pyridyl; wherein any of said pyridyl moieties is unsubstituted or substituted with 1 to 2 substituents selected from fluorine.

[0108] In one embodiment of the present invention, the compound of formula (I) is B 1 is N and B 2 is CR 10 and B 3 is CR 11 and B 4 is CR 12 and A is as defined for compounds of formula (IA): [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 10 , R 11 , R 12 and Z 1 is as defined for the compounds of formula (I) according to the invention).

[0109] Preferably, in the compound of formula (I-A2), R 1 is C1-C3 alkyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is as defined for compounds of formula (IA), and R 2 , R 10 , R11 , R 12 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0110] Preferably, in the compound of formula (I-A2), R 1 is C1-C3 alkyl; R 2 is hydrogen, halogen, C1-C3 alkyl, or C3-C6 cyclopropyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is as defined for compounds of formula (IA), and R 10 , R 11 , R 12 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0111] Preferably, in the compound of formula (I-A2), R 1 is C1-C3 alkyl; R 2 is hydrogen, halogen, C1-C3 alkyl, or C3-C6 cyclopropyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is A4, A6, A7, A9, or A10; R 10 is hydrogen, halogen, or cyano; R 11 , R 12 is hydrogen; Z 1 is as defined for the compounds of formula (I) according to the invention.

[0112] Preferably, in the compound of formula (I-A2), R 1 is C1-C3 alkyl; R 2 is hydrogen, halogen, C1-C3 alkyl, or C3-C6 cyclopropyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R5 and R 6 is hydrogen; A is A4, A6, A7, A9, or A10; R 10 is hydrogen, halogen, or cyano; R 11 , R 12 is hydrogen; Z 1 is 2-pyridyl, 3-pyridyl, or 4-pyridyl; wherein any of said pyridyl moieties is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, or C1-C4 alkyl.

[0113] In one embodiment of the present invention, the compound of formula (I) is B 1 is CR 9 and B 2 is N and B 3 is CR 11 and B 4 is CR 12 and A is as defined for compounds of formula (IA): [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 11 , R 12 and Z 1 is as defined for the compounds of formula (I) according to the invention).

[0114] Preferably, in the compound of formula (I-A3), R 1 is C1-C3 alkyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is as defined for compounds of formula (IA), and R 2 , R9 , R 11 , R 12 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0115] Preferably, in the compound of formula (I-A3), R 1 is C1-C3 alkyl; R 2 is hydrogen, halogen, C1-C3 alkyl, or C3-C6 cyclopropyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is as defined for compounds of formula (IA), and R 9 , R 11 , R 12 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0116] Preferably, in the compound of formula (I-A3), R 1 is C1-C3 alkyl; R 2 is hydrogen, halogen, C1-C3 alkyl, or C3-C6 cyclopropyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is A4, A6, A7, A9, or A10; R 9 is hydrogen, halogen, or cyano; R 11 , R 12 is hydrogen; Z 1 is as defined for the compounds of formula (I) according to the invention.

[0117] Preferably, in the compound of formula (I-A3), R 1 is C1-C3 alkyl; R 2 is hydrogen, halogen, C1-C3 alkyl, or C3-C6 cyclopropyl; R 3 is hydrogen; R 4is hydrogen or methyl; R 5 and R 6 is hydrogen; A is A4, A6, A7, A9, or A10; R 9 is hydrogen, halogen, or cyano; R 11 , R 12 is hydrogen; Z 1 is 2-pyridyl, 3-pyridyl, or 4-pyridyl; wherein any of said pyridyl moieties is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, or C1-C4 alkyl.

[0118] In one embodiment of the present invention, the compound of formula (I) is B 1 is CR 9 and B 2 is CR 10 and B 3 is N and B 4 is CR 12 and A is as defined for compounds of formula (IA): [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 12 and Z 1 is as defined for the compounds of formula (I) according to the invention).

[0119] Preferably, in the compound of formula (I-A4), R 1 is C1-C3 alkyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6is hydrogen; A is as defined for compounds of formula (IA), and R 2 , R 9 , R 10 , R 12 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0120] Preferably, in the compound of formula (I-A4), R 1 is C1-C3 alkyl; R 2 is hydrogen, halogen, C1-C3 alkyl, or C3-C6 cyclopropyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is as defined for compounds of formula (IA), and R 9 , R 10 , R 12 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0121] Preferably, in the compound of formula (I-A4), R 1 is C1-C3 alkyl; R 2 is hydrogen, halogen, C1-C3 alkyl, or C3-C6 cyclopropyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is A4, A6, A7, A9, or A10; R 9 , R 10 are independently selected from hydrogen, halogen, or cyano; R 12 is hydrogen; Z 1 is as defined for the compounds of formula (I) according to the invention.

[0122] Preferably, in the compound of formula (I-A4), R 1 is C1-C3 alkyl; R 2is hydrogen, halogen, C1-C3 alkyl, or C3-C6 cyclopropyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is A4, A6, A7, A9, or A10; R 9 , R 10 are independently selected from hydrogen, halogen, or cyano; R 12 is hydrogen; Z 1 is 2-pyridyl, 3-pyridyl, or 4-pyridyl; wherein any of said pyridyl moieties is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, or C1-C4 alkyl.

[0123] In one embodiment of the present invention, the compound of formula (I) is B 1 is CR 9 and B 2 is CR 10 and B 3 is CR 11 and B 4 is N and A is as defined for compounds of formula (IA): [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and Z 1 is as defined for the compounds of formula (I) according to the invention).

[0124] Preferably, in the compound of formula (I-A5), R 1 is C1-C3 alkyl; R 3 is hydrogen; R 4is hydrogen or methyl; R 5 and R 6 is hydrogen; A is as defined for compounds of formula (IA), and R 2 , R 9 , R 10 , R 11 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0125] Preferably, in the compound of formula (I-A5), R 1 is C1-C3 alkyl; R 2 is hydrogen, halogen, C1-C3 alkyl, or C3-C6 cyclopropyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is as defined for compounds of formula (IA), and R 9 , R 10 , R 11 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0126] Preferably, in the compound of formula (I-A5), R 1 is C1-C3 alkyl; R 2 is hydrogen, halogen, C1-C3 alkyl, or C3-C6 cyclopropyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is A4, A6, A7, A9, or A10; R 9 , R 10 are independently selected from hydrogen, halogen, or cyano; R 11 is hydrogen; Z 1 is as defined for the compounds of formula (I) according to the invention.

[0127] Preferably, in the compound of formula (I-A5), R 1is C1-C3 alkyl; R 2 is hydrogen, halogen, C1-C3 alkyl, or C3-C6 cyclopropyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; A is A4, A6, A7, A9, or A10; R 9 , R 10 are independently selected from hydrogen, halogen, or cyano; R 11 is hydrogen; Z 1 is 2-pyridyl, 3-pyridyl, or 4-pyridyl; wherein any of said pyridyl moieties is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, or C1-C4 alkyl.

[0128] The presence of one or more possible asymmetric carbon atoms in any of the compounds selected from compounds of formula (I), (IA), (I-A1), (I-A2), (I-A3), (I-A4), or (I-A5) according to the present invention, or the compounds listed in Tables A-1 to A-23, or the compounds listed in Table P (below), means that the compounds can exist in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms.

[0129] In one embodiment, the compound of formula (I) according to the present invention is selected from the compounds set forth in any one of Tables A-1 to A-23.

[0130] In another embodiment, the compound of formula (I) according to the present invention is selected from the compounds listed in Table P (below).

[0131] In another preferred embodiment, the compound of formula (I) according to the present invention is N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxamide, N-[2-(6-cyano-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(3,5-difluoro-2-pyridyl)-1,3,4-thiadiazole-2-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(3,5-difluoro-2-pyridyl)-1,3,4-thiadiazole-2-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(2,6-difluoro-3-pyridyl)-1,3,4-thiadiazole-2-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(2,6-difluoro-3-pyridyl)-1,3,4-thiadiazole-2-carboxamide, N- [2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(3-fluoro-2-pyridyl)isoxazole-3-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(5-fluoro-2-pyridyl)isoxazole-3-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(2-pyridyl)isoxazole-3-carboxamide, N-[2- (6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(2,6-difluoro-3-pyridyl)isoxazole-3-carboxamide, N-[2-(6-cyano-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(4,6-difluoro-3-pyridyl)-1,3,4-thiadiazole-2-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(4,6-difluoro-3-pyridyl)-1,3,4-Thiadiazole-2-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(6-fluoro-3-pyridyl)isoxazole-3-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-3-(3,5-difluoro-2-pyridyl)isoxazole-5-carboxamide, N-[2-(6-cyano-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-3-(3,5-difluoro-2-pyridyl)isoxazole-5-carboxamide Fluoro-2-pyridyl)isoxazole-5-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(5-cyclopropyl-1-methyl-pyrazol-4-yl)propyl]-3-(3,5-difluoro-2-pyridyl)isoxazole-5-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(5-cyclopropyl-1-methyl-pyrazol-4-yl)propyl]-5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(5-cyclopropyl-1-methyl-pyrazol-4-yl)propyl]-5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxamide )-2-(1-methylpyrazol-4-yl)propyl]-5-(3-fluoro-4-pyridyl)isoxazole-3-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-3-(3,5-difluoro-2-pyridyl)-1,2,4-oxadiazole-5-carboxamide, N-[2-(6-cyano-2-pyridyl)-2-(1,3,5-trimethylpyrazol-4-yl)propyl]-3-(3,5-difluoro-2-pyridyl)isoxazole-5-carboxamide N-[2-(6-cyano-2-pyridyl)-2-(1,3,5-trimethylpyrazol-4-yl)propyl]-5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxamide, N-[2-(6-cyano-2-pyridyl)-2-(1,3,5-trimethylpyrazol-4-yl)ethyl]-3-(3,5-difluoro-2-pyridyl)isoxazole-5-carboxamide, N-[2-(6-cyano-2-pyridyl)-2-(1,3,5-trimethylpyrazol-4-yl)ethyl]-5-(3,5-Difluoro-2-pyridyl)isoxazole-3-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1,5-dimethylpyrazol-4-yl)propyl]-5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1,5-dimethylpyrazol-4-yl)propyl]-3-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxamide N-[2-(6-chloro-2-pyridyl)-2-(1,3,5-trimethylpyrazol-4-yl)propyl]-3-(3,5-difluoro-2-pyridyl)isoxazole-5-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1,3,5-trimethylpyrazol-4-yl)propyl]-5-(3,5-difluoro-2-pyridyl)isoxazole-5-carboxamide ) isoxazole-3-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1,3,5-trimethylpyrazol-4-yl)ethyl]-3-(3,5-difluoro-2-pyridyl)isoxazole-5-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1,3,5-trimethylpyrazol-4-yl)ethyl]-5-(3,5-difluoro-2-pyridyl)isoxazole- 3-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-2-(3,5-difluoro-2-pyridyl)oxazole-4-carboxamide, or N-[2-(6-chloro-2-pyridyl)-2-(1,5-dimethylpyrazol-4-yl)propyl]-3-(3,5-difluoro-2-pyridyl)isoxazole-5-carboxamide.

[0132] In another preferred embodiment, the compound of formula (I) according to the invention is N-[2-(6-chloro-2-pyridyl)-2-[5-(methoxymethyl)-1-methyl-pyrazol-4-yl]propyl]-5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(5-methoxy-1-methyl-pyrazol-4-yl)propyl]-5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxamide, N-[2-(6-cyano-2-pyridyl) )-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)propyl]-3-(3,5-difluoro-2-pyridyl)isoxazole-5-carboxamide, N-[2-(6-cyano-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)propyl]-5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxamide, N-[2-(6-cyano-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)ethyl]-3-(3,5-difluoro N-[2-(6-cyano-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)ethyl]-5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxamide, N-[2-(6-cyano-2-pyridyl)-2-[5-(methoxymethyl)-1,3-dimethyl-pyrazol-4-yl]ethyl]-5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)ethyl]-5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxamide N-[2-(6-chloro-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)propyl]-3-(3,5-difluoro-2-pyridyl)isoxazole-5-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)propyl]-5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-[5-(methoxymethyl)-1,3-dimethyl-pyrazol-4-yl]propyl]-3-(3,5-Difluoro-2-pyridyl)isoxazole-5-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-[5-(methoxymethyl)-1,3-dimethyl-pyrazol-4-yl]propyl]-5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)ethyl]-3-(3,5-difluoro-2-pyridyl)isoxazole-5-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)ethyl]-3-(3,5-difluoro-2-pyridyl)isoxazole-5-carboxamide N-[2-(6-chloro-2-pyridyl)-2-[5-(methoxymethyl)-1,3-dimethyl-pyrazol-4-yl]ethyl]-5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxamide, N-[2-(6-chloro-2-pyridyl)-2-[5-(methoxymethyl)-1,3-dimethyl-pyrazol-4-yl]ethyl]-3-(3,5-difluoro-2-pyridyl)isoxazole-5-carboxamide, or N-[2-(6-chloro-2-pyridyl)-2-[5-(methoxymethyl)-1,3-dimethyl-pyrazol-4-yl]ethyl]-5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxamide.

[0133] According to a fifth aspect of the present invention, there is provided an intermediate compound of formula (III) or a salt thereof: [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , B 1 , B 2 , B 3 , B 4 , R 9 , R 10 , R 11 , and R 12 corresponds to the same definition as in the compounds of formula (I) according to the present invention) is provided.

[0134] The intermediate compound of formula (III) is R 1 , R2 , R 3 , R 4 , R 5 , R 6 , B 1 , B 2 , B 3 , B 4 , R 9 , R 10 , R 11 , and R 12 have the same definitions and corresponding preferences as for the compounds of formula (I) according to the invention.

[0135] Preferably, in the intermediate of formula (III), R 1 is C1-C3 alkyl; R 2 is hydrogen, halogen, C1-C3 alkyl, or C3-C6 cyclopropyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; B 1 is CR 9 and B 2 is CR 10 and B 3 is CR 11 and B 4 is CR 12 and;R 9 , R 10 are independently selected from hydrogen, halogen, or cyano; R 11 is hydrogen; Z 1 are as defined for the compounds of formula (I) according to the invention and the corresponding preferences.

[0136] More preferably, in the intermediate of formula (III), R 1 is C1-C3 alkyl; R 2 is hydrogen, halogen, C1-C3 alkyl, or C3-C6 cyclopropyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; B 1 is CR 9 and B2 is CR 10 and B 3 is CR 11 and B 4 is CR 12 and;R 9 , R 10 are independently selected from hydrogen, halogen, or cyano; R 11 is hydrogen; Z 1 is 2-pyridyl, 3-pyridyl, or 4-pyridyl; wherein any of said pyridyl moieties is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, or C1-C4 alkyl.

[0137] Even more preferably, in the intermediate of formula (III), R 1 is C1-C3 alkyl; R 2 is hydrogen, halogen, C1-C3 alkyl, or C3-C6 cyclopropyl; R 3 is hydrogen; R 4 is hydrogen or methyl; R 5 and R 6 is hydrogen; B 1 is CR 9 and B 2 is CR 10 and B 3 is CR 11 and B 4 is CR 12 and;R 9 , R 10 are independently selected from hydrogen, halogen, or cyano; R 11 is hydrogen; Z 1 is 2-pyridyl, 3-pyridyl, or 4-pyridyl; wherein any of said pyridyl moieties is unsubstituted or substituted with 1 to 2 substituents selected from fluorine.

[0138] The presence of one or more possible asymmetric carbon atoms in the compounds of formula (III) according to the invention means that such compounds can occur in chiral isomeric forms, ie in enantiomeric or diastereomeric forms.

[0139] According to a sixth aspect of the present invention, there is provided an intermediate of formula (II): [ka] (In the formula, A 1 , A 2 , A 3 , and Z 1 corresponds to the same definition as in the compounds of formula (I) according to the present invention).

[0140] The intermediate compound of formula (II) is 1 , A 2 , A 3 and Z 1 have the same definitions and corresponding preferences as for the compounds of formula (I) according to the invention.

[0141] In one embodiment of the present invention, the intermediate of formula (I) may be a compound of formula (II-1): [ka] In the formula, Z 1 is as defined for compounds of formula (I) according to the invention, and A is selected from A1 to A36 as defined above for compounds of formula (IA).

[0142] Preferably, in the intermediate of formula (II-1), Z 1 is as defined for the compounds of formula (I) according to the invention, and A is A4, A7, A9 or A10 [ka] is selected from: [ka] indicates the position of bonding to the C(=O) group, and the arrow indicates Z 1 The position of attachment to the group is indicated.

[0143] Even more preferably, in the intermediate of formula (II-1), A is selected from A4, A7, A9, or A10; Z 1 is 2-pyridyl, 3-pyridyl, or 4-pyridyl; any of said pyridyl moieties is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, or C1-C4 alkyl. Even more preferably, in the intermediate of formula (II-1), A is selected from A4, A7, A9, or A10, and Z 1 is 2-pyridyl, 3-pyridyl, or 4-pyridyl; wherein any of said pyridyl moieties is unsubstituted or substituted with 1 to 2 substituents selected from fluorine.

[0144] Compounds of formula (I) according to the present invention can be formed as shown in the following scheme, where, unless otherwise specified, the definition of each variable is as defined above for compounds of formula (I).

[0145] In any of the following schemes, the possible presence of one or more asymmetric carbon atoms in the compounds of formula (I) according to the invention means that the compounds can occur in chiral isomeric forms, i.e. in enantiomeric or diastereomeric forms.

[0146] Compounds of formula (I) can be prepared from compounds of formula (III) by reaction of compounds of formula (II) with dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide (DIC), or N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (EDAC·HCl) in combination with an additive such as 1-hydroxybenzotriazole (HOBt), hydroxy-3,4-dihydro-4-oxo-1,2,3-benzotriazine (HODhbt), N-hydroxysuccinimide (HOSu), 1-hydroxy-7-aza-1H-benzotriazole (HOAt), or 4-(N,N-dimethylamino)pyridine (DMAP). This reaction is shown in Scheme 1. [ka] Scheme 1

[0147] Alternatively, compounds of formula (I) may be prepared by reacting compounds of formula (IIa) with compounds of formula (III) in an inert solvent such as tetrahydrofuran (THF), ethyl acetate (EtOAc), dichloromethane (DCM), toluene, or the like, optionally in the presence of an inorganic base, such as aqueous sodium hydroxide or potassium carbonate, or an organic base, such as trimethylamine (TEA) or diisopropylamine. The latter reaction with an organic base may optionally be carried out in the presence of a catalyst, such as 4-dimethylaminopyridine (DMAP). 0 Compounds of formula (IIa), where is a halogen, preferably chlorine, can be prepared from compounds of formula (II) by treatment with a halogenating agent such as thionyl chloride (SOCl) or oxalyl chloride (COCl), optionally in the presence of a catalytic amount of N,N-dimethylformamide (DMF), in an inert solvent as described above (Scheme 2). [ka] Scheme 2

[0148] The acylation reaction of carboxylic acids, such as compounds of formula (II), with amines, such as compounds of formula (III), is well known to those skilled in the art and is described, for example, in Eur. J. Org. Chem. 2020, 4641-4651 and the references cited therein, as well as by the methods described below.

[0149] Compounds of formula (II) are commercially available or can be prepared according to or analogously to procedures described in the literature, for example, in WO 2018 / 019929, Org.Proc.Res.Dev.2020,24(2),228-234, WO 2018 / 019929, Lett.Org.Chem.2010,7(7),502-507, and J.Het Chem.2015,52(6),1823-1833.

[0150] A compound of formula (III) or a salt thereof (wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , B 1 , B 2 , B 3 and B 4 is as defined above for compounds of formula (I), can be reacted with a nitrile of formula (IV), where R 1 , R 2 , R 3 , R 4 , B 1 , B 2 , B 3 and B 4 can be prepared by one skilled in the art by the reaction between the Grignard reagent R (as defined for compounds of formula (I)) and a suitable nucleophile such as (dimethylsulfide)dihydroboron (BMS). 5 MgBr or R 6 MgBr (wherein, R 5 and R 6 (wherein ##STR1## is as defined above for compounds of formula (I)) may be added sequentially or simultaneously as nucleophiles to compounds of formula (IV) to allow the preparation of more highly substituted amines of formula (III). Such Grignard additions to nitriles can be carried out in inert solvents such as diethyl ether, tert-butyl methyl ether, and cyclopentyl methyl ether using Ti(O- i The reaction is carried out in the presence of a Lewis acid such as Pr)4 (see Synlett 2007, (4), 652-654). This reaction is shown in Scheme 3. [ka] Scheme 3

[0151] A compound of formula (IV) 1 , R 2 , R 3 , R4 , B 1 , B 2 , B 3 and B 4 (wherein R is as defined above for compounds of formula (I)) can be prepared by one skilled in the art according to known methods. More specifically, compounds of formula (IV), and intermediates thereto, can be prepared from compounds of formula (V) (Scheme 4). [ka] Scheme 4

[0152] For example, a compound of formula (IV) 1 , R 2 , R 3 , R 4 , B 1 , B 2 , B 3 and B 4 is as defined above for compounds of formula (I), and R 4 is different from hydrogen) can be prepared by the reaction of compounds of formula (IVa) (wherein R 4 is hydrogen, and R 1 , R 2 , R 3 , B 1 , B 2 , B 3 and B 4 is as defined above for compounds of formula (I), followed by the addition of a suitable alkylating agent R 4 -X 0 (In the formula, X 0 Compounds of formula (IVa) (wherein R is a halogen) can be prepared by one skilled in the art. 4 is hydrogen and R 1 , R 2 , R 3 , B 1 , B 2 , B 3 and B 4(wherein, as defined above for compounds of formula (I)) can be prepared from alcohols of formula (V) by treatment with cyanotrimethylsilane (TMSCN) in the presence of a base such as lithium carbonate in a non-polar solvent such as DCM at temperatures between 0° C. and the boiling point of the reaction mixture. Such transformations are well known in the literature under a variety of conditions, for example, as described in Org. Lett. 2008, 10, 4570 and references therein. This reaction is shown in Scheme 4.

[0153] Compounds of formula (V) may be prepared from compounds of formula (VI) either from compounds of formula (VIa), formula (VIb), formula (VIc), formula (VId) or formula (VIe), respectively, as shown in Scheme 5. [ka] Scheme 5

[0154] As shown in Scheme 5, a compound of formula (VII), wherein R 1 , R 2 and R 3 is as defined above for compounds of formula (I), and X 01 Metallation of the methyl group (M is bromo or iodo) with a suitable reagent, such as turboGrignard (isopropylmagnesium chloride-lithium chloride complex) or an alkyllithium such as n-butyllithium, gives the intermediate Grignard or alkyllithium reagent (M is MgX 01 or lithium) is obtained. CX 01Such metal insertion into the bond is well known to those skilled in the art and is generally carried out in an inert solvent such as an ether, e.g., tert-butyl methyl ether or THF, at temperatures generally between -78°C and room temperature. A solution of the metallated species (VIIa) is then treated with a compound of formula (VI), respectively (VIa), (VIb), (VIc), (VId), or (VIe), to give a compound of formula (V). Similar reactions of these types are described, for example, in WO 2012 / 102297 and Bio. Med. Chem. Lett. 2017, 27(17), 4044-4050 (X 01 is Br, n-butyllithium) and Ang.Chem.Int.Ed.2016,55(17),5332-5336, U.S. Patent Application Publication No. 2014 / 0349990, WO 2002 / 004424, WO 2021 / 009068 (X 01 is described in I, Turbo Grignard).

[0155] Compounds of formula (VI) and formula (VII) are either commercially available or readily prepared by methods known to those skilled in the art.

[0156] Further synthesis of compounds of formula (I) can be achieved by treating compounds of formula (VIII) with a base such as sodium hydride or n-butyllithium in an inert solvent such as THF, followed by the formation of compounds of formula (IX) (wherein R 4 is as described under formula (I), and X 02 is a leaving group such as a halogen, mesylate, or tosylate) to give a compound of formula (X). This reaction is shown in Scheme 6. [ka] Scheme 6

[0157] Then, a compound of formula (X) (wherein R 1 , R 2 , R 3 , and R 4is as defined above for compounds of formula (I)) is treated with a strong base such as sodium hydride or an alkyl lithium base such as n-butyllithium in an inert solvent such as THF or tert-butyl methyl ether at a temperature between −78° C. and room temperature, followed by the conversion of a compound of formula (XI), either a compound of formula (XIa), formula (XIb), formula (XIc), formula (XId) or formula (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 a halogen, preferably F, Cl or Br) to give compounds of formula (IV) (Scheme 7). [ka] Scheme 7

[0158] Compounds of formula (IV) are converted to compounds of formula (I) as previously described in Schemes 1, 2, and 3. One skilled in the art will recognize that the conversion of compound (VIII) to compounds of formula (IV) may be carried out sequentially or in the same reaction vessel to provide a streamlined conversion of compounds of formula (VIII) to compounds of formula (IV), as described in more detail in the preparative examples.

[0159] A compound of formula (Ia) 1 , R 2 , R 3 , R 5 , Q, 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 converting a compound of formula (VI), respectively a compound of formula (VIa), formula (VIb), formula (VIc), formula (VId) or formula (VIe), into a compound of formula (XII), wherein R5 can be prepared by treating a compound of formula (XIII) with an anhydride such as trifluoroacetic anhydride in an inert solvent such as DCM in the presence of a base, for example triethylamine. This reaction is shown in Scheme 8. [ka] Scheme 8

[0160] Those skilled in the art will appreciate that compounds of formula (VI) may be converted to compounds of formula (XIV) without isolating the intermediate of formula (XIII). Such a reaction, known as the Henry reaction, is well described in the literature, as evidenced by Tetrahedron 2001, 57(6), 915-945, and references cited therein. Compounds of formula (XIV) may be converted to compounds of formula (XV) (Scheme 9) by treatment with compounds of formula (VIIa) in an inert solvent such as THF (see Scheme 5). [ka] Scheme 9

[0161] Similar Michael addition of organometallics to nitroalkenes has been reported, for example, in Org. Lett. 2007, 9, 85-87. Compounds of formula (IIIa) (wherein R 1 , R 2 , R 3 , R 5 , B 1 , B 2 , B 3 and B 4 is as defined above for compounds of formula (I), and R 4 and R 6Reduction of the nitro group of a compound of formula (XV) to an amine to give (wherein is hydrogen) can be achieved by a number of methods generally known to those skilled in the art, such as Béchamp reduction or reduction with hydrogen in the presence of a metal catalyst (Scheme 10). [ka] Scheme 10

[0162] Compounds of formula (IIIa) are converted to compounds of formula (Ia) by the methods described in Schemes 1 and 2.

[0163] Further compounds according to the invention may be prepared by derivatization using key central intermediates later in the synthesis. For example, compounds of formula (I) (wherein B 1 is CX 04 and B 2 is CR 10 and B 3 is CR 11 and B 4 is CR 12 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 a halogen, preferably bromine or chlorine), i.e., a compound of formula (Ia): [ka] is amenable to further chemistry, including palladium-catalyzed carbonylation, Suzuki reactions, Stille couplings, copper-catalyzed introduction of sulfonyl groups, haloalkyl groups, and cyano moieties, as well as SnAr reactions with various nucleophiles. Examples of such reactions are shown in Scheme 11. [ka] Scheme 11

[0164] As shown in Scheme 11, a compound of formula (Ia) 1 is CX 04 and B 2 is CR 10 and B 3 is CR 11 and B 4 is CR 12 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 cyano), i.e., compounds of formula (Ib) can be obtained from compounds 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 temperatures between 0°C and 150°C. Such reactions are well known in the literature, for example, in J. Het. Chem. 1987, 24(2), 373-6; Liebigs Ann. Chem. 1994, (10), 1049-53; and Org. Prep. Proc. Int. 1985, 17(6), 391-9. Other methods for introducing a cyano group by substitution of a halogen atom are known in the art. See, for example, Science of Synthesis 2004, 19, 173-195.

[0165] A compound of formula (I) 1 is CR 9a and B 2 is CR 10 and B 3 is CR 11and B 4 is CR 12 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 C1-C4 haloalkyl, i.e., the compound of formula (Ic) can be converted to the compound of formula (Ia) (wherein 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 a halogen, preferably bromine, to a compound of formula (XVI) 9a is C1-C4 haloalkyl). Such a reaction is known in the literature (Org. Lett. 2014, 16(6), 1744-1747). 1 is CR 9b and B 2 is CR 10 and B 3 is CR 11 and B 4 is CR 12 and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R11 , 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- 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- 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), i.e., compounds of formula (Id) can be prepared by Suzuki reaction (as shown in Scheme 11). This can be achieved, for example, by reacting compounds of formula (Ia) (wherein X 04 is a leaving group such as, for example, chlorine, bromine or iodine, to a compound of formula (XVIIa) b1 For example, B(OH)2 or B(OR b1 )2, where R b1 can be a C1-C4 alkyl group, or two groups OR b1 (which may form a five-membered ring with the boron atom, e.g., pinacolboronic acid ester). This reaction is catalyzed by a palladium-based catalyst, e.g., tetrakis(triphenylphosphine)-palladium or (1,1'-bis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane (1:1 complex), in the presence of a base such as sodium carbonate or cesium fluoride in a solvent or solvent mixture such as, for example, a mixture of 1,2-dimethoxyethane and water, or a mixture of dioxane and water, or a mixture of methyl THF and water, preferably under an inert atmosphere. The reaction temperature can 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 are reviewed, for example, in J. Organomet. Chem. 1999, 576, 147-168.

[0166] Alternatively, the compound of formula (Ic) may be a compound of formula (XVIIb) b2 can also be prepared by the Stille reaction of a compound of formula (Ia) with a compound of formula (Ib), which is a trialkyltin derivative, preferably tri-n-butyltin. Such a Stille reaction is carried out in the presence of a palladium catalyst, such as tetrakis(triphenylphosphine)palladium(0) or (1,1'-bis(diphenylphosphino)-ferrocene)dichloropalladium-dichloromethane (1:1 complex), in an inert solvent such as DMF, acetonitrile, or dioxane, optionally in the presence of an additive such as cesium fluoride or lithium chloride, and optionally in the presence of a further catalyst, such as copper(I) iodide. Such Stille couplings are also well known to those skilled in the art and have been reported, 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. Many compounds of formula (XVIIa) and formula (XVIIb) are commercially available or can be prepared by those skilled in the art. Further compounds obtainable from compounds of formula (Ia) are shown in Scheme 12. [ka] Scheme 12

[0167] As shown in Scheme 12, a compound of formula (I) wherein B 1 is CX 04 and B 2 is CR 10 and B 3 is CR 11 and B 4 is CR 12 and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 10 , R 11 , R 12 , A 1 , A 2 , A3 and Z 1 Compounds of formula (Ia), in which R is as defined above for compounds of formula (I) and X is a leaving group such as chlorine, bromine, or iodine, can be treated with compounds of formula (XVIII) under Stille reaction conditions to give compounds of formula (Ie). Compounds of formula (Ie) can be isolated or directly hydrolyzed under aqueous acidic conditions to give compounds of formula (If). Such reactions are known in the literature and are described, for example, in Synthesis 2001, (10), 1551-1555 and Tetrahedron 2001, 57(13), 2507-2514. Compounds of formula (If) can be prepared by converting compounds of formula (If) to compounds of formula (XIX) (or salts thereof) (wherein R is an integer of 1 to 2) in an inert solvent such as methanol, ethanol, THF, or methyl-THF, optionally in the presence of an inorganic base such as sodium or potassium carbonate, or an organic base such as triethylamine. 13 is hydrogen or C1-C4 alkyl) to give a compound of formula (Ig) 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 of the preparation of such oximes are known in the literature (see, for example, Molecules 2019, 24, 2470 and the references cited therein) and are familiar to those skilled in the art.

[0168] A compound of formula (I) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R10 , 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 a leaving group such as, for example, chlorine, bromine or iodine, ie, compounds of formula (Ia), further compounds that can be prepared from these are shown in Scheme 13. [ka] Scheme 13

[0169] As shown in Scheme 13, compounds of formula (Ia) can be carbonylated to give compounds of formula (I), where 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 14 is C1-C4 alkyl), i.e., to give a compound of formula (Ih). In such an alkoxycarbonylation, a compound of formula (Ia) can be reacted with carbon monoxide, usually 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) dichloride Pd(dppf)Cl2, bis(triphenylphosphine)palladium(II) dichloride PdCl2(PPh3)2, or bis(diphenylphosphino)propane]palladium(II) dichloride PdCl2(dippp)), optionally in the presence of a phosphine ligand such as triphenylphosphine or 1,1'-bis(diphenylphosphino)ferrocene, to give a compound of formula (Ih). 14 is C1-C4 alkyl alcohol R 14The reaction is carried out in an OH solvent (typically methanol or ethanol), optionally in the presence of a cosolvent (e.g., toluene, dioxane, or N,N-dimethylformamide), and preferably in the presence of a base such as trimethylamine, at a temperature of 20°C to 200°C, preferably 50°C to 180°C. Such carbonylation reactions are well known to those skilled in the art and are well known in the literature (see J. Org. Chem. 2008, 73, 7102-7107 and the references cited therein). Such compounds of formula (Ih) can be readily saponified to compounds of formula (Ii) under conditions known to those skilled in the art, such as aqueous sodium, potassium, or lithium hydroxide solutions in methanol, ethanol, THF, or dioxane at room temperature, or up to reflux. Alternatively, the carboxylic acid compound of formula (Ii) may be produced by treating the ester compound of formula (Ih) with a halide anion, preferably a chloride anion, derived from, for example, lithium chloride (or alternatively, sodium or potassium chloride), in a solvent such as DMF, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone. The reaction temperature for such O-demethylation may preferably range from 20°C to the boiling point of the reaction mixture, or the reaction may be carried out under microwave irradiation. The compound of formula (Ii) can be converted into an amide of formula (Ij) (wherein 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 15 and R 16 are independently hydrogen or C1-C4 alkyl), i.e., a compound of formula (Ij). Such a reaction typically involves activation of the carboxyl group followed by the formation of a compound R 15 R 16 NH or by using a coupling agent to form a compound of formula R 15 R16 These methods involve the direct conversion of acids to amides by treatment with NH compounds. These methods are discussed in Schemes 1 and 2, referenced above.

[0170] The compound of formula (Ii) can be prepared by reacting a compound of formula (I) 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 9is an amino), i.e., a compound of formula (Ik), by the so-called Curtius rearrangement. In the Curtius rearrangement, a compound of formula (Ij) is treated with an organic azide in the presence of a suitable base, and optionally with or without 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 suitable solvents can be toluene, xylene, THF, or acetonitrile. An example of a suitable Lewis acid can be Zn(OTf)2, among others. The isocyanate formed in this rearrangement is reacted with water to form a carbamate, which, upon decarboxylation under the reaction conditions, gives the corresponding amine of formula (Ik). Alternatively, these reactions can be carried out in an alcohol, such as t-butyl alcohol, allowing the isolation of t-butyl carbamate. These are then cleaved in separate steps with an acid (such as trifluoroacetic acid) by methods known to those skilled in the art to give compounds of formula (Ik). Examples of such Curtius reactions are reported, for example, in Org. Lett. 2005, 7, 4107-4110, J. Med. Chem. 2006, 49(12), 3614-3627, and Tetrahedron 1974, 30, 2151-2157. Compounds of formula (Ik) thus obtained can be treated with compounds of formula (XX) according to the amidation method described above to give compounds of formula (Im) (wherein 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 18 is a C1-C4 alkyl). Those skilled in the art will appreciate that in any of the compounds of formula (I), when the latter group is a leaving group such as a halogen atom, the position R 9 , R 10 , R11 or R 12 It will be appreciated that such chemistry may be applied in

[0171] Compounds of formula (VI), (VII), (VIII), (IX), (XI), (XII), (XVI), (XVIIa), (XVIIb), (XIX), and (XX) can be readily prepared by one skilled in the art or purchased commercially.

[0172] A compound of formula (II) 1 is N and A 2 is O and A 3 is CH and Z 1 is as described in formula (I), i.e., compounds of formula (IIc) can be prepared as shown in Scheme 14. [ka] Scheme 14

[0173] As shown in Scheme 14, a compound of formula (IIc) (wherein Z 1 is as described above, and X 05 is C1-C4 alkyl) can be prepared by hydrolysis of a compound of formula (IIb), for example, by treatment with an alkaline earth metal hydroxide in water or with a water-miscible organic solvent such as THF, methanol, ethanol, etc. Such ester hydrolysis is well known to those skilled in the art. Compounds of formula (IIb) can be prepared by hydrolysis of a compound of formula (XXVII), where Z 1 is as defined above for compounds of formula (I), and X 05 is C1-C4 alkyl) with hydroxylamine hydrochloride in a polar solvent, such as ethanol, and optionally in the presence of, for example, TEA, K2CO3, or the like.

[0174] Compounds of formula (XXIII) can be prepared by reacting compounds of formula (XXI), where Z 1 is as defined above for compounds of formula (I), a compound of formula (XXII) or a compound of formula (XXIIa) (wherein X 05 is C1-C4 alkyl). Reaction sequences similar to those described in Scheme 14 for preparing compounds of formula (IIb) and (IIc) are described, for example, in CN 111072582, WO 2019 / 195810, and WO 2018 / 019929. Further reaction conditions for preparing compounds of formula (XXVII) are described, for example, in Bioorg. & Med. Chem. 2016, 109, 350-359.

[0175] A compound of formula (II) 1 is O and A 2 and A 3 is N and Z 1 is as described above), i.e., compounds of formula (IIe) can be prepared as shown in Scheme 15. [ka] Scheme 15

[0176] As shown in Scheme 15, compounds of formula (IIe) are obtained by ester hydrolysis of compounds of formula (IId) previously described in Scheme 14. Compounds of formula (IId) (wherein Z 1 is as defined in formula (I), and X 05is C1-C4 alkyl) can be prepared by reacting a compound of formula (XXIIa) with a compound of formula (XXIV), optionally in the presence of a base, for example, pyridine or triethylamine, in a solvent such as acetonitrile, chloroform, or THF. Similar reactions have been reported, for example, in Bioorg. & Med. Chem. 2016, 24(22), 5693-5701 and Chinese Patent No. 114933573. Compounds of formula (XXVIII), where Z 1 (wherein R is as defined above for compounds of formula (I)) can be obtained by treating compounds of formula (XXIX) with hydroxylamine hydrochloride in the presence of a base such as KCO or NaCO in a polar solvent, such as ethanol. The reaction can also be carried out without a base using a hydroxylamine solution. Such reactions are described, for example, in & Med. Chem. Lett. 2020, 30(21), 127508 and Bioorg. Med. Chem. Lett. 2016, 26(23), 5679-5684.

[0177] A compound of formula (XXIV) 1 is as defined above for compounds of formula (I), can also be prepared by Pd-catalyzed synthesis of compounds of formula (XXVI), where Z is as defined above for compounds of formula (I), using potassium ferricyanide trihydrate and hydroxylamine hydrochloride, as described, for example, in Org. Biomol. Chem. 2015, 13(9), 2541-2545. 1 can be prepared by a "one-pot" synthesis by cyanation and amidoximation of (as defined above for compounds of formula (I)).

[0178] A compound of formula (II) 1 and A 2 is N and A 3 is O and Z 1 is as described above (i.e., the compound of formula (IIg)), and A 1 and A 2 is N and A 3 is S and Z1 is as described above (i.e., compounds of formula (IIi)) can be prepared as shown in Scheme 16. [ka] Scheme 16

[0179] As shown in Scheme 16, compounds of formula (IIg) and (IIi) are accessible by ester hydrolysis of (IIf) and (IIg), respectively. In the latter compounds, X 05 and Z 1 is as described above. Compounds of formula (IIf) can be obtained from compounds of formula (IIf), which are obtained by dehydration of compounds of formula (XXVII). Compounds of formula (XXXI) can be obtained by acylation of hydrazides of formula (XXXII) with compounds of formula (XXIIa). Such reaction sequences for producing oxadiazoles are well known to those skilled in the art. Similar reactions are described in Bioorg. Med. Chem. Lett. 2005, 15, 1423-1428 and WO 2006 / 044617. Compounds of formula (XXVII) can also be obtained by acylation of activated carboxylic acids of formula (XXIXa), where Z 1 and X 05 (as described above and in Scheme 1, respectively) with a compound of formula (XXX). Compounds of formula (XXIXa) can be prepared from the corresponding acid of formula (XXIX), as described in Scheme 1. Such a reaction is described, for example, in J. Prakt. Chem. 1985, 327, 109-116. Compounds of formula (IIh) can also be prepared from the general intermediate of formula (XXVII), where Z 1 and X 05 (as described above) by treatment with Lawesson's reagent or neat phosphoric acid pentasulfide or in an inert solvent such as toluene or xylene. Similar reactions are known in the literature (see, for example, WO 2010 / 006713, WO 2009 / 149858, and J. Org Chem. 1961, 26, 4410-12).

[0180] A compound of formula (II) 1 is O and A 2 is N and A 3 is a methine, and Z 1 is as described above for compounds of formula (I), i.e., compounds of formula (IIk) can be prepared as shown in Scheme 17. [ka] Scheme 17

[0181] As shown in Scheme 17, compounds of formula (IIk) are readily available by hydrolysis of esters of formula (IIj) using methods well known to those skilled in the art and described above. Compounds of formula (IIj) can be obtained by reacting compounds of formula (XXXI) with compounds of formula (XXXII) in the presence of an oxidizing agent, such as (diacetoxyiodo)benzene or N-chlorosuccinimide, in an inert solvent such as methanol or DMF, respectively. Such reaction sequences are described, for example, in J. Het. Chem. 2013, 50(4), 774-780 and J. Chin. Chem. Soc. 2007, 54(3), 643-652. Compounds of formula (XXXI) are readily prepared from compounds of formula (XXXIII) (wherein Z1 is as described in formula (I)) by treatment with hydroxylamine under conditions well known to those skilled in the art.

[0182] A compound of formula (I) as defined in any of the embodiments of the present invention can be converted in a manner known per se into another compound as defined in any of the embodiments of the present invention by replacing one or more substituents of the starting compound with one or more other substituents according to the present invention in a conventional manner. Those skilled in the art will also understand that a compound of formula (I) can be further transformed into a further derivative of formula (I) by, for example, alkylation, nucleophilic substitution, elimination, C—C bond forming reactions in the presence of a metal catalyst, heteroatom-carbon bond formation in the presence of a metal catalyst, oxidation, and reduction.

[0183] Depending on the reaction conditions and the choice of starting materials suitable in each case, it may, for example, only be possible in one reaction step to replace one substituent with another substituent according to the invention, or it may be possible to replace several substituents with other substituents according to the invention in the same reaction step.

[0184] Salts of compounds of formula (I) can be prepared in a manner known per se: thus, for example, acid addition salts of compounds of formula (I) can be obtained by treatment with a suitable acid or with a suitable ion exchange reagent, and salts with bases can be obtained by treatment with a suitable base or with a suitable ion exchange reagent.

[0185] Salts of compounds of formula (I) can be converted in a customary manner, for example into the free compounds I (acid addition salts) by treatment with a suitable basic compound or a suitable ion exchange reagent, or into salts with a base, for example by treatment with a suitable acid or a suitable ion exchange reagent.

[0186] Salts of compounds of formula (I) can be converted into other salts (acid addition salts, e.g. other acid addition salts) of compounds of formula (I) in a manner known per se, for example by treating the salt of an inorganic acid, such as hydrochloric acid, with a suitable metal salt of the acid, such as sodium, barium or silver salt (e.g. silver acetate), in a suitable solvent (in which inorganic salts that form, for example, silver chloride, are insoluble and therefore precipitate from the reaction mixture).

[0187] Depending on the procedure or reaction conditions, compounds of formula (I) that have salt-forming properties may be available in the free form or in salt form.

[0188] The compounds of formula (I) and, where appropriate, their tautomers, in each free or salt form, can exist in the form of pure isomers, such as enantiomers and / or diastereomers, or as isomeric mixtures, such as enantiomeric mixtures, e.g. racemates, diastereomeric mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms occurring in the molecule and / or depending on the configuration of non-aromatic double bonds occurring in the molecule, in one form of the possible isomers or as mixtures thereof; the invention relates to the pure isomers and also to all possible isomeric mixtures, and is to be understood in this sense above and below, respectively, even if details of the stereochemistry are not specifically stated in each case.

[0189] Diastereomeric or racemic mixtures of compounds of formula (I), in free or salt form, depending on which starting materials and procedures are selected, can be separated in known manner on the basis of the physical chemical differences of the components into pure diastereomers or racemates, for example by fractional crystallization, distillation and / or chromatography.

[0190] Enantiomeric mixtures, such as racemates, which may be obtained in a similar manner can be resolved into their optical antipodes by known methods, for example, by recrystallization from an optically active solvent; by chromatography on a chiral adsorbent, for example, by high-performance liquid chromatography (HPLC) on acetylcellulose using suitable microorganisms; by cleavage with specific immobilized enzymes, in which only one enantiomer is complexed, for example, via the formation of inclusion compounds with chiral crown ethers; or by conversion to diastereomeric salts, for example, by reacting the basic end-product racemate with an optically active acid, such as a carboxylic acid, for example, camphoric acid, tartaric acid, or malic acid, or a sulfonic acid, for example, camphorsulfonic acid, and separating the diastereomeric mixtures thereby obtainable, for example, by fractional crystallization according to their different solubilities, from which the desired enantiomer can be liberated by the action of a suitable agent, for example, a basic agent, to give diastereomeric salts.

[0191] Pure diastereomers or enantiomers can be obtained according to the present invention not only by separating the appropriate isomeric mixture, but also by diastereoselective or enantioselective synthesis, which is a method known in the art, e.g., by carrying out the process according to the present invention using starting materials with the appropriate stereochemistry.

[0192] If the individual components have different biological activities, it may be advantageous to isolate or synthesize the respective more biologically effective isomer, e.g., enantiomer or diastereomer, or isomeric mixture, e.g., enantiomeric or diastereomeric mixture.

[0193] As an example, compounds with two or more asymmetric carbon atoms may exist in diastereoisomeric forms which can be optionally separated using, for example, supercritical fluid chromatography (SFC) chromatography with a chiral column. Such diastereomers may exhibit different fungicidal activity profiles, but all isomers and diastereomers form part of the present invention.

[0194] The compounds of formula (I) have at least two chiral carbon atoms (two stereocenters, the star (*) indicates the chiral carbon atoms) and therefore have at least four available stereoisomers. These at least four stereoisomers consist of two sets of enantiomers. [ka]

[0195] A compound of formula I, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , B 1 , B 2 , B 3 , B 4 , A 1 , A 2 , A 3 , A 4 and Z 1 is as defined for compounds of formula (I), and R 4 , and R 5 and R 6 The relationship between enantiomers and diastereomers for the 2-amino group (at least one of which is not hydrogen) is shown in Scheme 18. [ka] Scheme 18

[0196] Those skilled in the art will recognize that compounds of formula (I) (as shown in Scheme 18) 1 , R 2 , R 3 , R 4 , R5 , R 6 , B 1 , B 2 , B 3 , B 4 , A 1 , A 2 , A 3 , A 4 and Z 1 is as defined for formula (I), and R 4 , and R 5 and R 6 It is well understood that these diastereomers and enantiomers of , at least one of which is not hydrogen, are within the scope of the present invention.

[0197] The compounds of formula (I) and, where appropriate, their tautomers may each be available in free form or in salt form, where appropriate also in the form of hydrates, and / or may include other solvents, such as those that may have been used for the crystallization of compounds present in solid form.

[0198] As stated above, it has now surprisingly been found that the compounds of formula (I) of the present invention have a very advantageous level of biological activity for practical use in protecting plants from diseases caused by fungi.

[0199] The compounds of formula (I) according to the present invention can be used in the agricultural sector and related fields of use, for example, as active ingredients for controlling plant pests or against non-living organisms for the control of spoilage microorganisms or organisms potentially harmful to humans.The novel compounds are distinguished by excellent activity at low application rates, by being well tolerated by plants, and by being environmentally safe.They have very useful curative, preventive, and systemic properties and can be used to protect a large number of cultivated plants.The compounds of formula (I) can be used to suppress or eradicate pests that appear on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of different crops of useful plants, while simultaneously protecting those parts of the plant that grow later from, for example, phytopathogenic microorganisms.

[0200] The present invention further relates to a method for controlling or preventing infection of susceptible plants or plant propagation material and / or harvested food crops by microorganisms by treating the plants or plant propagation material 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 habitat.

[0201] The compound of formula (I) according to the present invention can also be used as a fungicide. As used herein, the term "fungicide" refers to a compound that controls, modifies, or prevents the growth of fungi. When used, the term "fungicidally effective amount" refers to the amount of such a compound or a combination of such compounds that can produce an effect on the growth of fungi. Controlling or modifying effects include all deviations from natural occurrence, such as killing, delaying, etc., and prevention includes the formation of a barrier or other defense in plants to prevent fungal infection.

[0202] To protect against fungal infections and phytopathogenic fungi occurring in the soil, the compounds of formula (I) according to the present invention may also be used as dressings for treating plant propagation material, such as seeds, such as fruits, tubers, or grains, or plant cuttings. The propagation material can be treated with a composition containing a compound of formula (I) before planting: for example, seeds can be treated with a dressing before sowing. The active compound of formula (I) can also be applied to seeds (coating) by impregnating the seeds in a liquid formulation or coating them with a solid formulation. The composition can also be applied to the planting site, for example, in the sowing furrow during sowing, when the propagation material is planted. The present invention also relates to a method for treating such plant propagation material and to the plant propagation material treated in this way.

[0203] Furthermore, the compounds of formula (I) according to the invention can be used to control fungi in relevant fields, for example in the protection of industrial materials, including wood and wood-related industrial products, food storage, hygiene control.

[0204] Additionally, the present invention can be used to protect non-living materials such as timber, wallboard and paint from fungal attack.

[0205] The compounds of formula (I) according to the invention are active, for example, against disease-causing fungi and fungal vectors as well as phytopathogenic bacteria and viruses. Fungi and fungal vectors as well as plant pathogenic bacteria and viruses associated with these diseases are, for example: Absidia corymbifera, Alternaria spp., Aphanomyces spp., Ascochyta spp., Aspergillus spp., including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, Aureobasidium spp., including A. pullulans, Blastomyces dermatitidis, and the like. dermatitidis, Botryosphaeria spp. including Blumeria graminis, Bremia lactucae, B. dothidea, and B. obtusa, Botrytis spp. including B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, and C. tropicalis, Cephaloascus fragrans fragrans, Ceratocystis spp., Cercospora spp. including C. arachidicola, Cercosporidium personatum, Cladosporium spp.), Claviceps purpurea, Coccidioides immitis, Cochliobolus spp., Colletotrichum spp. including C. musae, Corynespora spp. including Corynespora cassiicola, Cryptococcus neoformans, Diaporthe spp. including Diaporthe miriciae (also known as Diaporthe ueckeri or Diaporthe ueckerae), Didymella spp. spp.), Drechslera spp., Elsinoe spp., Epidermophyton spp., Erwinia amylovora, Erysiphe spp. including E. cichoracearum, Eutypa rata Fusarium spp., including F. lata, F. culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, and F. solani.), Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium spp., Hemileia spp., Histoplasma spp. including H. capsulatum spp., Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp., Monilinia spp., Mucor spp., M. graminicola, Mycosphaerella spp. including M. pomi, Oncobasidium theobromaeon theobromaeon, Ophiostoma piceae, Paracoccidioides spp., Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp., P. maydis, P. philippinensis and P. sorgi.Peronosclerospora spp. including P. sorghi, Peronospora spp., Phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp., Phoma spp., Phomopsis viticola, Phytophthora spp. including P. infestans, P. halstedii, Plasmopara spp. including P. viticola spp.), Pleospora spp., Podosphaera spp. including apple powdery mildew (P. leucotricha), Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp., Pseudoperonospora spp. including P. cubensis and P. humuli, Pseudoperonospora spp. including Pseudopeziza tracheophila Puccinia spp. including P. tracheiphila, P. hordei, P. recondita, P. striiformis, and P. triticina; Pyrenopeziza spp., Pyrenophora spp.; Pyricularia spp. including P. oryzae; and Pythium spp. including P. ultimum.), Ramularia spp., Rhizoctonia spp., Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium spp., Scedosporium spp. including S. apiospermum and S. prolificans, Schizothyrium pomi, Sclerotinia spp., Sclerotium spp. Septoria spp. including S. nodorum, S. tritici, Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix spp., Stagonospora nodorum, Stemphylium spp., Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia spp. Trichoderma spp., including T. harzianum, T. pseudokoningii, and T. viride; Trichophyton spp., Typhula spp., Uncinula necator, Urocystis spp., Ustilago spp., and Venturia spp., including V. inaequalis.), Verticillium spp. and Xanthomonas spp.

[0206] The compounds of formula (I) according to the invention may be used, for example, on turf, ornamental plants such as flowers, shrubs, broad-leaved trees or evergreen trees such as conifers, as well as for trunk injections, pest management, etc.

[0207] Within the scope of the present invention, target crops and / or useful plants to be protected are typically berry plants, such as blackberries, blueberries, cranberries, raspberries and strawberries; cereals, such as barley, maize (corn), millet, oats, rice, rye, sorghum, triticale and wheat; fiber plants, such as cotton, flax, hemp, jute and sisal; field crops, such as sugar and fodder beet, coffee, hops, mustard, rapeseed (canola), poppy, sugarcane, sunflower, tea and tobacco; fruit trees, such as apple, apricot, avocado, banana, cherry, citrus fruit, nectarine, peach, pear and plum; grasses, such as bermudagrass, bluegrass, bentgrass, centipedegrass, fescue, ryegrass, St. Augustine grass and zoysiagrass. herbs such as basil, borage, chives, coriander, 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; palms such as oil palm; ornamental plants such as flowers, shrubs and trees; other trees such as cocoa, coconut, olives and rubber; vegetables such as asparagus, eggplant, broccoli, cabbage, carrots, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and perennial and annual crops such as grapes.

[0208] The term "useful plants" should also be understood to include useful plants that have been rendered tolerant to herbicides such as bromoxynil or to certain classes of herbicides (e.g., HPPD inhibitors, ALS inhibitors such as primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyroyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen oxidase) inhibitors) by conventional methods of breeding (mutagenesis). Crops that have been rendered tolerant to imidazolinones, such as imazamox, by conventional methods of breeding (mutagenesis) include, for example, Clearfield® rapeseed (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-tolerant corn varieties commercially available under the trade names RoundupReady®, Herculex I®, and LibertyLink®.

[0209] It should be understood that the term "useful plants" also includes useful plants that have been transformed using recombinant DNA techniques so as to be able to synthesize one or more selectively acting toxins, such as those known from toxin-producing bacteria, particularly bacteria of the genus Bacillus.

[0210] Examples of such plants are YieldGard® (a corn variety expressing a CryIA(b) toxin); YieldGard Root-Feeding Nematode® (a corn variety expressing a CryIIIB(b1) toxin); YieldGard Plus® (a corn variety expressing a CryIA(b) and a CryIIIB(b1) toxin); Starlink® (a corn variety expressing a Cry9(c) toxin); Herculex I® (a corn variety expressing a CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety expressing a CryIA(c) toxin); Bollgard I® (a cotton variety expressing a CryIA(c) toxin); Bollgard II® (a cotton variety expressing CryIA(c) and CryIIA(b) toxins); VIPCOT® (a cotton variety expressing VIP toxin); NewLeaf® (a potato variety expressing CryIIIA toxin); Nature-Gard® Agrisure® GT Advantage (GA21 glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), Agrisure® RW (corn root nematode trait), and Protecta®.

[0211] The term "crop plant" should also be understood to include crop plants that have been transformed using recombinant DNA techniques to be able to synthesize one or more selectively acting toxins, such as those known from toxin-producing bacteria, particularly those belonging to the genus Bacillus.

[0212] Toxins that can be expressed by the transformed plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or vegetative insecticidal proteins (Vip), e.g., Vip1, Vip2, Vip3, or Vip3A; or insecticidal proteins from Photorhabdus luminescens, Xenorhabdus nematophilus, e.g., Photorhabdus spp. or Xenorhabdus spp. insecticidal proteins of nematode-symbiotic bacteria such as nematode toxins (e.g., scorpion toxins, spider toxins, vespid toxins, and other insect-specific neurotoxins); toxins produced by fungi such as streptomyces toxins, plant lectins such as pea lectin, barley lectin, or snowdrop lectin; agglutinins; proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, and papain inhibitors; ricin, corn-RIP, Ab Ribosome-inactivating proteins (RIPs) such as rin, rufin, saporin or bryodin; steroid metabolic enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

[0213] Furthermore, in the context of the present invention, delta-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or trophic insecticidal proteins (Vip), such as Vip1, Vip2, Vip3, or Vip3A, are also understood to be, in particular, hybrid toxins, truncated toxins, and modified toxins. Hybrid toxins are produced recombinantly by combining different domains of these proteins (see, for example, WO 02 / 15701). Truncated toxins are known, for example, as truncated Cry1Ab. Modified toxins have one or more amino acid substitutions in a naturally occurring toxin. In such amino acid substitutions, preferably a non-naturally occurring protease recognition sequence is inserted into the toxin, for example in the case of Cry3A055 a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see WO 2003 / 018810).

[0214] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP 0 374 753, WO 93 / 07278, WO 95 / 34656, EP 0 427 529, EP 0 451 878 and WO 03 / 052073.

[0215] Methods for preparing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above. Deoxyribonucleic acids of the CryI type and their preparation are known, for example, from WO 95 / 34656, EP 0 367 474, EP 0 401 979 and WO 90 / 13651.

[0216] The toxins contained in the transgenic plants confer resistance to harmful insects found in all insect taxa, but particularly in beetles (Coleoptera), two-winged insects (Diptera), and butterflies (Lepidoptera).

[0217] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known, and some are commercially available. Examples of such plants include YieldGard® (a corn variety expressing the Cry1Ab toxin); YieldGard Rootworm® (a corn variety expressing the Cry3Bb1 toxin); YieldGard Plus® (a corn variety expressing the Cry1Ab and Cry3Bb1 toxins); Starlink® (a corn variety expressing the Cry9C toxin); Herculex I® (a corn variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety expressing the Cry1Ac toxin); Bollgard I® (a cotton variety expressing the Cry1Ac toxin); Bollgard II® (a cotton variety expressing Cry1Ac and Cry2Ab toxins); VipCot® (a cotton variety expressing Vip3A and Cry1Ab toxins); NewLeaf® (a potato variety expressing Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), and Protecta®.

[0218] Further examples of such transgenic crops are: 1. Bt11 maize, registration number C / FR / 96 / 05 / 10, from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France. Genetically engineered maize (Zea mays) resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) through transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also has resistance to the herbicide glufosinate ammonium through transgenic expression of the PAT enzyme.

[0219] 2. Bt176 maize, registration number C / FR / 96 / 05 / 10, from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France. Genetically engineered maize (Zea mays) resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) through transgenic expression of the Cry1Ab toxin. Bt176 maize also has resistance to the herbicide glufosinate ammonium through transgenic expression of the PAT enzyme.

[0220] 3. MIR604 maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Maize conferred insect resistance by transgenic expression of a modified Cry3A toxin. The toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The generation of such transgenic maize plants is described in WO 2003 / 018810.

[0221] 4. MON 863 maize, registration number C / DE / 02 / 9, from Monsanto Europe SA270-272 Avenue de Tervuren, B-1150 Brussels, Belgium. MON863 expresses the Cry3Bb1 toxin and confers resistance to certain Coleoptera insects.

[0222] 5. IPC 531 Cotton, registration number C / ES / 96 / 02, from Monsanto Europe SA270-272 Avenue de Tervuren, B-1150 Brussels, Belgium.

[0223] 6. 1507 corn from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Maize genetically modified to express the Cry1F protein for resistance to certain Lepidoptera insects and the PAT protein for tolerance to the glufosinate-ammonium herbicide.

[0224] 7. NK603 x MON 810 maize, registration number C / GB / 02 / M3 / 03, from Monsanto Europe SA270-272 Avenue de Tervuren, B 1150 Brussels, Belgium. This maize is a conventionally bred hybrid maize variety obtained by crossing the genetically modified varieties NK603 and MON 810. NK603×MON810 maize transgenic expresses the protein CP4 EPSPS from Agrobacterium sp. strain CP4, which confers resistance to the herbicide Roundup® (containing glyphosate), and the Cry1Ab toxin from Bacillus thuringiensis subsp. kurstaki, which confers resistance to certain Lepidoptera, including the European corn borer.

[0225] The compounds of formula (I) according to the invention are effective against phytopathogenic diseases, in particular phytopathogenic fungi, such as Alternaria species on fruits, vegetables and potatoes; Botrytis cinerea on strawberries, tomatoes, sunflowers, pulses, vegetables and grapes; Rhizoctonia solani on potatoes and vegetables; Uncinula necator on grapes; Cladosporium cucumerinum, Didymella bryoniae, Sphaerotheca fuliginea and Glomerella lagenarium on Cucurbits; Leveillula taurica on Cucurbits and Solanaceae crops. taurica; Fusarium spp. in cereals; Leptosphaeria spp. in cereals; and Zymospetoria spp. in cereals.

[0226] As used herein, the term "habitat" means the field in which the plant is growing or in which the seeds of the plant to be cultivated have been sown or will be sown in the soil. It includes the soil, seeds and seedlings, and established vegetation.

[0227] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves and fruits.

[0228] The term "plant propagation material" is understood to refer to the reproductive parts of plants, such as seeds, and vegetative bodies, such as cuttings or tubers (e.g., potatoes), which can be used for their propagation. Examples include seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes, and parts of plants. Mention may also be made of germinated plants and seedlings that are transplanted after germination or emergence from the soil. These seedlings can be protected before transplanting by total or partial treatment by immersion. Preferably, "plant propagation material" is understood to refer to seeds.

[0229] The compounds of formula (I) according to the present invention can be used in their original form or, preferably, together with adjuvants conventionally used in the field of formulation. For this purpose, they can be conveniently formulated in a known manner into emulsifiable concentrates, coating pastes, directly sprayable or dilutable solutions or suspensions, diluted emulsions, wettable powders, soluble powders, dusts, granules, and capsules, for example, in polymeric materials. The application method, such as spraying, atomizing, dusting, scattering, coating, or pouring, as well as the type of composition, can be selected depending on the intended purpose and the current situation. The composition can also contain further adjuvants, such as stabilizers, antifoaming agents, viscosity modifiers, binders, or tackifiers, as well as fertilizers, sources of trace elements, or other ingredients for achieving special effects.

[0230] Suitable carriers and adjuvants, for example for agricultural applications, can be solid or liquid and are substances useful in formulation technology, such as natural or regenerated inorganic substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are described, for example, in WO 1997 / 33890.

[0231] Suspension concentrates are aqueous preparations in which fine solid particles of the active compound are suspended. Such formulations contain anti-settling and dispersing agents and may further contain wetting agents, as well as anti-foaming and crystal growth inhibitors to enhance activity. When used, these concentrates are diluted with water and typically 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.

[0232] Wettable powders are in the form of finely divided particles that disperse readily in water or other liquid carriers. The particles contain the active ingredient held in a solid matrix. Typical solid matrices include fuller's earth, kaolin clay, silica, and other readily wet organic or inorganic solids. Wettable powders usually contain 5% to 95% of the active ingredient and small amounts of wetting agents, dispersing agents, or emulsifying agents.

[0233] Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquids. They may consist solely of the active compound and a liquid or solid emulsifier, or may also contain a liquid carrier such as xylene, high-boiling aromatic naphtha, isophorone, and other non-volatile organic solvents. When used, these concentrates are dispersed in water or other liquid and typically 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.

[0234] Granular formulations include both extrudates and relatively coarse particles, and are usually applied undiluted to the area where treatment is required. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clay, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, gypsum, wood flour, ground corn cobs, ground peanut shells, sugar, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate, and other organic or inorganic materials that can absorb or be coated with the active compound. Granular formulations usually contain 5% to 25% active ingredient, which may include surfactants or vegetable oils such as high-boiling aromatic naphtha, kerosene, and other petroleum fractions; and / or adhesives such as dextrin, glue, or synthetic resins.

[0235] Dusts are free-flowing mixtures of the active ingredient and finely divided solids such as talc, clays, flours and other organic and inorganic solids, which act as dispersants and carriers.

[0236] Microcapsules are typically droplets or granules of an active ingredient enclosed in an inert, porous shell that allows the encapsulated material to be released into the environment at a controlled rate. The encapsulated droplets are typically 1 to 50 microns in diameter. The encapsulated liquid typically constitutes 50 to 95% of the capsule's weight and may contain solvent in addition to the active compound. Encapsulated granules are generally porous granules with a porous membrane that seals the pore openings of the granule, retaining the active species in liquid form within the pores of the granule. Granules typically range in diameter from 1 millimeter to 1 centimeter, preferably 1 to 2 millimeters. Granules are formed by extrusion, agglomeration, or prilling, or are naturally occurring. Examples of such materials are vermiculite, calcined clay, kaolin, attapulgite clay, sawdust, and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes, and starch xanthates.

[0237] Other useful formulations for pesticide applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene, and other organic solvents. Pressurized sprayers can also be used, in which the active ingredient is dispersed in finely divided form as a result of evaporation of the low-boiling dispersant solvent carrier.

[0238] Suitable agricultural adjuvants and carriers useful in formulating the compositions of the present invention in the formulation types described above are well known to those skilled in the art.

[0239] Liquid carriers that can be used include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetate, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidinone, 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 monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octyl amine Examples of suitable solvents include ethanol, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG 400), 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, ethylene glycol, propylene glycol, glycerin, and N-methyl-2-pyrrolidinone. Water is generally the carrier of choice for dilution of concentrates.

[0240] Suitable solid carriers include, for example, talc, titanium dioxide, pyroferritic clay, silica, attapulgite clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, and lignin.

[0241] A wide range of surfactants are advantageously employed in both the liquid and solid compositions, particularly those designed to be diluted with a carrier before application. When used, these agents typically comprise 0.1% to 15% by weight of the formulation. They may be anionic, cationic, nonionic, or polymeric in nature and may be used as emulsifiers, wetting agents, suspending agents, or for other purposes. Typical surfactants include salts of lauryl sulfate, such as diethanolammonium lauryl sulfate; alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; nonylphenol-C 18 Alkylphenol-alkylene oxide adducts such as ethoxylates; Tridecyl alcohol-C 16 ethoxylates; soaps such as sodium stearate; alkyl naphthalene sulfonates, for example, sodium dibutyl naphthalene sulfonate; dialkyl esters of sulfosuccinates, such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters, for example, sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride; polyethylene glycol esters of fatty acids, for example, polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkyl phosphate esters.

[0242] Other adjuvants commonly used in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, antifoaming agents, light-blocking agents, compatibilizers, defoamers, sequestering agents, neutralizing agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and adhesives.

[0243] In addition, other biocidal active ingredients or compositions can be combined with the composition of the present invention, used in the method of the present invention, and applied simultaneously or sequentially with the composition of the present invention.When applied simultaneously, these additional active ingredients can be formulated together with the composition of the present invention or mixed, for example, in a spray tank.These additional biocidal active ingredients can be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and / or plant growth regulators.

[0244] Pesticides are referred to herein using their common names and are known, for example, from “The Pesticide Manual”, 15th Ed., British Crop Protection Council 2009.

[0245] Additionally, the compositions of the present invention can be applied in conjunction with one or more systemic acquired resistance inducers ("SAR" inducers). SAR inducers are known and are described, for example, in U.S. Patent No. 6,919,298, and include, for example, salicylates and the commercially available SAR inducer acibenzolar-S-methyl.

[0246] The compound of formula (I) according to the present invention is usually used in the form of agrochemical compositions, and can be applied to the cropland or the plants to be treated simultaneously or successively with other compounds.These other compounds can be, for example, fertilizers or sources of trace elements or other preparations that affect plant growth.They can also be selective or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, and if necessary, also contain additional carriers, surfactants or application-promoting adjuvants that are commonly used in the technical field of formulations.

[0247] The compounds of formula (I) according to the invention may also be used in the form of (fungicidal) compositions for the control against or protection against phytopathogenic microorganisms, containing as active ingredient 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 available salt, and at least one of the adjuvants mentioned above.

[0248] Therefore, the present invention provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I) according to the present invention, 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, the composition may comprise, in addition to the compound of formula (I), at least one or more pesticide active compounds, for example, additional fungicidal active ingredients.

[0249] The compound of formula (I) according to the invention may be the only active ingredient of the composition or, if appropriate, may be mixed with one or more additional active ingredients, such as pesticides, fungicides, synergists, herbicides or plant growth regulators, which may in some cases result in unexpected synergistic effects.

[0250] Examples of suitable additional active ingredients include acyl amino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenic fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate 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, organophosphate fungicides, organotin fungicides, oxathiin fungicides, oxazole fungicides, phenylsulfamide 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.

[0251] Examples of suitable additional active ingredients include: petroleum, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenylbenzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylacetamide, 4-chlorophenylphenylsulfone, acetoprole, aldoxicarb, amidithione, amidothioate, amiton, amiton hydrogen oxalate, amitraz, alamite, arsenic trioxide, azobenzene, azotoate, benomyl, benoxafos, benzoin. Benzyl acetate, bixafen, brofenvalerate, bromocyclen, bromophos, bromopropylate, buprofezin, butocarboxim, butoxycarboxim, butylpyridaben, calcium polysulfide, camphechlor, carbanolate, carbophenothion, cymiazole, chinomethionate, chlorbeneside, chlordimeform, chlordimeform hydrochloride, chlorphenetole, chlorfenson, chlorfen sulfide, chlorobenzilate, chloromebuform, chloromethyluron, chlor Lopropylate, Chlorthiophos, Cinerin I, Cinerin II, Cinerin, Closantel, Coumaphos, Crotamiton, Crotoxyphos, Kufraneb, Cyanthoate, DCPM, DDT, Demefion, Demefion-O, Demefion-S, Demeton-methyl, Demeton-O, Demeton-O-methyl, Demeton-S, Demeton-S-methyl, Demeton-S-methyl sulfone, Dichlofluanid, Dichlorvos, Dicrifos, Dienochlor, Dimefox, Zinex, Zinex-diclexin, Zinocca CAP-4, Dinocap-6, Dinoctone, Dinopentone, Dinosulfone, Dinotervone, Dioxathion, Diphenylsulfone, Disulfiram, DNOC, Dofenapine, Doramectin, Endothion, Eprinomectin, Ethoate-methyl, Etrimphos, Fenazaflor, Fenbutatin Oxide, Fenothiocarb, Fenpyrad, Fenpyroximate, Fenpyrazamine, Fenson, Fentrifanil, Flubenzimine, Flucycloxuron, Fluenethyl, Fluorobenside, FMC 1137, Formetanate, Formetanate Hydrochloride, Formoparanate, γ-HCH, Gliodin, Halfenprox, Hexadecylcyclopropanecarboxylate, Isocarbophos, Jasmolin I,Jasmolin II, iodofenphos, lindane, malonobene, mecarbam, mefosfolan, mesulfen, methacrifos, methyl bromide, metolcarb, mexacarbate, milbemycin oxime, mipafox, monocrotophos, morphothion, moxidectin, naled, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one, nifururidide, nikkomycin, nitrilacarb, nitrilacarb 1:1 zinc chloride complex, omethoate, oxydeprophos, oxydisulfoton, p p'-DDT, parathion, permethrin, fenkapton, phosalone, phospholane, phosphamidon, polychloroterpenes, polynactin, proclonol, promacyl, propoxar, prothidathion, prothoate, pyrethrin I, pyrethrin II, pyrethrins, pyridaphenthion, pirimitate, quinalphos, quintiox, R-1492, phosglycine, rotenone, shradan, cebufos, selamectin, sofamid, SSI-121, sulfiram, sulfuramide, sulfotep, sulfur, diflobidazin, tau-fluvalinate, TEPP , Terbam, Tetradifon, Tetrasulf, Thiafenox, Thiocarboxim, Thiofanox, Thiometon, Thioquinox, Thuringiensin, Triamiphos, Triatene, Triazophos, Triazuron, Trifenofos, Trinactin, Vamidothion, Vaniliprole, Bethoxazin, Copper dioctanoate, Copper sulfate, Sibutrin, Dichlorn, Dichlorophen, Endothal, Fentin, Slaked lime, Nabam, Quinoclamine, Quinonamide, Simazine, Triphenyltin acetate, Triphenyltin hydroxide, Crufomate, Piperazine, Thiophanate, Chlorphen Loralose, fenthion, pyridin-4-amine, strychnine, 1-hydroxy-1H-pyridine-2-thione, 4-(quinoxalin-2-ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, copper hydroxide, cresol, dipyrithione, dodisin, fenaminosulf, formaldehyde, hydralgafen, kasugamycin, kasugamycin hydrochloride brine monohydrate, nickel bis(dimethyldithiocarbamate), nitrapyrin, octhilinone, oxolinic acid, oxytetracycline, potassium hydroxyquinoline sulfate,Probenazole, streptomycin, streptomycin sesquisulfate, tecloftalam, thiomersal, Adoxophyes orana GV, Agrobacterium radiobacter, Amblyseius spp., Anagrapha falcifera NPV, Anagrus atomus, Aphelinus abdominalis, Aphidius colemani, Aphidoletes aphidimyza, Autographa californica NPV, Bacillus sphaericus Neide, Beauveria bronniartii brongniartii, Chrysoperla carnea, Cryptolaemus montrouzieri, Cydia pomonella GV, Dacnusa sibirica, Diglyphus isaea, Encarsia formosa, Eretmocerus eremicus, Heterorhabditis bacteriophora and H. megidis, Hippodamia convergens, Leptomastix dactylopii, Macrolophus caliginosus caliginosus), Mamestra brassicae NPV, Metaphycus helvolus, Metarhizium anisopliae var. acridum,Metarhizium anisopliae var. anisopliae, Neodiprion sertifer NPV and N. lecontei NPV, Orius spp., Paecilomyces fumosoroseus, Phytoseiulus persimilis, Steinernema bibionis, Steinernema carpocapsae, Steinernema feltiae, Steinernema glaseri, Steinernema riobrave riobrave, Steinernema riobravis, Steinernema scapterisci, Steinernema spp., Trichogramma spp., Typhlodromus occidentalis, Verticillium lecanii), apholate, visadil, busulfan, dimatif, hemel, hempa, metepa, methiotepa, methyl apholate, molzide, penfluron, tepa, thiohempa, thiotepa, trethamine, uredepa, (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)-icosa-13-en-10-one, (Z)-tetradec-7-en-1-al, (Z)-tetradec-9-en-1-ol,(Z)-Tetradeca-9-en-1-yl acetate, (7E,9Z)-dodeca-7,9-dien-1-yl acetate, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate, 14-methyloctadec-1-ene, 4-methylnonan-5-ol and 4-methylnonan-5-one, α-multistriatin, brevicomin, codrelure, codlemone, curure, disparure, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodec-8,10-dien-1-yl acetate, dominicalure, ethyl 4-methyloctanoate, eugenol, frontalin, gran Dolure, Grandolure I, Grandolure II, Grandolure III, Grandolure IV, Hexalure, Ipsdienol, Ipsenol, Japonilure, Lineatin, Litrure, Lupulure, Medulure, Megatomoic Acid, Methyleugenol, Muscalure, Octadeca-2,13-dien-1-yl Acetate, Octadeca-3,13-dien-1-yl Acetate, Olfuralure, Orictalure, Ostramon, Siglua, Soldigin, Sulcatol, Tetradec-11-en-1-yl Acetate, Trimedulure, Trimedulure A, Trimedulure B1, Trimedulure B2, Trimedulure C, Tranquol, 2-(Octylthio)ethanol, Butopyronoxyl, Butoxy(Polypropylene Glycol), Dibutyl adipate, dibutyl phthalate, dibutyl succinate, diethyl toluamide, dimethylcarbate, dimethyl phthalate, ethyl hexanediol, hexamide, methoxine-butyl, methyl neodecanamide, oxamate, picaridin, 1-dichloro-1-nitroethane, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane, 1,2-dichloropropane and 1,3-dichloropropene, 1-bromo-2-chloroethane, 2,2,2-trichloro-1-(3,4-dichlorophenyl)acetate, 2,2-dichlorovinyl 2-ethylsulfinylethyl methylphosphate, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate, 2-(2-butoxyethoxy)ethyl thiocyanate, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenylmethylcarbamate mate, 2-(4-chloro-3,5-xylyloxy)ethanol, 2-chlorovinyl diethyl phosphate, 2-imidazolidone, 2-isovalerylindan-1,3-dione, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate, 2-thiocyanatoethyl laurate, 3-bromo-1-chloroprop-1-ene, 3-methyl-1-phenylpyrazol-5-yldimethylcarbamate, 4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate, acetione, acrylonitrile, aldrin, allosamidin, alixycarb, α-ecdysone, aluminum phosphide, aminocarb, anabasine, atidathion, azamethiphos, Bacillus thuringiensis (Bacillus thuringiensis) delta-endotoxin, barium hexafluorosilicate, barium polysulfide, bartholin, Bayer 22 / 190, Bayer 22408, beta-cyfluthrin, beta-cypermethrin, bioethanomethrin, biopermethrin, bis(2-chloroethyl) ether, borax, bromfenvinphos, bromo-DDT, bufencarb, butacarb, butathiophos, butonate, calcium arsenate, calcium cyanide, carbon disulfide, carbon tetrachloride, cartap hydrochloride, sevadine, chlorbicyclen, chlordane, chlordecone, chloroform, chloropicrin, chlorphoxim,Chlorprazophos, cis-resmethrin, cismethrin, clocithrin, copper acetoarsenite, copper arsenate, copper oleate, cumitoate, cryolite, CS 708, cyanofenphos, cyanophos, cyclethrin, cythioate, d-tetramethrin, DAEP, dazomet, decarbofuran, diamidaphos, dikapton, diclofenthion, dicresyl, dicyclanil, dieldrin, diethyl 5-methylpyrazol-3-yl phosphate, dilol, dimefluthrin, dimethane, dimethrin, dimethylvinphos, dimethiran, dinoprop, dinosam, dinoseb, diofenolan, dioxabenzophos, dicyclophos, DSP, ecdysterone, EI 1642, EMPC, EPBP, etaphos, ethiofencarb, ethyl formate, ethylene dibromide, ethylene dichloride, ethylene oxide, EXD, fenchlorphos, fenetacarb, fenitrothion, fenoxacrim, fenpyritrin, fensulfothion, fenthion-ethyl, flucofuron, fosmetiran, fospirate, fostietan, furathiocarb, fretrin, guazatine, guazatine acetate, sodium tetrathiocarbonate, halfenprox, HCH, HEOD, heptachlor, heterophos, HHDN, hydrogen cyanide, hikincarb, IPSP, isazophos, isobenzan, isodrin, isofenphos, isolane, isoprothiolane, isoxathion, juvenile hormone I, juvenile hormone II, juvenile hormone III, kerevan, kinoprene, lead arsenate, leptophos s, lilimphos, ritidathion, m-cumenylmethylcarbamate, magnesium phosphide, magidox, mecarfone, menazone, mercurous chloride, mesulfenphos, metam, metam-potassium, metam-sodium, methanesulfonyl fluoride, methoclotophos, methoprene, methotrin, methoxychlor, methyl isothiocyanate, methyl chloroform, methylene chloride, methoxadiazone, mirex, naphthalophos, naphthalene, NC-170, nicotine, nicotine sulfate, nithiazine, nornicotine, O-5-dichloro-4-iodophenyl O-ethylethylphosphonothioate, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate,O,O,O',O'-Tetrapropyldithiopyrophosphate, oleic acid, para-dichlorobenzene, parathion-methyl, pentachlorophenol, pentachlorophenyl laurate, pH 60-38, fenkapton, phosniclor, phosphine, phoxim-methyl, pyrimetaphos, polychlorodicyclopentadiene isomers, potassium arsenite, potassium thiocyanate, precocene I, precocene II, precocene III, primidophos, profluthrin, promecarb, prothiofos, pyrazophos, pyresmethrin, quassia, quinalphos-methyl, quinothione, lafoxanide, resmethrin, rotenone, kadethrin, ryania, ryanodine, sabadila, shradha cebufos, SI-0009, tiapronil, sodium arsenite, sodium cyanide, sodium fluoride, sodium hexafluorosilicate, sodium pentachlorophenoxide, sodium selenate, sodium thiocyanate, sulcofuron, sulcofuron-sodium, sulfuryl fluoride, sulproos, tard oil, tazimcarb, TDE, tebupirimfos, temephos, telalethrin, tetrachloroethane, cyclofos, thiocyclam, thiocyclam hydrogen oxalate, thiona Zin, thiosultap, thiosultap-sodium, tralomethrin, transpermethrin, triazamate, trichlormetaphos-3, trichloronate, trimethacarb, tolprocarb, triclopyricarb, triplen, veratridine, veratrine, XMC, ζmethrin, zinc phosphide, zolaprofos, meperfluthrin, tetramethylfluthrin, bis(tributyltin) oxide, bromoacetamide, ferric phosphate, niclosamide-olamine, tributyltin oxide, Pyrimorph, triphenmorph, 1,2-dibromo-3-chloropropane, 1,3-dichloropropene, 3,4-dichlorotetrahydrothiophene 1,1-dioxide, 3-(4-chlorophenyl)-5-methylrhodanine, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid, 6-isopentenylaminopurine, anicifluprine, benclothiaz, cytokinin, DCIP, furfural, isamidophos, kinetin, mulberry dark spot fungus (Myrothecium verrucaria) composition, tetrachlorothiophene, xylenol, zeatin,Potassium ethylxanthate, acibenzolar, acibenzolar-S-methyl, Reynoutria knotweed sachalinensis extract, α-chlorohydrin, anth, barium carbonate, bisthiosemi, brodifacoum, bromadiolone, bromethalin, chlorophacinone, cholecalciferol, coumachlor, coumafuryl, coumatetralyl, crimidine, difenacoum, difethialone, diphacinone, ergocalciferol, flocoumafen, fluoroacetamide, flupropazine, flupropazine hydrochloride, norbormide, fosacetim, phosphorus, pindone, pyrinuron, sciliroside, sodium fluoroacetate, thallium sulfate, warfarin, 2-(2-butoxyethoxy)ethyl piperonylate, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, farnesol and nerolidol, verbutin, MGK 264, piperonyl butoxide, piprotal, propyl isomers, S421, sesamex, sesamolin, sulfoxide, anthraquinone, copper naphthenate, copper oxychloride, dicyclopentadiene, thiram, zinc naphthenate, ziram, imanin, ribavirin, chlorinconazide, mercuric oxide, thiophanate-methyl, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, furametpyr, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, paclobu Trazol, pefurazoate, penconazole, prothioconazole, pyrifenox, prochloraz, propiconazole, pyrisoxazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole, ancymidol, fenarimol, nuarimol, bupirimate, dimethirimol, ethirimol, dodemorph, fenpropidin, fenpropimorph, spiroxamine, tridemorph, cyprodinil, mepanipyrim, pyrimethanil, fenpiclonil, fludioxonil, benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofrace, oxadixyl, carbendazim,Debacarb, fuberidazole, thiabendazole, chlozolinate, dichlozolin, mycrozolin, procymidone, vinclozolin, boscalid, carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, penthiopyrad, thifluzamide, dodine, iminoctadine, azoxystrobin, dimoxystrobin, enesterobrine, phenaminestrobin, flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, oryzastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyroxystrobin, ferbam, mancozeb, maneb, metiram, propineb, zineb, captafol, captan, fluoroimide, folpet, tolylfluanid, Bordeaux mixture, copper oxide, mancopper, oxine-copper, nitrotar-isopropyl, edifene Nphos, Iprobenfos, Fosdifen, Tolclofos-methyl, Anilazine, Benthiavalicarb, Blasticidin-S, Chloroneb, Chlorothalonil, Cyflufenamid, Cymoxanil, Cyclobutrifluram, Diclocymet, Diclomedine, Dicloran, Diethofencarb, Dimethomorph, Flumorph, Dithianon, Ethaboxam, Etridiazole, Famoxadone, Fenamidone, Fenoxanil, Felimzo fluazinam, flumethylsulfolim, fluopicolide, fluoxythioconazole, flusulfamide, fluxapyroxad, fenhexamid, fosetyl-aluminum, hymexazole, iprovalicarb, cyazofamid, metasulfocarb, metrafenone, pencycuron, phthalide, polyoxin, propamocarb, pyribencarb, proquinazid, pyroquilon, pyriophenone, quinoxyfen, quintozene, Tiadinil, triazoxide, tricyclazole, triforine, validamycin, valifenalate, zoxamide, mandipropamide, fluveneteram, isopyrazam, sedaxane, benzovindiflupyr, pydiflumetofen, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide, isoflucipram, isotianil, dipimethitrone, 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-pyrazole-3-a amine, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, fluindapyr, methoxystrobin (jiaxiangjunzhi), rubenmixianan, dichlorbenziazox, mandestrobin, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolinyl)amino]-2-methyl-1H-pyrazol-5-amine, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolinyl)amino]-2-methyl-1H-pyrazol-5-amine] ... 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-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl]methanesulfonate, but-3-ynyl N -[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine, pyridaclomethyl, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazo 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one, aminopyrifen, ametoctrazine, amisulbrom, penflufen, (Z,2E)-5-[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, aminopyrifen, ametoctrazine, amisulbrom, penflufen, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one thia-2-methoxyimino-N,3-dimethyl-pent-3-enamide, florylpicoxamide, fenpicoxamide, methallylpicoxamide, tebufloquine, ipflufenoquine, quinofumelin, isofetamide, ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate (which can be prepared from the method described in WO 2020 / 056090), ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate (which can be prepared from the method described in WO 2020 / 056090), ethyl 1-[[4-[[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enoxy]phenyl]methyl]pyrazole-3-carboxylate (which can be prepared from the method described in WO 2020 / 056090), methyl N-[[4-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (which can be prepared from the method described in WO 2020 / 097012), methyl N-[[4-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl] methyl]carbamate (which can be prepared from the method described in WO 2020 / 097012), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (which can be prepared from the method described in WO 2020 / 109391), 6-chloro-N-[2-(2-chloro-4-methyl-phenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl- Pyridazine-4-carboxamide (which can be prepared from the method described in WO 2020 / 109391), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (which can be prepared from 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, benzothiostrobin, fenamacril, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1), fluopyram, flufenoxadiazam, flutianil, fluopimomide, pyrapropoin, 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, Methyltetraprole, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidinemethanol, Fluoxapi Proline, Enoxastrobin, Methyl (Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazole-2-yl]phenoxy]prop-2-enoate, Methyl (Z)-3-methoxy-2-[2-methyl-5-(4-propyltriazole-2-yl)phenoxy]prop-2-enoate, 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 the method described in WO 2020 / 079111), methyl (Z)-2-(5-cyclohexyl-2-methyl -phenoxy)-3-methoxy-prop-2-enoate, methyl (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate (these compounds can be prepared from the method described in WO 2020 / 193387), 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-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-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, trinexapac, cumoxystrobin, zhongshengmycin n), thiodiazole copper, zinc thiazole, amethotractin, iprodione, seboxylamine, N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine (these compounds can be prepared from the method described in WO 2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (these compounds can be prepared from the method described in WO 2015 / 155075); can be prepared from 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 from the method described in WO 2018 / 228896);N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetan-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 from the method described in 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-1,3-dimethyl-butyl]-7,8-di Fluoro-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 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 the method described in WO 2017 / 153380);1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 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 (these compounds were prepared by the method described in WO 2017 / 025510). 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 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 from the method described in WO 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]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]urea, N,N-dimethyl-1-[[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, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, [phenyl]phenyl]methyl]-1,2,4-triazol-3-amine (these compounds can be prepared from the methods described in WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 093348 and WO 2017 / 118689); 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared from 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 from the method described in WO 2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile (this compound can be prepared from the method described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile (this compound can be prepared from the method described in WO 2016 / 156290); (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate (this compound can be prepared from the method described in WO 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone (this compound can be prepared from the method described in WO 2011 / 138281), N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide; 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-enamide (this compound can be prepared from the method described in WO 2018 / 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 from the method described in WO 2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (this compound can be prepared from 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 from 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 from the method described in WO 2018 / 065414); ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate (this compound can be prepared from the method described in WO 2018 / 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-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (these compounds can be prepared from the method described in WO 2018 / 202428);

[0252] The compounds of the present invention may also be used in combination with an antiparasitic agent. Such antiparasitic agents include compounds selected from the macrocyclic lactone class of compounds, such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin, and milbemycin derivatives, as described in EP 0357460, EP 0444964, and EP 0594291. Additional antiparasitic agents include semisynthetic and biosynthetic avermectin / milbemycin derivatives, such as those described in U.S. Pat. No. 5,015,630, WO 9415944, and WO 9522552. Additional antiparasitic agents include benzimidazoles, such as albendazole, cambandazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of this class. Further anthelmintics include imidazothiazoles and tetrahydropyrimidines, such as tetramisole, levamisole, pyrantel pamoate, oxantel, or morantel. Further anthelmintics include flukeicides, such as triclabendazole and clorsulon, and cestoicides, such as praziquantel and epsiprantel.

[0253] The compounds of the present invention may also be used in combination with derivatives and analogues of the paraherquamide / marcfortine class of anthelmintics, and antiparasitic oxazolines, such as those disclosed in U.S. Pat. No. 5,478,855, U.S. Pat. No. 4,639,771 and German Patent No. 19,520,936.

[0254] The compounds of the invention may also be used in combination with derivatives and analogues of the general class of dioxomorpholine antiparasitic agents as described in WO 9615121, and also with anthelmintic effective cyclic depsipeptides such as those described in WO 9611945, WO 9319053, WO 9325543, EP 0626375, EP 0382173, WO 9419334, EP 0382173 and EP 0503538.

[0255] The compounds of the present invention may be used in combination with other biocidal agents; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide; and neonicotinoids such as imidacloprid.

[0256] The compounds of the present invention may also be used in combination with terpene alkaloids, such as those described in WO 95 / 19363 or WO 04 / 72086, particularly the compounds disclosed therein.

[0257] Other examples of such biologically active compounds that may be used in combination with the compounds of the present invention include, but are not limited to: Organic phosphates: acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, bromophos, bromophos-ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorfenvinphos, chlormephos, demeton, demeton-S-methyl, demeton-S-methylsulfone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, ethoprophos, etrimphos, famflu, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonophos, formothion, fosthiazate, heptenophos, isazophos, isothioate, isoxathion, Malathion, methacrifos, methamidophos, methidathion, methyl parathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, paraoxon, parathion, parathion-methyl, phenthoate, phosalone, phospholane, phosphocarb, phosmet, phosphamidon, phorate, phoxim, pirimiphos, pirimiphos-methyl, profenofos, propafos, proethamfos, prothiofos, pyraclofos, pyridapenthione, quinalphos, sulprofos, temephos, terbufos, tebupirimphos, tetrachlorvinphos, thimeton, triazophos, trichlorfon, vamidothion.

[0258] Carbamates: alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801, isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl (methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717.

[0259] Pyrethroids: acrinathrin, allethrin, alphamethrin, (E)-(1R)-cis-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate 5-benzyl-3-furylmethyl, bifenthrin, β-cyfluthrin, cyfluthrin, α-cypermethrin, β-cypermethrin, bioallethrin, bioallethrin ((S)-cyclopentyl isomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin, cythithrin, cyphenothrin, Deltamethrin, empenthrin, esfenvalerate, etofenprox, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (D-isomer), imiprothrin, cyhalothrin, lambda-cyhalothrin, permethrin, fenothrin, prallethrin, pyrethrins (natural products), resmethrin, tetramethrin, transfluthrin, theta-cypermethrin, silafluofen, t-fluvalinate, tefluthrin, tralomethrin, zeta-cypermethrin.

[0260] Arthropod growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole, chlorfentadine; b) ecdysone agonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenile hormone-like substances: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.

[0261] Other antiparasitic agents: acequinocyl, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis thuringiensis), bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidin, cyromazine, diaclor, diafenthiuron, DBI-3204, dinactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, etofenprox, fenazaquin, flumite, MTI-800, fenpyroximate, fluacrypyrim, flubenzimine, flubrocythrinate, flufenzin, flufenprox, fluproxy Fen, halofenprox, hydramethylnon, IKI-220, Kanemite, NC-196, Niemgard, Nidinolterfuran, Nitenpyram, SD-35651, WL-108477, pyridalyl, propargite, protrifenbut, pymetrozine, pyridaben, pyrimidifen, NC-1111, R-195, RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601, silafluofen, cyromazine, spinosad, tebufenpyrad, tetradifon, tetranactin, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad, triazamate, triethoxyspinosyn, trinactin, belbutin, Bertalec, YI-5301.

[0262] Biological agents: Bacillus thuringiensis ssp. aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, viruses and fungi.

[0263] Fungicides: chlortetracycline, oxytetracycline, streptomycin.

[0264] Other biological agents: enrofloxacin, febantel, penetamate, meloxicam, cephalexin, kanamycin, pimobendan, clenbuterol, omeprazole, tiamulin, benazepril, pyriprole, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, ceftiofur, carprofen, metaflumizone, praziquantel, triclabendazole.

[0265] The following mixtures of compounds of formula (I) with active ingredients are preferred: The abbreviation "TX" means one compound selected from the compounds of formula (I), (IA), (I-A1), (I-A2), (I-A3), (I-A4), or (I-A5), or a compound selected from the compounds listed in Tables A-1 to A-23, or a compound selected from the compounds listed in Table P (below), and a compound selected from the group of substances consisting of: petroleum + TX, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX, 2,4-dichlorophenylbenzenesulfonate + TX, 2-fluoro-N-methyl-N-1-naphthylacetate Amide + TX, 4-chlorophenyl phenyl sulfone + TX, acetoprole + TX, aldoxicarb + TX, amidithione + TX, amidothioate + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, alamite + TX, arsenic trioxide + TX, azobenzene + TX, azotoate + TX, benomyl + TX, benoxafos + TX, benzyl benzoate + TX, bixafen + TX, brofenvalerate + TX, bromocyclen + TX, bromophos + TX, bromopropylate + TX, buprofezin + TX, butoca Carboxim + TX, Butoxycarboxim + TX, Butylpyridaben + TX, Calcium polysulfide + TX, Camphechlor + TX, Carbanolate + TX, Carbophenothion + TX, Cimiazole + TX, Chinomethionate + TX, Chlorbeneside + TX, Chlordimeform + TX, Chlordimeform hydrochloride + TX, Chlorphenetole + TX, Chlorfenson + TX, Chlorphenesulfide + TX, Chlorobenzilate + TX, Chlormebform + TX, Chlormethiron + TX, Chloropropylate + TX, Chlorthiophos + TX, Nerin I + TX, Cinerin II + TX, Cinerin + TX, Closantel + TX, Coumaphos + TX, Crotamiton + TX, Crotoxyphos + TX, Kufraneb + ​​TX, Cyanthoate + TX, DCPM + TX, DDT + TX, Demefion + TX, Demefion-O + TX, Demefion-S + TX, Demeton-methyl + TX, Demeton-O + TX, Demeton-O-methyl + TX, Demeton-S + TX, Demeton-S-methyl + TX, Demeton-S-methyl sulfone + TX, Dichlofluanid + TX, Dichlorvos + TX, Dicrifos + TX,Dienochlor +TX, Dimefox +TX, Zinex +TX, Zinex-Diclexin +TX, Dinocap-4 +TX, Dinocap-6 +TX, Dinoctone +TX, Dinopentone +TX, Dinosulfone +TX, Dinotervone +TX, Dioxathion +TX, Diphenylsulfone +TX, Disulfiram +TX, DNOC +TX, Dofenapine +TX, Doramectin +TX, Endothion +TX, Eprinomectin +TX, Ethoate-methyl +TX, Etrimphos +TX, Fenazaflor +TX, Fenbutatin oxide +TX, Fenothiocarb +TX, Fenpyrad +TX, Fenpyroximate +TX, Fenpyrazamine +TX, Fenson +TX, Fentrifanil +TX, Flubenzimine +TX, Flucycloxuron +TX, Fluenethyl +TX, Fluorbenside +TX, FMC 1137+TX, formetanate+TX, formetanate hydrochloride+TX, formparanate+TX, γ-HCH+TX, gliodin+TX, halfenprox+TX, hexadecylcyclopropanecarboxylate+TX, isocarbophos+TX, jasmolin I+TX, jasmolin II+TX, iodofenphos+TX, lindane+TX, malonoven+TX, mecarbam+TX, mefosphorane+TX, mesulfen+TX, methacrifos+TX, methyl bromide+TX, metolcarb+TX, mexacarbate+TX, milbemycin oxime+TX, mipafox+TX, monocrotophos+TX, morphothion+TX, moxidectin+TX, naled+TX, 4-chloro-2-(2-chloro-2-methyl-pro Pyr)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, Nifluridide + TX, Nikkomycin + TX, Nitrilacarb + TX, Nitrilacarb 1:1 zinc chloride complex + TX, Omethoate + TX, Oxydeprophos + TX, Oxydisulfoton + TX, pp'-DDT + TX, Parathion + TX, Permethrin + TX, Fenkapton + TX, Phosalone + TX, Phosphorane + TX, Phosphamidon + TX, Polychloroterpenes + TX, Polynactin + TX, Proclonol + TX, Promacyl + TX, Propoxar + TX, Protidathion + TX, Prothoate + TX, Pyrethrin I + TX, Pyrethrin II + TX, Pyrethrin + TX, Pyridaphenthion + TX, Pirimitate + TX,Quinalphos + TX, Quintiox + TX, R-1492 + TX, Phosglycine + TX, Rotenone + TX, Schrader + TX, Cebufos + TX, Selamectin + TX, Sofamid + TX, SSI-121 + TX, Sulfiram + TX, Sulfuramide + TX, Sulfotep + TX, Sulfur + TX, Diflobidazin + TX, τ-Fulvalinate + TX, TEPP + TX, Thelbam + TX, Tetradifon + TX, Tetrasulf + TX, Thiafenox + TX, Thiocarboxim + TX, Thiofanox + TX, Thiometon + TX, Thioquinox + TX, Thuringiensin + TX, Triamiphos + TX, Trialatin + TX, Triazophos + TX, Triazuron + TX, Trifenofos + TX, Trinactin + TX, Vamidothion + TX, Vaniliprole + TX, Bethoxadin + TX, Copper Dioctanoate + TX, copper sulfate +TX, sibutrin +TX, dichloren +TX, dichlorophen +TX, endothall +TX, fentin +TX, hydrated lime +TX, narbam +TX, quinoclamine +TX, quinonamide +TX, simazine +TX, triphenyltin acetate +TX, triphenyltin hydroxide +TX, crufomate +TX, piperazine +TX, thiophanate +TX, chloralose +TX, fenthion +TX, pyridin-4-amine +TX, strychnine +TX, 1-hydroxy-1H-pyridine-2-thione +TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide +TX, 8-hydroxyquinoline sulfate +TX, bronopol +TX, copper hydroxide +TX, cresol +TX, dipyrithione +TX, dodisin +TX, fenaminosulf +TX, formaldehyde +TX, hydrargafen +TX, Kasugamycin + TX, Kasugamycin hydrochloride hydrate + TX, Nickel bis(dimethyldithiocarbamate) + TX, Nitrapyrin + TX, Octilinone + TX, Oxolinic acid + TX, Oxytetracycline + TX, Hydroxyquinoline potassium sulfate + TX, Probenazole + TX, Streptomycin + TX, Streptomycin sesquisulfate + TX, Tecloftalam + TX, Thiomersal + TX, Adoxophyes orana GV + TX, Agrobacterium radiobacter + TX, Amblyseius spp. + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, Autographa californica NPV + TX, Bacillus sphaericus Neide + TX, Beauveria brongniartii + TX, Chrysoperla carnea + TX, Cryptolaemus montrouzieri + TX, Codling moth (Cydia pomonella) GV + TX, Leaf-staring wasp (Dacnusa sibirica) + TX, Diglyphus isaea + TX, Encarsia formosa + TX, Desert wasp (Eretmocerus eremicus + TX, Heterorhabditis bacteriophora and H. megidis + TX, Hippodamia convergens + TX, Leptomastix dactylopii + TX,Macrolophus caliginosus + TX, Mamestra brassicae NPV + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, Orius spp. + TX, Paecilomyces fumosoroseus + TX, Phytoseiulus persimmons persimilis + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Trichogramma spp. + TX, Typhlodromus occidentalis occidentalis) + TX, Verticillium lecanii + TX, Apholate + TX, Visadil + TX, Busulfan + TX, Dimatif + TX, Hemel + TX, Hempa + TX, Metepa + TX, Methiotepa + TX, Methyl Apholate + TX, Molzide + TX, Penfluron + TX, Tepa + TX, Thiohempa + TX, Thiotepa + TX, Tretamine + TX, Uredepa + TX,(E)-Deca-5-en-1-yl acetate and (E)-dec-5-en-1-ol + TX, (E)-tridec-4-en-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E,Z)-tetradec-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-ico octadec-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradec-9,12-dien-1-yl acetate + TX, 14-methyloctadec-1-ene + TX, 4-methylnonan-5-ol, and 4-methylnonan-5-one +TX, α-multistriatin +TX, Brevicomin +TX, Codrelua +TX, Codlemone +TX, Curua +TX, Disparua +TX, Dodec-8-en-1-yl acetate +TX, Dodec-9-en-1-yl acetate +TX, Dodeca-8,10-dien-1-yl acetate +TX, Dominicalua +TX, Ethyl 4-methyloctanoate +TX, Eugenol +TX, Frontalin +TX, Grandlure +TX, Grandlure I +TX, Grandlure II +TX, Grandlure III +TX, Grandlure IV +TX, Hexalua +TX, Ipsdienol +TX, Ipsenol +TX, Japonirua +TX, Lineatin +TX, Littlea +TX, Lupula +TX, Medula +TX, Megatomoic acid +TX, Methyleugenol +TX, Muscalua +TX, Octadeca-2,13-dien-1-yl acetate +TX, Octadeca-3,13-dien-1-yl acetate +TX, Olfuralua +TX, Orictalua +TX, Ostramon +TX, Siglua +TX, Soldigin +TX, Sulcatol +TX, Tetradec-11-en-1-yl acetate +TX, Trimedula +TX,Trimedlure A + TX, Trimedlure B1 + TX, Trimedlure B2 + TX, Trimedlure C + TX, Trunkol + TX, 2-(octylthio)ethanol + TX, Butopyronoxyl + TX, Butoxy(polypropylene glycol) + TX, Dibutyl adipate + TX, Dibutyl phthalate + TX, Dibutyl succinate + TX, Diethyltoluamide + TX, Dimethylcarbate + TX, Dimethyl phthalate + TX, Ethyl hexanediol + TX, Hexamide + TX, Methoxybutyl + TX, Methylneodecanamide + TX, Oxa mate + TX, picaridin + TX, 1-dichloro-1-nitroethane + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane + TX, 1,2-dichloropropane and 1,3-dichloropropene + TX, 1-bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methylphosphate + 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-chlorovinyldiethylphosphate + TX, 2-imidazolidone + TX, 2-isovalerylindan-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-phenylpi 5-pyrazol-yldimethylcarbamate + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate + TX, 5,5-dimethyl-3-oxocyclohex-1-enyldimethylcarbamate + TX, acetione + TX, acrylonitrile + TX, aldrin + TX, allosamidin + TX, alixycarb + TX, α-ecdysone + TX, aluminum phosphide + TX, aminocarb + TX, anabasine + TX, atidathion + TX, azamethiphos + TX, Bacillus thuringiensis delta endotoxin + TX,Barium hexafluorosilicate +TX, barium polysulfide +TX, bartholin +TX, Bayer 22 / 190 +TX, Bayer 22408 +TX, β-cyfluthrin +TX, β-cypermethrin +TX, bioethanomethrin +TX, biopermethrin +TX, bis(2-chloroethyl) ether +TX, borax +TX, bromfenvinphos +TX, bromo-DDT +TX, bufencarb +TX, butacarb +TX, butathiophos +TX, butonate +TX, calcium arsenate +TX, calcium cyanide +TX, carbon disulfide +TX, tetrachloroethyl ether +TX Carbon chloride + TX, Cartap hydrochloride + TX, Cevadine + TX, Chlorbicyclen + TX, Chlordane + TX, Chlordecone + TX, Chloroform + TX, Chloropicrin + TX, Chlorphoxim + TX, Chlorprazophos + TX, cis-Resmethrin + TX, Cismethrin + TX, Clocitrin + TX, Copper acetoarsenite + TX, Copper arsenate + TX, Copper oleate + TX, Cumitoate + TX, Cryolite + TX, CS 708+TX, cyanofenphos+TX, cyanophos+TX, cyclethrin+TX, cythioate+TX, d-tetramethrin+TX, DAEP+TX, dazomet+TX, decarbofuran+TX, diamidaphos+TX, dikapton+TX, diclofenthion+TX, dicresyl+TX, dicyclanil+TX, dieldrin+TX, diethyl 5-methylpyrazol-3-yl phosphate+TX, dilol+TX, dimefluthrin+TX, dimethane+TX, dimethryn+TX, dimethylvinphos+TX, dimethyllan+TX, dinoprop+TX, dinosam+TX, dinoseb+TX, diofenolan+TX, dioxabenzophos+TX, dicyclophos+TX, DSP+TX, ecdysterone+TX, EI 1642+TX, EMPC+TX, EPBP+TX, etaphos+TX, ethiofencarb+TX, ethyl formate+TX, ethylene dibromide+TX, ethylene dichloride+TX, ethylene oxide+TX, EXD+TX, fenchlorphos+TX, fenetacarb+TX, fenitrothion+TX, fenoxacrim+TX, fenpyrithrin+TX, fensulfothion+TX, fenthion-ethyl+TX, flucofuron+TX, fosmetiran+TX, fospirate+TX, fostietan+TX, furathiocarb+TX, fretrin+TX, guazatine+TX,Guazatine acetate + TX, sodium tetrathiocarbonate + TX, Halfenprox + TX, HCH + TX, HEOD + TX, Heptachlor + TX, Heterofos + TX, HHDN + TX, Hydrogen cyanide + TX, Hikincarb + TX, IPSP + TX, Isazophos + TX, Isobenzane + TX, Isodrin + TX, Isofenphos + TX, Isolane + TX, Isoprothiolane + TX, Isoxathion + TX, Juvenile hormone I + TX, Juvenile hormone II + TX, Juvenile hormone III + TX, Kereva phenanthrene + TX, lead arsenate + TX, leptophos + TX, lilimphos + TX, ritidathion + TX, m-cumenylmethylcarbamate + TX, magnesium phosphide + TX, magidox + TX, mecarfone + TX, menasone + TX, mercurous chloride + TX, mesulfenphos + TX, metam + TX, metam-potassium + TX, metam-sodium + TX, methanesulfonyl fluoride + TX, methoclotophos + TX, methoprene methotrin + TX, methoxychlor + TX, methyl isothiocyanate + TX, methyl chloroform + TX, methylene chloride + TX, methoxadiazone + TX, Mirex + TX, naphthalophos + TX, naphthalene + TX, NC-170 + TX, nicotine + TX, nicotine sulfate + TX, nithiazine + TX, nornicotine + TX, O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate + TX, O,O -Diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate + TX, O,O-Diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate + TX, O,O,O',O'-Tetrapropyldithiopyrophosphate + TX, Oleic acid + TX, para-dichlorobenzene + TX, parathion-methyl + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH 60-38+TX, Fenkapton+TX, Fosniclor+TX, Phosphine+TX, Phoxim-methyl+TX, Pyrimetaphos+TX, Polychlorodicyclopentadiene Isomers+TX, Potassium Arsenite+TX, Potassium Thiocyanate+TX, Precocene I+TX, Precocene II+TX, Precocene III+TX, Primidophos+TX, Profluthrin+TX, Promecarb+TX, Prothiofos+TX, Pyrazophos+TX, Pyresmethrin+TX, Quassia+TX, Quinalphos-methyl+TX,Quinotion +TX, Rafoxanide +TX, Resmethrin +TX, Rotenone +TX, Kadetrin +TX, Riania +TX, Ryanodine +TX, Sabadila +TX, Schradan +TX, Cebufos +TX, SI-0009 +TX, Tiapronil +TX, Sodium arsenite +TX, Sodium cyanide +TX, Sodium fluoride +TX, Sodium hexafluorosilicate +TX, Sodium pentachlorophenoxide +TX, Sodium selenate +TX, Sodium thiocyanate +TX, Sulcofuron +TX, Sulcofuron-sodium +TX, sulfuryl fluoride +TX, sulproos +TX, tar oil +TX, thazimcarb +TX, TDE +TX, tebupirimfos +TX, temephos +TX, telalethrin +TX, tetrachloroethane +TX, cyclofos +TX, thiocyclam +TX, thiocyclam hydrogen oxalate +TX, thionazine +TX, thiosultap +TX, thiosultap-sodium +TX, tralomethrin +TX, transpermethrin +TX, triazamate +TX, trichlormetaphos-3 +TX, trichloronate +TX, trimethacarb +TX , tolprocarb + TX, triclopiricarb + TX, triplen + TX, veratridine + TX, veratrine + TX, XMC + TX, zetamethrin + TX, zinc phosphide + TX, zolaprofos + TX, meperfluthrin + TX, tetramethylfluthrin + TX, bis(tributyltin) oxide + TX, bromoacetamide + TX, ferric phosphate + TX, niclosamide-olamine + TX, tributyltin oxide + TX, pyrimorph + TX, triphenmorph + TX, 1,2-dibromo-3-chloropropane + TX, 1,3-dichloro Propene + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, 2-fluoro-N-(3-methoxyphenyl)-9H-purin-6-amine + TX, benclothiaz + TX, cytokinin + TX, DCIP + TX, furfural + TX, isamidophos + TX, kinetin + TX, mulberry dark spot fungus (Myrothecium verrucaria) composition + TX, tetrachlorothiophene + TX, xylenol + TX,Zeatin + TX, Potassium Ethylxanthate + TX, Acibenzolar + TX, Acibenzolar-S-methyl + TX, Giant Knotweed (Reynoutria sachalinensis) Extract + TX, α-Chlorohydrin + TX, Anz + TX, Barium Carbonate + TX, Bisthiosemi + TX, Brodifacoum + TX, Bromadiolone + TX, Bromethalin + TX, Chlorophacinone + TX, Cholecalciferol + TX, Coumachlor + TX, Coumafuryl + TX, Coumatetralyl + TX, Crimidine + TX, Difenacoum + TX, Difethialone + TX, Diphacinone + TX, Ergocalciferol + TX, Flocoumafen + TX, Fluoroa Cetoamide + TX, flupropazine + TX, flupropazine hydrochloride + TX, norbormide + TX, fosacetim + TX, phosphorus + TX, pindone + TX, pyrinuron + TX, sciliroside + TX, sodium fluoroacetate + TX, thallium sulfate + TX, warfarin + TX, 2-(2-butoxyethoxy)ethyl piperonylate + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, farnesol and nerolidol + TX, berubutin + TX, MGK 264+TX, piperonyl butoxide+TX, piprotal+TX, propyl isomers+TX, S421+TX, sesamex+TX, sesamolin+TX, sulfoxide+TX, anthraquinone+TX, copper naphthenate+TX, copper oxychloride+TX, dicyclopentadiene+TX, thiram+TX, zinc naphthenate+TX, ziram+TX, imanin+TX, ribavirin+TX, mercuric oxide+TX, thiophanate-methyl+TX, azaconazole+TX, bitertanol+TX, bromuconazole+TX, cyproconazole+TX, difenoco azol + TX, diniconazole + TX, epoxiconazole + TX, fenbuconazole + TX, fluquinconazole + TX, flusilazole + TX, flutriafol + TX, furametpyr + TX, hexaconazole + TX, imazalil + TX, imibenconazole + TX, ipconazole + TX, metconazole + TX, myclobutanil + TX, paclobutrazol + TX, pefurazoate + TX, penconazole + TX, prothioconazole + TX, pyrifenox + TX, prochloraz + TX, propiconazole + TX,Pyrisoxazole + TX, simeconazole + TX, tebuconazole + TX, tetraconazole + TX, Triadimefon +TX, Triadimenol +TX, Triflumizole +TX, Triticonazole +TX, Ancymidol +TX, Fenarimol +TX, Nuarimol +TX, Bupirimate +TX, Dimethirimol +TX, Ethirimol +TX, Dodemorph +TX, Fenpropidin +TX, Fenpropimorph +TX, Spiroxamine +TX, Tridemorph +TX, Cyprodinil +TX, Mepanipyrim +TX, Pyrimethanil +TX, Fenpiclonil +TX, Fludioxonil +TX, Benalaxyl +TX, Furalaxyl +TX, Metalaxyl +TX, R- Metalaxyl + TX, Ofrace + TX, Oxadixyl + TX, Carbendazim + TX, Debacarb + TX, Fuberidazole + TX, Thiabendazole + TX, Chlozolinate + TX, Diclozolin + TX, Mycrozolin + TX, Procymidone + TX, Vinclozolin + TX, Boscalid + TX, Carboxin + TX, Fenfuram + TX, Flutolanil + TX, Mepronil + TX, Oxycarboxin + TX, Penthiopyrad + TX, Thifluzamide + TX, Dodine + TX, Iminoctadine + TX, Azoxystrobin + TX, Dimoxystrobin + TX X, Enesterobrine +TX, Phenaminestrobin +TX, Flufenoxystrobin +TX, Fluoxastrobin +TX, Kresoxim-methyl +TX, Metominostrobin +TX, Trifloxystrobin +TX, Oryzastrobin +TX, Picoxystrobin +TX, Pyraclostrobin +TX, Pyrametstrobin +TX, Pyraoxystrobin +TX, Ferbam +TX, Mancozeb +TX, Maneb +TX, Metiram +TX, Propineb +TX, Zineb +TX, Captafol +TX, Captan +TX, Fluorimide +TX, Folpet + TX, tolylfluanid + TX, Bordeaux mixture + TX, copper oxide + TX, mancopper + TX, oxine-copper + TX, nitrothar-isopropyl + TX, edifenphos + TX, iprobenfos + TX, phosdifen + TX, tolclofos-methyl + TX, anilazine + TX, benthiavalicarb + TX, blasticidin-S + TX, chloroneb + ​​TX, chlorothalonil + TX, cyflufenamid + TX, cymoxanil + TX, cyclobutrifluram + TX, diclocymet + TX, diclomedine + TX, dicloran + TX, diethofencarb + TX,Dimethomorph +TX, Flumorph +TX, Dithianon +TX, Ethaboxam +TX, Etridiazole +TX, Famoxadone +TX, Fenamidone +TX, Fenoxanil +TX, Ferimzone +TX, Fluazinam +TX, Fluopicolide +TX, Flusulfamide +TX, Fluxapyroxad +TX, Fenhexamid +TX, Fosetyl-aluminum +TX, Hymexazole +TX, Iprovalicarb +TX, Cyazofamid +TX, Metasulfocarb +TX, Metrafenone +TX, Pencycuron +TX, Phthalide +TX, Polyoxin + TX, propamocarb + TX, pyribencarb + TX, proquinazide + TX, pyroquilon + TX, pyriophenone + TX, quinoxyfen + TX, quintozene + TX, tiadinil + TX, triazoxide + TX, tricyclazole + TX, triforine + TX, validamycin + TX, valifenalate + TX, zoxamide + TX, mandipropamide + TX, flubeneteram + TX, isopyrazam + TX, sedaxane + TX, benzovindiflupyr + TX, pydiflumetofen + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carbo Phosphonic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, isoflucipram + TX, isotianil + TX, dipimethitrone + TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile + TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX, (R)-3-( (difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine + TX, fluindapyr + TX, methoxystrobin (jiaxiangjunzhi) + TX,Rubenmixianan + TX, diclobenthiazox + TX, mandestrobin + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol + TX, oxathiapiproline + TX, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]calcium phosphate Bamate + TX, Pyraziflumide + TX, Inpirfluxam + TX, Tolprocarb + TX, Mefentrifluconazole + TX, Ipfentrifluconazole + TX, 2-(Difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl]thiazol-2-yl]oxy-2,5-dimethyl phenyl]-N-ethyl-N-methyl-formamidine + TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl]methanesulfonate + TX, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, methyl N-[[5-[4-(2,4 -dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, pyridaclomethyl + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one + TX,1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX, aminopyrifen + TX, ametoctrazine + TX, amisulbrom + TX, penflufen + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX, flurylpicoxamide + TX, fenpicoxamide + TX, tebufloquine + TX, Ipflufenoquine + TX, quinofumelin + TX, isofetamide + 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, benzothiostrobin + TX, fenamacryl + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + T X, fluopyram + TX, flutianil + TX, fluopimomide + TX, pyrapropoin + TX, picarbutrazox + TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazole- 1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, methyltetraprole + TX, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidinemethanol + TX, fluoxapiprolin + TX, enoxastrobin + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX,4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, Trinexapac + TX, Cumoxystrobin + TX, Zhongshengmycin + TX, copper thiodiazole + TX, zinc thiazole + TX, amethotractin + TX, iprodione + TX, 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-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared from the method described in IPCOM000249876D); N-isopropyl-N-methyl-formamidine + TX (this compound can be prepared from the method described in IPCOM000249876D). propyl-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 from the method described in WO 2018 / 228896);N-ethyl-N'-[5-methoxy-2-methyl-4-[2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine + TX (these compounds can be prepared from the method described in WO 2019 / 110427); N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3 -carboxamide + TX, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro -Quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro 1-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX (these compounds can be prepared from the method described in WO 2017 / 153380);1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)-isoquinoline + TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX (these compounds were prepared by the method described in WO 2017 / 025510). 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline + TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole + TX (these compounds can be prepared from the methods described in WO 2016 / 156085);N-Methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N,2-Dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N-Ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl ]phenyl]methyl]propanamide + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2 ,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate + TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine + TX. The compounds in this paragraph can be prepared from the methods described in WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 093348 and WO 2017 / 118689;2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound can be prepared from 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 from the method described in WO 2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile + TX (this compound can be prepared from the method described in WO 2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound can be prepared from the method described in WO 2016 / 156290); (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate + TX (this compound can be prepared from the method described in WO 2016 / 156290). 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrolo-1,3,5,7(2H,6H)-tetrone + TX (this compound can be prepared by the method described in WO 2011 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide + TX; N-methyl-4-[5- (Trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX (this compound can be prepared from 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 from the method described in WO 2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX (this compound can be prepared from 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 from 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 from the method described in WO 2018 / 065414); ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate + TX (this compound can be prepared from the method described in WO 2018 / 158365 can be prepared); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl ]benzamide + TX, N-[N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX (these compounds can be prepared from the method described in WO 2018 / 202428), chlorinconazid + TX, flumethylsulfolim + TX, fluoxytioconazole + TX, flufenoxadiazam + TX, methallylpicoxamide + TX;

[0266] A reference in parentheses following an active ingredient, for example, [3878-19-1], refers to the Chemical Abstracts Registry Number. The aforementioned mixing partners are known. When active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: CDS TomLin; The British Crop Protection Council], they are listed therein under the entry number indicated in parentheses above for the particular compound; for example, the compound "abamectin" is listed under entry number (1). When a specific compound is mentioned above with "[CCN]," the compound in question is included in the "Compendium of Pesticide Common Names," which can be accessed via the Internet at [A. Wood; Compendium of Pesticide Common Names, Copyright 1995-2004]; for example, the compound "acetoprole" is listed at the Internet address http: / / www.alanwood.net / pesticides / acetoprole.html.

[0267] Most of the active ingredients mentioned above are referred to above by so-called "common names", where in each case the relevant "ISO common name" or another "common name" is used. If the name is not a "common name", the nature of the name used instead is given in parentheses for the particular compound. In that case, the IUPAC name, IUPAC / Chemical Abstracts name, "chemical name", "customary name", "compound name" or "development code" is used, or if none of these names and no "common name" is used, an "alternative name" is utilized. "CAS Registry Number" means the Chemical Abstracts Registry Number.

[0268] The active ingredient mixtures of compounds selected from the compounds of formula (I), (IA), (I-A1), (I-A2), (I-A3), (I-A4) or (I-A5), or the compounds listed in Tables A-1 to A-23, or the compounds listed in Table P (below), are preferably mixed in a ratio of 100:1 to 1:100, in particular 50:1 to 1:50, more particularly 20:1 to 1:20, even more particularly 10:1 to 1:10, and even more particularly 5:1 to 1:5, which are by weight.

[0269] The mixture may be used in a method for controlling pests, the method comprising the step of applying a composition comprising the mixture to the pest or its environment, excluding methods for treating the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body.

[0270] Mixtures comprising a compound selected from the group consisting of compounds of formula (IA), (I-A1), (I-A2), (I-A3), (I-A4), or (I-A5), or a compound selected from the compounds listed in Tables A-1 to A-23, or a compound selected from the compounds listed in Table P (infra), and one or more of the active ingredients described above, can be applied, for example, in a single "ready-mix" form, in combined spray mixtures composed of separate formulations of a single active ingredient, such as "tank mixes," and in combined use of a single active ingredient when applied sequentially, i.e., one after the other within a fairly short period of time, such as a few hours or days. The order in which the compound selected from the group consisting of compounds of formula (IA), (I-A1), (I-A2), (I-A3), (I-A4), or (I-A5), or a compound selected from the compounds listed in Tables A-1 to A-23, or a compound selected from the compounds listed in Table P (infra), and the active ingredients described above, is not essential to the practice of the invention.

[0271] The compositions according to the invention may also comprise further solid or liquid auxiliaries, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example epoxidized palm oil, rapeseed oil or soybean oil), antifoaming agents, for example silicone oils, preservatives, viscosity regulators, binders and / or tackifiers, fertilizers or other active ingredients for obtaining specific effects, for example bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0272] The compositions according to the invention can be prepared in a manner known per se in the absence of auxiliaries, for example by grinding, sieving and / or compressing the solid active ingredient, and in the presence of at least one auxiliaries, for example by intimately mixing and / or grinding the active ingredient together with the auxiliaries. These processes for preparing the compositions and the use of compound (I) for preparing these compositions are also the subject of the present invention.

[0273] Another aspect of the present invention relates to the use of a compound of formula (I) according to the present invention or a preferred individual compound as defined herein, or a composition comprising at least one compound of formula (I) or at least one preferred individual compound as defined herein, or a fungicidal or insecticidal mixture comprising at least one compound of formula (I) or at least one preferred individual compound as defined herein in admixture with other fungicides or insecticides as defined above, for controlling or preventing infection on plants, e.g. useful plants such as crop plants, their propagation material, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living material by phytopathogenic microorganisms, e.g. insects or preferably fungal organisms.

[0274] A further aspect of the present invention relates to a method for controlling or preventing infection of plants, such as useful plants, for example crop plants, their propagation material, for example seeds, harvested crops, for example harvested food crops, or non-living material, by phytopathogenic or spoilage microorganisms or organisms, in particular fungal organisms, that are potentially harmful to humans, which method comprises applying a compound of formula (I) according to the present invention or a preferred individual compound as defined herein as active ingredient to the plant, plant parts or its habitat, its propagation material, or any part of the non-living material.

[0275] Control or prevention means reducing damage caused by plant pathogenic microorganisms or organisms, such as insects or especially fungal organisms, or spoilage microorganisms or organisms potentially harmful to humans, to a level that demonstrates improvement.

[0276] Preferred methods for controlling or preventing infection of crop plants by phytopathogenic microorganisms, particularly fungal organisms, or insects include those in which the application of the compounds of formula (I) according to the present invention and agrochemical compositions containing at least one compound of formula (I) is a foliar treatment. The application frequency and application rate will vary depending on the risk of infection by the corresponding pathogen or insect. However, the compounds of formula (I) according to the present invention can also be introduced into the plant through the roots via the soil (systemic action) by drenching the plant habitat with a liquid formulation or by applying the compound to the soil in solid form, for example, in granular form (soil application). In rice crops, such granules can be applied to flooded rice fields. The compounds of formula (I) can also be applied to seeds (coating) by impregnating the seeds or tubers with a liquid formulation of the fungicide or coating them with a solid formulation.

[0277] Formulations, e.g. compositions, containing a compound of formula (I) according to the invention and, if desired, a solid or liquid auxiliary or a monomer encapsulating the compound of formula (I), may typically be prepared in a known manner by intimately mixing and / or grinding the compound with an extender, e.g., a solvent, a solid carrier, and, optionally, a surface-active compound (surfactant).

[0278] Advantageous application rates are usually from 5g to 2kg of active ingredient (ai) per hectare (ha), preferably from 10g to 1kg ai / ha, most preferably from 20g to 600g ai / ha.When used as a seed drench, convenient application rates are from 10mg to 1g of active substance per kg of seed.

[0279] As used herein, the term "g ai / ha" refers to the application rate given in grams [g] of active ingredient [ai] per unit surface [ha]. The unit hectare (symbol ha) is the area of ​​100m sides (1hm 2 ) square or 10,000 square metres. The hectare is a commonly used metric unit of area.

[0280] When the combinations of the invention are used for seed treatment, an amount of 0.001 to 50 g of compound of formula (I) per kg of seed, preferably 0.01 to 10 g per kg of seed, will generally be sufficient.

[0281] Preferably, the compositions comprising compounds of formula (I) according to the present invention are applied either prophylactically (meaning before the onset of the disease) or therapeutically (meaning after the onset of the disease).

[0282] The compositions of the present invention may be in any conventional form, such as a two-part system, dry seed treatment powder (DS), seed treatment emulsion (ES), seed treatment flowable concentrate (FS), seed treatment solution (LS), seed treatment water dispersible powder (WS), seed treatment capsule suspension (CF), seed treatment gel (GF), emulsion concentrate (EC), suspension concentrate (SC), suspoemulsion (SE), capsule suspension (CS), water dispersible granules (WG), emulsifiable granules, etc. They may be employed in the form of granules (EG), emulsions, water-in-oil (EO), emulsions, oil-in-water (EW), microemulsions (ME), oil dispersions (OD), oil-miscible flowables (OF), oil-miscible liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), technical concentrates (TK), dispersible concentrates (DC), wettable powders (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0283] Such compositions can be prepared in a conventional manner, for example, by mixing the active ingredient with suitable formulation inerts (diluents, solvents, fillers, and optionally other formulation ingredients such as surfactants, biocides, antifreeze agents, spreading agents, thickeners, and compounds providing auxiliary effects). Conventional sustained-release formulations can also be employed when long-lasting effectiveness is intended. In particular, formulations applied in spray form, such as water-dispersible concentrates (e.g., EC, SC, DC, OD, SE, EW, EO, etc.), wettable powders, and granules, can contain surfactants, such as wetting agents and dispersants, as well as other compounds providing auxiliary effects, such as condensation products of formaldehyde with naphthalenesulfonates, alkylarylsulfonates, ligninsulfonates, fatty alkyl sulfates, and ethoxylated alkylphenols and ethoxylated fatty alcohols.

[0284] The seed dressing formulation is applied to seeds in a manner known per se, using the combination of the present invention and a diluent in a suitable seed dressing formulation form, such as an aqueous suspension or a dry powder form with good adhesion to the seeds. 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 slow-release capsules or microcapsules.

[0285] Typically, the formulations contain 0.01 to 90% by weight of active agent, 0 to 20% of an agriculturally acceptable surfactant, and 10 to 99.99% of a solid or liquid inert compound and adjuvant, where the active agent is composed of at least a compound of formula (I) according to the present invention, optionally together with other active agents, particularly microbicides, preservatives, etc. Concentrate forms of the composition generally contain about 2 to 80% by weight, preferably about 5 to 70% by weight, of the active agent. The application form of the formulation can contain, for example, 0.01 to 20% by weight, preferably 0.01 to 5% by weight, of the active agent. Commercially available products are preferably formulated as concentrates, but end users will usually use diluted formulations.

[0286] Commercially available products are preferably formulated as concentrates, although end users will typically use diluted formulations.

[0287] Application rates vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pests to be controlled, the prevailing weather conditions and other factors which depend on the method, time of application and target crop. As a general guideline, the compounds may be applied at a rate of 1 to 2000 l / ha, in particular 10 to 1000 l / ha.

[0288] A preferred formulation may have the following composition (by weight):

[0289] Emulsifiable concentrate: Active ingredient: 1-95%, preferably 60-90% Surfactant: 1 to 30%, preferably 5 to 20% Liquid carrier: 1 to 80%, preferably 1 to 35%

[0290] Powder: Active ingredient: 0.1 to 10%, preferably 0.1 to 5% Solid carrier: 99.9 to 90%, preferably 99.9 to 99%

[0291] Suspension concentrate: Active ingredient: 5-75%, preferably 10-50% Water: 94-24%, preferably 88-30% Surfactant: 1 to 40%, preferably 2 to 30%

[0292] Wettable powder: Active ingredient: 0.5 to 90%, preferably 1 to 80% Surfactant: 0.5 to 20%, preferably 1 to 15% Solid carrier: 5 to 95%, preferably 15 to 90%

[0293] Granules: Active ingredient: 0.1 to 30%, preferably 0.1 to 15% Solid carrier: 99.5 to 70%, preferably 97 to 85%

[0294] The disclosure in this application makes available any and all combinations of the embodiments disclosed herein.

[0295] The compounds according to the following Tables A-1 to A-23 can be prepared according to the above-mentioned methods. The following examples are intended to illustrate the present invention and to show preferred compounds of formula (I). In any of the following Tables A-1 to A-23, the possible presence of one or more asymmetric carbon atoms in the compound of formula (I) according to the present invention means that the compound can occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms.

[0296] [ka]

[0297] [Table 1-1]

[0298] [Table 1-2]

[0299] [Table 1-3]

[0300] The following compounds represent specific compounds or formula (Iaa) set forth in Tables A-1 to A-23, where G is as defined in Table A. For example, compound A-1.G1 is R 2 , R 4 , R 5 , R 6 , R 10 , R 11 , and B 1 is as defined in Table A-1, and G is G1 as defined in Table A.

[0301] Table A-1: ​​This table provides 75 compounds A-1.G1 to A-1.G75 of formula (Iaa), where R 2 , R 4 , R 5 , R 6 , R 10 , and R 11 is H and B 1 is CH and G is as defined in Table A. For example, compound A-1.G1 has the following structure: [ka] It has.

[0302] Table A-2: This table provides 75 compounds A-2.G1 to A-2.G75 of formula (Iaa), where R 2 , R 4 , R 5, R 6 , R 10 , and R 11 is H and B 1 is CCl and G is as defined in Table A.

[0303] Table A-3: This table provides 75 compounds A-3.G1 to A-3.G75 of formula (Iaa), where R 2 is CH3 and R 4 , R 5 , R 6 , R 10 , and R 11 is H and B 1 is CH and G is as defined in Table A.

[0304] Table A-3: This table provides 75 compounds A-3.G1 to A-3.G75 of formula (Iaa), where R 2 is CH3 and R 4 , R 5 , R 6 , R 10 , and R 11 is H and B 1 is CH and G is as defined in Table A.

[0305] Table A-4: This table provides 75 compounds A-4.G1 to A-4.G75 of formula (Iaa), where R 2 is CH3 and R 4 , R 5 , R 6 , R 10 , and R 11 is H and B 1 is CCl and G is as defined in Table A.

[0306] Table A-5: This table provides 75 compounds A-5.G1 to A-5.G75 of formula (Iaa), where R 4 is CH3 and R 2 , R 5 , R 6 , R 10 , and R 11 is H and B 1is CH and G is as defined in Table A.

[0307] Table A-6: This table provides 75 compounds A-6.G1 to A-6.G75 of formula (Iaa), where R 4 is CH3 and R 2 , R 5 , R 6 , R 10 , and R 11 is H and B 1 is CCl and G is as defined in Table A. For example, compound A-6.G3 has the following structure: [ka] It has.

[0308] Table A-7: This table provides 75 compounds A-7.G1 to A-7.G75 of formula (Iaa), where R 4 is CH3 and R 2 , R 5 , R 6 , R 10 , and R 11 is H and B 1 is CBr and G is as defined in Table A.

[0309] Table A-8: This table provides 75 compounds A-8.G1 to A-8.G75 of formula (Iaa), where R 4 is CH3 and R 2 , R 5 , R 6 , R 10 , and R 11 is H and B 1 is the CCN and G is as defined in Table A.

[0310] Table A-9: This table provides 75 compounds A-9.G1 to A-9.G75 of formula (Iaa), where R 4 is CH3 and R 2 , R 5 , R 6 , R 10 , and R11 is H and B 1 is CCOCH3 and G is as defined in Table A.

[0311] Table A-10: This table provides 75 compounds A-10.G1 to A-10.G75 of formula (Iaa), where R 4 is CH3 and R 2 , R 5 , R 6 , R 10 , and R 11 is H and B 1 is CCOCH3 and G is as defined in Table A.

[0312] Table A-11: This table provides 75 compounds A-11.G1 to A-11.G75 of formula (Iaa), where R 4 is CH3 and R 2 , R 5 , R 6 , R 10 , and R 11 is H and B 1 is CC=N(OCH3)CH3, and G is as defined in Table A. For example, compound A11-G72 has the following structure: [ka] It has.

[0313] Table A-12: This table provides 75 compounds A-12.G1 to A-12.G75 of formula (Iaa), where R 4 is CH3 and R 2 , R 5 , R 6 , R 10 , and R 11 is H and B 1 is CNH2 and G is as defined in Table A.

[0314] Table A-13: This table provides 75 compounds A-13.G1 to A-13.G75 of formula (Iaa), where R 2 and R 4is CH3 and R 5 , R 6 , R 10 , and R 11 is H and B 1 is CCl and G is as defined in Table A.

[0315] Table A-14: This table provides 75 compounds A-14.G1 to A-14.G75 of formula (Iaa), where R 2 and R 4 is CH3 and R 5 , R 6 , R 10 , and R 11 is H and B 1 is the CCN and G is as defined in Table A.

[0316] Table A-15: This table provides 75 compounds A-15.G1 to A-15.G75 of formula (Iaa), where R 2 is Cl and R 4 is CH3 and R 5 , R 6 , R 10 , and R 11 is H and B 1 is CCl and G is as defined in Table A.

[0317] Table A-16: This table provides 75 compounds A-16.G1 to A-16.G75 of formula (Iaa), where R 2 is Cl and R 4 is CH3 and R 5 , R 6 , R 10 , and R 11 is H and B 1 is CCN and G is as defined in Table A. For example, compound A-16.G64 has the following structure: [ka] It has.

[0318] Table A-17: This table provides 75 compounds A-17.G1 to A-17.G75 of formula (Iaa), where R 4 is CH3 and R 10 is Cl and R 2 , R 5 , R 6 , and R 11 is H and B 1 is CH and G is as defined in Table A.

[0319] Table A-18: This table provides 75 compounds A-18.G1 to A-18.G75 of formula (Iaa), where R 4 is CH3 and R 10 is CN and R 2 , R 5 , R 6 , and R 11 is H and B 1 is CH and G is as defined in Table A.

[0320] Table A-19: This table provides 75 compounds A-19.G1 to A-19.G75 of formula (Iaa), where R 4 is CH3 and R 11 is Cl and R 2 , R 5 , R 6 , and R 10 is H and B 1 is CH and G is as defined in Table A.

[0321] Table A-20: This table provides 75 compounds A-20.G1 to A-20.G75 of formula (Iaa), where R 4 is CH3 and R 11 is CN and R 2 , R 5 , R 6 , and R 10 is H and B 1 is CH and G is as defined in Table A.

[0322] Table A-21: This table provides 75 compounds A-21.G1 to A-21.G75 of formula (Iaa), where R 4 is CH3 and R 11 is OCH3 and R 2 , R 5 , R 6 , and R 10 is H and B 1 is CCl and G is as defined in Table A.

[0323] Table A-22: This table provides 75 compounds A-22.G1 to A-22.G75 of formula (Iaa), where R 4 is CH3 and R 2 , R 5 , R 6 , R 10 , and R 11 is H and B 1 is N and G is as defined in Table A. For example, compound A-22.G18 has the following structure: [ka] It has.

[0324] Table A-23: This table provides 75 compounds A-23.G1 to A-23.G75 of formula (Iaa), where R 4 is CH3, R10 is Cl, and R 2 , R 5 , R 6 , and R 11 is H and B 1 is N and G is as defined in Table A. [Example]

[0325] The following examples are intended to illustrate the present invention but not to limit it in any way.

[0326] The compounds of the present invention are distinguishable from known compounds by their high efficacy at low application rates, which can be verified by one skilled in the art using the experimental procedures outlined in the examples, and where necessary using low application rates, for example 60 ppm, 20 ppm or 2 ppm.

[0327] Compounds of formula (I) may have many benefits including, inter alia, advantageous levels of biological activity or excellent properties for use as agrochemical active ingredients (e.g., high biological activity, advantageous spectrum of activity, high safety profile (including improved crop tolerance), improved physicochemical properties or high biodegradability) for protecting plants against diseases caused by fungi.

[0328] Throughout this specification, temperatures are given in degrees Celsius and "mp" means melting point. LC-MS means liquid chromatography mass spectrometry, and a description of the equipment and methods follows.

[0329] 1 H NMR and 19 F NMR measurements were recorded on a Bruker 400 MHz spectrometer, and chemical shifts were expressed in terms of TMS ( 1 H) and CFCl3 ( 19 F) are shown in ppm relative to standard. Spectra were taken in deuterated solvents as indicated. Compounds were characterized using one of the following LCMS methods. Characteristic LCMS values ​​obtained for each compound include retention time ("Rt", recorded in minutes) and observed molecular ion (M+H). + or (MH) - It was.

[0330] The following LC-MS methods were used for compound analysis:

[0331] Method A (LC-MS): Spectra were recorded on a Waters mass spectrometer (SQD2 or QDA single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative polarity switch), capillary voltage: 0.8–3.00 kV, cone range: 25, source temperature: 120–150 °C, desolvation temperature: 500–600 °C, cone gas flow: 50 L / h, desolvation gas flow: 1000 L / h, mass range: 110–850 Da) and a Waters Acquity UPLC: quaternary solvent manager, heated column compartment, and diode array detector. Column: Acquity UPLC HSS T3 C18, 1.8 μm, 30 × 2.1 mm, Temperature: 40 °C, DAD wavelength range (nm): 200–400, Solvent gradient: A = water + 5% acetonitrile + 0.05% HCOOH, B = acetonitrile + 0.1% HCOOH. Gradient: 10% B for 0 min; 10–50% B for 0–0.2 min; 50–100% B for 0.2–0.6 min; 100% B for 0.6–1.3 min; 100–10% B for 1.3–1.4 min; 10% B for 1.4–1.6 min; Flow rate (mL / min): 0.6.

[0332] Method B (LC-MS): Spectra were recorded on a Waters mass spectrometer (Acquity QDa mass spectrometer) equipped with an electrospray source (polarity: positive and negative polarity switch), capillary voltage: 0.8 kV, cone range: 25 V, extractor voltage: V (no extraction voltage for the QDa detector), source temperature: 120 °C, desolvation temperature: 600 °C, cone gas flow rate: 50 L / h, desolvation gas flow rate: 1000 L / h, mass range: 110–850 Da) and a Waters Acquity UPLC: quaternary solvent manager, heated column compartment, diode array detector. Column: Acquity UPLC HSS T3 C18, 1.8 μm, 30 × 2.1 mm, temperature: 40 °C, DAD wavelength range (nm): 200–400, solvent gradient: A = water + 5% acetonitrile + 0.05% HCOOH, B = acetonitrile + 0.1% HCOOH. Gradient: 10% B for 0 min; 10–50% B for 0–0.2 min; 50–100% B for 0.2–0.6 min; 100% B for 0.6–1.3 min; 100–10% B for 1.3–1.4 min; 10% B for 1.4–1.6 min; flow rate (mL / min) 0.6.

[0333] Method C (LC-MS): Spectra were recorded on an Agilent Technologies mass spectrometer (6410 Triple Quadrupole Mass Spectrometer) equipped with an electrospray source (polarity: positive or negative ion, MS2 scan, capillary voltage: 4.00 kV, fragmentor voltage: 100 V, desolvation temperature: 350 °C, gas flow rate: 11 L / min, nebulizer gas: 45 psi, mass range: 110–1000 Da) and an Agilent 1200 Series HPLC with a quaternary pump, heated column compartment, and VWD detector. Column: KINETEX EVO C18, 2.6 μm, 50 × 4.6 mm, temperature: 40 °C, detector VWD wavelength: 254 nm, solvent gradient: A = water + 5% acetonitrile, 0.1% HCOOH, B = acetonitrile + 0.1% HCOOH. Gradient: 0 min 10% B, 90% A; 0.9–1.8 min 100% B; 1.8–2.2 min 100–10% B; 2.2–2.5 min 10% B; flow rate (mL / min) 1.8.

[0334] Method D (LC-MS): Spectra were recorded on an Agilent Technologies mass spectrometer (MSD-IQ mass spectrometer) equipped with an electrospray source (polarity: positive or negative ion, MS2 scan, capillary voltage: 3.5 kV, fragmentor voltage: 110 V, desolvation temperature: 325 °C, gas flow rate: 13 L / min, nebulizer gas: 55 psi, mass range: 110–850 Da) and an Agilent 1290 Series HPLC with a quaternary pump, heated column compartment, and diode array detector. Column: Agilent Poroshell 120 EC-C18, 1.9 μm, 50 × 2.1 mm, temperature: 40 °C, DAD wavelength range (nm): 190–400, solvent gradient: A = water + 5% acetonitrile, 0.1% HCOOH, B = acetonitrile + 0.1% HCOOH. Gradient: 0–0.5 min 10% B, 90% A; 1.2–1.5 min 95% B, 5% A; 1.8–2.5 min 10% B, 90% A: flow rate (ml / min) 0.8.

[0335] Formulation Examples

[0336] [Table 2]

[0337] This combination is thoroughly mixed with adjuvants and the mixture is thoroughly ground in a suitable mill to give a wettable powder which is diluted with water to give a suspension of the desired concentration.

[0338] [Table 3]

[0339] This combination is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to obtain a powder that can be used directly as a seed treatment.

[0340] emulsifiable concentrate Active ingredient 10% Octylphenol polyethylene glycol ether (4-5 mol ethylene oxide) 3% Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (35 mol ethylene oxide) 4% Cyclohexanone 30% Xylene mixture 50%

[0341] Emulsions of any desired dilution that can be used for plant protection are obtained from this concentrate by dilution with water.

[0342] [Table 4]

[0343] Ready-to-use dusts are obtained by combining and mixing with a carrier and grinding the mixture in a suitable mill. Such dusts can also be used as dry seed dressings.

[0344] Extruded Granules Active ingredient 15% Sodium lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 82%

[0345] This combination is mixed with an adjuvant, ground, and the mixture is wetted with water. The mixture is extruded and then dried in a stream of air.

[0346] Coated Granules Active ingredient 8% Polyethylene glycol (molecular weight 200) 3% Kaolin 89%

[0347] The finely ground combination is applied uniformly in a mixer to kaolin wetted with polyethylene glycol, thus obtaining coated granules that do not generate dust.

[0348] Suspension concentrate Active ingredient 40% Propylene glycol 10% Nonylphenol polyethylene glycol ether (15 mol ethylene oxide) 6% Sodium lignosulfonate 10% Carboxymethylcellulose 1% Silicone oil (in the form of a 75% emulsion in water) 1% water 32%

[0349] The finely ground combination is thoroughly mixed with adjuvants to obtain a suspension concentrate, which can then be diluted with water to obtain a suspension of any desired dilution, and such dilutions can be used to treat and protect living plants and plant propagation material against infection by microorganisms by spraying, pouring, or dipping.

[0350] Flowable concentrate for seed treatment Active ingredient 40% Propylene glycol 5% Copolymer butanol PO / EO 2% Tristyrene phenol + 10-20 moles EO 2% 1,2-Benzisothiazolin-3-one (in the form of a 20% aqueous solution) 0.5% Monoazo dye calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2% Water 45.3%

[0351] The finely ground composite is thoroughly mixed with adjuvants to obtain a flowable formulation, which can be diluted with water to obtain a solution of any desired dilution and used directly for seed treatment. Such dilutions can be used to treat and protect living plants and plant propagation material against microbial infection by spraying, pouring, or dipping.

[0352] Sustained-release capsule suspension 28 parts of the combination are mixed with 2 parts aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenylisocyanate (8:1) mixture. This mixture is emulsified in a mixture of 1.2 parts polyvinyl alcohol, 0.05 parts antifoaming agent, and 51.6 parts water until the desired particle size is achieved. To this emulsion, a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts water is added. The mixture is stirred until the polymerization reaction is complete. The resulting capsule suspension is stabilized by adding 0.25 parts thickener and 3 parts dispersant. This capsule suspension formulation contains 28% active ingredient. The median capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension using equipment suitable for that purpose.

[0353] Formulation types include emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water dispersible granules (WG), emulsifiable granules (EG), emulsions, water-in-oil (EO), emulsions, oil-in-water (EW), microemulsions (ME), oil dispersions (OD), oil-miscible flowables (OF), oil-miscible liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), technical concentrates (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG) or any technically preferred formulation in combination with an agriculturally acceptable adjuvant.

[0354] Abbreviation CDCl3 deuterated chloroform DABCO 1,4-diazabicyclo[2.2.2]octane, also known as triethylenediamine or TEDA DCC dicyclohexylcarbodiimide DCM dichloromethane (methylene chloride or methylene dichloride) DMF Dimethylformamide DMSO dimethyl sulfoxide DMSO-d6 Deuterated dimethyl sulfoxide EtOAc ethyl acetate HATU 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium-3-oxide-hexafluorophosphate HCl Hydrochloric acid h / hrs time LC-MS Liquid Chromatography Mass Spectrometry (LC-MS or LCMS) rh relative humidity RT room temperature (rt or RT) Rt retention time ssp. subspecies T3P Propanephosphonic Anhydride, also known as 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphorinane-2,4,6-trioxide TBME tert-butyl methyl ether TEA Triethylamine (Et3N) THF tetrahydrofuran

[0355] Preparation Examples Compounds of formula (I) according to the invention may be prepared using the synthetic techniques described both above and below.

[0356] "Mp" means melting point (°C). The free radical represents a methyl group. 1 H NMR and 19 F NMR measurements were recorded on a Bruker 400 MHz spectrometer (or 600 MHz spectrometer as indicated) and chemical shifts were expressed in terms of TMS ( 1 H) standard and CFCl3( 19 F) are given in ppm relative to a standard. Spectra were measured in deuterated solvents as indicated. For compound characterization, one of the following LC-MS methods was used: Characteristic LCMS values ​​obtained for each compound were the retention time ("Rt", recorded in minutes) and the observed molecular ion (M+H). + or (MH) - It was.

[0357] Example P1: Preparation of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(3,5-difluoro-2-pyridyl)-1,3,4-thiadiazole-2-carboxamide (compound P-3, Table P) [ka] Step 1: Preparation of 2-(1-methylpyrazol-4-yl)propanenitrile [ka] To a solution of 2-(1-methyl-1H-pyrazol-4-yl)acetonitrile (1.5 g, 11.8 mmol) in THF (35 mL) at −78° C. under argon was added n-butyllithium (5.9 mL, 11.8 mmol, 2.5 M in hexanes). The resulting pale yellow suspension was stirred at this temperature for 25 min, followed by the addition of iodomethane (0.73 mL, 11.8 mmol). The resulting yellow reaction mixture was stirred at −78° C. for 5 min, warmed to room temperature, and stirred for an additional 30 min. The reaction mixture was diluted with water and extracted with EtOAc (×3). The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give 2-(1-methylpyrazol-4-yl)propanenitrile. The crude reaction product was used directly in the next step.

[0358] Step 2: Preparation of 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propanenitrile [ka] To a solution of 2-(1-methylpyrazol-4-yl)propanenitrile (1.59 g, 11.8 mmol) in THF (35 mL) was added N-butyllithium (5.9 mL, 11.8 mmol, 2.5 M in hexanes) at −78° C. under argon. The resulting pale green suspension was stirred at this temperature for 10 min, and then 2,6-dichloropyridine (1.77 g, 11.8 mmol) was slowly added. The resulting green suspension was stirred at −78° C. for 5 min, warmed to room temperature, and stirred for an additional 10 min under argon. The reaction mixture was diluted with water and extracted with EtOAc (×3). The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue was purified by flash chromatography eluting with EtOAc / cyclohexane to give 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propanenitrile as a pale yellow oil. LCMS (Method A): Retention time 1.04 min, m / z 247 (M+H).

[0359] Step 3: Preparation of 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propan-1-amine [ka] A sample of 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propanenitrile (1.00 g, 4.05 mmol) dissolved in THF (12 mL) was treated dropwise with borane dimethyl sulfide complex (1.15 mL, 12.2 mmol) at room temperature under argon. The resulting yellow solution was stirred at 65 °C for 3 h and then cooled to 0 °C. The orange solution was then carefully treated dropwise with concentrated aqueous HCl (2.72 mL, 16.3 mmol) (strong gas evolution!). The reaction mixture was then stirred at 50 °C for 1 h, then cooled to room temperature again and basified to pH 12 with 6 N NaOH. The resulting mixture was extracted with EtOAc (×3). The combined organic layers were washed once with brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure to give 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propan-1-amine as a light brown oil. LCMS (Method B): Retention time 0.26 min, m / z 251 (M+H).

[0360] Step 4: Preparation of tert-butyl N-[(3,5-difluoropyridine-2-carbonyl)amino]carbamate [ka] A solution of tert-butyl N-aminocarbamate (0.82 g, 6.26 mmol) in EtOAc (12 mL) was treated dropwise with a solution of 3,5-difluoropyridine-2-carbonyl chloride (1.17 g, 6.26 mmol) in EtOAc (12 mL) at room temperature under argon. The reaction mixture was stirred at room temperature for 1 hour, at which time LCMS showed the reaction was complete. The reaction mixture was diluted with water and extracted with EtOAc (×3). The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure to give the title compound as a pale yellow solid. LCMS (Method B): Retention time 0.57 min, m / z 174 (M-99).

[0361] Step 5: Preparation of 3,5-difluoropyridine-2-carbohydrazide [ka] A sample of tert-butyl N-[(3,5-difluoropyridine-2-carbonyl)amino]carbamate (1.7 g, 6.2 mmol) was dissolved in HCl / dioxane (16 mL, 4 mol / L) and stirred at room temperature for 12 hours. After completion of the reaction (monitored by LCMS and TLC), the reaction mixture was quenched with sodium bicarbonate and extracted with EtOAc (×3). The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure to give 3,5-difluoropyridine-2-carbohydrazide as a pale yellow solid. LCMS (Method B): Retention time 0.16 min, m / z 174 (M+1).

[0362] Step 6: Preparation of methyl 2-[2-(3,5-difluoropyridine-2-carbonyl)hydrazino]-2-oxoacetate [ka] A solution of 3,5-difluoropyridine-2-carbohydrazide (0.7 g, 4 mmol) and triethylamine (1 mL, 10 mmol) in acetonitrile (7 mL) was cooled to 0 °C and treated dropwise with methyl oxalyl chloride (0.4 mL, 4 mmol). The resulting reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was then diluted with water (20 mL) and extracted with EtOAc (×3). The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure to give methyl 2-[2-(3,5-difluoropyridine-2-carbonyl)hydrazino]-2-oxo-acetate. LCMS (Method B): Retention time 0.19 min, m / z 260 (M+1).

[0363] Step 7: Preparation of methyl 5-(3,5-difluoro-2-pyridyl)-1,3,4-thiadiazole-2-carboxylate [ka] A solution of methyl 2-[2-(3,5-difluoropyridine-2-carbonyl)hydrazino]-2-oxoacetate (0.5 g, 2 mmol) and phosphorus pentasulfide (0.1 mL, 1 mmol) in toluene (5 mL) was refluxed for 3 hours. The reaction progress was monitored by LCMS, and upon completion, the reaction mixture was quenched with water and extracted with EtOAc (×3). The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure to give the crude product, which was purified by silica gel column chromatography (eluting with 0–25% EtOAc in cyclohexane) to give methyl 5-(3,5-difluoro-2-pyridyl)-1,3,4-thiadiazole-2-carboxylate. LCMS (Method B): Retention time 1.02 min, m / z 258 (M+1).

[0364] Step 8: Preparation of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(3,5-difluoro-2-pyridyl)-1,3,4-thiadiazole-2-carboxamide (Compound P-3, Table P) To a solution of methyl 5-(3,5-difluoro-2-pyridyl)-1,3,4-thiadiazole-2-carboxylate (0.05 g, 0.19 mmol) in toluene (1 mL) was added 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propan-1-amine (0.058 g, 0.23 mmol) at 0 °C. To this was added a solution of trimethylaluminum solution (2.0 mol / L) in toluene (0.29 mL, 0.58 mmol), and then the mixture was heated to 70 °C. After completion of the reaction (LCMS analysis), the reaction mixture was slowly quenched in ice-cold brine solution, and then the brine solution was extracted with EtOAc (x3). The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure. The crude product was adsorbed onto silica and purified by normal phase column chromatography using (0-60% EtOAc in cyclohexane) to give the pure compound N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(3,5-difluoro-2-pyridyl)-1,3,4-thiadiazole-2-carboxamide as a white solid. LCMS (Method B): Retention time 1.15 min, m / z 476 (M+H). 1 H NMR(400MHz,CDCl3)δ ppm 8.46(d,J=2.25Hz,1H),8.30(br t,J=6.32Hz,1H),7.59(t,J=7.82Hz,1H),7.45(ddd,J=9.72,7.72,2.31Hz,1H),7.33(s ,1H),7.29-7.21(m,2H),7.14-7.10(m,1H),4.18-4.03(m,2H),3.87(s,3H),1.74(s,3H)

[0365] Example P2: Preparation of N-[2-(6-cyano-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(3,5-difluoro-2-pyridyl)-1,3,4-thiadiazole-2-carboxamide (compound P-2, Table P) [ka] A solution of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(3,5-difluoro-2-pyridyl)-1,3,4-thiadiazole-2-carboxamide (0.1 g, 0.21 mmol, prepared as described in Example P1, see above) and zinc cyanide (0.05 g, 0.42 mmol) in N,N-dimethylformamide (1.05 mL) was degassed under nitrogen for 10 minutes. To this solution was added tetrakis(triphenylphosphine)palladium(0) (24.5 mg, 0.021 mmol), and the resulting light brown suspension was stirred in a microwave at 120 °C for 3 hours. The reaction progress was monitored by LCMS, and upon completion, the reaction mixture was cooled and diluted with ice-cold water (20 mL). The mixture was extracted with EtOAc (x3), and the combined organic layers were then washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The crude product was absorbed onto silica gel and purified by combiflash eluting with 0-80% EtOAc in cyclohexane to give the product as a yellow gummy solid. The product was further purified by reverse-phase column chromatography using 0-70% acetonitrile in water to give N-[2-(6-cyano-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(3,5-difluoro-2-pyridyl)-1,3,4-thiadiazole-2-carboxamide as a yellow gummy mass. LCMS (Method B): Retention time 1.04 min, m / z 467 (M+H). 1 H NMR(400MHz,CDCl3)δ ppm 8.46(d,J=2.25Hz,1H),8.00(br t,J=6.44Hz,1H),7.77(t,J=7.85Hz,1H),7.63(d,J=7.67Hz,1H),7.45-7.42(m,2H),7 .30-7.31(m,1H),7.26(d,J=0.75Hz,1H),4.25-4.05(m,2H),3.88(s,3H),1.76(s,3H)

[0366] Example P3: Preparation of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxamide (compound P-1, Table P) [ka] Step 1: Preparation of 3,5-difluoro-N-methoxy-N-methyl-pyridine-2-carboxamide [ka] To a suspension of 3,5-difluoropyridine-2-carboxylic acid (10 g, 62.8 mmol) and N,O-dimethylhydroxylamine hydrochloride (6.56 g, 66.0 mmol) in EtOAc (250 mL) was added 1-propanephosphonic anhydride (74.8 mL, 125 mmol) followed by N,N-diisopropylethylamine (33.0 mL, 188 mmol) at room temperature. The resulting reaction mixture was stirred at room temperature for 18 hours, and TLC analysis indicated completion of the reaction. The reaction mixture was diluted with water (100 mL) and extracted with EtOAc (×3). The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The crude product was purified by combi flash chromatography to give 3,5-difluoro-N-methoxy-N-methyl-pyridine-2-carboxamide as a brown liquid. LCMS (Method B): Retention time 0.60 min, m / z 203 (M+H).

[0367] Step 2: Preparation of 1-(3,5-difluoro-2-pyridyl)ethenone [ka] A solution of methylmagnesium bromide (2 M in THF, 33 mL, 98.9 mmol) was added dropwise to 3,5-difluoro-N-methoxy-N-methyl-pyridine-2-carboxamide (10 g, 49.4 mmol) in dry THF (150 mL) at −15° C. under nitrogen. The resulting light brown suspension was warmed to room temperature and stirred for 1 h, at which point LCMS and TLC analysis indicated completion of the reaction. The reaction mixture was slowly quenched with concentrated hydrochloric acid (10.7 mL, 118 mmol) at 0° C. The mixture was extracted with EtOAc (×3), and the organic layers were combined, washed successively with water and brine, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to afford 1-(3,5-difluoro-2-pyridyl)ethanone as a brown liquid, which was used without further purification. LCMS (Method A): Retention time 0.94 min, m / z 158.0 (M+H).

[0368] Step 3: Preparation of ethyl 5-(3,5-difluoro-2-pyridyl)-5-hydroxy-4H-isoxazole-3-carboxylate [ka] To a solution of 1-(3,5-difluoro-2-pyridyl)ethanone (2.00 g, 12.09 mmol) and diethyl oxalate (9.22 mL, 66.5 mmol) in toluene (40 mL) was added potassium tert-butoxide (1.39 g, 12.1 mmol) at −78° C. The cooling bath was removed, and the resulting suspension was warmed to room temperature and stirred for 20 minutes. The reaction mixture was then cooled to −5° C. to 0° C., and hydroxylamine hydrochloride (1.71 g, 24.2 mmol) and acetic acid (2.16 mL, 36.2 mmol) were added, and the resulting reaction mixture was stirred at room temperature for 12 hours. The reaction mixture was poured into water (50 mL) and extracted with EtOAc (×3). The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The resulting crude residue containing ethyl 5-(3,5-difluoro-2-pyridyl)-5-hydroxy-4H-isoxazole-3-carboxylate was used directly in the next step. LCMS (Method B): Retention time 1.63 min, m / z 272 (M+).

[0369] Step 4: Preparation of ethyl 5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxylate [ka] To a solution of ethyl 5-(3,5-difluoro-2-pyridyl)-5-hydroxy-4H-isoxazole-3-carboxylate (12.8 g, 47.0 mmol) in toluene (256 mL) was added p-toluenesulfonic acid (8.52 g, 47.0 mmol) at room temperature, and the reaction mixture was heated to 90 °C and stirred for 16 h. After completion of the reaction, the mixture was cooled to 0 °C and slowly quenched with saturated aqueous sodium bicarbonate solution. The mixture was extracted with EtOAc (3 × 25 mL), and the combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified on a reverse-phase column and then again on a normal phase column to give ethyl 5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxylate as a white solid. LCMS (Method B): Retention time 1.88 min, m / z 255.0 (M+H).

[0370] Step 5: Preparation of 5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxylic acid [ka] To a solution of ethyl 5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxylate (4.95 g, 18.5 mmol) in THF (20 mL) and water (5 mL) was added lithium hydroxide hydrate (0.88 g, 37.0 mmol) at room temperature, and the resulting reaction mixture was stirred at room temperature for 2 hours. After completion of the reaction, the reaction mixture was diluted with water and extracted with TBME. The aqueous layer was then acidified with 2 N HCl. This precipitated a solid, which was filtered on a Buchner funnel and dried under reduced pressure to give 5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxylic acid as an off-white solid. LCMS (Method B): Retention time 0.31 min, m / z 227 (M+H).

[0371] Step 6: Preparation of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxamide (Compound P-1, Table P) To a solution of 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propan-1-amine (13.7 g, 53.6 mmol, prepared as described in Example P1, see below) and 5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxylic acid (13.5 g, 53.6 mmol) in EtOAc (214 mL) was added N,N-diisopropylethylamine (28.1 mL, 161 mmol) and 1-propanephosphonic anhydride (63.9 mL, 107 mmol) at room temperature. The reaction mixture was stirred at room temperature while being monitored by TLC and LCMS. After completion of the reaction, the mixture was diluted with cold water and extracted with EtOAc (×3). The combined organic layers were washed with brine (40 mL), dried over sodium sulfate, and concentrated under reduced pressure. The crude product was purified by reverse-phase combiflash using 0-70% acetonitrile in water as the eluent to give the product N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(3,5-difluoro-2-pyridyl)isoxazole-3-carboxamide as an off-white solid. LCMS (Method B): Retention time 1.12 min, m / z 459 (M+H). 1 H NMR(400MHz,CDCl3)δ ppm 8.52(d,1H),8.01(t,1H),7.61-7.57(t,1H),7.43-7.39(m,1H),7.33(s,1H),7. 28-7.22(m,3H),7.12-7.10(d,1H),4.12-4.01(m,2H),3.88(s,3H),1.73(s,3H) 19 F NMR(400MHz,CHLOROFORM-d)δ ppm -114.22(s,1 F)-118.96(s,1 F)

[0372] Example P4: Preparation of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(2,6-difluoro-3-pyridyl)-1,3,4-thiadiazole-2-carboxamide (compound P-7, Table P) [ka] Step 1: Preparation of 2,6-difluoropyridine-3-carbonyl chloride [ka] A sample of 2,6-difluoropyridine-3-carboxylic acid (10.0 g, 59.7 mmol) was dissolved in EtOAc (200 mL) and treated dropwise with oxalyl chloride (7.89 mL, 89.6 mmol). Catalytic dimethylformamide (0.46 mL, 5.9 mmol) was added dropwise, and the resulting reaction mixture was allowed to stir at room temperature for 1 hour. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to provide the crude title product, which was used directly without further purification.

[0373] Step 2: Preparation of tert-butyl N-[(2,6-difluoropyridine-3-carbonyl)amino]carbamate [ka] A solution of 2,6-difluoropyridine-3-carbonyl chloride (11 g, 58.8 mmol) in EtOAc (110 mL) was added dropwise to a stirred solution of tert-butyl N-aminocarbamate (7.78 g, 58.8 mmol) in EtOAc (80 mL) at room temperature. The resulting reaction mixture was allowed to stir at room temperature, then diluted with water and extracted with EtOAc (×3). The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give the crude title compound as a white solid, which was used directly in the next step without further purification. LCMS (Method B): Retention time 0.99 min, m / z 174 (M-100).

[0374] Step 3: Preparation of 2,6-difluoropyridine-3-carbohydrazide [ka] A sample of tert-butyl N-[(2,6-difluoropyridine-3-carbonyl)amino]carbamate (8.9 g, 31 mmol) was dissolved in 4 M hydrochloric acid in dioxane (77 mL, 310 mmol) under stirring, and the resulting reaction mixture was allowed to stir at room temperature for 12 hours. After completion of the reaction, the reaction mixture was diluted with water and extracted with EtOAc (×3). The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give the title compound as a pale yellow solid, which was used directly in the next step without further purification. LCMS (Method B): Retention time 0.19 min, m / z 174 (M+H).

[0375] Step 4: Preparation of methyl 2-[2-(2,6-difluoropyridine-3-carbonyl)hydrazino]-2-oxoacetate [ka] A solution of 2,6-difluoropyridine-3-carbohydrazide (3.45 g, 18.9 mmol) and triethylamine (5.3 mL, 37.9 mmol) in DCM (35 mL) was cooled to 0 °C and treated dropwise with methyl oxalyl chloride (1.82 mL, 18.9 mmol). The reaction progress was monitored by LCMS, and upon completion, the reaction mixture was quenched with 150 mL of saturated sodium bicarbonate solution and extracted with EtOAc (2 × 100 mL). The combined organic layers were washed successively with water and brine, dried over sodium sulfate, and concentrated under reduced pressure to afford the title compound as a pale yellow solid, which was used directly in the next step without further purification. LCMS (Method C): Retention time 0.30 min, m / z 260 (M+H).

[0376] Step 5: Preparation of methyl 5-(2,6-difluoro-3-pyridyl)-1,3,4-thiadiazole-2-carboxylate [ka] To a solution of methyl 2-[2-(2,6-difluoropyridine-3-carbonyl)hydrazino]-2-oxo-acetate (0.75 g, 2.31 mmol) in THF (15 mL) was added Lawesson's reagent (1.15 g, 2.78 mmol), and the reaction mixture was refluxed for 3 h. The reaction progress was monitored by LCMS, and upon completion, the reaction mixture was diluted with water and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by silica gel chromatography (eluting with 0–30% EtOAc in cyclohexane) to afford methyl 5-(2,6-difluoro-3-pyridyl)-1,3,4-thiadiazole-2-carboxylate as a pale yellow solid. LCMS (Method A): Retention time 1.07 min, 258 (M+H).

[0377] Step 6: Preparation of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(2,6-difluoro-3-pyridyl)-1,3,4-thiadiazole-2-carboxamide (Compound P-7, Table P) To a solution of methyl 5-(2,6-difluoro-3-pyridyl)-1,3,4-thiadiazole-2-carboxylate (0.15 g, 0.55 mmol) and 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propan-1-amine (0.17 g, 0.66 mmol, prepared as described in Example P1, see above) in toluene (3 mL) was added trimethylaluminum (2.0 mol / L) in toluene (0.83 mL, 1.66 mmol) dropwise at 0 °C, and the resulting reaction mixture was stirred at 70 °C for 2 hours. After completion of the reaction, the reaction mixture was slowly quenched with ice-cold brine solution and extracted with EtOAc (3 × 20 mL). The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure. The crude product was adsorbed onto silica and purified by normal phase column chromatography eluting with 0 to 50% EtOAc in cyclohexane to give N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(2,6-difluoro-3-pyridyl)-1,3,4-thiadiazole-2-carboxamide as a light brown solid. LCMS (Method B): Retention time 1.17 min, m / z 476 (M+H). 1 H NMR(400MHz,CDCl3)δ ppm 8.92-9.00(m,1H),8.41(br t,J=6.30Hz,1H),7.60(t,J=7.65Hz,1H),7.32(s,1H),7.23-7.30(m,2H),7.12(d,J=7 .70Hz,1H),7.08(dd,J=8.38,2.63Hz,1H),4.04-4.18(m,2H),3.88(s,3H),1.74(s,3H)

[0378] Example P5: Preparation of N-[2-(6-cyano-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(2,6-difluoro-3-pyridyl)-1,3,4-thiadiazole-2-carboxamide (compound P-6, Table P) [ka] To a solution of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(2,6-difluoro-3-pyridyl)-1,3,4-thiadiazole-2-carboxamide (70 mg, 0.14 mmol) in 1,4-dioxane (0.35 mL) and water (0.35 mL) in a microwave (MV) vial, potassium acetate (13.8 mg, 0.14 mmol) and potassium ferrocyanide (27 mg, 0.07 mmol) were added, and the resulting reaction mixture was degassed with nitrogen for 5 minutes. To this reaction mixture was added (2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) methanesulfonate (12.1 mg, 0.014 mmol), and the microwave vial was sealed and heated in a microwave at 110°C for 2 hours. The solution was cooled to room temperature, quenched with water, and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by combiflash chromatography (silica gel) eluting with 10–20% EtOAc in cyclohexane to give N-[2-(6-cyano-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-5-(2,6-difluoro-3-pyridyl)-1,3,4-thiadiazole-2-carboxamide as a pale yellow solid. LCMS (Method B): Retention time 1.10 min, m / z 467 (M+H). 1H NMR(400MHz,CDCl3)δ ppm 8.92-8.99(m,1H),8.12(br t,J=6.44Hz,1H),7.79(t,J=7.88Hz,1H),7.64(dd,J=7.57,0.81Hz,1H),7.45(dd,J=8.19,0.81Hz, 1H),7.25-7.30(m,2H),7.08(dd,J=8.38,2.75Hz,1H),4.08-4.23(m,2H),3.89(s,3H),1.76(s,3H)

[0379] Example P6: Preparation of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-3-(3,5-difluoro-2-pyridyl)-1,2,4-oxadiazole-5-carboxamide (compound P-18, Table P) [ka] Step 1: Preparation of 3,5-difluoro-N'-hydroxy-pyridine-2-carboxamidine [ka] To a suspension of 3,5-difluoropyridine-2-carbonitrile (10 g, 70.0 mmol) in methanol (10 mL / g, 100 mL) were added potassium carbonate (14.5 g, 105.0 mmol) and hydroxylamine hydrochloride (12.7 g, 175.0 mmol). The reaction mixture was stirred at room temperature for 2 hours. After completion of the reaction (monitored by LCMS and TLC), the reaction mixture was diluted with water (60 mL) and extracted with EtOAc (2 × 50 mL). The combined organic layers were washed with brine, dried over NaSO, and concentrated under reduced pressure to give the crude product, which was purified by combi flash using 40-60% EtOAc in cyclohexane to give 3,5-difluoro-N'-hydroxy-pyridine-2-carboxamidine as a solid. LCMS (Method D): Retention time 0.29 min, m / z 174 (M+H).

[0380] Step 2: Preparation of methyl 3-(3,5-difluoro-2-pyridyl)-1,2,4-oxadiazole-5-carboxylate [ka] To a solution of 3,5-difluoro-N'-hydroxy-pyridine-2-carboxamidine (0.1 g, 0.58 mmol) in acetonitrile (3.5 mL / mmol, 2.0 mL) and pyridine (0.14 mL, 1.73 mmol), methyl 2-chloro-2-oxo-acetate (0.11 g, 0.08 mL, 0.87 mmol) was added under argon at 0 °C. The reaction mixture was warmed to room temperature and stirred for 30 minutes, then stirred at 80 °C for 2 hours. After completion of the reaction (monitored by LCMS and TLC), the reaction mixture was diluted with water (50 mL) and saturated ammonium chloride and extracted with DCM (3 × 80 mL). The combined organic layers were dried over NaSO and concentrated under reduced pressure to give the crude product. This was purified by combi flash using 30-40% EtOAc in cyclohexane to give methyl 3-(3,5-difluoro-2-pyridyl)-1,2,4-oxadiazole-5-carboxylate as a white solid. LCMS (Method A): Retention time 1.01 min, m / z 242 (M+H). 1 H NMR(400MHz,CDCl3)δ ppm 8.61(d,J=2.00Hz,1H)7.49(t,J=8.44Hz,1H)4.13(s,3H)

[0381] Step 3: Lithium; Preparation of 3-(3,5-difluoro-2-pyridyl)-1,2,4-oxadiazole-5-carboxylate [ka] To a solution of methyl 3-(3,5-difluoro-2-pyridyl)-1,2,4-oxadiazole-5-carboxylate (0.5 g, 2.1 mmol) in THF and water (2:1, 7.5 mL) was added lithium hydroxide monohydrate (89 mg, 2.1 mmol) at room temperature. The reaction mixture was stirred at room temperature for 2 hours. After completion of the reaction (monitored by LCMS), the reaction mixture was concentrated under reduced pressure to give lithium; 3-(3,5-difluoro-2-pyridyl)-1,2,4-oxadiazole-5-carboxylate. LCMS (Method A): Retention time 0.23 min, m / z 228 (M+H). 1 H NMR(400MHz,DMSO-d6)δ ppm 8.72-8.78(m,1H)8.19-8.28(m,1H)

[0382] Step 4: Preparation of N-[2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propyl]-3-(3,5-difluoro-2-pyridyl)-1,2,4-oxadiazole-5-carboxamide (compound P-18, Table P) To a suspension of 2-(6-chloro-2-pyridyl)-2-(1-methylpyrazol-4-yl)propan-1-amine (100 mg, 0.4 mmol) and lithium; 3-(3,5-difluoro-2-pyridyl)-1,2,4-oxadiazole-5-carboxylate (0.44 mmol) in EtOAc (5 mL / mmol) was added N-ethyl-N-isopropyl-propan-2-amine (1.6 mmol) and T3P (50% by weight) in EtOAc (1.2 mmol, 50% by weight) at 0 °C. The reaction mixture was warmed to room temperature and stirred for 24 h, at which time LCMS and TLC analysis indicated completion of the reaction. The reaction mixture was diluted with water (20 ml) and extracted with EtOAc (2 × 25 ml). The combined organic layers were dried over Na2SO4 and concentrated under reduced pressure to give the crude product. This was absorbed onto Celite and purified by reverse phase combi flash using CH3CN and water as eluents to give the title product. LCMS (Method A): rt=1.06, m / z=460 (M+H). 1 H NMR(400MHz,CDCl3)δ ppm 8.58(d,J=2.38Hz,1H)8.46(br s,1H)7.60(t,J=7.88Hz,1H)7.46(ddd,J=9.60,7.66,2.38Hz,1H)7.24- 7.31(dd,2H)7.12(d,J=7.38Hz,1H)4.03-4.15(m,2H)3.88(s,3H)1.73(s,3H)

[0383] Preparation of intermediates: Using the methods described in the examples above, and the intermediates described below, further examples of compounds of formula (I) can be produced.

[0384] Example I-1: Preparation of 2-(6-chloro-2-pyridyl)-2-(5-cyclopropyl-1-methyl-pyrazol-4-yl)propan-1-amine [ka] Step 1: Preparation of 5-cyclopropyl-1-methyl-pyrazole [ka] 5-Bromo-1-methyl-pyrazole (1.0 g, 6.1 mmol) was dissolved in toluene (20 mL) and N,N-dimethylformamide (4.0 mL). To this solution, cyclopropylboronic acid (1.7 g, 19 mmol) and cesium carbonate (7.9 g, 24 mmol) were added, and the reaction mixture was purged with nitrogen for 10 minutes. To this solution, Pd(dppf)Cl2·CHCl2 (0.25 g, 0.30 mmol) was added, and the resulting reaction mixture was stirred at 100 °C for 6 hours. After completion of the reaction (monitored by LCMS and TLC), the reaction mixture was quenched with water (20 mL) and filtered through Celite. The filtrate was extracted with EtOAc (2 × 30 mL), and the combined organic layers were dried over sodium sulfate and concentrated under reduced pressure to give crude 5-cyclopropyl-1-methyl-pyrazole, which was used directly in the next step. LCMS: (Method A): Retention time 0.87 min, m / z 123 (M+H).

[0385] Step 2: Preparation of 4-bromo-5-cyclopropyl-1-methyl-pyrazole [ka] To a stirred solution of 5-cyclopropyl-1-methyl-pyrazole (2 g, 14.7 mmol) in acetonitrile (80 mL) was added N-bromosuccinimide (2.94 g, 16.2 mmol), and the reaction mixture was allowed to stir at room temperature for 18 hours. After completion of the reaction (monitored by LCMS and TLC), the reaction mixture was quenched with water, and the aqueous layer was extracted with EtOAc (×3). The combined organic layers were washed successively with sodium thiosulfate, brine, then dried over sodium sulfate, and concentrated under reduced pressure to give the crude product. The crude compound was purified by combi flash using 0-10% EtOAc in cyclohexane to give the title compound. LCMS: (Method A): Retention time 1.13 min, m / z 201 (M+H).

[0386] Step 3: Preparation of (6-chloro-2-pyridyl)-(5-cyclopropyl-1-methyl-pyrazol-4-yl)methanol [ka] 4-Bromo-5-cyclopropyl-1-methyl-pyrazole (1.0 g, 4.7 mmol) was dissolved in THF (10 mL) under argon and cooled to −78° C. To this solution was added dropwise n-butyllithium (2.5 mol / L) in hexane (2.4 mL, 1.6 g, 4.7 mmol). The resulting reaction mixture was stirred at this temperature for 30 minutes, and 6-chloropyridine-2-carbaldehyde (0.74 g, 5.2 mmol) in THF (10 mL) was added dropwise at −78° C. After stirring at this temperature for 1 hour, the reaction mixture was warmed to room temperature and stirred for an additional hour. The reaction mixture was then cooled to 0° C. and then acidified with 2 N hydrochloric acid. The aqueous layer was extracted with EtOAc (3×100 mL), and the combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by combi flash using 30-40% EtOAc in cyclohexane to give (6-chloro-2-pyridyl)-(5-cyclopropyl-1-methyl-pyrazol-4-yl)methanol as a white solid. LCMS: (Method A): Retention time 1.10 min, m / z 264 (M+H).

[0387] Step 4: Preparation of 2-(6-chloro-2-pyridyl)-2-(5-cyclopropyl-1-methyl-pyrazol-4-yl)acetonitrile [ka] To a solution of (6-chloro-2-pyridyl)-(5-cyclopropyl-1-methyl-pyrazol-4-yl)methanol (0.6 g, 2.28 mmol) in acetonitrile (22.8 mL) was added lithium carbonate (0.034 g, 0.45 mmol), trimethylsilyl cyanide (1.41 mL, 1.05 g, 10.2 mmol), and iodine (1.04 g, 4.10 mmol) at room temperature. The reaction mixture was heated to 60 °C and stirred for 6 hours. After completion of the reaction (monitored by LCMS and TLC), the reaction mixture was cooled to room temperature, quenched with saturated sodium thiosulfate solution, and extracted with EtOAc (3 × 100 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure to give the crude product as a light brown residue. The crude compound was purified by combi flash using 5-40% EtOAc in cyclohexane to give the title compound as a pale yellow gummy mass. LCMS: (Method A): Retention time 1.24 min, m / z 273 (M+H).

[0388] Step 5: Preparation of 2-(6-chloro-2-pyridyl)-2-(5-cyclopropyl-1-methyl-pyrazol-4-yl)propanenitrile [ka] To a solution of 2-(6-chloro-2-pyridyl)-2-(5-cyclopropyl-1-methyl-pyrazol-4-yl)acetonitrile (0.10 g, 0.367 mmol) in THF (1.10 mL) under argon, n-butyllithium (2.5 mol / L) in hexane (0.22 mL) was added dropwise over a period of 15 minutes at −78° C. The resulting pale yellow suspension was stirred at this temperature for 25 minutes, and iodomethane (0.034 mL, 0.55 mmol) was added. The resulting yellow solution was stirred at −78° C. for 15 minutes and then warmed to room temperature. After stirring at room temperature for 2 hours, the reaction was shown to be complete (monitored by LCMS and TLC). The reaction mixture was then quenched with saturated aqueous ammonium chloride solution (20 mL), extracted with EtOAc (2×20 mL), dried over sodium sulfate, filtered, and concentrated under reduced pressure to give the crude product as a brown oil. This was purified by combi flash chromatography eluting with 30-40% EtOAc in cyclohexane to give the title compound as a pale yellow gum. LCMS (Method A): Retention time 1.25 min, m / z 287.1 (M+H).

[0389] Step 6: Preparation of 2-(6-chloro-2-pyridyl)-2-(5-cyclopropyl-1-methyl-pyrazol-4-yl)ethanamine To a solution of 2-(6-chloro-2-pyridyl)-2-(5-cyclopropyl-1-methyl-pyrazol-4-yl)propanenitrile (0.040 g, 0.14 mmol) in THF (0.41 mL) was added borane dimethyl sulfide complex (0.70 mL, 1.40 mmol) dropwise at room temperature under a nitrogen atmosphere. The resulting reaction mixture was stirred at 60° C. for 6 hours and then cooled to 0° C. Concentrated HCl (0.093 mL, 0.56 mmol) was added dropwise to the reaction mixture (strong gas evolution!), and the resulting reaction mixture was stirred at 60° C. for 1 hour. The reaction mixture was cooled to room temperature and basified to pH 12 with 6 N NaOH. The resulting mixture was extracted with EtOAc (×3), and the combined organic layers were washed once with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give the title compound as a light brown oil, which can be used to prepare compounds of Formula (I) without further purification. LCMS (Method A): Retention time 0.92 min, m / z 291.1 (M+H).

[0390] Example I-4: Preparation of 2-(3,5-difluoro-2-pyridyl)oxazole-4-carboxylic acid [ka] Step 1: Preparation of ethyl 2-(3,5-difluoro-2-pyridyl)oxazole-4-carboxylate [ka] A solution of ethyl oxazole-4-carboxylate (CAS[23012-14-8], 0.34 g, 2.44 mmol) and 2-bromo-3,5-difluoropyridine (CAS[660425-16-1], 0.5 g, 2.44 mmol) in 1,4-dioxane (3.5 mL) was stirred at room temperature. To this solution were added pivalic acid (0.0852 mL, 0.73 mmol), potassium carbonate (0.70 g, 4.89 mmol), tri-tert-butylphosphonium tetrafluoroborate (CAS[131274-22-1], 0.14 g, 0.48 mmol), and palladium(II) acetate (0.056 g, 0.24 mmol), and the reaction mixture was warmed to 90 °C and stirred at this temperature for 16 h (monitored by LCMS and TLC). The reaction mixture was quenched with water (20 mL) and extracted with EtOAc (3 x 20 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure to give the crude compound. This was purified by combi flash using 0-50% EtOAc in cyclohexane as the eluent to give the title compound as a brown gummy mass. LCMS: (Method A): Retention time 1.00 min, m / z 255 (M+H).

[0391] Step 2: Preparation of 2-(3,5-difluoro-2-pyridyl)oxazole-4-carboxylic acid To a solution of ethyl 2-(3,5-difluoro-2-pyridyl)oxazole-4-carboxylate (0.2 g, 0.78 mmol) in THF (0.8 mL) and water (0.2 mL) was added lithium hydroxide (0.075 g, 3.14 mmol), and the resulting reaction mixture was stirred at room temperature. After completion of the reaction (monitored by LCMS and TLC), the reaction mixture was quenched with ice-cold water (20 mL) and extracted with TBME (2 × 20 mL). The organic layer was discarded, and the aqueous layer was acidified with 2 N HCl and extracted with EtOAc (3 × 20 mL). The combined extracts were dried over sodium sulfate, filtered, and concentrated under reduced pressure to give the title compound as an off-white solid. LCMS: (Method A): Retention time 0.41 min, m / z 227 (M+H).

[0392] Example I-3: Preparation of 2-(6-chloro-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)propan-1-amine [ka] Step 1: Preparation of 5-chloro-1,3-dimethyl-pyrazole-4-carbaldehyde [ka] A solution of 2,5-dimethylpyrazol-3-ol (10 g, 44.6 mmol) and phosphorus(V) oxychloride (21.2 mL) was stirred at 90° C. for 1 h. After completion of the reaction (monitored by LCMS and TLC), the reaction mixture was concentrated under reduced pressure, and the residue was treated with saturated aqueous sodium bicarbonate (until the pH was basic). The aqueous layer was extracted with EtOAc (×3). The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give the crude product. The crude product was purified by combi flash using 20-30% EtOAc in cyclohexane to give 5-chloro-1,3-dimethyl-pyrazole-4-carbaldehyde as a white solid. LCMS (Method D): Retention time 1.0 min, m / z 159 (M+H).

[0393] Step 2: Preparation of 5-methoxy-1,3-dimethyl-pyrazole-4-carbaldehyde [ka] To a solution of 5-chloro-1,3-dimethyl-pyrazole-4-carbaldehyde (8.3 g, 52 mmol) in methanol (83 mL) was added sodium methanolate (23 mL, 100 mmol) at room temperature under argon. The resulting reaction mixture was stirred at 60 °C for 6 h, at which point LCMS and TLC showed the reaction was complete. The reaction mixture was diluted with water (50 mL) and saturated aqueous ammonium chloride solution and extracted with EtOAc (150 mL × 3). The combined organic layers were dried over NaSO and concentrated under reduced pressure to give the crude product. This was purified by combi flash using 30-40% EtOAc in cyclohexane to give the title compound as a white solid. LCMS (Method A): Retention time 0.34 min, m / z 155 (M+H).

[0394] Step 3: Preparation of 2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)acetonitrile [ka] To a solution of potassium tert-butoxide (11 g, 95 mmol) in 1,2-dimethoxyethane (130 mL) under argon, tosylmethyl isocyanide (11 g, 54 mmol) in DME (5 mL) was added at -65°C. The reaction mixture was stirred at -65 to -60°C for approximately 1 to 2 hours. 5-Methoxy-1,3-dimethyl-pyrazole-4-carbaldehyde (6.3 g, 39 mmol) in DME (5 mL) was added to the reaction mixture over 1 hour at -65 to -60°C and stirred at this temperature for 2 hours (Note: A thick mass was observed). Methanol (4.1 mL) was added at -65°C to obtain a clear solution. The reaction mixture was then heated to 80°C for 2 hours. After completion of the reaction (monitored by LCMS and TLC), it was cooled to 0 °C, quenched with 5% acetic acid in water (until the pH was slightly acidic), stirred for 5 minutes, and then diluted with EtOAc (10 mL). Both the aqueous and organic layers were separated, the aqueous layer was extracted with EtOAc (60 mL), and the combined organic layers were washed with brine solution (10 mL), dried over Na2SO4, and concentrated under reduced pressure. The crude compound was purified by combi flash using 50-70% EtOAc in cyclohexane to give the title compound as a brown liquid. LCMS (Method D): Retention time 0.74 min, m / z 166 (M+H).

[0395] Step 4: Preparation of 2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)propanenitrile [ka] To a solution of potassium tert-butoxide (83 mg, 0.72 mmol) and 2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)acetonitrile (100 mg, 0.60 mmol) in DMSO (1 mL) was added iodomethane (0.042 mL, 0.66 mmol) at room temperature, and the reaction mixture was stirred under nitrogen at room temperature for 30 minutes. The reaction mixture was diluted with cold water (20 mL) and saturated aqueous ammonium chloride solution and extracted with EtOAc (40 mL × 3). The combined organic layers were washed with brine, dried over Na2SO4, and concentrated under reduced pressure. The crude compound was purified by combi flash using 50-60% EtOAc in cyclohexane to give the title compound as a colorless liquid. LCMS (Method D): Retention time 1.31 min, m / z 180 (M+H).

[0396] Step 5: Preparation of 2-(6-chloro-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)propanenitrile [ka] A solution of 2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)propanenitrile (1.5 g, 6.7 mmol) in DMSO (15 mL) and potassium tert-butoxide (1.2 g, 11 mmol) was stirred at room temperature for 10 minutes, and then 2,6-dichloropyridine (1.1 g, 7.4 mmol) in DMSO (5 mL) was added dropwise. The reaction mixture was stirred under nitrogen at room temperature for 30 minutes. After completion of the reaction (monitored by LCMS and TLC), the reaction mixture was diluted with cold water (20 mL) and saturated ammonium chloride and extracted with EtOAc (40 mL × 3). The combined organic layers were washed with brine, dried over Na2SO4, and concentrated under reduced pressure. The crude product was purified by combi flash using 50-70% EtOAc in cyclohexane to give the title compound as a yellow oil. LCMS (Method A): Retention time 1.06 min, m / z 291 (M+H).

[0397] Step 6: Preparation of 2-(6-chloro-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)propan-1-amine [ka] To a solution of 2-(6-chloro-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)propanenitrile (1.53 g, 4.21 mmol) in THF (12.6 mL) was added borane dimethyl sulfide complex (21 mL, 42.1 mmol) at room temperature under nitrogen. The resulting reaction mixture was stirred at 70° C. for 1 hour. Upon completion, 6N HCl was added dropwise to the reaction mixture (0.95 mL, 5.75 mmol, strong gas evolution!) and stirred at 60° C. for 1 hour. After cooling to room temperature, it was basified to pH 12 with 6N NaOH and extracted with EtOAc (50 mL) × 3). The combined organic layers were washed with brine, dried over NaSO, and concentrated under reduced pressure to give the title compound as a yellow oil, which was used in the next step without further purification. LCMS (Method A): Retention time 0.13 min, m / z 295 (M+H).

[0398] Those skilled in the art will appreciate that omitting step 4 can result in the following compound: [ka] It will be appreciated that this allows the

[0399] Example I-4: Preparation of [2-(6-cyano-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)propyl]ammonium chloride [ka] Step 1: Preparation of tert-butyl N-[2-(6-chloro-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)propyl]carbamate [ka] To a solution of 2-(6-chloro-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)propan-1-amine (1.5 g, 4.3 mmol) in THF (23 mL) in water (15 mL) was added sodium bicarbonate (1.7 g, 19 mmol) and di-tert-butyl dicarbonate (1.1 mL, 4.3 mmol) at 0 °C. The resulting reaction mixture was stirred at room temperature for 2 h, quenched with water, and extracted with EtOAc (×3). The combined organic layers were washed with brine, dried over NaSO, and concentrated under reduced pressure to give the crude product, which was purified by combi flash using 60-80% EtOAc in cyclohexane to give the title compound as a yellow oil. LCMS (Method A): Retention time 1.11 min, m / z 395 (M+H).

[0400] Step 2: Preparation of tert-butyl N-[2-(6-cyano-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)propyl]carbamate [ka] To a solution of tert-butyl N-[2-(6-chloro-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)propyl]carbamate (1.4 g, 3.2 mmol) in toluene (7.0 mL) and water (7.0 mL), potassium acetate (0.89 g, 8.9 mmol) and potassium ferrocyanide (4.9 g, 13 mmol) were added at room temperature. The reaction mixture was degassed under nitrogen for 10 minutes. To this reaction mixture was added (2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) methanesulfonate (1.4 g, 1.6 mmol), and the reaction mixture was stirred at 90°C for 4 hours. The reaction mixture was quenched with water and extracted with EtOAc (x3), and the combined organic layers were washed with brine, dried over Na2SO4, and concentrated under reduced pressure to give the crude product, which was purified by combi flash using 80% EtOAc in cyclohexane to give the title compound as a brown oil. LCMS (Method D): Retention time 1.76 min, m / z 386 (M+H).

[0401] Step 3: Preparation of [2-(6-cyano-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)propyl]ammonium chloride To a solution of tert-butyl N-[2-(6-cyano-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)propyl]carbamate (320 mg, 0.74 mmol) in diethyl ether (3.2 mL) was added 2 M HCl in diethyl ether (1.5 mL, 3 mmol) at 0° C. The reaction mixture was warmed to room temperature and stirred at room temperature for 6 hours. After completion, the reaction mixture was concentrated under reduced pressure at 30° C. to provide the title compound as a yellow solid. LCMS (Method A): Retention time 0.39 min, m / z 286 (M+H).

[0402] Example I-5: Preparation of [2-(6-cyano-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)ethyl]ammonium chloride (same procedure as for 2-(6-cyano-2-pyridyl)-2-(5-methoxy-1,3-dimethyl-pyrazol-4-yl)propyl]ammonium chloride) [ka] LCMS (Method A): Retention time 0.20 min, m / z 272 (M+H).

[0403] Example I-6: Preparation of 2-(6-chloro-2-pyridyl)-2-[5-(methoxymethyl)-1,3-dimethyl-pyrazol-4-yl]ethanamine [ka] Step 1: Preparation of (2,5-dimethylpyrazol-3-yl)methanol [ka] To a solution of ethyl 2,5-dimethylpyrazole-3-carboxylate (0.2 g, 1 mmol) in ethanol (2 mL) was added sodium borohydride (0.2 g, 57 mmol) at room temperature. The reaction mixture was stirred at 60° C. for 3 hours. After completion of the reaction (monitored by LCMS and TLC), the reaction mixture was quenched with saturated ammonium chloride solution and extracted with EtOAc (×3). The combined organic layer was washed successively with water and brine; dried over Na SO and concentrated under reduced pressure to give the title compound. LCMS (Method A): Retention time 0.37 min, m / z 127 (M+H).

[0404] Step 2: Preparation of 5-(methoxymethyl)-1,3-dimethyl-pyrazole [ka] To a solution of (2,5-dimethylpyrazol-3-yl)methanol (0.6 g, 4.75 mmol) in THF (6 mL) at 0° C., sodium hydride (0.20 g, 5.23 mmol) was added and stirred for 30 minutes, followed by the addition of iodomethane (0.32 mL, 5.23 mmol), and the resulting reaction mixture was warmed to room temperature and stirred for 3 hours. The reaction mixture was diluted with 2 N HCl (20 mL) and extracted with EtOAc (2×30 ml). The combined organic layers were washed with cold water, brine, dried over Na SO , and concentrated under reduced pressure to give the title compound. LCMS (Method A): Retention time 0.94 min, m / z 141 (M+H).

[0405] Step 3: Preparation of 5-(methoxymethyl)-1,3-dimethyl-pyrazole-4-carbaldehyde [ka] To a solution of 5-(methoxymethyl)-1,3-dimethyl-pyrazole (0.7 g, 5 mmol) in DMF (3 mL, 40 mmol) was added phosphorus oxychloride (2 mL, 20 mmol) at 0° C. The reaction mixture was stirred at 80° C. for 6 hours (monitored by LCMS). After completion of the reaction, the reaction mixture was slowly poured into crushed ice, and 6N NaOH solution was added until the pH reached 12. The resulting reaction mixture was extracted with EtOAc (3×30 mL), and the combined organic layers were washed successively with water and brine, dried over anhydrous NaSO, and concentrated under reduced pressure. The title product was obtained as a brown solid. 1 H NMR(400MHz,CDCl3)δ ppm 9.96(s,1H)4.75(s,2H)3.85(s,3H)3.38(s,3H)2.45(s,3H)

[0406] Step 4: Preparation of 2-[5-(methoxymethyl)-1,3-dimethyl-pyrazol-4-yl]acetonitrile [ka] The same procedure was followed as in Example I-3, Step 3. LCMS (Method A): Retention time 0.20 min, m / z 180 (M+H). 1H NMR(400MHz,CDCl3)δ ppm 4.47(s,2H)3.82(s,3H)3.52(s,2H)3.39(s,3H)2.27(s,3H)

[0407] Step 5: Preparation of 2-(6-chloro-2-pyridyl)-2-[5-(methoxymethyl)-1,3-dimethyl-pyrazol-4-yl]acetonitrile [ka] The same procedure was followed as in Example I-3, Step 5. LCMS (Method A): Retention time 1.01 min, m / z 291 (M+H). 1H NMR(400MHz,CDCl3)δ ppm 7.66(t,1H)7.24-7.32(m,2H)5.27(s,1H)4.49-4.61(m,2H)3.83(s,3H)3.36(s,3H)2.23(s,3H)

[0408] Step 6: Preparation of 2-(6-chloro-2-pyridyl)-2-[5-(methoxymethyl)-1,3-dimethyl-pyrazol-4-yl]ethanamine [ka] The same procedure as in Step 6 of Example I-3 was carried out. LCMS (Method A): Retention time: 0.39 min, m / z 295 (M+H).

[0409] Examples of compounds of formula (I) that have been synthesized are shown in Table P.

[0410] [Table 5-1]

[0411] [Table 5-2]

[0412] [Table 5-3]

[0413] [Table 5-4]

[0414] [Table 5-5]

[0415] [Table 5-6]

[0416] [Table 5-7]

[0417] [Table 5-8]

[0418] Biological Examples Example B-1: Alternaria solani / Tomato / Leaf disc (summer blight) Tomato leaf discs (cv. Baby) were placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compounds diluted in water. The discs were inoculated with a fungal spore suspension two days after application. The inoculated discs were incubated in a climate cabinet under a 12 / 12 h light / dark photoperiod at 23°C / 21°C (day / night) and 80% relative humidity. When an appropriate level of disease damage had developed on the untreated test discs (5-7 days after application), the efficacy of the compounds was evaluated as the percentage of disease control compared to the untreated ones.

[0419] The following compounds provided at least 80% control of Alternaria solani at 200 ppm when compared to untreated controls that exhibited widespread disease development under identical conditions: P-5, P-9, P-10, P-12, P-13, P-14, P-15, P-16, P-17, P-18, P-20, P-22, P-23, P-24, P-25, P-26, P-27, P-28, P-39, P-42, P-43, and P-45.

[0420] Example B-2: Botryotinia fuckeliana (Botrytis cinerea) / Liquid Culture (Grey Mold) Cryogenically preserved fungal conidia are mixed directly into nutrient medium (Vogel's medium). A solution of the test compound (DMSO) is placed in a 96-well microtiter plate, after which the nutrient medium containing the fungal spores is added. The test plate is incubated at 24°C, and growth inhibition is measured photometrically 3-4 days after application.

[0421] The following compounds provided at least 80% control of Botryotinia fuckeliana at 20 ppm when compared to untreated controls that exhibited widespread disease development under identical conditions: P-1, P-2, P-3, P-4, P-5, P-7, P-8, P-9, P-10, P-12, P-13, P-14, P-15, P-16, P-17, P-18, P-23, P-24, P-25, P-26, P-38, and P-39.

[0422] Example B-3: Glomerella lagenarium (Colletotrichum lagenarium) / Liquid Culture (Anthracnose) Cryogenically preserved fungal conidia are mixed directly into nutrient medium (PDB potato dextrose medium). A solution of the test compound (DMSO) is placed in a 96-well microtiter plate, after which the nutrient medium containing the fungal spores is added. The test plates are incubated at 24°C, and growth inhibition is measured photometrically 3-4 days after application.

[0423] The following compounds provided at least 80% control of Glomerella lagenarium at 20 ppm when compared to untreated controls that exhibited widespread disease development under identical conditions: P-1, P-2, P-3, P-4, P-5, P-7, P-8, P-9, P-10, P-11, P-12, P-13, P-14, P-15, P-16, P-17, P-18, P-23, P-24, P-38, and P-39.

[0424] Example B-4: Blumeria graminis f.sp. tritici (powdery mildew fungus (Erysiphe graminis f.sp. tritici)) / wheat / leaf disc preventative (powdery mildew in wheat) 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. One day after application, powdery mildew-infected plants were inoculated onto the leaf segments by shaking them over the test plates. The inoculated leaf segments were incubated in a climate chamber at 20°C and 60% relative humidity under a 24-hour dark followed by 12-hour light / 12-hour dark photoperiod. When an appropriate level of disease damage had developed on the untreated test leaf segments (6-8 days after application), the efficacy of the compounds was evaluated as the percentage of disease control compared to the untreated ones.

[0425] The following compounds provided at least 80% control of Blumeria graminis f.sp. tritici at 200 ppm when compared to untreated controls that exhibited widespread disease development under identical conditions: P-1, P-2, P-3, P-9, P-10, P-11, P-12, P-13, P-14, P-15, P-16, P-17, P-18, P-22, P-23, P-24, P-25, P-26, P-27, P-28, P-29, P-35, P-38, P-39, P-40, P-41, and P-43.

[0426] Example B-5: Fusarium culmorum / Liquid culture (Blight) Cryogenically preserved fungal conidia are mixed directly into nutrient medium (PDB potato dextrose medium). A solution of the test compound (DMSO) is placed in a 96-well microtiter plate, after which the nutrient medium containing the fungal spores is added. The test plate is incubated at 24°C, and growth inhibition is measured photometrically 3-4 days after application.

[0427] The following compounds provided at least 80% control of Fusarium culmorum at 20 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-1, P-3, P-4, P-5, P-8, P-9, P-10, P-12, P-13, P-16, P-17, P-18, P-23, and P-26.

[0428] Example B-6: Fusarium culmorum / wheat / spikelet prevention (fusarium head blight) Wheat spikelets (cv. Monsun) are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compounds diluted in water. One day after application, the spikelets are inoculated with a fungal spore suspension. The inoculated spikelets are incubated in a climate chamber under a 72-hour semi-dark light regime followed by a 12-hour light / 12-hour dark light regime at 20°C and 60% relative humidity. When an appropriate level of disease damage appears on untreated test spikelets (6-8 days after application), the efficacy of the compounds is evaluated as the percentage of disease control compared to the untreated control.

[0429] The following compounds provided at least 80% control of Fusarium culmorum at 200 ppm when compared to untreated controls under the same conditions, which showed widespread disease development: P-3, P-9, P-13, P-18, and P-23.

[0430] Example B-7: Gibberella zeae (Fusarium graminearum) / wheat / spikelet prevention (Scab disease) Wheat spikelets (cv. Monsun) are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compounds diluted in water. One day after application, the spikelets are inoculated with a fungal spore suspension. The inoculated test leaf discs are incubated in a climate chamber under a 72-hour semi-dark light regime followed by a 12-hour light / 12-hour dark light regime at 20°C and 60% relative humidity. When an appropriate level of disease damage appears on the untreated test spikelets (6-8 days after application), the efficacy of the compounds is evaluated as the percentage of disease control compared to the untreated control.

[0431] The following compounds provided at least 80% control of Gibberella zeae at 200 ppm when compared to untreated controls under the same conditions, which showed widespread disease development: P-1, P-9, P-13, P-18, and P-23.

[0432] Example B-8: Wheat leaf spot fungus (Phaeosphaeria nodorum) (Septoria nodorum) / Wheat / Leaf spot prevention (leaf spot disease) Wheat leaf segments (cv. Kanzler) placed on agar in multiwell plates (24-well format) are sprayed with the formulated test compounds diluted in water. The leaves are inoculated with a fungal spore suspension two days after application. The inoculated test leaf segments are incubated in a climate cabinet at 20°C and 75% relative humidity under a 12-hour light / 12-hour dark photoperiod. When an appropriate level of disease damage has developed on the untreated test leaf segments (5-7 days after application), the efficacy of the compound is evaluated as the percentage of disease control compared to the untreated ones.

[0433] The following compounds provided at least 80% control of wheat leaf spot fungus (Phaeosphaeria nodorum) at 200 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-3, P-4, P-5, P-8, P-9, P-10, P-13, P-14, P-15, P-16, P-17, P-18, P-20, P-23, P-24, P-25, P-26, P-27, P-28, P-35, P-38, P-39, and P-45.

[0434] Example B-9: Monographella nivalis (Microdochium nivale) / Liquid Culture (Root Rot of Cereals) Cryogenically preserved fungal conidia are mixed directly into nutrient medium (PDB potato dextrose medium). A solution of the test compound (DMSO) is placed in a 96-well microtiter plate, after which the nutrient medium containing the fungal spores is added. The test plate is incubated at 24°C, and growth inhibition is measured photometrically 4-5 days after application.

[0435] The following compounds provided at least 80% control of Monographella nivalis at 20 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-1, P-3, P-4, P-5, P-7, P-8, P-9, P-10, P-12, P-13, P-14, P-16, P-17, P-18, P-20, P-23, P-24, P-25, P-26, and P-39.

[0436] Example B-10: Mycosphaerella arachidis (Cercospora arachidicola) / Liquid Culture (Early Spot Disease) Cryogenically preserved fungal conidia are mixed directly into nutrient medium (PDB potato dextrose medium). A solution of the test compound (DMSO) is placed in a 96-well microtiter plate, after which the nutrient medium containing the fungal spores is added. The test plate is incubated at 24°C, and growth inhibition is measured photometrically 4-5 days after application.

[0437] The following compounds provided at least 80% control of Mycosphaerella arachidis at 20 ppm when compared to untreated controls that exhibited widespread disease development under identical conditions: P-1, P-3, P-4, P-5, P-6, P-7, P-8, P-9, P-10, P-13, P-15, P-16, P-17, P-18, P-19, P-20, P-23, P-24, P-25, P-26, P-28, P-35, P-38, and P-39.

[0438] Example B-11: Puccinia recondita f.sp. tritici / wheat / leaf disk treatment (brown rust) Wheat leaf segments (cv. Kanzler) are placed on agar in multiwell plates (24-well format). The leaf segments are inoculated with a fungal spore suspension. The plates are kept in the dark at 19°C and 75% relative humidity. The formulated test compounds diluted in water are applied one day after sowing. The leaf segments are incubated in a climate cabinet under a 12-hour light / 12-hour dark light regime at 19°C and 75% relative humidity until an appropriate level of disease damage appears on the untreated test leaf segments (6-8 days after application), at which point the efficacy of the compounds is assessed as the percentage of disease control compared to the untreated.

[0439] The following compounds provided at least 80% control of Puccinia recondita f.sp. tritici at 200 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-26.

[0440] Example B-12: Puccinia recondita f.sp. tritici / wheat / prevention of leaf disc disease (brown rust) Wheat leaf segments (cv. Kanzler) placed on agar in a multiwell plate (24-well format) are sprayed with the formulated test compound diluted in water. One day after application, the leaf segments are inoculated with a fungal spore suspension. The inoculated leaf segments are incubated in a climate cabinet at 19°C and 75% relative humidity u...

Claims

1. Compounds of formula (I) 【Chemistry 1】 (In the formula, R 1 is hydrogen, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl, C 2 ~C 4 Alkynyl, or C 3 ~C 6 cycloalkyl; R 2 is hydrogen, halogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Alkoxy, C 2 ~C 4 Alkenyl, C 2 ~C 4 Alkynyl, C 1 ~C 4 Haloalkyl, C 3 ~C 6 Cycloalkyl, C 1 ~C 2 Alkyl-C 1 ~C 4 Alkoxy, C 1 ~C 2 Alkyl-C 1 ~C 4 Alkoxy-C 1 ~C 2 Alkoxy, C 1 ~C 4 Alkylcarbonyl, N—C 1 ~C 4 Alkoxy-C 1 ~C 4 Alkyl-carbonimidoyl, N-hydroxy-C 1 ~C 4 Alkyl-carbonimidoyl, or C 1 ~C 4 alkoxycarbonyl; R 3 is hydrogen, halogen, or C 1 ~C 4 alkyl; R 4 is hydrogen, halogen, C 1 ~C 4 Alkyl, cyano, C 1 ~C 4 Alkylcarbonyl, C 1 ~C 4 Alkoxycarbonyl, C 1 ~C 4 alkylaminocarbonyl, or di(C 1 ~C 4 alkylamino)carbonyl; R 5 and R 6 is hydrogen or C 1 ~C 4 independently selected from alkyl; A 1 , A 2 and A 3 is CR 7 , N, N.R. 8 , O, or S, with the proviso that A 1 , A 2 and A 3 is selected from N, O, or S, and A 1 , A 2 and A 3 is O or S; R 7 and R 8 is hydrogen, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl, or C 2 ~C 4 independently selected from alkynyl; B 1 is CR 9 or N, and B 2 is CR 10 or N, and B 3 is CR 11 or N, and B 4 is CR 12 or N, provided that B 1 , B 2 , B 3 , and B 4 is N; R 10 , R 11 , R 12 and R 13 is hydrogen, halogen, amino, hydroxy, carboxylic acid, cyano, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 1 ~C 4 Alkoxy, C 1 ~C 4 Haloalkoxy, C 2 ~C 4 Alkenyloxy, C 2 ~C 4 Alkynyloxy, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 4 Alkoxy-C 1 ~C 4 Alkyl, N-C 1 ~C 4 Alkylamino, N,N-di(C 1 ~C 4 alkyl)amino, C 1 ~C 4 Alkoxycarbonyl, C 1 ~C 4 Alkylcarbonyl, N—C 1 ~C 4 Alkoxy-C 1 ~C 4 Alkyl-carbonimidoyl, N-hydroxy-C 1 ~C 4 Alkyl-carbonimidoyl, C 1 ~C 4 Alkylaminocarbonyl, di(C 1 ~C 4 alkyl)aminocarbonyl, C 1 ~C 4 Alkylcarbonylamino, C 1 ~C 4 alkylsulfonylamino, trifluoromethylsulfonyloxy, phenyl, 5- or 6-membered heteroaryl, or C 3 ~C 6 cycloalkyl; wherein said 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms independently selected from N, O, or S, provided that not more than one is O or S; and wherein said phenyl, 5- or 6-membered heteroaryl, and C 3 ~C 6 Any of the cycloalkyls may be unsubstituted or may be substituted with halogen, cyano, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl or C 1 ~C 4 substituted with 1, 2, or 3 substituents independently selected from alkoxy; Z 1 is selected from 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrazin-2-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, or pyrimidin-5-yl; wherein any of the pyridyl-, pyrazine-pyridazine, and pyrimidine moieties is unsubstituted or selected from halogen, C 1 ~C 4 Haloalkyl, cyano, C 1 ~C 4 Alkyl, C 3 ~C 6 Cycloalkyl, C 2 ~C 4 Alkynyl, C 1 ~C 4 Haloalkoxy, C 1 ~C 4 Alkoxy, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 alkylsulfinyl, or C 1 ~C 4 substituted with 1, 2, or 3 substituents independently selected from alkylsulfonyl; or an agriculturally acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.

2. R 1 is C 1 ~C 3 2. The compound of formula (I) according to claim 1, wherein the compound is alkyl.

3. R 2 is hydrogen, halogen, C 1 ~C 3 Alkyl, or C 3 ~C 6 is cycloalkyl; R 3 3. A compound of formula (I) according to claim 1 or 2, wherein is hydrogen.

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

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

6. Z 1 is 2-pyridyl, 3-pyridyl, or 4-pyridyl; any of said pyridyl moieties is unsubstituted or is selected from halogen, C 1 ~C 4 Haloalkyl, or C 1 ~C 4 A compound of formula (I) according to any one of claims 1 to 5, substituted with 1, 2 or 3 substituents independently selected from alkyl.

7. Z 1 The compound of formula (I) according to claim 6, wherein is 3-fluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3,4-difluoro-2-pyridyl, 2,6-difluoro-3-pyridyl, or 3,5-difluoro-2-pyridyl.

8. The compound of formula (I) can be a compound of formula (IA): 【Chemistry 2】 (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 9 , R 10 , R 11 , R 12 , B 1 , B 2 , B 3 , B 4 and Z 1 corresponds to the same definition as in the compounds of formula (I) according to any one of claims 1 to 7, and A is 【Transformation 3】 where: 【Chemistry 4】 indicates the position of bonding to the C(=O) group, and the arrow indicates Z 1 The compound of formula (I) according to any one of claims 1 to 7, wherein R is a substituted or unsubstituted aryl group, ... and R is a substituted or unsubstituted aryl group.

9. A is A4, A7, A9, or A10 【Transformation 5】 is selected from: 【Transformation 6】 indicates the position of bonding to the C(=O) group, and the arrow indicates Z 1 The compound of formula (IA) according to claim 8, wherein the position of attachment to the group is indicated.

10. B 1 is CR 9 and B 2 is CR 10 and B 3 is CR 11 and B 4 is CR 12 where: R 9 and R 10 are independently selected from hydrogen, halogen, or cyano; R 11 and R 12 is hydrogen, halogen, cyano, C 1 ~C 4 Alkyl, or C 1 ~C 4 The compound of any one of claims 1 to 9, independently selected from alkoxy.

11. R 9 and R 10 is independently selected from hydrogen, chloro, bromo, or cyano; R 11 and R 12 The compound of claim 10 , wherein is hydrogen.

12. A pesticide composition comprising a fungicidally effective amount of a compound according to any one of claims 1 to 11.

13. 13. The pesticide composition of claim 12, further comprising at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

14. 12. A method for controlling or preventing infection of useful plants by phytopathogenic microorganisms, which comprises applying to said plant, a part thereof or its habitat a fungicidally effective amount of a compound according to any one of claims 1 to 11, or a composition comprising said compound.

15. Use of a compound according to any one of claims 1 to 11 as a fungicide.

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