Microbicide pyrazole derivatives

Abstract

Compounds of formula (I) which may be used as fungicides: JPEG2025532976000134.jpg57161, wherein the substituents are as defined in claim 1, and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of these compounds.

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 infestation of plants, harvested food crops, seeds, or non-living materials by phytopathogenic microorganisms, particularly fungi. DETAILED DESCRIPTION OF THE INVENTION

[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, 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; R 3 and R 4 are independently selected from hydrogen, halogen, or C1-C4 alkyl; R 5 and R 6 are independently selected from hydrogen or C1-C4 alkyl; R 7is selected from hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimidoyl, C1-C4 alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4 alkylaminocarbonyl, di(C1-C6 alkylamino)carbonyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5- to 6-membered heteroaryl is independently selected from N, O, or S. containing 1, 2, 3, or 4 heteroatoms, wherein phenyl and 5-6 membered heteroaryl are unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, cyano, carboxy, C1-C4 alkyl, or C1-C4 alkoxy; and C3-C6 cycloalkyl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, cyano, C1-C4 alkyl, or C1-C4 alkoxy; B 1 But, CR 10 or N; B 2 But, CR 11 or N; R 8 , R 9 , R 10 and R 11 are independently hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, N-C1-C4 alkylamino, N,N-diC 1~4selected from alkylamino, C1-C6 alkoxycarbonyl, C1-C4 alkylcarbonyl, N—C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C1-C4 alkyl-carbonimidoyl, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, amino, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms individually selected from N, O, or S, and any of the phenyl, 5- to 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; A 1 But, CR 12a or N; A 2 But, CR 13a or N; A 3 But, CR 14a or N; R 12a , R 13a and R 14a are independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, or C2-C4 alkynyl; Z 1is selected from C1-C4 alkyl, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms individually selected from N, O, or S, and either the phenyl, the 5- or 6-membered heteroaryl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, or C2-C4 alkynyl, and the 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. or an agrochemically acceptable salt, stereoisomer, or N-oxide thereof.

[0003] Surprisingly, it has been found that the compounds of formula (I) have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases caused by fungi.

[0004] According to a second aspect of the present invention there is provided an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) according to the present invention. Such 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 infestation of useful plants by phytopathogenic microorganisms, which comprises applying a fungicidally effective amount of a compound of formula (I) according to the present invention or a composition comprising a compound of formula (I) to the plant, a part thereof or its habitat.

[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, this use may exclude methods involving the treatment of the human or animal body by surgery or therapy and diagnostic methods carried out on the human or animal body.

[0007] According to a fifth aspect of the present invention, there is provided a compound of formula (IIb), a compound of formula (III) and a compound of formula (IV), each as described herein.

[0008] The compounds of formula (I) having at least one basic center can form, for example, acid addition salts with strong inorganic acids, such as mineral acids, for example, perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphorus-containing acids, and hydrohalic acids; with strong organic carboxylic acids, for example, unsubstituted or halogen-substituted C1-C4 alkanecarboxylic acids, such as acetic acid; saturated or unsaturated dicarboxylic acids, for example, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, phthalic acid; hydroxycarboxylic acids, for example, ascorbic acid, lactic acid, malic acid, tartaric acid, citric acid, or benzoic acid; or with organic sulfonic acids, for example, unsubstituted or halogen-substituted C1-C4 alkane or arylsulfonic acids, for example, 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, for example alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or organic amines, for example morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, for example ethyl, diethyl, triethyl or dimethylpropylamine, or mono-, di- or trihydroxy-lower alkylamines, for example mono-, di- or triethanolamine.

[0009] 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.

[0010] 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.

[0011] The compounds of formula (I) according to the invention also include the hydrates which may be formed during salt formation.

[0012] When a substituent is designated as "optionally substituted," it means that such substituent may be substituted with one or more of the same or different substituents, for example, 1, 2, or 3 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. As used herein, the term "optionally substituted" can be used interchangeably with "unsubstituted or substituted."

[0013] As used herein, the term "halogen" or "halo" refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine. This also applies correspondingly to halogen in combination with other meanings, such as haloalkyl, haloalkenyl, haloalkynyl, haloalkoxy, and halocycloalkyl.

[0014] As used herein, amino refers to the group —NH 2 .

[0015] As used herein, cyano refers to a -CN group.

[0016] As used herein, the term "hydroxyl" or "hydroxy" refers to an --OH group.

[0017] As used herein, the term "carboxylic acid" refers to a -COOH group.

[0018] As used herein, "C1-C n The term "alkyl" refers to a saturated straight or branched hydrocarbon group having 1 to n carbon atoms bonded via any of the carbon atoms, such as any one of the following groups: methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, -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.

[0019] 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.

[0020] 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.

[0021] As used herein, "C3-C n The term "cycloalkyl" refers to 3 to n-membered cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0022] As used herein, "C1-C n The term "alkoxy" refers to a straight or branched saturated alkyl group having 1 to n carbon atoms (as defined above) attached through an oxygen atom, i.e., any one of, for example, methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy, and 1,1-dimethylethoxy groups. As used herein, "C2-C n The term "alkenyloxy" refers to a straight or branched saturated alkenyl chain having 2 to n carbon atoms (as defined above) attached through an oxygen atom.

[0023] As used herein, "C1-C n Alkoxy-C1~C n The term "alkyl" refers to C1-C n It 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 nThe term "haloalkyl" refers to a linear or branched saturated alkyl group having 1 to n carbon atoms bonded via any of the carbon atoms (as defined above), in which some or all of the hydrogen atoms in these groups may be replaced by fluorine, chlorine, bromine and / or iodine, i.e., for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-difluoroethyl, 2,2-difluoroethyl. and any one of chloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl, and nonafluorobutyl. Thus, the term "C1-C2 fluoroalkyl" refers to 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 C-C alkyl groups each substituted with one or more halogen atoms, 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 C-C alkyl groups each substituted with one or more halo atoms, which may be the same or different. n Cycloalkyl group or C1-C n Refers to an alkoxy group.

[0025] 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.

[0026] As used herein, "C1-C n Haloalkylthio" or "C1-C n The term "haloalkylsulfanyl" refers to a C1-C alkyl group linked through a sulfur atom. n Refers to haloalkyl groups.

[0027] As used herein, "C1-C n The term "alkylsulfinyl" refers to a C1-C alkyl group linked through the sulfur atom of the sulfinyl (or S(=O)-) group. n Refers to an alkyl group.

[0028] 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.

[0029] 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.

[0030] As used herein, "C1-C n The term "alkylcarbonyl" refers to a C1-C alkyl group linked through the carbon atom of the carbonyl (C=O) group. n Refers to an alkyl group.

[0031] As used herein, "C1-C n The term "alkoxycarbonyl" refers to a C1-C alkyl group linked through the carbon atom of a carbonyl (or C=O) group. n Refers to the alkoxy moiety.

[0032] As used herein, the term "benzoyl" refers to a phenyl group attached through the carbon atom of a carbonyl (C=O) group.

[0033] As used herein, "C1-C n The term "alkylaminocarbonyl" refers to a C1-C alkylaminocarbonyl group linked through the carbon atom of the carbonyl (C=O) group. n Alkylamino group (or R a NHC(=O)-, (wherein R a However, C1~C n It refers to an alkyl group.

[0034] 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 an alkyl group.

[0035] As used herein, the term "N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl" refers to 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, a )=NO(R b ) group.

[0036] As used herein, the term "N-hydroxy-C-C alkyl-carbonimidoyl" refers to R a is a C1-C4 alkyl group as generally defined above, a )=NOH group.

[0037] As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic ring group containing 1, 2, 3, or 4 heteroatoms individually 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" refers to a C1-C6 heteroaryl group. n Alkyl" or "Heteroaryl C3-C n The term "cycloalkyl" refers to C1-C6 alkyl groups each substituted with a heteroaryl group. n Alkyl or C3-C n It refers to a cycloalkyl group. Heteroaryl C1-C n Alkyl or heteroaryl C3-C n Cycloalkyl groups may be optionally substituted on the heteroaryl, alkyl and / or cycloalkyl group.

[0038] 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.

[0039] As used herein, the term "pest" refers to insects and mollusks found in agriculture, horticulture, forestry, storage of plant-based products (such as fruit, grain, and lumber), and pests associated with damage to man-made structures. The term pest encompasses all stages in the life cycle of a pest.

[0040] As used herein, the term "effective amount" refers to the amount of a compound or salt thereof that produces a desired effect upon one or more applications.

[0041] 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.

[0042] As used herein, the terms "room temperature" or "RT" or "rt" refer 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.

[0043] 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 , B 1 , B 2 , A 1 , A 2 , A 3 and Z. For any one of these substituents, any definition given below may be combined with any definition of any other substituent given below or elsewhere in this specification.

[0044] 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 selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or C3-C6 cycloalkyl. Preferably, R 1is C1-C4 alkyl. More preferably, R 1 is methyl, ethyl, or isopropyl. Most preferably, R 1 is methyl.

[0045] 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 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 selected from 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 selected from the group consisting of hydrogen, halogen, methyl, ethyl, cyclopropyl, C1-C2 alkylcarbonyl, N-C1-C2 alkoxy-C-C1-C2 alkyl-carbonimidoyl, or N-hydroxy-C1-C2 alkyl-carbonimidoyl. 2 is selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, cyclopropyl, acetyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, or -C(CH3)=NOH. In a preferred embodiment of the present invention, R 2 is selected from hydrogen, halogen, or C1-C4 alkyl. 2is hydrogen, chlorine, or methyl.

[0046] In one embodiment, R 3 is selected from hydrogen, halogen, or C1-C4 alkyl. 3 is selected from hydrogen, halogen, or C1-C4 alkyl. 3 is hydrogen or C1-C4 alkyl. More preferably, R 3 is hydrogen or methyl. Most preferably, R 3 is hydrogen.

[0047] In one embodiment of the present invention, R 4 is selected from hydrogen, halogen, or C1-C4 alkyl. 4 is hydrogen, halogen, or C1-C4 alkyl. Preferably, R 4 is hydrogen, chlorine, bromine, fluorine, methyl, or ethyl. More preferably, R 4 is hydrogen, chlorine, bromine, or methyl. Even more preferably, R 4 is hydrogen or methyl. In one embodiment of the present invention, R 4 is hydrogen. In another embodiment of the present invention, R 4 is methyl.

[0048] In one embodiment of the present invention, R 5 and R 6 is independently selected from hydrogen or C1-C6 alkyl. 5 and R 6 are independently selected from hydrogen or C1-C4 alkyl. Preferably, R 5 and R 6 are independently selected from hydrogen, methyl, or ethyl. More preferably, R 5 and R 6 is independently selected from hydrogen or methyl. Even more preferably, R 5 and R 6 is hydrogen.

[0049] In one embodiment of the present invention, R 7 is selected from hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimidoyl, N-methoxy-N-methyl-carbonyl, C1-C4 alkylaminocarbonyl, di(C1-C6 alkylamino)carbonyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5- to 6-membered heteroaryl contains one heteroatom selected from N, and the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with one or two substituents independently selected from halogen, C1-C4 haloalkyl, cyano, or C1-C4 alkyl, and the C3-C6 cycloalkyl is unsubstituted or substituted with one substituent selected from cyano. Preferably, R 7 is selected from hydrogen, methyl, acetyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methoxycarbonyl, ethoxycarbonyl, N-methoxy-N-methyl-carbonyl, methylaminocarbonyl, dimethylaminocarbonyl, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, [4-(trifluoromethyl)pyrazol-1-yl], [3-(trifluoromethyl)pyrazol-1-yl], (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), (5-chloropyrazol-1-yl), (5-fluoropyrazol-1-yl), (3,5-dimethylpyrazol-1-yl), (5-methylpyrazol-1-yl), pyrazol-1-yl, cyclopropyl, or 1-cyanocyclopropyl. More preferably, R 7 is selected from hydrogen, methyl, acetyl, —C(CH3)═NOCH3, —C(CH3)═NOCH2CH3, —C(CH3)═NOH, phenyl, 4-cyanophenyl, pyrazol-1-yl, cyclopropyl, or 1-cyanocyclopropyl. Even more preferably, R 7is selected from hydrogen, methyl, cyclopropyl, or 1-cyanocyclopropyl.

[0050] In another embodiment, R 7 is selected from hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl. Preferably, R 7 is hydrogen, methyl, cyclopropyl, or 1-cyanocyclopropyl. Even more preferably, R 7 is hydrogen, methyl, or cyclopropyl. 7 is hydrogen or methyl. In another embodiment, R 7 is hydrogen. In yet another embodiment, R 7 is methyl.

[0051] In one embodiment of the present invention, R 8 and R 9 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy. 8 and R 9 are independently selected from hydrogen, halogen, methyl, methoxy, or cyano. More preferably, R 8 and R 9 are independently selected from hydrogen, methyl, chlorine, fluorine, bromine, or methoxy. Even more preferably, R 8 and R 9 is hydrogen or methoxy.

[0052] In another embodiment of the present invention, R 8 is selected from hydrogen, halogen, or cyano. More preferably, R 8 is hydrogen, cyano, or bromine. Even more preferably, R 8 is hydrogen.

[0053] In another embodiment, R 9is hydrogen, halogen, C1-C3 alkyl, C1-C2 haloalkyl, C1-C3 haloalkoxy, C1-C4 alkoxy, C1-C3 alkenyloxy, C1-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-C-C1-C2 alkyl-carbonimidoylhydroxy, C1-C2 alkylaminocarbonyl, di(C1-C2 alkylamino)carbonyl, trifluoromethylsulfonyloxy, cyano, carboxy, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyano is 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. Preferably, R 9is 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-methoxyethoxymethyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, 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, and R is selected from aryl, 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. 9is hydrogen, chloro, bromo, fluoro, methyl, methoxy, propoxy, allyloxy, methoxymethyl, 2-methoxyethoxymethyl, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, [4-(trifluoromethyl)pyrazol-1-yl], [3-(trifluoromethyl)pyrazol-1-yl], (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), (5-chloropyrazol-1-yl), (4- More preferably, R is selected from the group consisting of 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. 9 is hydrogen, chloro, fluoro, methyl or methoxy. Most preferably, R 9 is hydrogen or methoxy.

[0054] In one embodiment of the present invention, B 1 is CR 10 and B 2 is CR 11 or B 1 is N and B 2 is CR 11 or B 1 is CR 10 and B 2 is N. Preferably, B 1 is CR 10 and B 2 is CR 11 is.

[0055] In one embodiment of the present invention, R 10 and R 11are 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-diC 1-4 and R is selected from alkylamino, C1-C6 alkoxycarbonyl, C1-C4 alkylcarbonyl, N—C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C1-C4 alkyl-carbonimidoyl, hydroxy, trifluoromethylsulfonyloxy, carboxy, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein said 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms individually selected from N, O, or S, and 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. Preferably, R 10 and R 11is 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-methoxyethoxymethyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, 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, and R is selected from aryl, 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. 10 and R 11are independently hydrogen, chloro, bromo, fluoro, methyl, methoxy, propoxy, allyloxy, methoxymethyl, 2-methoxyethoxymethyl, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, [4-(trifluoromethyl)pyrazol-1-yl], [3-(trifluoromethyl)pyrazol-1-yl], (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), (5-chloropyrazol-1-yl), (3-chloropyrazol-1-yl), (5-

[0023] In some embodiments, the aryl group is selected from the group consisting of (4-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), (4-chloropyrazol-1-yl), pyrazol-1-yl, C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, cyclopropyl, and 1-cyanocyclopropyl.

[0056] In another embodiment, R 10 and R 11 are independently selected from hydrogen, halogen, C1-C3 alkyl, or C1-C4 alkoxy. 10 and R 11 are independently selected from hydrogen or halogen. More preferably, R 10 and R 11 is hydrogen.

[0057] In one embodiment of the present invention, A 1 is CR 12a , or N and A 2 is CR 13a , or N and A 3 is CR 14a , or N. Preferably, A 1 , A 2 , and A 3 At least two of A are selected from N. More preferably, A 1 , A 2 , and A 3 is N.

[0058] In one embodiment of the present invention, R 12a , R 13a and R 14a are independently selected from hydrogen, halogen, C1-C4 alkyl, C3-C6 cycloalkyl, or C1-C4 haloalkyl. 12a , R 13a and R 14a are independently selected from hydrogen, halogen, methyl, cyclopropyl, or trifluoromethyl. More preferably, R 12a , R 13a and R 14a is hydrogen.

[0059] In another embodiment, A 1 is CR 12a , or N, 2 is CR 13a , or N, 3 is CR 14a , or N, 1 , A 2 , and A 3 At least two of are selected from N and R 12a , R 13a , R 14a is hydrogen.

[0060] In one embodiment of the present invention, Z 1is selected from C1-C4 alkyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5- to 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms individually selected from N, O, or S; either the phenyl or the 5- to 6-membered heteroaryl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, C1-C4 alkynyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, or C1-C4 alkylsulfonyl; and the 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.

[0061] In another embodiment, Z 1 is selected from C1-C3 alkyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5- to 6-membered heteroaryl contains 1, 2, or 3 heteroatoms individually selected from N, O, or S; either the phenyl or the 5- to 6-membered heteroaryl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from fluoro, chloro, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl; and the C3-C6 cycloalkyl is unsubstituted or substituted with 1 or 2 substituents selected from methyl.

[0062] In another embodiment, Z 1is selected from C1-C3 alkyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6 cycloalkyl, where the 5- to 6-membered heteroaryl contains one heteroatom selected from N, O, or S, and either the phenyl or the 5- to 6-membered heteroaryl is unsubstituted or substituted with one or two substituents independently selected from fluoro, chloro, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and the C3-C6 cycloalkyl is unsubstituted or substituted with one or two substituents selected from methyl. Preferably, Z 1 are 1-methylpyrazol-4-yl, 2,3,4-trifluorophenyl, 2,3-difluorophenyl, 3,4-difluorophenyl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2-pyridyl, 2-fluoro-4-methoxyphenyl, 2-fluoro-4-methylsulfonyl-phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3,5-difluoro-2-furyl, 3-fluoro-4-furyl, 4-fluorophenyl, 3,5-difluoro-2-furyl, 4-fluorophenyl, 3,5-difluoro-2-furyl, 4-fluorophenyl, 3,5-difluoro-2-furyl, 4-fluorophenyl, 3,5-difluoro-2-furyl, 4-fluorophenyl, 4-fluorophenyl, 3,5-difluoro-2-furyl, 4-fluorophenyl, 4-fluorophenyl, 4-fluorophenyl, 4-fluorophenyl, 4-fluorophenyl, 4-fluorophenyl, 4-fluorophenyl, 4-fluorophenyl, 4-furyl ... More preferably, Z is selected from the group consisting of 2-fluoro-2-furyl, 5-fluoro-2-furyl, 3,5-difluoro-2-thienyl, 3-fluoro-2-thienyl, 5-fluoro-2-thienyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3-methoxyphenyl, 4-ethynyl-2-fluoro-phenyl, 4-fluoro-2-methoxy-phenyl, cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, n-propyl, and phenyl. 1is selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2-chlorophenyl, 2-fluorophenyl, 3,5-difluoro-2-pyridyl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-fluorophenyl, 3-methylphenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, 4-methylphenyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, or phenyl. Even more preferably, Z 1 is selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 3,5-difluoro-2-pyridyl, 2,4-difluorophenyl, 2-fluorophenyl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, cyclobutyl, cyclohexyl, cyclopentyl, or phenyl. Even more preferably, Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, 4-fluorophenyl, or phenyl.

[0063] In another embodiment of the present invention, Z 1 is selected from C1-C4 alkyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5- to 6-membered heteroaryl contains 1, 2, or 3 heteroatoms individually selected from N, O, or S, and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy, and wherein the C3-C6 cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen or C1-C4 alkyl. Preferably, Z 1is selected from phenyl or 5- to 6-membered heteroaryl, wherein the 5- to 6-membered heteroaryl contains one heteroatom selected from N or S, and the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with one or two substituents independently selected from fluoro, chloro, C1-C4 alkyl, or C1-C4 alkoxy. More preferably, Z 1 is selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2-pyridyl, 2-fluorophenyl, 3,5-difluoro-2-furyl, 3-fluoro-2-furyl, 5-fluoro-2-furyl, 3,5-difluoro-2-thienyl, 3-fluoro-2-thienyl, 5-fluoro-2-thienyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, cyclobutyl, cyclohexyl, cyclopentyl, or methyl. Even more preferably, Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2-pyridyl, 3,5-difluoro-2-furyl, 3-fluoro-2-furyl, 5-fluoro-2-furyl, 3,5-difluoro-2-thienyl, 3-fluoro-2-thienyl, 5-fluoro-2-thienyl, 2-fluorophenyl, 4-fluorophenyl, or phenyl.

[0064] In another embodiment of the present invention, Z 1is selected from phenyl, 5- to 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains one heteroatom selected from N or S, and the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with one or two substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy, and the C3-C6 cycloalkyl is unsubstituted or substituted with one substituent selected from halogen or C1-C4 alkyl. Preferably, Z 1 is selected from phenyl or 5- to 6-membered heteroaryl, wherein said 5- or 6-membered heteroaryl contains one heteroatom selected from N or S, and said phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with one or two substituents independently selected from fluoro, chloro, C1-C4 alkyl, or C1-C4 alkoxy.

[0065] In the present invention, therefore, R as defined above 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 , B 2 , A 1 , A 2 , A 3 and Z 1 Compounds of formula (I) having all combinations / sequences of:

[0066] The embodiments according to the present invention are as follows.

[0067] In one embodiment of the present invention, a compound of formula (I) R 1 is selected from hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, or C3-C6 cycloalkyl; R2 is selected from hydrogen, halogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C1-C4 alkylcarbonyl, N—C1-C4 alkoxy-C—C1-C4 alkyl-carbonimidoyl, N-hydroxy-C—C1-C4 alkyl-carbonimidoyl or C1-C6 alkoxycarbonyl; R 3 and R 4 are independently selected from hydrogen, halogen, or C1-C6 alkyl; R 5 and R 6 are independently selected from hydrogen or C1-C6 alkyl; R 7 is selected from hydrogen, C1-C6 alkyl, C1-C6 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimidoyl, C1-C6 alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C6 alkylaminocarbonyl, di(C1-C6 alkylamino)carbonyl, phenyl, 5- to 6-membered heteroaryl, and C3-C6 cycloalkyl, wherein the 5- to 6-membered heteroaryl is independently selected from N, O, or S. wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, cyano, carboxy, C1-C4 alkyl, and C1-C4 alkoxy; and the C3-C6 cycloalkyl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, cyano, C1-C4 alkyl, and C1-C4 alkoxy; B 1 But, CR 10 and N, B 2 But, CR 11 and N, R 8 , R 9 , R 10 and R 11are independently hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, NC 1-4 Alkylamino, N,N-diC 1-4 selected from alkylamino, C1-C6 alkoxycarbonyl, C1-C4 alkylcarbonyl, N—C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C1-C4 alkyl-carbonimidoyl, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, amino, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S, and 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; A 1 But, CR 12a or N; A 2 But, CR 13a or N; A 3 But, CR 14a or N; R 12a , R 13a and R 14a are independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, or C2-C4 alkynyl; Z 1is selected from C1-C4 alkyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms individually selected from N, O, or S, and wherein either of said phenyl, 5- or 6-membered heteroaryl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, and C2-C4 alkynyl, and wherein the C3-C6 cycloalkyl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, and C1-C4 alkoxy. or an agrochemically acceptable salt, stereoisomer, or N-oxide thereof.

[0068] In one embodiment, in the compounds of formula (I) according to the present invention, During the ceremony, R 1 is hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or C3-C6 cycloalkyl; R 2 is hydrogen, halogen, or C1-C4 alkyl; R 3 and R 4 are independently selected from hydrogen, halogen, or C1-C4 alkyl; R 5 and R 6 is independently selected from hydrogen and C1-C4 alkyl; R 7 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, wherein the C3-C6 cycloalkyl is unsubstituted or substituted with one substituent selected from halogen, C1-C4 haloalkyl, cyano, C1-C4 alkyl, or C1-C4 alkoxy; B 1 But, CR10 , and N; B 2 But, CR 11 , and N; R 8 and R 9 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; R 10 and R 11 are independently selected from hydrogen, halogen, C1-C3 alkyl, or C1-C4 alkoxy; A 1 But, CR 12a or N; A 2 But, CR 13a or N; A 3 But, CR 14a or N; R 12a , R 13a and R 14a are independently selected from hydrogen, halogen, C1-C4 alkyl, C3-C6 cycloalkyl, or C1-C4 haloalkyl; Z 1 is phenyl, a 5- to 6-membered heteroaryl, or a C3-C6 cycloalkyl, wherein the 5- to 6-membered heteroaryl contains one heteroatom selected from N and S, and wherein the phenyl and the 5- to 6-membered heteroaryl are unsubstituted or substituted with one or two substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy, and the C3-C6 cycloalkyl is unsubstituted or substituted with one substituent selected from halogen or C1-C4 alkyl.

[0069] In one embodiment of the present invention, the compound of formula (I) is a compound of formula (II): [ka] (In the formula, R 1 , R2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B 2 and Z 1 is as defined for the compounds of formula (I) according to the invention, A, [ka] is selected from: [ka] indicates a bond to a C(=O) group, and an asterisk ( * ) but Z 1 indicates the nitrogen with a bond to the group, R 12a , R 13a and R 14a are independently selected from hydrogen, halogen, C1-C4 alkyl, C3-C6 cycloalkyl, or C1-C4 haloalkyl.

[0070] In one embodiment of the present invention, R 12a , R 13a and R 14a is independently selected from hydrogen, halogen, methyl, cyclopropyl, or trifluoromethyl.

[0071] In another embodiment of the present invention, R 12a , R 13a and R 14a is hydrogen.

[0072] Preferably, in the compound of formula (II), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and Z 1is as defined for compounds of formula (I) according to the invention, A is selected from A1, A2, A3, A4, A5, A6, A7, or A8, and R 12 , R 13 and R 14 is hydrogen, and B 1 is CR 10 and B 2 is CR 11 and R 10 and R 11 is as defined for the compounds of formula (I) according to the invention.

[0073] More preferably, in the compound of formula (II), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and Z 1 is as defined for compounds of formula (I) according to the invention, A is selected from A1, A2, A3, A4, A5, A6, A7, or A8, and R 12 , R 13 and R 14 is hydrogen, and B 1 is CH and B 2 is CH.

[0074] In one embodiment of the present invention, in the compound of formula (II), A is [ka] is selected from: [ka] indicates a bond to a C(=O) group, and an asterisk ( * ) but Z 1 The nitrogen with the bond to the group is shown.

[0075] In a preferred embodiment of the present invention, in the compound of formula (II), A is [ka] is selected from: [ka] indicates a bond to a C(=O) group, and an asterisk ( * ) but Z 1 The nitrogen with the bond to the group is shown.

[0076] Preferably, in the compound of formula (II), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the invention, A is selected from A1, A2 or A3, B 1 is CR 10 and B 2 is CR 11 and R 10 and R 11 is as defined for the compounds of formula (I) according to the invention.

[0077] More preferably, in the compound of formula (II), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and Z 1 is as defined in the compounds of formula (I) according to the present invention, A is selected from A1, A2 or A3, B 1 is CH and B 2 is CH.

[0078] Even more preferably, in the compound of formula (II), R 1 , R 2 , R3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the invention, A is selected from A1 or A2, B 1 is CH and B 2 is CH.

[0079] In one embodiment of the present invention, in the compound of formula (II), A is [ka] is selected from: [ka] indicates a bond to a C(=O) group, and an asterisk ( * ) but Z 1 The nitrogen with the bond to the group is shown.

[0080] In one embodiment of the present invention, the compound of formula (II) is B 1 and B 2 Compounds of formula (II-A), wherein is CH and A is as defined for compound (II): [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the invention).

[0081] In a variant of this embodiment of the invention, the compound of formula (II-A) is B 1 and B 2is CH and R 3 , R 5 , R 6 is hydrogen and A is as defined for compound (II): [ka] (In the formula, R 1 , R 2 , R 4 , R 7 , R 8 , R 9 and Z 1 are as defined for the compounds of formula (I) according to the present invention).

[0082] Preferably, in the compound of formula (II-A1) of the present invention, R 1 is C1-C4 alkyl, preferably methyl, ethyl, or isopropyl; R 2 is hydrogen, fluorine, chlorine, or methyl; R 4 is hydrogen or methyl, R 7 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 8 and R 9 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; A is as defined for compound (II), and Z 1 is defined for the compounds of formula (I) according to the invention.

[0083] Preferably, in the compound of formula (II-A1) of the present invention, R 1 is C1-C4 alkyl, preferably methyl, ethyl, or isopropyl; R 2 is hydrogen, fluorine, chlorine, or methyl; R 4 is hydrogen or methyl, R 7 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 8 and R 9 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; A is selected from A1 or A2; Z 1 is defined for the compounds of formula (I) according to the invention.

[0084] Preferably, in the compound of formula (II-A1) of the present invention, R 1 is C1-C4 alkyl, preferably methyl, ethyl, or isopropyl; R 2 is hydrogen, fluorine, chlorine, or methyl; R 4 is hydrogen or methyl, R 7 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 8 and R 9 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; A is selected from A1 or A2; Z 1 is phenyl, a 5- to 6-membered heteroaryl, or a C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains one heteroatom selected from N or S, and the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with one or two substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy, and the C3-C6 cycloalkyl is unsubstituted or substituted with one substituent selected from halogen or C1-C4 alkyl.

[0085] In one embodiment of the present invention, the compound of formula (II) is B 1 and B2 is CH and A is A1 [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and Z 1 are as defined for the compounds of formula (I) according to the present invention).

[0086] In a variant of this embodiment of the invention, the compound of formula (II-B) is B 1 and B 2 is CH and R 3 , R 5 , R 6 is hydrogen and A is A1 [ka] (In the formula, R 1 , R 2 , R 4 , R 7 , R 8 , R 9 and Z 1 are as defined for the compounds of formula (I) according to the present invention).

[0087] Preferably, in the compound of formula (II-B1) of the present invention, R 1 is C1-C4 alkyl, preferably methyl, ethyl, or isopropyl; R 2 is hydrogen, fluorine, chlorine, or methyl; R 4 is hydrogen or methyl, R 7 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R8 and R 9 are independently selected from hydrogen, halogen, cyanoC1-C4 alkyl, or C1-C4 alkoxy; Z 1 is defined for the compounds of formula (I) according to the invention.

[0088] Preferably, in the compound of formula (II-B1) of the present invention, R 1 is C1-C4 alkyl, preferably methyl, ethyl, or isopropyl; R 2 is hydrogen, fluorine, chlorine, or methyl; R 4 is hydrogen or methyl, R 7 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 8 and R 9 are independently selected from hydrogen, halogen, cyanoC1-C4 alkyl, or C1-C4 alkoxy; Z 1 is phenyl, a 5- to 6-membered heteroaryl, or a C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains one heteroatom selected from N or S, and the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with one or two substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy, and the C3-C6 cycloalkyl is unsubstituted or substituted with one substituent selected from halogen or C1-C4 alkyl.

[0089] In one embodiment of the present invention, the compound of formula (II) is B 1 and B 2 Compounds of formula (II-C), wherein is CH and A is A2: [ka] (In the formula, R 1 , R2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the invention).

[0090] In a variant of this embodiment of the invention, the compound of formula (II-C) is B 1 and B 2 is CH and R 3 , R 5 , R 6 is hydrogen and A is A2 [ka] (In the formula, R 1 , R 2 , R 4 , R 7 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the invention).

[0091] Preferably, in the compound of formula (II-C1) of the present invention, R 1 is C1-C4 alkyl, preferably methyl, ethyl, or isopropyl; R 2 is hydrogen, fluorine, chlorine, or methyl; R 4 is hydrogen or methyl, R 7 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 8 and R 9 are independently selected from hydrogen, halogen, cyanoC1-C4 alkyl, or C1-C4 alkoxy; Z 1 is defined for the compounds of formula (I) according to the invention.

[0092] Preferably, in the compound of formula (II-C1) of the present invention, R 1 is C1-C4 alkyl, preferably methyl, ethyl, or isopropyl; R 2 is hydrogen, fluorine, chlorine, or methyl; R 4 is hydrogen or methyl, R 7 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 8 and R 9 are independently selected from hydrogen, halogen, cyanoC1-C4 alkyl, or C1-C4 alkoxy; Z 1 is phenyl, a 5- to 6-membered heteroaryl, or a C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains one heteroatom selected from N or S, and the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with one or two substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy, and the C3-C6 cycloalkyl is unsubstituted or substituted with one substituent selected from halogen or C1-C4 alkyl.

[0093] In one embodiment of the present invention, the compound of formula (II) is B 1 and B 2 Compounds of formula (II-D), wherein is CH and A is A3: [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and Z 1is as defined for the compounds of formula (I) according to the invention).

[0094] In a variant of this embodiment of the invention, the compound of formula (II-D) is B 1 and B 2 is CH and R 3 , R 5 , R 6 is hydrogen and A is A3: [ka] (In the formula, R 1 , R 2 , R 4 , R 7 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the invention).

[0095] Preferably, in the compound of formula (II-D1) of the present invention, R 1 is C1-C4 alkyl, preferably methyl, ethyl, or isopropyl; R 2 is hydrogen, fluorine, chlorine, or methyl; R 4 is hydrogen or methyl, R 7 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 8 and R 9 are independently selected from hydrogen, halogen, cyanoC1-C4 alkyl, or C1-C4 alkoxy; Z 1 is defined for the compounds of formula (I) according to the invention.

[0096] Preferably, in the compound of formula (II-D1) of the present invention, R 1 is C1-C4 alkyl, preferably methyl, ethyl, or isopropyl; R 2 is hydrogen, fluorine, chlorine, or methyl; R 4 is hydrogen or methyl, R 7 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 8 and R 9 are independently selected from hydrogen, halogen, cyanoC1-C4 alkyl, or C1-C4 alkoxy; Z 1 is phenyl, a 5- to 6-membered heteroaryl, or a C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains one heteroatom independently selected from N or S, and the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with one or two substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy, and the C3-C6 cycloalkyl is unsubstituted or substituted with one substituent selected from halogen or C1-C4 alkyl.

[0097] The following intermediates are novel and as such form additional aspects of the invention.

[0098] According to a sixth aspect of the present invention, there is provided an intermediate compound of formula (III): [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B 2 is defined for the compounds of formula (I) according to the invention) or a salt thereof.

[0099] The intermediate compound of formula (III) is R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B 2 have the same definitions and corresponding preferences as for the compounds of formula (I) according to the invention.

[0100] 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.

[0101] According to a seventh aspect of the present invention, there is provided an intermediate compound of formula (IV): [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B 2 is defined for the compounds of formula (I) according to the present invention.

[0102] The intermediate compound of formula (IV) is R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B 2 have the same definitions and corresponding preferences as for the compounds of formula (I) according to the invention.

[0103] The possible presence of one or more asymmetric carbon atoms in the compounds of formula (IV) according to the invention means that the compounds can occur in chiral isomeric forms, ie enantiomeric or diastereomeric forms.

[0104] According to an eighth aspect of the present invention, there is provided an intermediate compound of formula (IIb): [ka] (In the formula, R 0 is C1-C6 alkyl, and A 1 , A 2 , A 3 and Z 1 is defined for the compounds of formula (I) according to the invention) or a salt thereof.

[0105] The intermediate compound of formula (IIb) 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.

[0106] In one embodiment, R 0 is a C1-C4 alkyl, and A 1 , A 2 , A 3 is N and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0107] In one embodiment, the compound of formula (IIb) is a compound of formula (IIb-1): [ka] (In the formula, Z 1 is as defined for the compounds of formula (I) according to the invention, and R 0is as defined for compounds of formula (IIb), and A is selected from A1, A2, A3, A4, A5, A6, A7, or A8 as defined above for compounds of formula (II).

[0108] Preferably, in the compound of formula (IIb-1), A is selected from the following: [ka] During the ceremony, [ka] indicates a bond to a C(=O) group, and an asterisk ( * ) but Z 1 indicates a nitrogen having a bond to a group, Z 1 is as defined for the compounds of formula (I) according to the invention, and R 0 is as defined for compounds of formula (IIb).

[0109] More preferably, in the compound of formula (IIb-1), A is selected from A1 or A2, and Z 1 is as defined for the compounds of formula (I) according to the invention, and R 0 is as defined for compounds of formula (IIb).

[0110] In another embodiment of the present invention, in the compound of formula (IIb-1), A is A1 and Z 1 is as defined for the compounds of formula (I) according to the invention, and R 0 is as defined for compounds of formula (IIb).

[0111] The presence of one or more possible asymmetric carbon atoms in any of the compounds selected from the compounds of formula (I), (II), (IIA), (II-A1), (II-B), (II-B1), (II-C), (II-C1), (II-D), or (II-D1) according to the present invention, or the compounds selected from the compounds listed in Tables A-1 to A-24, or Table P (below), means that the compounds can exist in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms.

[0112] More preferably, the compound of formula (I) according to the present invention is selected from the compounds listed in any one of Tables A-1 to A-24.

[0113] Even more preferably, the compounds of formula (I) according to the present invention are selected from the compounds listed in Table P (below).

[0114] In one embodiment of the present invention, the compound of formula (I) is selected from: [1-(2-fluorophenyl)pyrazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(2,4-difluorophenyl)pyrazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(2-fluorophenyl)pyrazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2,5-dimethyl-1-(2,2,2-trifluoroethyl)pyrrol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, (1,5-dimethylpyrazol-3-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, (2-phenyltriazol-4-yl)-[4-(1,3,5-trimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, (1-phenyltriazol-4-yl)-[4-(1,3,5-trimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(2,4-difluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(4-fluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(1-phenylimidazol-4-yl)methanone, [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(1-phenyltriazol-4-yl)methanone, [2,5-dimethyl-1-(5-methylisoxazol-3-yl)pyrrol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, (1-benzyltriazol-4-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone, (1-isopropyltriazol-4-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(1-phenylpyrazol-3-yl)methanone, [1-(4-fluorophenyl)-5-methyl-triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2-(4-fluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(1-phenyl-1,2,4-triazol-3-yl)methanone, (1-tert-butylimidazol-4-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(4-fluorophenyl)pyrazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, (5-cyclopropyl-1-methyl-pyrazol-3-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(3-fluoro-2-pyridyl)-1,2,4-triazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(3-fluorophenyl)-3-methyl-pyrazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, (5-benzyl-1-methyl-pyrazol-3-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-[1-[5-(trifluoromethyl)-2-pyridyl]triazol-4-yl]methanone, [1-(2-methoxyphenyl)imidazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, (5-cyclopropyl-1-ethyl-pyrazol-3-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(2,6-difluorophenyl)pyrazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(3,4-difluorophenyl)pyrazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone, [1-(2,4-difluorophenyl)-1,2,4-triazol-3-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2-(2,4-difluorophenyl)tetrazol-5-yl]-[6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone, [(1R,4R)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone, [(1S,4S)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone, [2-(2,4-difluorophenyl)tetrazol-5-yl]-[(1S,4S)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2(2,4-difluorophenyl)tetrazol-5-yl]-[(1R,4R)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2-(2,4-difluorophenyl)triazol-4-yl]-[rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(2,4-difluorophenyl)triazol-4-yl]-[rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone, or [2-(2,4-Difluorophenyl)tetrazol-5-yl]-[rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone.

[0115] In a preferred embodiment of the invention, the compound of formula (I) is selected from: [(1S,4S)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[1-(2,4-difluorophenyl)triazol-4-yl]methanone, [(1S,4S)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[1-(3,5-difluoro-2-pyridyl)triazol-4-yl]methanone, [1-(3,5-difluoro-2-pyridyl)triazol-4-yl]-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2-(2,4-difluorophenyl)tetrazol-5-yl]-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(3,5-difluoro-2-pyridyl)triazol-4-yl]-[rac-(1S,4S)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(3,5-difluoro-2-pyridyl)triazol-4-yl]-[(1S,4S)-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [(1S,4S)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[2-(2,4-difluorophenyl)tetrazol-5-yl]methanone, [1-(2,4-difluorophenyl)triazol-4-yl]-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone, [2-(2,4-Difluorophenyl)tetrazol-5-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone, [(1S,4S)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone, [1-(2,4-difluorophenyl)triazol-4-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2-(2,4-difluorophenyl)tetrazol-5-yl]-[6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2-(2,4-difluorophenyl)tetrazol-5-yl]-[(1S,4S)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [(1R,4R)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone, [1-(3,5-difluoro-2-pyridyl)triazol-4-yl]-[(1R,4R)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [(1R,4R)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[1-(2,4-difluorophenyl)triazol-4-yl]methanone, (1-phenyltriazol-4-yl)-[4-(1,3,5-trimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(1-phenyltriazol-4-yl)methanone, [2-(4-fluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2-(2,4-difluorophenyl)triazol-4-yl]-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [(1S,4S)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[2-(2,4-difluorophenyl)triazol-4-yl]methanone, or [2-(2,4-Difluorophenyl)tetrazol-5-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone.

[0116] 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).

[0117] Compounds of formula (I) according to the present invention can be formed as shown in Schemes 1-19 below, where, unless otherwise specified, the definition of each variable is as defined above for compounds of formula (I).

[0118] In particular, R 4 and R 6 is hydrogen and R 5 is hydrogen or methyl 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).

[0119] In any of the following schemes 1 to 19, 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. enantiomeric or diastereomeric forms.

[0120] The compound of formula (I) can be prepared by a person skilled in the art according to known methods. More specifically, the compound of formula (I) can be prepared by reacting a compound of formula (III) or a salt thereof (wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I)) to a compound of formula (II) 1 , A 2 , A 3 and Z 1 can be prepared by reaction of a methyl group with a methyl group, which is as defined above for compounds of formula (I). This reaction is shown in Scheme 1. [ka] Scheme 1

[0121] In Scheme 1, a compound of formula (II) 1 , A 2 , A 3 and Z 1 where X is as defined above for compounds of formula (I), can be activated to compounds of formula (IIa) by methods known to those skilled in the art and described, for example, in Tetrahedron 2005, 61(46), 10827-10852. For example, compounds of formula (IIa) (where X 0is a halogen) is formed by treating a compound of formula (II) with, for example, oxalyl chloride or thionyl chloride in an inert solvent such as methylene dichloride or tetrahydrofuran (THF) in the presence of a catalytic amount of N,N-dimethylformamide (DMF) at a temperature between 20°C and 100°C, preferably 25°C. Compounds of formula (IIa) can be converted to compounds of formula (III) (wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I), optionally in the presence of a base such as triethylamine or pyridine, to provide compounds of formula (I). Alternatively, compounds of formula (I) can be prepared by treatment of compounds of formula (II) with dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) or 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU) in an inert solvent such as pyridine, DMF, acetonitrile, CHCl, or THF, optionally in the presence of a base such as triethylamine, at a temperature between 30° C. and 180° C. to provide activated compounds of formula (IIa), where X 0 However, as described below, G 01 , G 02 , or G 03 Finally, compounds of formula (II) can be activated by reaction with a coupling reagent such as propanephosphonic anhydride (T3P), as described, for example, in Synthesis 2013, 45, 1569, to give compounds of formula (IIa) (wherein X 0 However, as described below, G 04 Further reaction of the compound of formula (III) with an amine (or a salt thereof) provides the compound of formula (I). [ka]

[0122] Compounds of formula (II) can be converted by ester hydrolysis to compounds of formula (IIb) (wherein A 1 , A 2 , A 3 is N and Z 1 is as described in formula (I), and R 0 where R is C1-C4 alkyl). Various conditions can be used, for example, aqueous sodium hydroxide or aqueous lithium hydroxide and THF, or dimethoxyethane, or methanol, or an organic water-miscible solvent such as ethanol. Such ester hydrolysis is well known to those skilled in the art. Compounds of formula (IIb) can also be directly converted to compounds of formula (I) by reacting compounds of formula (IIb) with compounds of formula (III) in the presence of trimethylaluminum or trimethylaluminum-DABCO complex in an inert solvent such as toluene or methylene chloride. Such reactions have been reported in the literature (see Tetrahedron Lett. 1977, 4171-4174, and Tetrahedron Lett. 2006, 5767-5769, and references cited therein). Compounds of formula (II) and (IIb) are commercially available or can be synthesized as described below.

[0123] A compound of formula (IIIa) 4 and R 6 is hydrogen and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B 2 where R is as defined above for compounds of formula (I), can be prepared by one skilled in the art according to known methods.

[0124] For example, a compound of formula (IIIa) 4 and R 6 is hydrogen and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I), can be prepared by reacting a compound of formula (IVa) 4 and R 6 is hydrogen and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B 2 (wherein H is as defined above for compounds of formula (I)) by treatment with a reducing agent such as NaBHCN and an acid, for example, hydrochloric acid or acetic acid, in a protic solvent such as methanol or ethanol. Such reactions are well known in the literature, and similar reactions are described, for example, in Deng, Zeping et al., Chinese Patent No. CN103772278 and Synthesis 1979, 4, 281-3. Alternatively, compounds of formula (IIIa) can be prepared from compounds of formula (IVa) by reduction with hydrogen in the presence of a suitable metal catalyst, such as Pd, Ir, or Rh, with a suitable ligand, for example, a diphosphine [1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), or 1,4-bis(diphenylphosphino)butane (dppb)]. A similar reaction has been reported, for example, in Reaction Kinetics and Catalysis Letters 2007, 92, 99-104. This reaction is shown in Scheme 2. [ka] Scheme 2

[0125] Alternatively, compounds of formula (IIIa) can be prepared as shown in Scheme 3.

[0126] As shown in Scheme 3, a compound of formula (IIIb) (wherein R 4 , R 6 and R 7 is hydrogen and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I), can be converted to compounds of formula (VI) (wherein X 0 is a leaving group such as a halogen, and R 0 is C1-C6 alkyl) to give a compound of formula (V), 4 , R 6 and R 7 is hydrogen and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I). Alternatively, compounds of formula (V) can be converted to compounds of formula (R 0 CO)2O(wherein, R 0is C1-C6 alkyl) in an inert solvent such as methylene chloride, THF, or 2-methyl-THF, optionally in the presence of a base such as triethylamine or dimethylaminopyridine, at a temperature between 0°C and 60°C. Compounds of formula (V) are then metallated with a base, for example, an alkyl metal base such as tert-butyllithium, and an additive such as N,N,N',N'-tetramethylethylenediamine (TMEDA), in an inert polar solvent such as THF or 2-methyl-THF, at low temperatures, for example, -78°C to room temperature. X -X 0 an electrophile of formula X 0 is as already defined, and R X is C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4 alkylaminocarbonyl, di(C1-C4 alkylamino)carbonyl or C3-C6 cycloalkyl, wherein C3-C6 cycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkoxy, to give a compound of formula (Va), wherein R 4 and R 6 is hydrogen and R 5 is hydrogen or methyl, and R 0 is C1-C6 alkyl, and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I). This reaction is shown in Scheme 3. [ka] Scheme 3

[0127] Compounds of formula (Va) can be prepared by methods known to those skilled in the art from compounds of formula (IIIa) (wherein R 4 and R 6 is hydrogen and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I). For example, a compound of formula (Va) 0 is tert-butyl) can be treated with an organic or inorganic acid such as trifluoroacetic acid or HCl to provide a compound of formula (IIIa). This reaction is shown in Scheme 4. [ka] Scheme 4

[0128] A compound of formula (IVa) 4 and R 6 is hydrogen and R 5が、 hydrogen or methyl, R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I), can be converted to compounds of formula (VIII), wherein R 1 , R 2 and R 3 is as defined above for compounds of formula (I), and X 0 is a halogen, preferably chlorine, bromine or iodine, with a compound of formula (VII) 5 is hydrogen or methyl, and R 7 , R 8 , R 9 , B 1and B 2 can be prepared by reacting (as defined above for compounds of formula (I)) with (as defined above for compounds of formula (I)). This reaction is shown in Scheme 5. [ka] Scheme 5

[0129] The Suzuki-Miyaura cross-coupling reaction of a compound of formula (VIII) with a compound of formula (VII) is well known to those skilled in the art and is typically carried out in the presence of a palladium catalyst such as tetrakis(triphenylphosphine)-palladium(0) or [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane complex and a base such as sodium carbonate or potassium carbonate, in a solvent such as N,N-dimethylformamide, dioxane, or a dioxane-water mixture, at a temperature between room temperature and 160°C, optionally under microwave heating conditions, and preferably under an inert atmosphere. Such reactions are reviewed, for example, in J. Organomet. Chem. 1999, 576, 147-168. Those skilled in the art will also recognize that the reaction is reversible, i.e., the reaction of a compound of formula (X) (wherein R 1 , R 2 and R 3 is as defined above for compounds of formula (I)) and a compound of formula (IX) 5 is hydrogen or methyl, and R 7 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I), and X 0 is a halogen, preferably chlorine, bromine or iodine, to give a compound of formula (IVa), 4 and R 6 is hydrogen and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B2 It will be appreciated that the reaction can result in a methyl group (which is as defined above for compounds of formula (I)). This reaction is shown in Scheme 6. [ka] Scheme 6

[0130] Further cross-coupling chemistry, i.e., C—H activation, can also be used to give compounds of formula (IVa), where R 4 and R 6 is hydrogen and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B 2 (wherein R is as defined above for compounds of formula (I)) can also be used in the preparation of (Scheme 7). [ka] Scheme 7

[0131] As shown in Scheme 7, a compound of formula (IX) (wherein R 5 is hydrogen or methyl, and R 7 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I), and X 0 is a halogen, preferably chlorine, bromine or iodine, can be reacted with a compound of formula (XI) (wherein R is a palladium catalyst, typically palladium acetate Pd(OAc)2, in the presence of a suitable ligand, for example 1,10-phenanthroline, in the presence of a base such as cesium carbonate or potassium carbonate, in an inert solvent such as chlorobenzene, toluene or xylene, at a temperature between room temperature and 180°C, optionally under microwave heating conditions, preferably under an inert atmosphere. 1 , R 2 and R3 is reacted with (as defined above for compounds of formula (I)). Similar reactions have been reported in the literature, for example in Chemical Science 2013, 4, 2374-2379.

[0132] Compounds of formula (III) can also be prepared from compounds of formula (XVI) (Scheme 8). [ka] Scheme 8

[0133] As shown in Scheme 8, a compound of formula (III) can be prepared by condensing a compound of formula (XVI), where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I), and R 01 can be prepared by one skilled in the art by carbamate deprotection of a common carbamate protecting group substituent, such as methyl, tert-butyl, allyl, 2,2,2-trichloroethyl, or benzyl. 01 When is methyl, for example, a suitable solvent such as dichloromethane and a suitable reagent such as iodotrimethylsilane can be employed, and the product can be obtained by heating at room temperature to 200°C, preferably at 20°C to the boiling point of the reaction mixture, as described in J. Am. Chem. Soc. 1992, 114, 5959. The compound of formula (III) thus obtained is converted to a compound of formula (I) (Scheme 1).

[0134] A compound of formula (XVI) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R7 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I), and R 01 (wherein R is as defined above) can be prepared by the reaction of an aldehyde of formula (XV) (including formaldehyde in its various forms) (wherein R 7 is as defined above for compounds of formula (I)) and a compound of formula (XIV) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I), and R 01 (as described above) can be formed by the Pictet-Spengler reaction (Scheme 9). [ka] Scheme 9

[0135] The Pictet-Spengler reaction produces a compound of formula (XIV), where R 1 , R 2 , R 3 , R 8 , R 9 is as described in formula (I), and B 1 But, CR 10 and B 2 But, CR 11 and R 01 is as above) is stereospecific, i.e., compound of formula (XIVa) is converted into compound of formula (XVa) 7 is C1-C4 alkyl) to form a pyrazole ring and R 7This leads to a racemic compound of formula rac-syn-(XVIa) having a syn relationship with the substituents (Scheme 10). [ka] Scheme 10

[0136] A further consequence of the stereospecific formation of compounds of formula rac-syn-(XVIa) in the Pictet-Spengler reaction is that chiral compounds of formula (XVIa) can be obtained if the synthesis starts from an optically pure compound of formula (XIVa). This is the case when compounds of formula (XIV) (R 1 , R 2 is methyl, and R 8 , R 9 , R 11 , and R 11 is hydrogen and R 0 is methyl), i.e., (S)-(XIVb) and (R)-(XIVb), as shown in Scheme 11, and (XV)(R 7 After Pictet-Spengler reaction with (S,S)-syn-(XVIb) and (R,R)-syn-(XVIb), respectively, (S,S)-syn-(XVIb) and (R,R)-syn-(XVIb) are obtained. [ka] Scheme 11

[0137] A compound of formula (XIV) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I), wherein R 01as defined above) can be prepared by the reaction of an amine of formula (XIII) (wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , B 1 and B 2 can be prepared by reaction of a compound of formula (I) (as defined above for compounds of formula (I)) with a suitable protecting reagent such as methyl chloroformate (Scheme 12). [ka] Scheme 12

[0138] A compound of formula (XIII) or a salt thereof (wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , B 1 and B 2 where R is as defined above for compounds of formula (I), can be reacted with a nitrile of formula (XII), where R is a nitrile of formula (XII), in a suitable aprotic solvent such as tetrahydrofuran, as described, for example, in J. Org. Chem. 1981, 47, 3153. 1 , R 2 , R 3 , R 4 , R 8 , R 9 , B 1 and B 2(XII) can be prepared by one skilled in the art by reaction of the Grignard reagent R (where R is as defined above for the compound of formula (I)) with a suitable nucleophile such as (dimethylsulfide)dihydroboron (BMS). The nitrile of formula (XII) can also be reduced to a primary amine using hydrogen in the presence of a hydrogen donor, e.g., ethanol or methanol, in the presence of a catalyst such as a platinum salt or Raney nickel. Many additional conditions for reducing nitriles to primary amines are well known to those skilled in the art. Alternatively, the Grignard reagent R 5 MgBr or R 6 MgBr (wherein, R 5 and R 6 (wherein X is as defined above for compounds of formula (I)) may be added sequentially or simultaneously as a nucleophile to compounds of formula (XII) to allow the preparation of more highly substituted amines of formula (XIII). 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 This reaction is carried out in the presence of a Lewis acid such as Pr) (see Synlett (2007), (4), 652-654). This reaction is shown in Scheme 13. [ka] Scheme 13

[0139] A compound of formula (XII) 1 , R 2 , R 3 , R 4 , R 8 , R 9 , B 1 and B 2 where X 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 (XII) and intermediates thereto can be prepared from compounds of formula (XVII) as shown in Scheme 14. [ka] Scheme 14

[0140] For example, a compound of formula (XII) 1 , R 2 , R 3 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I), and R 4 is different from hydrogen) can be prepared by the reaction of a compound of formula (XIIa) (wherein R 1 , R 2 , R 3 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I), followed by the addition of a suitable alkylating agent R 4 -X(where R 4 is a C1-C4 alkyl and X is a halogen).

[0141] A compound of formula (XIIa) 4 is hydrogen and R 1 , R 2 , R 3 , R 8 , R 9 , B 1 and B 2 (wherein X is as defined above for compounds of formula (I)) can be prepared from alcohols of formula (XVII) by treatment with cyanotrimethylsilane (TMSCN) in the presence of a base such as lithium carbonate in a non-polar solvent such as dichloromethane 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 14.

[0142] A compound of formula (III)1 But, CR 10 and B 2 But, CR 11 and R 1a is C1-C4 alkyl, and R 2a is hydrogen, halogen or C1-C4 alkyl, and R 3 is hydrogen and R 4a , R 5a , R 6a , R 7a is hydrogen or C1-C4 alkyl, and R 8 , R 9 , R 10 , and R 11 is as defined previously in formula (I), i.e., a compound of formula (IIIc) [ka] Further synthesis of the compound of formula (XVIII) [ka] (In the formula, R 1a is C1-C4 alkyl, and R 2a is hydrogen, halogen or C1-C4 alkyl, and R 4a , R 5a , R 6a , R 7a is hydrogen or C1-C4 alkyl, and R 8 , R 9 , R 10 , and R 11 (wherein X is as defined above in formula (I)) can also be prepared by treating a compound of formula (IIIc) with a strong acid, such as sulfuric acid, hydrochloric acid, hydrobromic acid, trifluoroacetic acid, triflic acid, or methanesulfonic acid, or a Lewis acid, such as aluminum oxychloride or bismuth(III) triflate, in an inert solvent, such as chlorobenzene or nitrobenzene, at a temperature between 0°C and 180°C, to give a compound of formula (IIIc). These can be converted to a compound of formula (I) as described above. Those skilled in the art will appreciate that such cyclization can be carried out by treating a compound of formula (XIX) [ka] and (R 4a is methyl) a compound of formula (XX) [ka] It is understood that the compound can be prepared via intermediates such as the substituent R 1a , R 2a , R 3a , R 4a , R 5a , R 6a , R 7a , R 8 , R 8 , R 9 , R 10 and R 11 is as described above. Depending on the reaction conditions, these intermediates can be isolated and / or further directly converted to compounds of formula (IIIc). 7 It will be appreciated that when is a C1-C4 alkyl, mixtures of diastereomeric racemates (syn-IIIc) and racemates (anti-IIIc) can be obtained in controllable ratios such that one isomer is formed preferentially over the other (Scheme 15). [ka] Scheme 15

[0143] Compounds (XVIII), (XIX), and (XX) can be prepared as shown in Scheme 16 below and as described in the experimental section. [ka] Scheme 16

[0144] As shown in Scheme 16, a benzylamine of formula (XXI) is used to alkylate a compound of formula (XXII) in an inert solvent such as DMF or DMA in the presence of a base such as triethylamine (EtN). The compound (XXIII) thus obtained can be isolated or directly treated in situ with BOC-anhydride to give a compound of formula (XXIV). The compound of formula XXIV can be reduced with a hydride source (e.g., NaBH in MeOH / THF) to give the target molecule (XVIIIb), which can then be cyclized with, for example, camphorsulfonic acid in EtOAc to give a compound of formula (XIXb). Alternatively, the compound of formula (XXIV) can be converted to a Grignard reagent R in an inert ether solvent (e.g., THF). 4 MgBr to give a compound of formula (XVIIIa), which can be cyclized with, for example, camphorsulfonic acid in EtOAc to give a compound of formula (XIXa). In compounds (XIX) and (XVIII), R 1a is C1-C4 alkyl, and R 2a is hydrogen, halogen, or C1-C4 alkyl, and R 4a is hydrogen or C1-C4 alkyl, and R 5a , R 6a , and R 7a is hydrogen or C1-C4 alkyl, and R 8 , R 9 , R 10 , and R 11 is as previously defined for formula (I).

[0145] A further aspect of this Friedel-Crafts chemistry should also be noted. When chemistry is carried out starting from chiral amines (XXI), i.e., R 7a When R is C1-C4 alkyl, the stereochemistry is retained in the final compound of formula (I). 7 When is methyl, as shown below in Scheme 17: [ka] Scheme 17

[0146] Compounds of formula (XVII) can be prepared by methods known to those skilled in the art. Compounds of formula (XXI) and (XXII) can be readily prepared by those skilled in the art or are commercially available.

[0147] Compounds of formula II are either commercially available or can be synthesized as described below.

[0148] Compound (A) of formula (IIb) 1 , A 2 , A 3 is N and Z 1 is as described for the compounds of formula (I) of the present invention, and R 0 is C1-C6 alkyl), that is, the formula (IIba) [ka] is a diazonium salt of formula (XXV) [ka] (In the formula, Z 1 is as defined for the compounds of formula (I) of the present invention, and Y - However, depending on the conditions under which the diazotization step is carried out, a counter ion, e.g., Cl - Or BF4 - and a compound of formula (XXVI) [ka] (In the formula, R 0The compound of formula (XXV) defined immediately above can be prepared from a primary amine of formula (XXVII) by reaction with a diazotization reagent, such as a salt of nitrous acid, e.g., sodium nitrite. The solvent can be an aqueous solution of an acid, e.g., dilute hydrochloric acid or tetrafluoroboric acid. The counterion Y - is defined by the acid used. Diazotation reactions are commonly used in organic synthesis, even on an industrial scale, and are known to those skilled in the art.

[0149] To reduce the risk of decomposition of the intermediate of formula (XXV), the diazotization and cycloaddition steps can be carried out consecutively without the need to isolate (XXV). This variant is also described in Tetrahedron 2020, 76(14), 131063 (Scheme 18). [ka] Scheme 18

[0150] Compounds of formula (XXVII) are commercially available (e.g., R 0 is methyl, CAS [6832-16-2]).

[0151] Very similarly, compounds of formula (IIba) 1 , A 2 , A 3 is N and Z 1 is as described for formula (I)) can be converted into a compound of formula (XXVIII): [ka] (In the formula, R 0 is C1-C6 alkyl, and Ar 1 wherein R is phenyl or p-tolyl) can be reacted with a compound of formula (XXV) in the presence of a base, such as pyridine, at a temperature between −50° C. and 50° C. to give a compound of formula (IIba). Such a reaction has ample precedent in the literature, for example, Chem. Comm. 2017, 53(69), 9620-9623, Ang. Chem. Int. Ed. 2017, 56(47), 15044-15048, and J. Am. Chem. Soc. 2016, 138(44), 14609-14615. Compounds of formula (XXVIII) can be prepared as described in the above-mentioned literature and are exemplified in the preparative examples of the present application.

[0152] Alternatively, a compound of formula (IIba) 1 , A 2 , and A 3 is N and Z 1 is as defined in formula (I)) is a compound of formula (XXIX) [ka] (In the formula, A 1 , A 2 , and A 3 is N and R 0 is as defined above) with a boronic acid derivative of formula (XXX) [ka] (In the formula, Z 1 The Chan-Lam type coupling reaction is usually carried out in a solvent such as dichloromethane, in the presence of a catalytic amount of a copper-based catalyst, at a mild reaction temperature, in the presence of a base such as potassium carbonate, in the atmosphere or under oxygen. 1 , A 2 , and A 3It should be noted that , (wherein N is N) exists in tautomeric form, i.e. [ka]

[0153] Those skilled in the art will recognize that the coupling product of this reaction may be any one of the regioisomers or a mixture thereof, but by selecting the reaction conditions as described in J. Org. Chem. 2014, 79, 6703-6707, this reaction exhibits excellent regioselectivity for the compound of formula (IIba). Those skilled in the art will recognize that this Chan-Lam coupling is a general method for preparing the compound of formula (IIb). Compound of formula (IIbb) [ka] (In the formula, Z 1 , R 12a , and R 0 are as previously defined (see J. Med. Chem. 2018, 61, 8, 3370-3388 and WO 14 / 041106, 2014)), compounds of formula (IIbc) and (IIbd) [ka] (In the formula, Z 1 , R 12a , R 13a , R 14a , and R 0 is as defined in formula (I) (see WO 15 / 155626, 2015, EP 2390252, 2011)), and compounds of formula (IIbe) [ka] (In the formula, Z 1 , R 12a , R 13a , R 14a , and R 0is as defined by formula (I) (see J. Med. Chem. 2017, 60(14), 6166-6190, Org. Lett. 2008, 10(8), 1653-1655, and Bio. Med. Chem. Lett. 2009, 19(5), 1451-1456), examples of which are given in the literature as representative examples.

[0154] A compound of formula (IIba) 1 , A 2 , and A 3 is N and Z 1 A further method for the preparation of (wherein R is as defined in formula (I)) is shown in Scheme 19. [ka] Scheme 19

[0155] As shown in Scheme 19, the sequence involves diazotizing a compound of formula (XXVII) as previously described, followed by the addition of a compound of formula (XXXI) (wherein R 0 is C1-C6 alkyl) in the presence of a mild base, such as sodium acetate, to give a compound of formula (XXXII). 1 and R 0 (wherein R is as previously defined) is treated with aqueous ammonia in a miscible organic solvent, such as tetrahydrofuran or 2-methyltetrahydrofuran, at a temperature between 0°C and 30°C to give a compound of formula (XXXIII). Finally, the compound of formula (XXXIII) is diazotized with a salt of nitrous acid, such as sodium nitrite, in a weakly acidic medium, such as aqueous acetic acid or hydrochloric acid, at a temperature between -20°C and 0°C, whereupon the resulting diazonium salt spontaneously cyclizes to give the tetrazole compound of formula (IIba). The reaction sequence has been previously described in WO 13 / 087805, 2013.

[0156] The compound of formula (IIb) can be prepared by reacting a compound of formula (XXIX) [ka] with a compound of formula (XXXIV) [ka] (In the formula, Z 1 is as described above in formula I, and X 0 is a halogen, preferably chlorine, bromine, or iodine) in an inert aprotic or protic solvent in the presence of a base, for example, an alkaline earth metal base such as NaOH, KOH, LiOH, CsCO, or KCO. Such alkylation is well known to those skilled in the art and has been used in this context to prepare compounds of formula (IIb), for example, as described in WO 14 / 168221, WO 10 / 043000, and WO 14 / 32498. Those skilled in the art will understand that this can result in a mixture of regioisomeric compounds that can be separated by chromatographic techniques, or that pure isomers can be obtained by a gentle choice of conditions and additives (e.g., palladium catalysts for the so-called Buchwald amination). 1 Heteroaryl or aryl SnAr reactions (with or without copper catalysis) can be used to prepare compounds of formula (IIb) (see, e.g., Polyhedron 2019, 165, 22-30; U.S. Patent Application No. 18 / 0170909; Org. Lett. 2022, 24(20), 3620-3625; J. Org. Chem. 2017, 82(14), 7420-7427; Chem. Comm. 2021, 57(57), 7047-7050; ACS Catalysis 2019, 9(12), 10674-10679; Synthesis 2017, 49(23), 5120-5130; J. Org. Chem. 2019, 84(12), 8160-8167; and references cited therein).

[0157] 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.

[0158] 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.

[0159] 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).

[0160] 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.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] 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.

[0165] If the individual components have different biological activities, it may be advantageous to isolate or synthesize the respective more biologically active isomer, e.g., enantiomer or diastereomer, or isomeric mixture, e.g., enantiomeric or diastereomeric mixture.

[0166] 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.

[0167] The compounds of formula (I) have three chiral carbon atoms (three stereocenters, star-shaped ( * ) indicates a chiral carbon atom, and therefore eight stereoisomers are available. These eight stereoisomers consist of four sets of enantiomers. [ka]

[0168] The relationship between enantiomers and diastereomers for compounds of formula (I) is shown in Scheme 20.

[0169] Those skilled in the art will recognize that compounds of formula (I) (as shown in Scheme 20) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 , B 2 , A(A 1 , A 2 , A 3 ) and Z 1 It is well understood that these diastereomers and enantiomers of formula (I) are within the scope of the present invention. [ka] Scheme 20

[0170] 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.

[0171] As stated above, it has now been surprisingly 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.

[0172] 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 damaging 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, for example, from phytopathogenic microorganisms.

[0173] The present invention further relates to a method for controlling or preventing infestation 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.

[0174] 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.Control or modification effect includes 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.

[0175] For protection against fungal infections and phytopathogenic fungi occurring in the soil, the mixtures 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 dressed 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 the seeds with a solid formulation. This 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.

[0176] 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.

[0177] Additionally, the present invention can be used to protect non-living materials such as timber, wallboard and paint from fungal attack.

[0178] The compounds of formula (I) according to the invention are effective against, for example, disease-causing fungi and fungal vectors as well as plant pathogenic bacteria and viruses, such as, for example: Absidia corymbifera, Alternaria spp., Aphanomyces spp., Ascochyta spp., Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, Botryosphaeria spp. including Blumeria graminis, Bremia lactucae, B. dothidea, 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, Ceratocystis spp., Cercospora spp. including C. arachidicola, Cercosporidium personatum, and Cladosporium spp. spp.), Claviceps purpurea, Coccidioides immitis, Cochliobolus spp., C. masaeColletotrichum spp. including Colletotrichum musae, Cryptococcus neoformans, Diaporthe spp., Didymella 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, and Glomerella sigulate. cingulate, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium spp., Hemileia spp., Histoplasma spp. including H. capsulatum.), Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp., Monilinia spp., Mucor spp., Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae piceae, Penicillium spp. including Paracoccidioides spp., P. digitatum, P. italicum, Peronosclerospora spp. including Petriellidium spp., P. maydis, P. philippinensis and P. sorghi, Phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp. spp.), Phoma spp., Phomopsis viticola, Phytophthora spp. including P. infestans, Plasmopara spp. including P. halstedii, P. viticola, Pleospora spp., Podosphaera spp.Podosphaera spp. including P. leucotricha, Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp., Pseudoperonospora spp. including P. cubensis and P. humuli, Pseudoperonospora spp. including Pseudoperonospora trakeiphila, ... Puccinia spp. including P. tracheiphila, P. hordei, P. recondita, P. striiformis, P. triticina, Pyrenopeziza spp., Pyrenophora spp., Pyricularia spp. including P. oryzae, Pythium spp. including P. ultimum, Ramularia spp., Rhizoctonia spp., Rhizomucor pusillu, Rhizopus aridis arrhizus, Rhynchosporium spp., Scedosporium spp. including S. apiospermum and S. prolificans, Schizothyrium pomi, Sclerotinia spp., Sclerotium spp., S. nodorum, Septoria spp. including S. tritici), Sphaerotheca macularis, Sphaerotheca fusca, Sphaerotheca fuliginea, Sporothorix spp., Stagonospora nodorum, Stempphylium spp., Stereum hirsutum, Stagonospora, 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., Venturia spp., including Vibrio inaequalis, Verticillium spp., and Xanthomonas spp.

[0179] 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.

[0180] 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.

[0181] 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), for example Clearfield® summer rape (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®.

[0182] 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.

[0183] Examples of such plants are YieldGard® (corn varieties expressing CryIA(b) toxin); YieldGard Rootworm® (corn varieties expressing CryIIIB(b1) toxin); YieldGard Plus® (corn varieties expressing CryIA(b) and CryIIIB(b1) toxins); Starlink® (corn varieties expressing Cry9(c) toxin); Herculex I® (corn varieties expressing CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton varieties expressing CryIA(c) toxin); Bollgard I® (cotton varieties expressing 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); NatureGard® Agrisure® GT Advantage (GA21 glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), Agrisure® RW (corn root nematode trait), and Protecta®.

[0184] The term "crop plant" should also be understood to include crop plants that have been transformed using recombinant DNA techniques so as to be capable of synthesizing one or more selectively acting toxins, such as those known from toxin-producing bacteria, particularly those belonging to the genus Bacillus.

[0185] 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 bacteria, e.g., Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus, etc. insecticidal proteins of nematode-symbiotic bacteria such as Azotoxins; toxins produced by animals such as scorpion toxins, spider toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi such as Streptomycete toxins, plant lectins such as pea lectin, barley lectin or snowdrop lectin; agglutinins; proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ricin, Ribosome-inactivating proteins (RIPs) such as maize-RIP, abrin, ruffin, 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 sodium or calcium blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

[0186] 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, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the natural toxin are replaced. In such amino acid substitutions, preferably a non-naturally occurring protease recognition sequence is inserted into the toxin, for example, in the case of Cry3A055, a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see WO 2003 / 018810).

[0187] 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.

[0188] Methods for the preparation of such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP 0 367 474, EP 0 401 979 and WO 90 / 13651.

[0189] The toxins contained in the genetically modified plants confer resistance to harmful insects on the plants, which can be from any taxonomic group of insects, but are particularly commonly found among beetles (Coleoptera), two-winged insects (Diptera), and butterflies (Lepidoptera).

[0190] 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®.

[0191] Further examples of such transformed crops are as follows: 1. Bt11 maize, registration number C / FR / 96 / 05 / 10, manufactured by Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France. Genetically engineered maize (Zea mays) that confers resistance to European corn borers (Ostrinia nubilalis and Sesamia nonagrioides) through the transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also achieves tolerance to the herbicide glufosinate-ammonium through the transgenic expression of the enzyme PAT. 2. Bt176 maize, registration number C / FR / 96 / 05 / 10, manufactured by Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France. This is genetically engineered maize (Zea mays) that is resistant to European corn borers (Ostrinia nubilalis and Sesamia nonagrioides) through the transgenic expression of the Cry1Ab toxin. Bt176 maize also achieves tolerance to the herbicide glufosinate-ammonium through the transgenic expression of the enzyme PAT. 3. MIR604 maize, registration number C / FR / 96 / 05 / 10, manufactured by Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France. Maize conferred insect resistance through transgenic expression of a modified Cry3A toxin. The toxin is Cry3A055 modified by the insertion of a cathepsin-G-proteinase recognition sequence. The preparation of such transgenic maize plants is described in WO 2003 / 018810. 4. MON863 maize, registration number C / DE / 02 / 9, manufactured by Monsanto Europe SA270-272 Avenue de Tervuren, B-1150 Brussels, Belgium. MON863 expresses the Cry3Bb1 toxin and confers resistance to certain coleopteran insects. 5. IPC531 cotton, registration number C / ES / 96 / 02, manufactured by Monsanto Europe SA270-272 Avenue de Tervuren, B-1150 Brussels, Belgium. 6. 1507 corn, registration number C / NL / 00 / 10, manufactured by Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium. Maize genetically engineered for expression of the protein Cry1F to achieve resistance to certain lepidopteran insects and for expression of the PAT protein to achieve tolerance to the herbicide glufosinate ammonium. 7. NK603 x MON 810 corn, registered under registration number C / GB / 02 / M3 / 03, manufactured by Monsanto Europe SA270-272 Avenue de Tervuren, B1150 Brussels, Belgium. This conventional hybrid corn variety is a cross between the genetically modified varieties NK603 and MON 810. NK603 x MON810 corn transgenicly expresses the CP4 EPSPS protein from Agrobacterium sp. strain CP4, which confers resistance to the Roundup® herbicide (containing glyphosate), and the Cry1Ab toxin from Bacillus thuringiensis subsp. kurstaki, which confers resistance to certain Lepidoptera, including the European corn borer.

[0192] The compounds of formula (I) according to the invention are effective against diseases caused by plant pathogens, in particular 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 solanaceous crops. taurica; Fusarium spp. in cereals; Leptosphaeria spp. in cereals; and Zymospetoria spp. in cereals.

[0193] 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.

[0194] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves and fruits.

[0195] The term "plant propagation material" is understood to refer to reproductive parts, such as seeds, of plants, and vegetative parts, such as cuttings or tubers, for example 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 to be transplanted after germination or emergence from the soil. These seedlings can be protected by a complete or partial immersion treatment before transplanting. Preferably, "plant propagation material" is understood to refer to seeds.

[0196] 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 formulations for achieving special effects.

[0197] Suitable carriers and adjuvants, for example those 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.

[0198] Suspension concentrates are aqueous formulations in which finely divided 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 in 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.

[0199] 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.

[0200] Emulsifiable concentrates are homogeneous liquid compositions that are dispersible in water or other liquids and 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.

[0201] 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% of the 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.

[0202] 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.

[0203] 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.

[0204] 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.

[0205] Suitable agricultural adjuvants and carriers useful in formulating compositions of the present invention in the formulation types described above are well known to those skilled in the art.

[0206] 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 alcohol Examples of solvents include methyl amine, 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.

[0207] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, fuller's earth, cottonseed hulls, wheat flour, soy flour, pumice, wood flour, walnut hulls, and lignin.

[0208] A wide variety of surfactants are advantageously employed in both liquid and solid compositions, particularly those designed to be diluted with a carrier before application. These agents, when used, typically comprise 0.1% to 15% (by weight) of the formulation. They may be anionic, cationic, nonionic, or polymeric in character and may be used as emulsifying agents, wetting agents, suspending agents, or for other purposes. Typical surfactants include alkyl sulfates such as diethanolammonium lauryl sulfate; alkylaryl sulfonates, for example, calcium dodecylbenzene sulfone sulfate; alkylphenol-alkylene oxide adducts, for example, nonylphenol-C.sub.18 ethoxylate; alcohol-alkylene oxide adducts, for example, tridecyl alcohol-C.sub.16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalene sulfonates, for example, sodium dibutylnaphthalene 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 dialkyl phosphate esters.

[0209] 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.

[0210] 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.

[0211] 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.

[0212] 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.

[0213] 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 other carriers, surfactants or application-promoting adjuvants that are commonly used in the technical field of formulation.

[0214] The compounds of formula (I) according to the invention may also be used in the form of (fungicidal) compositions for the control of 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 adjuvant as described above.

[0215] Therefore, the present invention provides a composition, preferably a fungicidal composition, containing 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 contain at least one or more insecticidal active compounds, such as additional fungicidal active ingredients, in addition to the compound of formula (I).

[0216] 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.

[0217] Examples of suitable additional active ingredients include the following: 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, and mercuric fungicides. , morpholine fungicides, organophosphorus 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.

[0218] Examples of suitable additional active ingredients include: petroleum oil, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenylbenzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylacetamide, 4-chlorophenylphenylsulfone, acetoprole, aldoxicarb, amidothioate, amiton, amiton hydrogen oxalate, amitraz, alamite, arsenic oxide, azobenzene, azotoate, benomyl, benoxafos, benzyl benzoate, bixafen, brofenvalerate, bromocycline. , Bromophos, Bromopropylate, Buprofezin, Butocarboxim, Butoxycarboxim, Butylpyridaben, Calcium polysulfide, Camphechlor, Carbanolate, Carbophenothion, Cimiazole, Chinomethionate, Chlorbenside, Chlordimeform, Chlordimeform Hydrochloride, Chlorphenetole, Chlorfenson, Chlorphenesulfide, Chlorbenzilate, Chlormebuform, Chlormethiron, Chlorpropylate, Chlorthiophos, Cinerin I, Cinerin II, Cinerin, Closantel, Coumaphos, Crotamito chlorpheniramine, crotoxyphos, khuraneb, 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, zynex, zynocap-diclexin, zynocap-4, zynocap-6, dinocton, dinopenton, dinosulfone, dinotervon, dioxathion, diphenyl sulfone, disulfiram, DNOC , dofenapine, doramectin, endothion, eprinomectin, ethoate-methyl, etrimphos, fenazaflor, fenbutatin oxide, fenothiocarb, fenpyrad, fenpyroximate, fenpyrazamine, fenson, fentrifanil, flubenzimine, flucycloxuron, fluenil, fluorbenside, FMC1137, formetanate, formetanate hydrochloride, formparanate, γ-HCH, gliodin, halfenprox, hexadecylcyclopropanecarboxylate, isocarbophos, jasmolin I,Jasmolin II, jodofenphos, lindane, malonoven, 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, nifluride, nikkomycin, nitrilacarb, nitrilacarb 1:1 zinc chloride complex, omethoate, oxydeprophos, oxydisulf Photon, pp'-DDT, parathion, permethrin, fenkapton, phosalone, phospholane, phosphamidon, polychloroterpenes, polynactin, proclonol, promacyl, propoxur, prothidathion, prothoate, pyrethrin I, pyrethrin II, pyrethrins, pyridaphenthion, pirimitate, quinalphos, quinthiofos, R-1492, phosglycine, rotenone, shladan, cebufos, selamectin, sofamid, SSI-121, sulfiram, sulfuramide, sulfotep, sulfur, diflobidazin, tau-fluvarine To, TEPP, Terbam, Tetradifon, Tetracal, Thiafenox, Thiocarboxim, Thiofanox, Thiometon, Thioquinox, Thuringensin, Triamiphos, Triatene, Triazophos, Triazuron, Tripenophos, Trinactin, Vamidothion, Vaniliprole, Bethoxazin, Copper dioctanoate, Copper sulfate, Sibutrin, Dichlorophen, Endothal, Fentin, Hydrated lime, Nabam, Quinoclamine, Quinonamide, Simazine, Triphenyltin acetate, Triphenyltin hydroxide, Crufomate, Piperazine, Thiofane , chloralose, 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 hydrate, nickel bis(dimethyldithiocarbamate), nitrapyrin, octhilinone, oxolinic acid, oxytetracycline, potassium hydroxyquinoline sulfate,Probenazole, streptomycin, sesquisulfate, tecloftalam, thiomersal, Anopheles gambiae GV, Agrobacterium radiobacter, Amblyseius spp., Anagrapha falcifera NPV, Anagrus atomus, Aphelinus abdominalis, Aphidius colemani, Autographa californica NPV, Bacillus sphaericus Neide, Beauveria 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, 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, Steinernema riobravis, Steinernema scapteriscis, Steinernema spp., Trichogramma spp., Typhlodromus occidentalis, Verticillium lecanii lecanii), afolate, visadil, busulfan, dimatif, hemel, hempa, metepa, methiotepa, methyl afolate, molzide, penfluron, tepa, thiohempa, thiotepa, tretamine, 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)-icos-13-en-10-one, (Z)-tetradec-7-en-1-al, (Z)-tetradec-9-en-1-ol, (Z)-tetradec-9-en-1-yl acetate, (7E,9Z)-dodeca-7,9-dien-1-yl acetate, (9Z,11E)-tetradec-9,11-dien-1-yl acetate, (9Z,12E)-tetradec-9,12-dien-1-yl acetate, 14-methyloctadec-1-ene, 4-methylnonan-5-ol and 4-methylnonan-5-one, α-multistriatin, brevicomin, codruar, codrumon, curel,Disparlure, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodec-8,10-dien-1-yl acetate, dominicale, ethyl 4-methyloctanoate, eugenol, frontalin, grandlure, grandlure I, grandlure II, grandlure III, grandlure IV, Hexalure, Ipsdienol, Ipsenol, Japonilure, Linetin, Litlure, Looplure, Medlure, Megatomoic acid, Methyleugenol, Maskal, Octadeca-2,13-dien-1-yl acetate, Octadeca-3,13-dien-1-yl acetate, Olfuralure, Ostramon, Siglua, Soldigin, Sulcatol, Tetradec-11-en-1-yl acetate, Trimedlure, Trimedlure A, Trimedlure B1, Trimedlure B2, Trimedlure C, trunc-call, 2-(octylthio)ethanol, butopyronoxyl, butoxy(polypropylene glycol), dibutyl adipate, dibutyl phthalate, dibutyl succinate, diethyl toluamide, dimethyl carbamate, dimethyl phthalate, ethyl hexanediol, hexamide, methoquin-butyl, methyl neodecanoamide, oxapartona, 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)ethyl acetate, 2,2-dichlorovinyl 2-ethylsulfinylethyl methylphosphate, 2-(1,3-dithiolan-yl)phenyl dimethylcarbamate, 2-(2-butoxyethylene) (4-chloro-3,5-xyloxy)ethyl thiocyanate, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenylmethylcarbamate, 2-(4-chloro-3,5-xyloxy)ethanol, 2-chlorovinyl diethyl phosphate, 2-imidazolidone, 2-isovaleryldan-1,3-dione, 2-methyl(prop-2-ynyl)aminophenylmethylcarbamate, 2-thiocyanatoethyl laurate, 3-bromo-1-chloroprop-1-ene,3-methyl-1-phenylpyrazol-5-yl dimethyl carbamate, 4-methyl(prop-2-ynyl)amino-3,5-xylylmethyl carbamate, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethyl carbamate, acetion, acrylonitrile, aldrin, allosamidin, alixycarb, α-ecdysone, aluminum phosphide, aminocarb, Anabasine, acidathione, azamethiphos, Bacillus thuringiensis delta-endotoxin, barium hexafluorosilicate, barium polysulfide, bartholin, Bayer 22 / 190, Bayer 22408, beta-cyfluthrin, beta-cypermethrin, bioethanometrin, biopermethrin, bis(2-chloroethyl) ether, borax, bromfenvinphos, bromo-DDT, bufencarb, butacarb, butathiophos, butonate, calcium arsenate, calcium cyanide, carbon disulfide, carbon tetrachloride, cartap hydrochloride, cevazine, Lorbicycline, chlordane, chlordecone, chloroform, chloropicrin, chlorfoxime, chlorprazophos, cis-resmethrin, cismethrin, clocitrin, copper acetoarsenate, copper arsenate, copper oleate, cumitoate, cryolite, CS708, cyanofenphos, cyanophos, cyclethrin, thioate, d-tetramethrin, DAEP, dazomet, decarbofuran, diamidaphos, dikapton, diclofenthion, dicresyl, dicyclanil, dieldrin, diethyl 5-methylpyrazol-3-ylphosphate To, dilor, dimefluthrin, dimethane, dimethrine, dimethylvinphos, dimethirane, dinopropa, dinosam, dinoseb, diofenolan, dioxabenzophos, dicyclophos, DSP, ecdysterone, EI1642, EMPC, EPBP, etaphos, ethiofencarb, ethyl formate, ethylene dibromide, ethylene dichloride, ethylene oxide, EXD, fenchlorphos, fenetacarb, fenitrothion, fenoxacrim, fenpyrithrin, fensulfothion, fenthion-ethyl, flucofuron, fosmethirane, Hospirate, 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, lilimphos, ritidathion, m-cumenylmethylcarbamate,Magnesium phosphide, Magidox, Mecarfone, Menazone, Chloride solution, Metanadium, Metanadium, Metasodium, Metasodium, Metadium, Methanesulfonyl fluoride, Metocrotophos, 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-ethylphosphonothioate, O,O-Diethyl 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, paradichlorobenzene, oleic acid, paradichlorobenzene, parathion methyl, pentachlorophenol, pentachlorophenyl laurate, PH60-38, phenol kapton, phosnichlor, phosphine, phoxim methyl, pyrimetaphos, polychlorodicyclopentadiene isomers, potassium arsenite, thiocyanide Potassium arsenate, precocene I, precocene II, precocene III, primidophos, profluthrin, promecarb, prothiofos, pyrazophos, pyresmethrin, quasia, quinalphos-methyl, quinothione, lafoxanide, resmethrin, rotenone, kadethrin, ryania, ryanodine, sabadila), shradan, cebufos, SI-0009, tiapronil, sodium arsenite, sodium cyanide, sodium fluoride, sodium hexafluorosilicate, pentachlorophenoxide, sodium selenate, sodium thiocyanate, sulcofuron, sulcofuron Lucofron-sodium, sulfuryl fluoride, sulprofos, tar oil, thazimcarb, TDE, tebupirimphos terallethrin, tetrachloroethane, cyclofos, thiocyclam, thiocyclam hydrogen oxalate, thionazine, thiosultap, thiosultap-sodium, tralomethrin, transpermethrin, triazamate, trichlormethaphos 3, trichloronat, trimethacarb, tolprocarb, triclopiricarb, triplen, veratridine, veratrine, veratrine, veratrine, veratrine, XMC, zetamethrine, zinc phosphide, zolaprofos,and 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, 2-fluoro-N-(3-methoxyphenyl)-2-methyl-2-propanol, 2-fluoro-N-(3-methoxyphenyl)-2-methyl ... (phenyl)-9H-purin-6-amine, benclothiazide, cytokinin, DCIP, furfural, isamidophos, kinetin, Myrothecium verrucaria composition, tetrachlorothiophene, xylenol, zeatin, potassium ethylxanthate, acibenzolar, acibenzolar-S-methyl, Reynoutria sachalinensis extract, alpha-chlorohydrin, alpha-chlorohydrin, acibrohydrin, sodium, acibrohydrin chlorlophacinone, cholecalciferol, coumacrol , 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 piperonate, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, nerolidol and farnesol, berubutin, MGK264, Peronyl butoxide, piprotal, propyl isomers, S421, sesamex, sesasmolin, sulfoxide, anthraquinone, copper naphthenate, copper oxychloride, dicyclopentadiene, thiram, zinc naphthenate, ziram, imanin, ribavirin, mercury oxide, thiophanate-methyl, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, furametpyr, hexaconazole, imazalil,Imibenconazole, ipconazole, metconazole, myclobutanil, paclobutrazol, 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, remetalaxyl, ofuras, oxadixyl, carbendazim, debacarb, fuberidazole, thiabendazole, chlozolinate, diclozolin, mycrozolin, procymidone, vinclozolin, boscalid, carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, penthiopyrad, thifluzamide, dodine, iminooctadine, azoxystrobin, dimoxystrobin, enestrobulin , phenaminestrobin, flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, ferbam, mancozeb, maneb, metiram, propineb, zineb, captafol, captan, fluoroimide, folpet, tolylfluoanid, Bordeaux mixture, copper oxide, copper manate, copper oxine, nitrothal-isopropyl, edifenphos, iprobenfos, phosdifen, tolclofo s-methyl, anilazine, benthiavalicarb, blasticidin-S, chloroneb, chlorothalonil, cyflufenamid, cymoxanil, cyclobutrifluram, diclocymet, diclomedine, dicloran, diethofencarb, dimethomorph, flumorph, dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, ferimzone, fluazinam, fluopicolide, flusulfamide, fluxapyroxad, fenhexamid, fosetyl-aluminum, hymexazole, iprovalicarb, cyazofamid,Metasulfocarb, metrafenone, pencycuron, phthalide, polyoxin, propamocarb, pyribencarb, proquinazide, pyroquilon, pyriophenone, quinoxyfen, quintozene, tiadinil, triazoxide, tricyclazole, triforine, validamycin, valifenalate, zoxamide, mandipropamide, flubeneteram, isopyrazam, sedaxane, benzovindiflupyr, pi Diflumetofen, 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-di Methyl-indan-4-yl]pyridine-3-carboxamide, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, fluindapyr, methoxystrobin (jiaxiangjunzhi), lvbenmixianan, diclobenthiazox, mandestrobin, 3-(4,4-difluoro-3,4-dihydro-3,, 3-Dimethylisoquinolin-1-yl)quinolone, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol, oxathiapiproline, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenylmethylene]amino]oxymethyl]-2-pyridyl]carbamate, pyraziflumide, impirfluxam, troprocarb, mefentrifluconazole, ipfentrifluconazole, 2-(difluoromethyl)-N-[(3R)-3-ethoxybenzoate N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethylphenyl]-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-chlorophenyl]methanesulfonate, but-3-ynyl N-carbamate, N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate methyl, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine, pyridaclomethyl, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide, 1-4-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, atctrazine, amisulbrom, penflufen, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide, flurylpicoxamide, 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 by 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 by the method described in WO 2020 / 056090), methyl N-[[4-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (which can be prepared by the method described in WO 2020 / 097012), methyl N- [[4-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (which can be prepared by the method described in WO 2020 / 097012), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (which can be prepared by the method described in WO 2020 / 109391), 6-chloro-N-[2-(2-chloro-4-methyl-phenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide (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-triazoline) 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]benzonitrile, methyltetraprole, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidineethanol, fluoxapiprolin, 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 ]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 by 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 by 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, Zhongshe ngmycin, 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- 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 are described in WO 2015 / 155075). (These compounds can be prepared from the method described in IPCOM000249876D), N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenylethyl)phenyl]-N-methyl-formamidine, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methylphenyl]-N-isopropyl-N-methyl-formamidine (these compounds can be prepared by the method described in WO 2018 / 228896), N-ethyl-N'-[5-methoxy-2-methyl-4-[2-trifluoromethyl)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 by 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 amide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, 8-Fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-((1R)-1-benzyl N-((1S)-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 by 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 1-(6-chloro-7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 1-(6-chloro-7-methylpyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline (these compounds can be prepared from 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 are disclosed in International Publication No. 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-di Methyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]methyl]isoxazolidin-3-one, 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]-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 methods described in WO 2017 / 0 29179), 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). can be prepared from the method described in WO 2016 / 156290), 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]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 by 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 by 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 by 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-(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-C-methyl-carbonylimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (these compounds can be prepared by the method described in WO 2018 / 202428).

[0219] 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.

[0220] 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.

[0221] 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.

[0222] The compounds of the invention may be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide; neonicotinoids such as imidacloprid.

[0223] 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.

[0224] 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: Organophosphates: 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, famfur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazophos, fonofos, formothion, fosthiazate, heptenophos, isazophos, isothioate, isoxathion, malathion, methacryl phos, 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, proetamphos, prothiofos, pyraclofos, pyridapenthione, quinalphos, sulprofos, temephos, terbufos, tebupirimphos, tetrachlorvinphos, timeton, triazophos, trichlorfon, vamidothion. 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. 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 fluthrin, 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. Arthropod growth regulators: a) Chitin synthesis inhibitors: Benzoyl ureas: Chlorfluazuron, Diflubenzuron, Fluazuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novaluron, Teflubenzuron, Triflumuron, Buprofezin, Diofenolan, Hexythiazox, Etoxazole, Chlorfentadine; b) Ecdysone antagonists: Halofenozide, Methoxyfenozide, Tebufenozide; c) Juvenoids: Pyriproxyfen, Methoprene (including S-Methoprene), Fenoxycarb; d) Lipid biosynthesis inhibitors: Spirodiclofen. Other antiparasitic drugs: acequinocyl, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis thuringiensis), bensultap, bifenazate, binapropacryl, bromopropylate, BTG-504, BTG-505, camfechlor, 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, fluproxifen, halofen Enprox, hydramethylnon, IKI-220, Kanemite, NC-196, Niemgard, nidinorterfuran, 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, verbutin, Bertarec, YI-5301. Biological agents: Bacillus thuringiensis subspecies aizawai, kurstaki, Bacillus thuringiensis delta-endotoxin, baculovirus, entomopathogenic bacteria, viruses and fungi. Bactericides: chlortetracycline, oxytetracycline, streptomycin. Other biological agents: enrofloxacin, febantel, penethamate, meloxicam, cephalexin, kanamycin, pimobendan, clenbuterol, omeprazole, tiamulin, benazepril, pyriprole, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, ceftiour, carprofen, metaflumizone, praziquarantel, triclabendazole.

[0225] The following mixtures of compounds of formula (I) with active ingredients are preferred: The abbreviation "TX" means a compound of formula (I), (II), (II-A), (II-A1), (II-B), (II-B1), (II-C), (II-C1), (II-D), or (II-D1) according to the present invention, or one compound selected from the compounds listed in Tables A-1 to A-24, or Table P (below): Petroleum + TX, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX, 2,4-dichlorophenylbenzenesulfonate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 4-chlorophenyl phenyl sulfone + TX, acetoprole + TX, aldoxicarb + TX, amidothioate + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, alamite + TX, arsenic oxide + TX, azobenzene + TX, azotoate + TX, benomyl + TX, benoxafos + TX, benzyl benzoate + TX, bixafen + TX, brofenvalerate + TX, bromocycline + TX, bromophos + TX, bromopropylate + TX, buprofezin + TX, butocarboxim + TX, butoxycarboxim + TX, butylpyridaben + TX, calcium polysulfide + TX, camphechlor + TX, carbanolate + TX, carbophenothion + TX, cymiazole + TX, chinomethionate + TX, chlorbenesid + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorphenetole + TX, chlorfenson + TX, chlorfe Insulfide + TX, chlorobenzilate + TX, chlormebform + TX, chloromethiuron + TX, chloropropylate + TX, chlorthiophos + TX, cinerin I + TX, cinerin II + TX, cinerin + TX, closantel + TX, coumaphos + TX, crotamiton + TX, crotoxyphos + TX, khuraneb + ​​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, Dinocap-Diclexin +TX, Dinocap-4 +TX, Dinocap-6 +TX, Dinocton +TX, Dinopenton +TX, Dinosulfone +TX, Dinotervon +TX, Dioxathion +TX, Diphenylsulfone +TX, Disulfiram +TX, DNOC +TX, Dofenapine +TX, Doramectin +TX, Endothion +TX,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, Fluenil +TX, Fluorobenside +TX, FMC1137 +TX, Formetanate +TX, Formetanate hydrochloride +TX, Formparanate +TX, γ-HCH +TX, Gliodin +TX, Halfenpro ox + TX, hexadecylcyclopropanecarboxylate + TX, isocarbophos + TX, jasmolin I + TX, jasmolin II + TX, jodofenphos + TX, lindane + TX, malonoven + TX, mecarbam + TX, mefosfolan + TX, mesulfen + TX, methacrifos + TX, methyl bromide + TX, metolcarb + TX, mexacarbate + TX, milbemycin oxime + TX, mipafox + TX, monocrotophos + TX, morphothion + TX, moxidectin + TX, naled + TX, 4-chloro-2-(2-chloro-2-methyl) (6-ethyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, Nifluride + 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, Promacil + TX, Propoxur +TX, Protidathion +TX, Protoate +TX, Pyrethrin I +TX, Pyrethrin II +TX, Pyrethrin +TX, Pyridaphenthion +TX, Pirimitate +TX, Quinalphos +TX, Quinthiofos +TX, R-1492 +TX, Phosglycine +TX, Rotenone +TX, Schladan +TX, Cebufos +TX, Selamectin +TX, Sofamid +TX, SSI-121 +TX, Sulfiram +TX, Sulfuramide +TX, Sulfotep +TX, Sulfur +TX, Diflobidazin +TX, Tau-fluvalinate +TX, TEPP +TX, Thelbam +TX,Tetradifon +TX, Tetracal +TX, Thiafenox +TX, Thiocarboxim +TX, Thiofanox +TX, Thiometon +TX, Thioquinox +TX, Thuringensin +TX, Triamiphos +TX, Triaten +TX, Triazophos +TX, Triazuron +TX, Trifenofos +TX, Trinactin +TX, Vamidothion +TX, Vaniliprole +TX, Bethoxadin +TX, Copper dioctanoate +TX, Copper sulfate +TX, Sibutrin +TX , dichlorophen + TX, endothall + TX, fentin + TX, hydrated lime + TX, nabam + 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-(quinoxazone) Salin-2-ylamino)benzenesulfonamide + TX, 8-hydroxyquinoline sulfate + TX, Bronopol + TX, Copper hydroxide + TX, Cresol + TX, Dipyrithione + TX, Dodisin + TX, Fenaminosulf + TX, Formaldehyde + TX, Hydralgafen + TX, Kasugamycin + TX, Kasugamycin hydrochloride hydrate + TX, Nickel bis(dimethyldithiocarbamate) + TX, Nitrapyrin + TX, Octilinone + TX, Oxolinic acid + TX, oxytetracycline + TX, hydroxyquinoline potassium sulfate + TX, probenazole + TX, streptomycin + TX, streptomycin + TX, sesquisulfate + TX, tecloftalam + TX, thiomersal + TX, Anopheles gambiae GV + TX, Agrobacterium radiobacter + TX, Amblyseius species + TX, Anagrapha falcifera + TX, Anagrus atomus + TX, Aphidius colemani + TX, Aphidius colemani + TX, Autographa californica NPV + TX, Bacillus sphaericus Neide + TX, Beauveria brongnaartii + TX, Chrysoperla carnea + TX, Cryptolaemus montrouzieri + TX,Cydia pomonella GV+TX, Dacnusa sibirica+TX, Diglyphus isaea+TX, Encarsia formosa+TX, Eretmocerus eremicus+TX, Heterorhabditis bacteriophora and H. megidis+TX, Hippodamia convergens+TX, Leptomastix dactylopii+TX, Macrolophus caliginosus+TX, Mamestra brassicae nucleopolyhedrovirus 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 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 + TX, Verticillium lecanii + TX, Afolate + TX, Visadil + TX, Busulfan + TX, Dimatif + TX, hemel + TX,hempa + TX, metepa + TX, methiotepa + TX, methyl aphorate + TX, molzide + TX, penfluron + TX, tepa + TX, thiohempa + TX, thiotepa + TX, tretamine + TX, uredepa + TX, (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol + TX, (E)-tridec-4-en-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E,Z) -Tetradeca-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-icos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-ene octadec-1-ene + 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-multi Striatin + TX, Brevicomin + TX, Codlua + TX, Codlumon + TX, Curel + TX, Disparlua + TX, Dodec-8-en-1-yl acetate + TX, Dodec-9-en-1-yl acetate + TX, Dodec-8 + TX, 10-dien-1-yl acetate + TX, Dominicale + TX, Ethyl 4-methyloctanoate + TX, Eugenol + TX, Frontalin + TX, Grandlure + TX, Grandlure I+TX, grandlure II+TX, grandlure III+TX, grandlure IV+TX, hexalure+TX, ipsdienol+TX, ipsenol+TX, japonilure+TX, linetin+TX, Litlure+TX, Looplure+TX, medlure+TX, megatomoic acid+TX, methyleugenol+TX, maskal+TX, octadeca-2,13-dien-1-yl acetate + TX, octadeca-3,13-dien-1-yl acetate + TX, Olfrua + TX, Ostramon + TX, Cigla + TX, Soldigin + TX, Sulcatol + TX, Tetradec-11-en-1-yl acetate + TX, Trimedlure + TX, Trimedlure A + TX, Trimedlure B1 + TX, Trimedlure B2 + TX, Trimedlure C + TX, trunc-call + TX, 2-(octylthio)ethanol + TX, Butopyronoxyl + TX, Butoxy(polypropylene glycol) + TX, Dibutyl adipate + TX, Dibutyl phthalate + TX, Dibutyl succinate + TX, Diethyl toluamide + TX, Dimethyl carbamate + TX, Dimethyl phthalate + TX, ethyl hexanediol + TX, hexamide + TX, methoquin-butyl + TX, methyl neodecaneamide + TX, oxapartone + TX, picaridin + TX, 1-dichloro-1-nitroethane + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)-ethane + TX, 1,2-dichloropropane and 1,3-dichloropropene + TX, 1-bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methylphosphate +TX, 2-(1,3-dithiolan-yl)phenyl dimethyl carbamate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methyl carbamate + TX, 2-(4-chloro-3,5-xyloyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidone + TX, 2-isovaleryldan-1,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenyl methyl carbamate + TX, 2-lauric acid thiocyanatoate ethyl + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-methyl-1-phenylpyrazol-5-yldimethylcarbamate + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate + TX, 5,5-dimethyl-3-oxocyclohex-1-enyldimethylcarbamate + TX, acetione + TX, acrylonitrile + TX, aldrin + TX, allosamidin + TX, alixycarb + TX, α-ecdysone + TX, aluminum phosphide + TX, aminocarb + TX, anabasine + TX, acidathione + TX,Azamethiphos + TX, Bacillus thuringiensis delta-endotoxin + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, bartholin + TX, Bayer 22 / 190 + TX, Bayer 22408 + TX, beta-cyfluthrin + TX, beta-cypermethrin + TX, bioethanometrin + TX, biopermethrin + TX, bis(2-chloroethyl) ether + TX, borax + TX, bromfenvinphos + TX, bromo-DDT + TX, bufencarb + TX, butacarb + TX, butathiophos + TX, butonate + TX , calcium arsenate + TX, calcium cyanide + TX, carbon disulfide + TX, carbon tetrachloride + TX, cartap hydrochloride + TX, sevadin + TX, chlorbicycline + TX, chlordane + TX, chlordecone + TX, chloroform + TX, chloropicrin + TX, chlorfoxime + TX, chlorprazophos + TX, cis-resmethrin + TX, cismethrin + TX, clocitrin + TX, copper acetoarsenate + TX, copper arsenate + TX, copper oleate + TX, chumithoate + TX, cryolite + TX, CS708 + TX, cyanofenphos + TX, cyanophos +TX, cyclethrin +TX, thioate +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, dilor +TX, dimefluthrin +TX, dimethane +TX, dimethryn +TX, dimethylvinphos +TX, dimethyllan +TX, dinopropa +TX, dinosam +TX, dinoseb +TX, diofenolan +TX , dioxabenzophos + TX, dicyclophos + TX, DSP + TX, ecdysterone + TX, EI1642 + 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, fosmetilan + TX,Hospiret + TX, Hostietan + TX, Furathiocarb + TX, Frethrin + TX, Guazatine + TX, Guazatine acetate + TX, Sodium tetrathiocarbonate + TX, Halfenprox + TX, HCH + TX, HEOD + TX, Heptachlor + TX, Heterofos + TX, HHDN + TX, Hydrogen cyanide + TX, Hikincarb + TX, IPSP + TX, Isazophos + TX, Isobenzane + TX, Isodrin + TX, Isofenphos + TX, Isolane + TX, Isoprothiolane + TX, Isoxathion + TX, Juvenile hormone I + TX, Juvenile hormone II+TX, Kerevan+TX, Kinoprene+TX, Lead arsenate+TX, Leptophos+TX, Lilimphos+TX, Ritidathion+TX, m-Cumenylmethylcarbamate+TX, Magnesium phosphide+TX, Magidox+TX, Mecarfone+TX, Menasone+TX, Chloride solution+TX, Metanadium+TX, Metanadium+TX, Metasodium+TX, Metasodium+TX, Metasodium+TX, Metasodium+TX, Methanesulfonyl fluoride+TX, Metocrotophos+TX, Methoprene+TX, Methotrin+TX, Methoxychlor+TX, Methyl isothiocyanate +Tx, methyl chloroform +Tx, methylene chloride +Tx, methoxadiazone +Tx, mirex +Tx, naphthalophos +Tx, naphthalene +Tx, NC-170 +TX, nicotine +TX, nicotine sulfate +TX, nithiazine +TX, nornicotine +TX, O-5-dichloro-4-iodophenyl O-ethylphosphonothioate +TX, O,O-diethyl 4-methyl 2-oxo-2H-chromen-2-yl phosphorothioate +TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate +TX, O,O,O',O '-Tetrapropyldithiopyrophosphate +TX, Oleic acid +TX, Paradichlorobenzene +TX, Oleic acid +TX, Paradichlorobenzene +TX, Parathion methyl +TX, Pentachlorophenol +TX, Pentachlorophenyl laurate +TX, PH60-38 +TX, Phenol Kapton +TX, Phosnichlor +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, Quasia + TX, Quinalphos-methyl + TX, Quinothione + TX, Lafoxanide + TX, Resmethrin + TX, Rotenone + TX, Cadethrin + TX, Riania + TX, Ryanodine + TX, Sabadila + TX, Shradan + TX, Cebufos + TX, SI-0009 + TX, Tiapronil + TX, Sodium arsenite + TX, Sodium cyanide + TX, Sodium fluoride + TX, Hexafluoro Sodium silicate +TX, pentachlorophenoxide +TX, sodium selenate +TX, sodium thiocyanate +TX, sulcofuron +TX, sulcofuron-sodium +TX, sulfuryl fluoride +TX, sulprofos +TX, tar oil +TX, thazimcarb +TX, TDE +TX, tebupirimfos +TX, telallethrin +TX, tetrachloroethane +TX, cyclofos +TX, thiocyclam +TX, thiocyclam hydrogen oxalate +TX, thionazine +TX, thiosultap +TX, thiosultap-sodium +TX, tralomethrin +TX, trans Permethrin + TX, triazamate + TX, trichlormethaphos 3 + TX, trichloronat + TX, trimethacarb + TX, tolprocarb + TX, triclopyricarb + TX, triplen + TX, veratridine + TX, veratrine + TX, veratrine + TX, veratrine + TX, XMC + TX, zetamethrin + TX, zinc phosphide + TX, zolaprofos + TX, and meperfluthrin + TX, tetramethylfluthrin + TX, bis(tributyltin) oxide + TX, bromoacetamide + TX, ferric phosphate + TX, niclosamide-olamine + TX, Tributyltin oxide + TX, pyrimorph + TX, triphenmorph + TX, 1,2-dibromo-3-chloropropane + TX, 1,3-dichloropropene + TX, 3,4-dichlorotetrahydrothiophene, 1,1-dioxide + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, 2-fluoro-N-(3-methoxyphenyl)-9H-purin-6-amine + TX, benclothiaz + TX, cytokinin + TX,DCIP+TX, Furfural+TX, Isamidophos+TX, Kinetin+TX, Myrothecium verrucaria Composition+TX, Tetrachlorothiophene+TX, Xylenol+TX, Zeatin+TX, Potassium Ethylxanthate+TX, Acibenzolar+TX, Acibenzolar-S-methyl+TX, Reynoutria sachalinensis Extract+TX, α-Chlorohydrin+TX, Alpha-Chlorohydrin+TX, Acibrohydrin+TX, Dimethicone+TX, Acibrohydrin+TX, Chlorophacinone+TX, Cholecalciferol+TX, Coumacrol+TX, Coumafuryl+TX, Coumatetralyl+TX, Crimidine+TX, Difenacoum+TX, Difethialone+TX, Diphacinone+TX, Ergocalciferol Ferol + TX, flocoumafen + TX, fluoroacetamide + TX, flupropazine + TX, flupropazine hydrochloride + TX, norbormide + TX, fosacetim + TX, phosphorus + TX, pindone + TX, pyrinuron + TX, sciliroside + TX, sodium fluoroacetate + TX, thallium sulfate + TX, warfarin + TX, 2-(2-butoxyethoxy)ethyl piperonate + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, nerolidol + TX and farnesol, berubutin + TX, MGK264 + TX, piperonyl butoxide + TX, piperotal + TX, propyl isomer + TX, S421 + TX, sesamex + TX, sesasmolin + TX, sulfoxide + TX, anthraquinone + TX, copper naphthenate + TX, Copper oxychloride +TX, dicyclopentadiene +TX, thiram +TX, zinc naphthenate +TX, ziram +TX, imanin +TX, ribavirin +TX, mercuric oxide +TX, thiophanate-methyl +TX, azaconazole +TX, bitertanol +TX, bromuconazole +TX, cyproconazole +TX, difenoconazole +TX, diniconazole +TX, epoxiconazole +TX, fenbuconazole +TX, fluquinconazole +TX, flusilazole +TX, flutriafol +TX, furametpyr +TX, hexaconazole +TX, imazalil + TX, Imibenconazole + TX, Ipconazole + TX, Metconazole + TX, Myclobutanil + TX, Paclobutrazol + TX, Pefurazoate + TX, Penconazole + TX, Prothioconazole + TX, Pyrifenox + TX, Prochloraz + TX, Propiconazole + TX, Pyrisoxazole + TX, Simeconazole + TX, Tebuconazole + TX, Tetraconazole + TX, Triadimefon + TX, Triadimenol + TX, Triflumizole + TX, Triticonazole + TX, Ancymidol + TX, Fenarimol + TX, Nuarimo acetaminophen + TX, bupirimate + TX, dimethirimol + TX, ethirimol + TX, dodemorph + TX, fenpropizin + TX, fenpropimorph + TX, spiroxamine + TX, tridemorph + TX, cyprodinil + TX, mepanipyrim + TX, pyrimethanil + TX, fenpiclonil + TX, fludioxonil + TX, benalaxyl + TX, furalaxyl + TX, metalaxyl + TX, remetalaxyl + TX, ofuras + TX, oxadixyl + TX, carbendazim + TX, debacarb + TX, fuberidazole + TX, thiabendazole + TX , chlozolinate + TX, dichlozolin + TX, mycrozolin + TX, procymidone + TX, vinclozolin + TX, boscalid + TX, carboxin + TX, fenfuram + TX, flutolanil + TX, mepronil + TX, oxycarboxin + TX, penthiopyrad + TX, thifluzamid + TX, dodine + TX, iminooctadine + TX, azoxystrobin + TX, dimoxystrobin + TX, enestrobulin + TX, phenaminestrobin + TX, flufenoxystrobin + TX, fluoxastrobin + TX, kresoxim-methyl + TX,Metominostrobin +TX, trifloxystrobin +TX, orysastrobin +TX, picoxystrobin +TX, pyraclostrobin +TX, pyrametostrobin +TX, pyroxystrobin +TX, ferbam +TX, mancozeb +TX, maneb +TX, metiram +TX, propineb +TX, zineb +TX, captafol +TX, captan +TX, fluoroimide +TX, folpet +TX, tolylfluoanid +TX, Bordeaux mixture +TX, copper oxide +TX, copper manate +TX, copper oxine +TX, nitrothal-isopropyl +TX, edifen Nphos + TX, Iprobenfos + TX, Fosdifen + 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, Proquinazid +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, fluveneteram + TX, isopyrazam + TX, sedaxane + TX, benzovindiflupyr + TX, pydiflumetofen + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, isoflucipram + TX, isotianil + TX, dipimethitrone + TX,6-Ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile + TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide Ruboxamide + 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, Chmethoxystrobin (jiaxiangjunzhi) + TX, Lvbenmixianan + TX, Diclobentiazox + TX, Mandest Robin + 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)-phenylmethylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, pyraziflumide + TX, impirfluxam + TX, Troprocarb + 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-dimethylphenyl]-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-chlorophenyl]methanesulfonate + TX, but-3-ynyl N-carbamate + TX, N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate methyl + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trimethyl- Fluorophenyl)pyridazine + TX, pyridaclomethyl + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 1-4-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, atctrazine + TX, amisulbrom + TX, pe Nflufen + TX, (Z,2E)-5-[2-[2,4-dichloro-phenoxy]phenyl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX, florylpicoxamide + TX, fenpicoxamide + TX, tebufloquine + TX, ipflufenoquine + TX, quinofumelin + TX, isofetamide + TX, N-(2)-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, N-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide d + TX, benzothiostrobin + TX, fenamacril + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, fluopyram + TX, flutianil + TX, fluopimomide + TX, pyrapropoin + TX, picarbutrazox + TX, 2-N-(3-ethyl-1,1-dimethylindan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX,4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, Methyltetraprole + TX, 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-di-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, Trinapac + TX, Cumoxystrobin + TX, Zhongshengmycin + TX, Copper thiodiazole + TX, Zinc thiazole + TX, Amectotractin + 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 (1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine + TX (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 + TX (these compounds can be prepared from the method described in IPCOM000249876D), N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenylethyl)phenyl]-N-methyl-formamidine + TX, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methylphenyl]-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)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX 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-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX (these compounds can be prepared by the method described in WO 2017 / 153380), 1-(6,7-dimethylpyrazolo[1,5-a] 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 1-(6-chloro-7-methylpyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX (these compounds can be prepared from 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-isoquinoline + TX, fluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline + TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole + TX (these compounds can be prepared by the method described in WO 2016 / 156085), N-methoxy-N-[[4-[5-(trifluoromethyl)-2H-pyridyl]methyl] ... 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]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, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidine-3 1 + 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 of 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 2016 / 156290), 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 2014 / 006945), 2,6-dimethyl-1H,5H-[ 1,4]dithiino[2,3-c,5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone + TX (this compound can be prepared by the method described in WO 2011 / 138281), N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide + TX, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, (Z,2E)-5-[1-(2,

[0043] 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 / 2022). 742), 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX (this compound can be prepared by the method described in WO 2014 / 095675), (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4

[0033] 2-oxo-N-propyl-2-[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-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazoline and 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-carbonylimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX (these compounds can be prepared by the method described in WO 2018 / 202428), chlorinconazide + TX, flumethylsulfolim + TX, fluoxythioconazole + TX, flufenoxadiazam + TX, methallylpicoxamide + TX.

[0226] A reference in parentheses following an active ingredient, such as [3878-19-1], refers to the Chemical Abstracts Registry number. The aforementioned mixing partners are known. When the 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 shown in parentheses above for the particular compound; for example, the compound "abamectin" is listed under entry number (1). When a "CCN" is added to a particular compound listed above, the compound in question is included in the "Compendium of Pesticide Common Names," which is accessible 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.

[0227] Most of the active ingredients listed 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.

[0228] The active ingredient mixture of the compounds of formula (I), (II), (II-A), (II-A1), (II-B), (II-B1), (II-C), (II-C1), (II-D), or (II-D1) according to the present invention, or the compounds selected from the compounds listed in Tables A-1 to A-24 or Table T1 (hereinafter), is preferably in a mixing 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 preferably 5:1 to 1:5, and these mixing ratios are by weight.

[0229] A mixture as described above may be used in a method for controlling pests, the method comprising applying a composition comprising a mixture as described above to the pest or its environment, excluding methods for treating the human or animal body by surgery or therapy or diagnostic methods performed on the human or animal body.

[0230] Mixtures comprising a compound selected from formula (I), (II), (II-A), (II-A1), (II-B), (II-B1), (II-C), (II-C1), (II-D), or (II-D1) according to the present invention, or a compound selected from the compounds listed in Tables A-1 to A-24 or Table P (below), and one or more active ingredients as described above, can be applied, for example, in a single "ready-mix" form, as combined spray mixtures made up of separate formulations of a single active ingredient, such as "tank mixes," and in combinations of the single active ingredients when applied sequentially, i.e., one after the other within a fairly short period of time, such as a few hours or days. The compounds of formula (I), (II), (II-A), (II-A1), (II-B), (II-B1), (II-C), (II-C1), (II-D), or (II-D1) according to the present invention, or mixtures selected from compounds selected from those listed in Tables A-1 to A-24 or Table P (below), and the active ingredients described above, are not essential for practicing the present invention.

[0231] 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 achieving specific effects, for example bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0232] The compositions according to the invention are 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 auxiliary, for example by intimately mixing the active ingredient with one or more auxiliaries and / or grinding. These methods for preparing the compositions and the use of compound (I) for preparing these compositions are also the subject of the present invention.

[0233] 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 infestation 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.

[0234] A further aspect of the present invention relates to a method for controlling or preventing infestation of plants, such as useful plants, for example crop plants, their plant propagation material, for example seeds, harvested crops, for example harvested food crops, or non-living material, by plant pathogenic 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, part of the plant or its habitat, its plant propagation material, or any part of the non-living material.

[0235] 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.

[0236] Preferred methods for controlling or preventing infestation of crop plants by phytopathogenic microorganisms, particularly fungal organisms, or insects include those in which the compounds of formula (I) according to the present invention and agrochemical compositions containing at least one compound of formula (I) are applied as foliar treatments. The frequency and rate of application depend on the risk of damage 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 irrigating the plant locus 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.

[0237] 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).

[0238] Advantageous application is usually from 5 g to 2 kg of active ingredient (ai) per hectare (ha), preferably from 10 g to 1 kg ai / ha, most preferably from 20 g to 600 g ai / ha. When used as a seed drench, a convenient dosage is from 10 mg to 1 g of active substance per kg of seed.

[0239] As used herein, the term "g ai / ha" refers to the application rate expressed in grams [g] of active ingredient [ai] per unit surface [ha]. The unit hectare (symbol ha) is an area of ​​1.00m square meters (1hm 2 ) square or 10,000 square meters. The hectare is a commonly used unit of area in the metric system.

[0240] 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.

[0241] Preferably, the compositions comprising compounds of formula (I) according to the invention are applied either prophylactically (meaning before the onset of the disease) or therapeutically (meaning after the onset of the disease).

[0242] The compositions of the present invention may be in any conventional form, such as, for example, two-part systems, dry seed treatment powders (DS), seed treatment emulsions (ES), seed treatment flowable concentrates (FS), seed treatment solutions (LS), seed treatment water dispersible powders (WS), seed treatment capsule suspensions (CF), seed treatment gels (GF), emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water dispersible granules (WG), emulsifiable granules (WG), etc. (EG), emulsion, water-in-oil (EO), emulsion, oil-in-water (EW), microemulsion (ME), oil dispersion (OD), oil-miscible flowable (OF), oil-miscible liquid (OL), soluble concentrate (SL), ultra-low volume suspension (SU), ultra-low volume liquid (UL), technical concentrate (TK), dispersible concentrate (DC), wettable powder (WP), or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0243] 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 used when long-lasting effectiveness is desired. 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.

[0244] 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.

[0245] 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.

[0246] Commercially available products are preferably formulated as concentrates, although end users will typically utilize diluted formulations.

[0247] 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.

[0248] A preferred formulation may have the following composition (by weight): 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% Dust: Active ingredient: 0.1 to 10%, preferably 0.1 to 5% Solid carrier: 99.9 to 90%, preferably 99.9 to 99% Suspension concentrate: Active ingredient: 5-75%, preferably 10-50% Water: 94-24%, preferably 88-30% Surfactant: 1 to 40%, preferably 2 to 30% 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% Granules: Active ingredient: 0.1 to 30%, preferably 0.1 to 15% Solid carrier: 99.5 to 70%, preferably 97 to 85%

[0249] The disclosure in this application makes available any and all combinations of the embodiments disclosed herein.

[0250] The compounds according to the following Tables A-1 to A-24 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 A-1 to A-24, 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.

[0251] Table A: This table shows compounds of formula (Ia) according to the invention: [ka] wherein G according to the compound of formula (I) of the present invention is: [ka] The present invention discloses 20 substituent definitions (G) where the G substituents are as defined below.

[0252] [Table 1]

[0253] Thus, the following compounds are specifically set forth in Tables A-1 to A-24 using the substituents of formula (Ia) below. Table A-1: ​​This table provides 20 compounds of formula (Ia) (A-1.01) to (A-1.20), R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 is H and the G substitution is as defined in Table A. For example, compound (A-1.01) has the following structure: [ka] Compound (A-1.01) Table A-2: This table provides 20 compounds of formula (Ia) (A-2.01) to (A-2.20), R 2 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 is H and R 2 is CH3 and the G substitution is as defined in Table A. For example, compound (A-2.09) has the following structure: [ka] Compound (A-2.09) Table A-3: This table provides 20 compounds of formula (Ia) (A-3.01) to (A-3.20), R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 is H and R 2 is Cl and the G substitutions are as defined in Table A. Table A-4: This table provides 20 compounds of formula (Ia) (A-4.01) to (A-4.20), R 2 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 is H and R 4 is CH3 and the G substitution is as defined in Table A. For example, compound (A-4.06) has the following structure: [ka] Compound (A-4.06) Table A-5: This table provides 20 compounds of formula (Ia) (A-5.01) to (A-5.20), R 5 , R 6 , R 7 , R 8 , R9 , R 10 and R 11 is H and R 2 and R 4 is CH3 and the G substitution is as defined in Table A. Table A-6: This table provides 20 compounds of formula (Ia) (A-6.01) to (A-6.20), R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 is H and R 2 is Cl and R 4 is CH3 and the G substitution is as defined in Table A. Table A-7: This table provides 20 racemic-Syn-(A-7.01) to racemic-Syn-(A-7.20) of formula (Ia), R 2 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 and R 11 is H and R 7 is CH3 and the G substituents are as defined in Table A. All compounds in this table have R 7 The substituent has a syn relationship with the pyrazole substituent. For example, the compound racemic-Syn-(A-7.06) has the following structure: [ka] Compound Racemic-Syn-(A-8.01) Table A-9: This table provides 20 racemic-Syn-(A-9.01) to racemic-Syn-(A-9.20) of formula (Ia), 4 , R 5 , R 6 , R 8 , R 9 , R 10 and R 11 is H and R 2 is Cl and R 7is CH3 and the G substituents are as defined in Table A. All compounds in this table have R 7 The substituent has a syn relationship with the pyrazole substituent. For example, compound (A-9.14) has the following structure: [ka] Compound Racemic-Syn-(A-8.01) Table A-9: This table provides 20 racemic-Syn-(A-9.01) to racemic-Syn-(A-9.20) of formula (Ia), 4 , R 5 , R 6 , R 8 , R 9 , R 10 and R 11 is H and R 2 is Cl and R 7 is CH3 and the G substituents are as defined in Table A. All compounds in this table have R 7 The substituent has a syn relationship with the pyrazole substituent. For example, compound (A-9.14) has the following structure: [ka] Compound racemic -Syn- (A-9.14) Table A-10: This table provides six compounds of formula (Ia) (A-10.01) to (A-10.06), R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 is H and R 11 is Br and the G substituents are as defined in Table A. Table A-11: This table provides six compounds of formula (Ia) (A-11.01) to (A-11.06), R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R9 and R 10 is H and R 11 is Cl and the G substituents are as defined in Table A. Table A-12: This table provides six compounds of formula (Ia) (A-12.01) to (A-12.06), R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 is H and R 11 is CN, and the G substituents are as defined in Table A. Table A-13: This table provides six compounds of formula (Ia) (A-13.01) to (A-13.06), R 2 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 is H and R 4 is CH3 and R 11 is Br and the G substituents are as defined in Table A. Table A-14: This table provides six compounds of formula (Ia) (A-14.01) to (A-14.06), R 2 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 is H and R 4 is CH3 and R 11 is Cl and the G substituents are as defined in Table A. Table A-15: This table provides six compounds of formula (Ia) (A-15.01) to (A-15.06), R 2 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 is H and R 4 is CH3 and R 11is CN, and the G substituents are as defined in Table A. Table A-16: This table provides six racemic forms of formula (Ia) from racemic-Syn-(A-16.01) to racemic-Syn-(A-16.006), R 2 , R 4 , R 5 , R 6 , R 8 , R 9 and R 10 is H and R 7 is CH3 and R 11 is Br and the G substituents are as defined in Table A. All compounds in this table have R 7 The substituent has a syn relationship with the pyrazole substituent. For example, the compound racemic-Syn-(A-16.04) has the following structure: [ka] Compound Racemic-Syn-(A-16.04) Table A-17: This table provides six racemic forms of formula (Ia) from racemic-Syn-(A-17.01) to racemic-Syn-(A-17.006), R 2 , R 4 , R 5 , R 6 , R 8 , R 9 and R 10 is H and R 7 is CH3 and R 11 is Cl and the G substituents are as defined in Table A. All compounds in this table have R 7 The substituent has a syn relationship with the pyrazole substituent. Table A-18: This table provides six racemic forms of formula (Ia) from racemic-Syn-(A-18.01) to racemic-Syn-(A-18.006), 2 , R 4 , R 5 , R 6 , R 8 , R 9 and R 10 is H and R 7 is CH3 and R 11is CN and the G substituents are as defined in Table A. All compounds in this table have R 7 The substituent has a syn relationship with the pyrazole substituent. Table A-19: This table provides six racemic forms of formula (Ia) from racemic-Syn-(A-19.01) to racemic-Syn-(A-19.006), R 4 , R 5 , R 6 , R 8 , R 9 and R 10 is H and R 2 and R 7 is CH3 and R 11 is Br and the G substituents are as defined in Table A. All compounds in this table have R 7 The substituent has a syn relationship with the pyrazole substituent. Table A-20: This table provides six racemic forms of formula (Ia) from racemic-Syn-(A-20.01) to racemic-Syn-(A-20.006), R 4 , R 5 , R 6 , R 8 , R 9 and R 10 is H and R 2 and R 7 is CH3 and R 11 is Cl and the G substituents are as defined in Table A. All compounds in this table have R 7 The substituent has a syn relationship with the pyrazole substituent. Table A-21: This table provides six racemic forms of formula (Ia) from racemic-Syn-(A-21.01) to racemic-Syn-(A-21.006), R 4 , R 5 , R 6 , R 8 , R 9 and R 10 is H and R 2 and R 7 is CH3 and R 11 is CN and the G substituents are as defined in Table A. All compounds in this table have R 7The substituent has a syn relationship with the pyrazole substituent. For example, the compound racemic-Syn-(A-21.01) has the following structure: [ka] Compound Racemic-Syn-(A-21.01) Table A-22: This table provides three compounds of formula (Ia) (A-22.01) to (A-22.03), R 4 , R 5 , R 6 , R 7 , R 8 , R 10 and R 11 is H and R 2 is CH3 and R 9 is Br and the G substituents are as defined in Table A. Table A-23: This table provides three compounds of formula (Ia) (A-23.01) to (A-23.03), R 4 , R 5 , R 6 , R 7 , R 8 , R 10 and R 11 is H and R 2 is CH3 and R 9 is OCH3 and the G substituents are as defined in Table A. Table A-24: This table provides three compounds of formula (Ia) (A-24.01) to (A-24.03), R 4 , R 5 , R 6 , R 7 , R 8 , R 10 and R 11 is H and R 2 is CH3 and R 9 is CN, and the G substituents are as defined in Table A. [Example]

[0254] The examples that follow are intended to illustrate the present invention and are not intended to limit it in any way.

[0255] 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.

[0256] 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.

[0257] Throughout this specification temperatures are given in degrees Celsius and "mp" means melting point. LC / MS means liquid chromatography mass spectrometry, with a description of the equipment and methods as follows:

[0258] 1 H NMR and 19 F NMR measurements were recorded on a Brucker 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 are the retention time ("Rt", recorded in minutes) and the observed molecular ion (M+H). + or (MH) - It was.

[0259] LC-MS Method A: Spectra were recorded on a Waters Corporation mass spectrometer (SQD, SQDII, or QDA single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative ion), capillary: 0.8-3.00 kV, cone: 5-30 V, source temperature: 120-150 °C, desolvation temperature: 350-600 °C, cone gas flow: 50-150 L / h, desolvation gas flow: 650-1000 L / h, mass range: 50-900 Da, and a Waters Corporation Acquity UPLC: binary pump, heated column compartment, diode array detector, and ELSD. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm; Temperature: 60 °C; DAD wavelength range (nm): 210–400; Run time: 1.5 min; Solvent: A = water + 5% MeOH + 0.05% HCOOH; B = acetonitrile + 0.05% HCOOH; Flow rate (ml / min): 0.85; Gradient: 10% B isocratic for 0.2 min, then 10–100% B for 1.0 min, 100% B isocratic for 0.2 min, 100–10% B for 0.05 min, 10% B isocratic for 0.05 min.

[0260] LC-MS Method B: Spectra were recorded on a Waters Corporation mass spectrometer (SQD, SQDII, or QDA single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive ion or negative ion). Optimized mass parameters were: ionization method: electrospray (ESI), polarity: positive / negative polarity switch, scan type: full scan, capillary (kV): 0.8, cone voltage (V): 23, source temperature (°C): 120, desolvation gas flow rate (L / h): 1000, desolvation temperature (°C): 600, gas flow rate @ cone (L / h): 50; mass range: 110–1200 Da; gradient conditions: Solvent A: water with 0.1% formic acid:acetonitrile = 95:5 v / v, Solvent B: acetonitrile with 0.05% formic acid.

[0261] [Table 2]

[0262] Recording was performed under the following conditions: PDA wavelength range: 200-400 nm, column: Acquity UPLC HSS T3 C18, column length: 30 mm, column inner diameter: 2.1 mm, particle size: 1.8 μ, column oven temperature: 40°C.

[0263] LC-MS Method C: Spectra were recorded on a Waters Corporation mass spectrometer (SQD, SQDII, or QDA single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive ion or negative ion). Optimized mass parameters were: ionization method: electrospray (ESI), polarity: positive / negative polarity switch, scan type: full scan, capillary (kV): 3.00, cone voltage (V): 41.00, source temperature (°C): 150, desolvation gas flow rate (L / h): 1000, desolvation temperature (°C): 500, gas flow rate @ cone (L / h): 50, mass range: 110–1000 Da, gradient conditions: Solvent A: water with 0.1% formic acid:acetonitrile = 95:5 v / v, Solvent B: acetonitrile with 0.05% formic acid.

[0264] [Table 3]

[0265] PDA wavelength range: 200~400nm, Column: Acquity UPLC HSS T3 C18, column length: 30 mm, column inner diameter: 2.1 mm, particle size: 1.8 μ, column oven temperature: 40°C.

[0266] LC-MS Method D: Spectra were recorded on a Waters Corporation mass spectrometer (SQD, SQDII, or QDA single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative ion), using optimized mass parameters: ionization method: electrospray (ESI), polarity: positive / negative polarity switch, scan type: MS2 scan, capillary (kV): 4.00, fragmentor (V): 100.00, gas temperature (°C): 350, gas flow rate (L / min): 11, nebulizer gas (psi): 40; mass range: 110–1000 Da, detection (VWD): 254 nm, gradient conditions: solvent A: water with 0.1% formic acid:acetonitrile = 95:5 v / v, solvent B: acetonitrile with 0.1% formic acid.

[0267] [Table 4]

[0268] Recording was performed using a KINETEX EVO C18 column, a column length of 50 mm, an inner diameter of the column of 4.6 mm, a particle size of 2.6 m, and a column oven temperature of 40°C.

[0269] LC-MS Method E: Instrument specifications: UHPLC Agilent 1290 Series LCMSD system equipped with DAD\ELSD and Agilent LC\MSD (G6125B) mass spectrometer. Column: Agilent Poroshell 120 SB-C18 4.6 × 30 mm 2.7 μm. Column temperature: 60 °C. Mobile phase: A - water (0.1% formic acid), B - acetonitrile (0.1% formic acid). Flow rate: 3 ml / min. Gradient: 0.01 min - 1% B, 1.5 min - 100% B, 1.73 min - 100% B. MS ionization mode: electrospray ionization (ESI). MS scan range: 83–600 m / z. UV detection: 215 nm, 254 nm, 280 nm.

[0270] LC-MS Method F: 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: 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.

[0271] LC-MS Method G: 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°C, 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 0.2–0.2 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.

[0272] LC-MS Method H: Spectra were recorded on a Waters Corporation ACQUITY mass spectrometer (SQD or SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative ion, capillary: 3.0 kV, cone: 30 V, extractor: 3.00 V, source temperature: 150 °C, desolvation temperature: 400 °C, cone gas flow: 60 L / h, desolvation gas flow: 700 L / h, mass range: 140-800 Da) and a Waters Corporation ACQUITY UPLC equipped with a solvent degasser, binary pump, heated column compartment, and diode array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm; Temperature: 60 °C; DAD wavelength range (nm): 210–400; Solvent gradient: A = water / methanol 9:1 + 0.1% formic acid, B = acetonitrile + 0.1% formic acid; Gradient: 0–100% B in 3.0 min; Flow rate (ml / min) 0.75.

[0273] Formulation example

[0274] [Table 5]

[0275] This combination is thoroughly mixed with adjuvants and the mixture is thoroughly ground in a suitable mill to obtain a wettable powder, which is diluted with water to obtain a suspension of the desired concentration.

[0276] [Table 6]

[0277] This combination is thoroughly mixed with an adjuvant and the mixture is thoroughly ground in a suitable mill to obtain a dust that can be used directly as a seed treatment.

[0278] 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%

[0279] Emulsions of any desired dilution that can be used for plant protection are obtained from this concentrate by dilution with water.

[0280] [Table 7]

[0281] Ready-to-use dusts are obtained by combining and mixing with a carrier and grinding the mixture in a suitable mill. Such powders can also be used as dry fertilizers for seeds.

[0282] Extruded Granules Active ingredient 15% Sodium lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 82% 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.

[0283] Coated Granules Active ingredient 8% Polyethylene glycol (molecular weight 200) 3% Kaolin 89% This micronized combination is applied uniformly in a mixer to kaolin wetted with polyethylene glycol, thus obtaining coated granules that do not generate dust.

[0284] Suspension concentrate Active ingredient 40% Propylene glycol 10% Nonylphenol polyethylene glycol ether (ethylene oxide 15 mol) 6% Sodium lignosulfonate 10% Carboxymethylcellulose 1% Silicone oil (in the form of a 75% emulsion in water) 1% water 32% 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 microbial infestation by spraying, pouring, or dipping.

[0285] 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% 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 microbial infestation by spraying, pouring, or dipping.

[0286] extended-release capsule suspension 28 parts of the combination are mixed with 2 parts aromatic solvent and 7 parts toluene diisocyanate / polymethylene-polyphenylisocyanate (8:1) mixture. This mixture is emulsified in a mixture of 1.2 parts polyvinyl alcohol, 0.05 parts 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 average capsule diameter is 8 to 15 microns. The resulting formulation is applied to seeds as an aqueous suspension in equipment suitable for this purpose.

[0287] 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 desirable formulation in combination with agriculturally acceptable adjuvants.

[0288] Abbreviation CDCl3 deuterated chloroform DABCO 1,4-diazabicyclo[2.2.2]octane, also known as triethylenediamine or TEDA DCC dicyclohexylcarbodiimide DIPEA Diisopropylethylamine (N,N-diisopropylethylamine) DMA Dimethylacetamide DMF Dimethylformamide DMSO dimethyl sulfoxide DMSO-d6 Deuterated dimethyl sulfoxide EDC 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Et3N Triethylamine EtOAc ethyl acetate HATU 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide-hexafluorophosphate HCl Hydrochloric acid hr / hrs hours / hours LC-MS Liquid Chromatography Mass Spectrometry (LC-MS, LC / MS or LCMS) rh relative humidity rt room temperature Rt retention time ssp. subspecies TBME Methyl tert-butyl ether or tert-butyl methyl ether

[0289] Preparation Examples: Compounds of formula (I) according to the invention may be prepared using the synthetic techniques described both above and below.

[0290] "Mp" means melting point (°C). The free radical represents a methyl group.

[0291] Example P1: Preparation of [2-(2,4-difluorophenyl)tetrazol-5-yl]-[6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (compound P-31, Table P)

[0292] Step 1: Preparation of 4-(1,5-dimethylpyrazol-4-yl)isoquinoline [ka] A suspension of 4-bromoisoquinoline (2.0 g, 9.4204 mmol), 1,5-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (2.3484 g, 10.362 mmol), and potassium carbonate (1.4322 g, 10.362 mmol) in a toluene / methanol mixture (30 mL, 5:1) was degassed with argon in a microwave vial for several minutes, and then tetrakis(triphenylphosphaniumyl)palladium (0.545 g, 0.471 mmol) was added. The reaction mixture was heated to 100 °C and stirred under microwave irradiation for 1 hour. After cooling to room temperature, the reaction mixture was poured into water and extracted with EtOAc. The organic layer was separated, dried over Na SO , filtered, and concentrated in vacuo. Purification of the crude material by flash chromatography on silica gel (eluting with EtOAc / 30% methanol) afforded the title compound. LCMS (Method A): m / z 225 [M+H], retention time 0.51 min

[0293] Step 2: Preparation of 4-(1,5-dimethylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline [ka] To a solution of 4-(1,5-dimethylpyrazol-4-yl)isoquinoline (2.00 g, 8.96 mmol) in methanol (90 mL) was added sodium cyanoborohydride (3.55 g, 53.7 mmol) at room temperature. The reaction mixture was stirred at room temperature, and then hydrochloric acid (1.25 M in methanol) was added until a pH of 2-3 was reached. After stirring at room temperature for 30 minutes, the reaction mixture was diluted with water, basified with 2 N sodium hydroxide, and the mixture was extracted with EtOAc (3 × 25 mL). The combined organic layers were dried over NaSO, filtered, and concentrated in vacuo. The resulting yellow oil was used without further purification. LCMS (Method A): m / z 228 [M+H]. Retention time 0.29 min The hydrochloride salt of the title product (4-(1,5-dimethylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline; hydrochloride) could be obtained by treating the yellow oil with 2M HCl in diethyl ether followed by concentration in vacuo.

[0294] Step 3: Preparation of ethyl (2E)-2-(p-tolylsulfonylhydrazono)acetate [ka] A solution of 4-methylbenzenesulfonohydrazide (2 g, 10.7 mmol) in ethanol (40 mL) was treated with ethyl 2-oxoacetate (2.63 g, 12.8 mmol) at room temperature. The reaction mixture was stirred for 1 hour and concentrated in vacuo to remove ethanol. The resulting residue was diluted with water and extracted with EtOAc. The organic phase was separated and the solvent evaporated in vacuo to give ethyl (2E)-2-(p-tolylsulfonylhydrazono)acetate, which was used directly in the next step. LCMS (Method B): m / z 271[M+H], retention time 1.06 min. 1 H NMR(400MHz,CDCl3)δ ppm 9.31(s,1H),7.85(d,J=8.31Hz,2H),7.34(d,J=8.07Hz,2H),7.23(s,1H),4.27(q,J=7.09Hz,2H),2.44(s,3H)1.23-1.37(m,3H).

[0295] Step 4: Preparation of ethyl 2-(2,4-difluorophenyl)tetrazole-5-carboxylate [ka] A solution of 2,4-difluoroaniline (1.00 g, 7.74 mmol) in a solution of 6 M hydrochloric acid (6 mL, 36 mmol) and ethanol (5 mL) in deionized water was cooled to 0 °C. Sodium nitrite (0.64 g, 9.29 mmol) was added to the solution, and the resulting solution was stirred for 1 h and then added dropwise to a solution of ethyl (2E)-2-(p-tolylsulfonylhydrazono)acetate (2.3 g, 8.51 mmol) in pyridine (20 mL) at −20 °C. The reaction mixture was slowly warmed to room temperature and then stirred for 5 h. The resulting mixture was diluted with 1 N HCl, and the aqueous layer was extracted with EtOAc. The combined organic layers were dried over NaSO and concentrated in vacuo to give the crude product, which was purified by column chromatography eluting with 30% EtOAc in hexane to give ethyl 2-(2,4-difluorophenyl)tetrazole-5-carboxylate as a reddish oil. 1 H NMR(400MHz,CDCl3)δ ppm 7.86-7.94(m,1H),7.11-7.21(m,2H),4.60(q,J=7.21Hz,2H),1.51(t,J=7.13Hz,3H)

[0296] Step 5: Preparation of [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-(1,5-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-31, Table P) [ka] (Compound P-31, Table P). A solution of ethyl 2-(2,4-difluorophenyl)tetrazole-5-carboxylate (0.1 g, 0.39 mmol) in toluene (2 mL) was treated with 4-(1,5-dimethylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline hydrochloride (0.12 g, 0.47 mmol), and the solution was then cooled in an ice bath. To this was added a trimethylaluminum solution (2.0 mol / L) in toluene (0.6 mL, 1.18 mmol) dropwise at 0° C., and the resulting mixture was then heated to 80° C. for 2 hours. After completion of the reaction, the mixture was diluted with EtOAc and quenched with 1N aqueous HCl solution. The organic layer was separated, and the aqueous layer was back-extracted with EtOAc. The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography to give [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone as a white solid. LCMS (Method C): m / z 436 (M+H), retention time 1.07 min.

[0297] Example P2: Preparation of [1-(2,4-difluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (compound P-8, Table P)

[0298] Step 1: Preparation of methyl 1-(2,4-difluorophenyl)triazole-4-carboxylate: [ka] A solution of 1-azido-2,4-difluorobenzene (0.30 g, 1.8 mmol) in methanol (3.6 mL) was treated successively with anhydrous copper(II) sulfate (0.053 g, 0.33 mmol), sodium ascorbate (0.46 g, 2.3 mmol) in water (3.6 mL), and then methyl prop-2-ynoate (0.14 g, 0.14 mL, 1.7 mmol). The reddish reaction mixture was stirred at room temperature for 2 days while being monitored by LCMS. The reaction mixture was then concentrated in vacuo, and the residue was taken up in water and EtOAc. The organic layer was separated and washed with brine. The separated organic layer was dried over MgSO4, filtered, and concentrated in vacuo. The crude product was purified on a silica gel cartridge (Rf 200) eluting with cyclohexane / EtOAc to give the title compound as a white solid. LCMS (Method A): m / z 240 (M+H), 0.79 min. 1 H NMR(400MHz,CDCl3)δ ppm;8.59(d,J=2.57Hz,1H),7.96-8.05(m,1H),7.09-7.17(m,2H),4.02(s,3H)

[0299] Step 2: Preparation of 1-(2,4-difluorophenyl)triazole-4-carboxylic acid [ka] A sample of methyl 1-(2,4-difluorophenyl)triazole-4-carboxylate (0.31 g, 1.3 mmol) was dissolved in tetrahydrofuran (6.5 mL) and water (3.2 mL) under argon to give a pale brown solution. To this was added lithium hydroxide monohydrate (0.047 g, 1.9 mmol), and the mixture was stirred at room temperature. After 3 h, LCMS indicated the desired mass and consumption of starting material. The tetrahydrofuran was evaporated in vacuo, and then 2N aqueous HCl (approximately 0.5 mL) was added to keep the aqueous phase at pH 3-4. The resulting pale red suspension was filtered, and the white cake was washed with water and cyclohexane and dried in vacuo at 55 °C to give 1-(2,4-difluorophenyl)triazole-4-carboxylic acid as a white solid. LCMS (Method A): m / z 226 (M+H), retention time 0.63 min. 1 H NMR(400MHz,DMSO-d6)δ ppm 7.27-7.52(m,1H),7.73(ddd,J=11.10,8.71,2.57Hz,1H),7.95(td,J=8.80,5.87Hz,1H),9.15(d,J=1.47Hz,1H),13.26-13.60(bs,1H).

[0300] Step 3: Preparation of 4-(1-methylpyrazol-4-yl)isoquinoline [ka] Prepared similarly to Example P1, Step 1 LCMS (Method A): m / z 210 (M+H), retention time 0.41 min 1 H NMR(400MHz,CDCl3)δ ppm:9.20(s,1H),8.51(s,1H),8.10-8.18(m,1H),8.03(d,J=8.07Hz,1H),7.78-7 .81(m,1H),7.70-7.76(m,1H),7.66-7.68(m,1H),7.62-7.66(m,1H),4.06(s,3H)

[0301] Step 4: Preparation of 4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline [ka] Prepared analogously to Example P1, step 2. The crude product was used without further purification.

[0302] Step 5: Preparation of [1-(2,4-difluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Synthetic P-8, Table P) [ka] (Compound P-8, Table P) Under argon, a mixture of 4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline (0.090 g, 0.40 mmol) and 1-(2,4-difluorophenyl)triazole-4-carboxylic acid (0.090 g, 0.40 mmol) dissolved in EtOAc (3 mL) was treated with 1-propanephosphonic anhydride (0.60 mL, 1.0 mmol) and N,N-diisopropylethylamine (0.28 mL, 1.6 mmol). The resulting solution was stirred at room temperature. After 17 h, LCMS indicated the reaction was complete. The reaction mixture was poured into water and extracted with EtOAc. The organic layer was washed with saturated sodium bicarbonate solution, followed by 1 M HCl, water, and brine. The organic layer was dried over Na2SO4 and concentrated in vacuo. Purification of the crude material by flash chromatography on silica gel (eluting with EtOAc in cyclohexane) afforded the title product. LCMS (Method A) m / z 421 (M+H), retention time 0.92 min.

[0303] Example P3: Preparation of 2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone (Compound P-32, Table P)

[0304] Step 1: Preparation of (1-methylpyrazol-4-yl)-phenyl-methanol [ka] A one-necked round-bottom flask equipped with a magnetic stir bar was charged with 1-methyl-1H-pyrazole-4-carbaldehyde (2.20 g, 19.2 mmol) and tetrahydrofuran (40 mL). To the colorless solution, 1 molar phenylmagnesium bromide (21 mL, 21.1 mmol) in THF was added dropwise over 15 min at 0–5°C under an argon atmosphere. After the addition, the ice bath was removed, and the white suspension was stirred at room temperature for 2.5 h. The reaction mixture was poured into saturated ammonium chloride solution (40 mL) and extracted with EtOAc (2 × 40 mL). The combined organic layers were washed with brine, dried over NaSO, and concentrated in vacuo to give the crude product as a colorless oil. The crude product was purified by combiflash (silica gel, gradient: EtOAc in cyclohexane) to give the desired product, (1-methylpyrazol-4-yl)-phenyl-methanol, as a colorless oil. LCMS (Method A) m / z 189 [M+H], retention time: 0.62 min. 1 H NMR(400MHz,CDCl3)δ ppm 7.26-7.43(m,6H),7.18(s,1H),5.80(s,1H),3.81(s,3H),2.89(br s,1H)

[0305] Step 2: Preparation of 2-(1-methylpyrazol-4-yl)-2-phenyl-acetonitrile [ka] A round-bottom flask equipped with a magnetic stir bar and a condenser was charged with (1-methylpyrazol-4-yl)-phenyl-methanol (3.45 g, 15.6 mmol) and dichloromethane (156 mL). Then, lithium carbonate (0.23 g, 3.1 mmol), trimethylsilyl cyanide (9.0 mL), and iodine (7.23 g, 28.0 mmol) were added sequentially at room temperature. The mixture was stirred at 35 °C for 1 h. The reaction mixture was then cooled to room temperature, poured into saturated sodium thiosulfate (250 mL), and extracted with dichloromethane (2 × 150 mL). The combined organic layers were washed with brine, dried over Na SO , and concentrated in vacuo to give the crude product, which was purified by combiflash (silica gel, gradient: EtOAc in cyclohexane) to give the desired title compound as a yellow oil. LCMS (Method A) m / z 198 [M+H], retention time: 0.78 min. 1 H NMR(400MHz,CDCl3)δ ppm 7.33-7.43(m,6H),7.32(s,1H),5.09(s,1H),3.87(s,3H)

[0306] Step 3: Preparation of 2-(1-methylpyrazol-4-yl)-2-phenyl-propanenitrile [ka] A 250 mL three-necked flask equipped with a magnetic stir bar and a condenser was charged with 2-(1-methylpyrazol-4-yl)-2-phenyl-acetonitrile (3.22 g, 16.3 mmol) and tetrahydrofuran (65 mL). A solution of n-butyllithium (7.8 mL, 19.6 mmol) in hexane was added dropwise at −70° C. under a nitrogen atmosphere (a small exotherm to −65° C. was observed). The orange solution was stirred at this temperature for 30 minutes, after which iodomethane (1.54 mL, 24.5 mmol) was added dropwise at −70° C. The resulting yellow solution was stirred at −78° C. for 5 minutes, then warmed to ambient temperature and stirred for 30 minutes. The reaction mixture was then poured into water (90 mL) and extracted with EtOAc. The organic layer was washed with brine, dried over Na2SO4, and concentrated in vacuo to give the crude product as an orange oil. This was purified by combiflash (silica gel, gradient: EtOAc in cyclohexane) to give the title compound as a yellow oil. LCMS (Method A) m / z 211 [M+H], retention time: 0.84 min. 1 H NMR(400MHz,CDCl3)δ ppm 7.28-7.49(m,7H),3.88(s,3H),2.04(s,3H)

[0307] Step 4: Preparation of 2-(1-methylpyrazol-4-yl)-2-phenyl-propan-1-amine [ka] A 250 mL three-necked flask equipped with a magnetic stir bar was charged with 2-(1-methylpyrazol-4-yl)-2-phenylpropanenitrile (2.82 g, 13.3 mmol) and tetrahydrofuran (40 mL). To the yellow solution, borane dimethyl sulfide complex (4.0 mL, 40.0 mmol) was added dropwise at room temperature under an argon atmosphere, and the resulting colorless mixture was stirred at 65 °C for 2 h. After the reaction mixture was cooled to 0 °C, hydrochloric acid (8.9 mL, 53.7 mmol) was added dropwise (strong gas evolution), and the mixture was stirred at 65 °C for 1 h and allowed to stand at room temperature overnight. The mixture was diluted with water (80 mL), basified with 13 mL of 6 M NaOH (pH 12), and extracted twice with EtOAc. The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo to give the title compound as a yellow oil, which was used in the next step without further purification. LCMS (Method A) m / z216[M+H], retention time: 0.39 minutes

[0308] Step 5: Preparation of methyl N-[2-(1-methylpyrazol-4-yl)-2-phenyl-propyl]carbamate [ka] A sealed tube equipped with a magnetic stir bar was charged with 2-(1-methylpyrazol-4-yl)-2-phenyl-propan-1-amine (3.01 g, 11.2 mmol) and dichloromethane (45 mL). Methyl chloroformate (1.1 mL, 13.4 mmol) was added dropwise at 0-10 °C under an argon atmosphere, followed by triethylamine (4.7 mL, 33.6 mmol). The ice bath was removed, and the mixture was stirred at room temperature for 1 h. The reaction mixture was poured into water, and the organic phase was separated. The aqueous phase was extracted twice with EtOAc. The combined organic layers were dried over Na2SO4 and concentrated in vacuo. The crude material was purified by combiflash (silica gel, gradient: EtOAc in cyclohexane) to give the title compound as a colorless gum. LCMS (Method A) m / z 274[M+H], retention time: 0.80 min.

[0309] Step 6: Preparation of methyl 4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinoline-2-carboxylate [ka] A one-necked round-bottom flask equipped with a magnetic stir bar was charged with methyl N-[2-(1-methylpyrazol-4-yl)-2-phenyl-propyl]carbamate (422 mg, 1.54 mmol), hydrochloric acid (5.00 mL / mmol, 9.26 g, 7.72 mL, 94.0 mmol), and paraformaldehyde (93 mg, 0.97 mmol). The mixture was stirred at room temperature for 40 minutes, and LCMS analysis indicated the reaction was complete. The reaction mixture was slowly poured into water (30 mL), neutralized with sodium bicarbonate, and extracted with EtOAc (3 × 20 mL). The combined organic layers were washed with brine, dried over NaSO, and concentrated in vacuo to afford the crude title compound as a colorless gum, which was used directly without further purification. LCMS (Method A) m / z 286 [M+H], retention time: 0.87 min.

[0310] Step 7: Preparation of 4-methyl-4-(1-methylpyrazol-4-yl)-2,3-dihydro-1H-isoquinoline [ka] A one-necked round-bottom flask equipped with a magnetic stir bar was charged with methyl 4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinoline-2-carboxylate (3.86 g, 13.5 mmol), 1,2-dichloroethane (5.00 mL / mmol, 68 mL), and iodotrimethylsilane (8.37 g, 5.69 mL, 40.6 mmol). The mixture was stirred at 60 °C under an argon atmosphere for 45 minutes (LCMS analysis indicated the reaction was complete). After cooling to room temperature, the reaction mixture was slowly poured into saturated sodium bicarbonate solution (30 mL). The resulting mixture was extracted with EtOAc (2 × 50 mL), and the combined organic layers were washed with brine, dried over Na SO , and concentrated in vacuo to give the title compound as a dark orange gum. LCMS (Method A), m / z 228 [M+H], retention time: 0.61 min.

[0311] Step 8: Preparation of [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone (Synthetic P-32, Table P) [ka] (Compound P-32, table) To a cooled solution of ethyl 2-(2,4-difluorophenyl)tetrazole-5-carboxylate (0.2 g, 0.78 mmol) and 4-methyl-4-(1-methylpyrazol-4-yl)-2,3-dihydro-1H-isoquinoline (0.21 g, 0.94 mmol) in toluene (48 mL) was added a solution of trimethylaluminum (2.0 mol / L) in toluene (1.2 mL, 2.36 mmol) dropwise at 0° C. The resulting mixture was heated to 90° C. for 3 h, and LCMS analysis indicated the reaction was complete. The reaction mixture was diluted with EtOAc and diluted with 1N The mixture was quenched with HCl solution. The mixture was extracted with EtOAc (3 × 25 mL), and the combined organic layers were dried over NaSO, filtered, and concentrated in vacuo. The crude product was purified by chromatography on silica gel using a cyclohexane / EtOAc gradient to give [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone. LCMS (Method C), m / z 436[M+H], retention time: 1.06 min. 1H NMR(400MHz, CDCl3)δ ppm 7.79-7.88(m,1H),6.99-7.22(m,7H),6.72(s,1H),5.10-5.21(m,1H),4.87-5. 00(m,1H),4.23(d,J=13.45Hz,1H),3.84-3.96(m,1H),3.67(s,3H),1.59(s,3H)

[0312] Example P4: Preparation of [1-(2,4-difluorophenyl)-1,2,4-triazol-3-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Synthesis P-33, Table P)

[0313] Step 1: Preparation of methyl 1-(2,4-difluorophenyl)-1,2,4-triazole-3-carboxylate [ka] Prepared as described in Org. Lett. 2018, 20, 6930-6933. Thus, a solution of 2,4-difluorobenzenediazonium tetrafluoroborate (500 mg, 0.5 g, 2.1939 mmol, prepared as described in J. Am. Chem. Soc. 1956, 78, 2593-6) in tetrahydrofuran (8.8 mL) was cooled to 0 °C and treated with lithium acetate dihydrate (0.44765 g, 4.3879 mmol), Cu(OAc) (0.10 equiv., 0.03985 g, 0.21939 mmol) and methyl 2-isocyanacetate (1.20 equiv., 0.2609 g, 0.239 mL, 2.6327 mmol) were added at 0 °C, and the mixture was stirred at this temperature for 4 h. LCMS analysis after this time showed the reaction was complete. The reaction mixture was poured into water (25 mL) and the mixture was extracted with EtOAc (2 x 20 mL). The combined organic layers were washed with brine, dried over NaSO and concentrated in vacuo. The crude material was purified by column chromatography (24 g SiO, eluting with an EtOAc / cyclohexane gradient) to give the title compound as an oil. 1 H NMR(400MHz,CDCl3)δ ppm 8.68(d,J=2.81Hz,1H),7.93-8.00(m,1H),7.08-7.14(m,2H),4.08(s,3H)

[0314] Step 2: Preparation of [1-(2,4-difluorophenyl)-1,2,4-triazol-3-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Synthetic P-33, Table P) [ka] (Compound P-33, Table P) A sample of 4-(1,5-dimethylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline hydrochloride (0.13 g, 0.50 mmol, prepared as described in Example P1) was added to a solution of methyl 1-(2,4-difluorophenyl)-1,2,4-triazole-3-carboxylate (0.100 g, 0.41 mmol) in toluene (3.0 mL) in a microwave vial. The reaction mixture was stirred under an argon atmosphere for 5 minutes, and then bis(trimethylaluminum)-1,4-diazabicyclo[2.2.2]octane adduct (0.27 g, 1.04 mmol) was added. The reaction mixture was stirred at room temperature for 5 minutes and then stirred in a microwave at 70 °C for 2 hours. After cooling to room temperature, the reaction mixture was diluted with water and extracted with EtOAc (×3). The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo. The crude product was purified by chromatography on silica gel using 50-70% cyclohexane / EtOAc as the eluent system to give [1-(2,4-difluorophenyl)-1,2,4-triazol-3-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone as a gum. LCMS (Method D): m / z (M+H) 435, retention time 1.38 minutes 1 H NMR(400MHz,CDCl3)δ ppm 8.59-8.50(m,1H),7.89-7.75(m,1H),7.25-6.92(m,7H),5.24 -5.13(m,1H)4.78(d,1H)4.15-4.49(m,2H),3.70-3.52(m,4H),2.18-1.98(m,3H)

[0315] Example P5: Preparation of [2-(2,4-difluorophenyl)triazol-4-yl]-[rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone (compound P-40, Table P)

[0316] Step 1: (1,5-Dimethylpyrazol-4-yl)-phenyl-methanol [ka] Preparation as in Example 3, Step 1 LCMS (Method A): m / z (M+H) 203, retention time 0.68 minutes 1 H NMR(400MHz,CDCl3)δ ppm 2.23(s,3H)2.28(d,J=4.00Hz,1H)3.76(s,3H)5.80(d,J=3.63Hz,1H)7.22(s,1H)7.27-7.32(m,1H)7.33-7.44(m,4H)

[0317] Step 2: 2-(1,5-dimethylpyrazol-4-yl)-2-phenyl-acetonitrile [ka] Preparation as in Example 3, Step 2 LCMS (Method A): m / z (M+H) 212, retention time 0.82 minutes 1 H NMR(400MHz,CDCl3)δ=7.46-7.28(m,6H),5.05(s,1H),3.78(s,3H),2.18(s,3H)

[0318] Step 3: 2-(1,5-dimethylpyrazol-4-yl)-2-phenyl-ethanamine [ka] Preparation as in Example 3, Step 3 LCMS (Method A): m / z (M+H) 216, retention time 0.60 min 1 H NMR(400MHz,CDCl3)δ ppm 2.09(s,3H)3.20(dd,J=7.45,2.00Hz,2H)3.75(s,3H)3.79(t,J=7.27Hz,1H)7.16-7.25(m,3H)7.26-7.33(m,2H)7.42(s,1H)

[0319] Step 4: Methyl N-[2-(1,5-dimethylpyrazol-4-yl)-2-phenyl-ethyl]carbamate [ka] Preparation as in Example 3, Step 4 LCMS (Method A): m / z (M+H) 274, retention time 0.76 minutes 1 H NMR(400MHz,CDCl3)δ ppm 1.57(d,J=6.90Hz,3H)2.18(br d,J=6.90Hz,3H)3.05-3.27(m,1H)3.78(br s,3H)3.84(s,3H)3.99-4.09(m,1H)4.09-4.38(m,1H)5.22-5.47(m,1H)6.92-7.01(m,1H)7.07-7.27(m,4H 1 H NMR(400MHz,CDCl3)δ ppm 2.03-2.13(m,3H)3.62-3.74(m,5H)3.77(s,3H)3.94-4.05(m,1H)4.72(br s,1H)7.21-7.26(m,3H)7.27-7.34(m,2H)7.38(s,1H)

[0320] Step 5: Preparation of methyl rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxylate [ka] A one-necked round-bottom flask equipped with a magnetic stir bar was charged with methyl N-[2-(1,5-dimethylpyrazol-4-yl)-2-phenyl-ethyl]carbamate (2.0 g, 7.3 mmol), hydrochloric acid (37 mL, 450 mmol), and acetaldehyde (0.83 mL, 15 mmol). The mixture was stirred at room temperature for 2 hours. The reaction mixture was slowly poured into water (500 mL) and neutralized with NaHCO (strong gas evolution). The mixture was extracted with EtOAc (3 × 50 mL), and the combined organic layers were washed with brine, dried over NaSO, filtered, and concentrated in vacuo. The crude product was purified by chromatography to give the title compound as an oil. LC-MS (Method A): Retention time 0.87 min, 300 (M+H) 1 H NMR(400MHz,CDCl3)δ ppm 1.57(d,J=6.90Hz,3H)2.18(br d,J=6.90Hz,3H)3.05-3.27(m,1H)3.78(br s,3H)3.84(s,3H)3.99-4.09(m,1H)4.09-4.38(m,1H)5.22-5.47(m,1H)6.92-7.01(m,1H)7.07-7.27(m,4H

[0321] Step 6. Preparation of rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-1,2,3,4-tetrahydroisoquinoline [ka] A sample of methyl rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxylate (1.3 g, 4.1 mmol) in 1,2-dichloroethane (21 mL) was treated with iodotrimethylsilane (1.7 mL, 12 mmol), and the mixture was stirred under argon at 60° C. for 1 hour, at which point LCMS analysis indicated the reaction was complete. The reaction was cooled to room temperature, and then 10% HCl (22 mL) was added to the reaction under ice cooling. The mixture was concentrated in vacuo to remove volatiles, and the remaining aqueous solution was adjusted to pH 8 with 10% NaOH (aq). The mixture was extracted with CH2Cl2 (4 x 25 mL) and the combined organic layers were dried over Mg2SO4, filtered and concentrated in vacuo to give the title product as a single diastereomer (>97:3 syn:anti), which was sufficiently pure for use in the following step. LC-MS (Method A): m / z242(M+H), retention time 0.35 min 1 H NMR(600MHz,CDCl3)δ ppm 1.86(d,J=6.9Hz,3H)2.23(s,3H)3.27(dd,J=12.5,10.8Hz,1H)3.59(dd,J=12.8,5.6Hz,1H)3.83(s,3H)4.58(dd,J=10.6, 5.4Hz,1H)4.80(q,J=6.8Hz,1H)7.00(d,J=7.8Hz,1H)7.11(s,1H)7.16(d,J=7.6Hz,1H)7.18-7.22(m,1H)7.25-7.28(m,1H)

[0322] Step 7: Preparation of ethyl 2-[(2,4-difluorophenyl)hydrazono]-3-oxo-propanoate [ka] To a two-necked round-bottom flask equipped with a nitrogen inlet was added 2,4-difluoroaniline (4.00 g, 30.9 mmol) in water (32 mL) and concentrated HCl (12 mL, 35%) at room temperature. The reaction mixture was cooled to 0 °C, and a cold solution of sodium nitrite (2.56 g, 37.1 mmol) in water (32 mL) was added, and the resulting mixture was stirred at 0 °C for 5 minutes. In a separate round-bottom flask, a solution of ethyl 3-(dimethylamino)prop-2-enoate (12.0 g, 23.4 mmol) and potassium acetate (4.61 g, 46.4 mmol) in ethanol (40 mL) was stirred and cooled to 0 °C. To this was added the above diazotization solution dropwise at 0 °C, and the reaction mixture was allowed to warm to room temperature and stirred for 18 hours. LCMS indicated the formation of the desired product. The reaction was diluted with water and extracted with EtOAc (3 × 50 mL). The combined organic layers were washed with brine, dried over Na2SO4 and concentrated in vacuo to give crude ethyl 2-[(2,4-difluorophenyl)hydrazono]-3-oxo-propanoate as a brown solid, which was used directly in the next step. LCMS (Method B): m / z257[M+H], retention time = 1.09 min

[0323] Step 8: Preparation of ethyl 2-[(2,4-difluorophenyl)hydrazono]-3-hydroxyimino-propanoate [ka] To a solution of ethyl 2-[(2,4-difluorophenyl)hydrazono]-3-oxopropanoate (3.00 g, 5.85 mmol) in ethanol (30 mL) was added potassium acetate (1.45 g, 14.6 mmol) and hydroxylamine hydrochloride (0.49 g, 7.02 mmol). The reaction mixture was stirred at 80° C. for 2 hours. LCMS showed complete conversion to the desired product. The reaction mixture was cooled to room temperature, diluted with water, and extracted with EtOAc (3×50 mL). The combined organic layers were washed with brine, dried over NaSO, and concentrated in vacuo to give the title compound as a yellow solid, which was used directly in the next step. LCMS (Method B): m / z272[M+H], retention time = 1.16 min

[0324] Step 9: Preparation of ethyl 2-(2,4-difluorophenyl)triazole-4-carboxylate [ka] A sample of ethyl 2-[(2,4-difluorophenyl)hydrazono]-3-hydroxyimino-propanoate (3.4 g, 6.3 mmol) was treated with acetic anhydride (34 mL, 10 mL / g) at room temperature. The reaction mixture was then stirred at 140° C. for 1 h. The reaction mass was monitored by LC-MS. After completion, the reaction mixture was cooled and quenched with ice and cold brine. The reaction mixture was extracted with EtOAc (3×25 mL), and the combined organic layers were dried over NaSO and concentrated in vacuo to give the crude product. This was purified by combiflash using EtOAc / cyclohexane (5:95) as the eluent to give the title compound as a brown solid. LCMS (Method C): m / z254[M+H], retention time = 1.19 minutes

[0325] Step 10: Lithium; Preparation of 2-(2,4-difluorophenyl)triazole-4-carboxylate [ka] A stirred solution of ethyl 2-(2,4-difluorophenyl)triazole-4-carboxylate (0.10 g, 0.31 mmol) in tetrahydrofuran (0.4 mL) and water (0.1 mL) was treated with lithium hydroxide (11.0 mg, 0.47 mmol), and the reaction was stirred at room temperature for 3 hours. After completion of the reaction, the reaction mixture was concentrated in vacuo, and the residue was triturated with methyl tert-butyl methyl ether (TBME). This afforded lithium 2-(2,4-difluorophenyl)triazole-4-carboxylate, which was used directly in the next step. LCMS (Method B): m / z224[M+H], retention time = 0.29 min

[0326] Step 11: Preparation of [2-(2,4-difluorophenyl)triazol-4-yl]-[rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-40, Table P) [ka] (rac-syn-compound P-40, Table P) A suspension of lithium, 2-(2,4-difluorophenyl)triazole-4-carboxylate (0.231 g, 1.0 mmol, 100% by weight), and rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-1,2,3,4-tetrahydroisoquinoline (0.241 g, 1.0 mmol) in EtOAc (9 mL) was treated with DIPEA (0.7 g, 5 mmol) and 1-propanephosphonic anhydride (TP3, 2 mL, 3 mmol, 50% by weight in EtOAc) at 0° C. The reaction mixture was stirred at room temperature for 2 hours. After completion of the reaction, the reaction mixture was diluted with water (15 mL) and extracted with EtOAc (3×20 mL). The combined organic layers were washed with brine (20 mL), dried over NaSO, filtered, and concentrated in vacuo to give the crude product. This was purified by combiflash using 0-80% cyclohexane / EtOAc as eluent to give the title compound as a brown solid. LCMS (Method B), m / z 449 (M+H), retention time 1.14 min.

[0327] Example P6: Preparation of [2-(2,4-difluorophenyl)tetrazol-5-yl]-[6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (compound P-34, Table P).

[0328] Step 1: Preparation of (3-methoxyphenyl)-(1-methylpyrazol-4-yl)methanol [ka] A one-necked round-bottom flask equipped with a magnetic stir bar was charged with 4-iodo-1-methyl-1h-pyrazole (5.14 g, 23.5 mmol) and tetrahydrofuran (64 mL). To this solution, isopropylmagnesium chloride lithium chloride complex (1.3 mol / L) in THF (25 mL, 32.0 mmol) was added dropwise under argon at 0°C. The mixture was stirred at 0°C for 45 minutes, and then 3-methoxybenzaldehyde (2.68 mL, 21.3 mmol) was added dropwise under argon at 0°C. The mixture was stirred at this temperature for 10 minutes, then allowed to reach room temperature and stirred for 2 hours. The reaction mixture was then poured into water (100 mL) and extracted with EtOAc (2 x 80 mL). The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo. The crude material was purified by flash chromatography (80 g SiO.sub.2, EtOAc / cyclohexane gradient) to give (3-methoxyphenyl)-(1-methylpyrazol-4-yl)methanol. LCMS (Method B): m / z 219[M+H], retention time 0.21 min. 1 H NMR(400MHz,CDCl3)δ ppm:7.39(s,1H),7.26-7.33(m,1H),7.28(s,1H),6.96-7.05(m,2H),6.82-6.90(m,1H),5.72-5.88(m,1H),3.84(s,3H),3.82(s,3H)

[0329] Step 2: Preparation of 2-(3-methoxyphenyl)-2-(1-methylpyrazol-4-yl)acetonitrile [ka] A solution of (3-methoxyphenyl)-(1-methylpyrazol-4-yl)methanol (4 g, 9.16 mmol) in acetonitrile (18 mL) was treated with iodine (4.18 g, 16.5 mmol) and lithium carbonate (0.13 g, 1.83 mmol), followed by the dropwise addition of trimethylsilyl cyanide (5.26 mL, 41.2 mmol) at room temperature. The resulting mixture was stirred at 50 °C for 8 h. The reaction mixture was cooled to room temperature, poured into saturated sodium thiosulfate (400 mL), and extracted with EtOAc (2 × 100 mL). The combined organic layers were washed with brine, dried over Na SO , and concentrated in vacuo. The crude product was purified by silica gel chromatography to give 2-(3-methoxyphenyl)-2-(1-methylpyrazol-4-yl)acetonitrile. LCMS (Method B): m / z 228 [M+H], retention time 1.00 min. 1 H NMR(400MHz,CDCl3)δ ppm 7.41(s,1H),7.27-7.37(m,2H),6.87-6.99(m,3H),5.06(s,1H),3.89(s,3H),3.83(s,3H)

[0330] Step 3: Preparation of 2-(3-methoxyphenyl)-2-(1-methylpyrazol-4-yl)ethanamine [ka] A solution of 2-(3-methoxyphenyl)-2-(1-methylpyrazol-4-yl)acetonitrile (3.2 g, 14 mmol) in tetrahydrofuran (42 mL) was treated dropwise with borane dimethyl sulfide complex (4.0 mL, 42 mmol) at room temperature under argon. The resulting yellow solution was stirred at 65 °C for 3 hours and then cooled to 0 °C before adding 6 M hydrochloric acid (9.4 mL, 4.0, 57 mmol) dropwise (strong gas evolution). The resulting mixture was then stirred at 50 °C for 1 hour and then allowed to cool to room temperature. The reaction mixture was then diluted with water and basified to pH 12 with NaOH 6N. The mixture was extracted three times with EtOAc, and the combined organic layers were washed once with brine, dried over anhydrous NaSO, and concentrated in vacuo to give 2-(3-methoxyphenyl)-2-(1-methylpyrazol-4-yl)ethanamine as a brown oil, which was used directly for further chemical reactions. LCMS (Method B): m / z 232[M+H], retention time 0.36 min. 1 H NMR(400MHz,DMSO-d6)δ ppm 7.52(s,1H),7.29(s,1H),7.20(t,J=7.44Hz,1H),6.72-6.87(m,3H),3.77(s,3H),3.80(m,1H),3.73(s,3H),3.42(s,1H)3.03-2.99(m,2H).

[0331] Step 4: Preparation of 6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline [ka] A 25 mL round-bottom flask equipped with a magnetic stir bar was charged with 2-(3-methoxyphenyl)-2-(1-methylpyrazol-4-yl)ethanamine (80 mg, 0.34 mmol), hydrochloric acid 37% (1.7 mL), and acetaldehyde (0.19 mL, 3.46 mmol). The mixture was stirred at room temperature for 3 hours, then slowly poured into water and neutralized with saturated aqueous NaHCO3 solution until pH 8 (strong gas evolution). The mixture was extracted with EtOAc, and the combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo to give the title compound. LCMS (Method B): m / z 258[M+H], retention time 0.19 min.

[0332] Step 5: Preparation of [2-(2,4-difluorophenyl)tetrazol-5-yl]-[6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-34, Table P) [ka] (Compound P-34, Table P). A mixture of 6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline (0.25 g, 0.97 mmol), 2-(2,4-difluorophenyl)tetrazole-5-carboxylic acid (0.24 g, 1.06 mmol), N,N-diisopropylethylamine (0.39 g, 2.91 mmol), and T3P (50% by weight in EtOAc (1.72 mL, 2.91 mmol)) was stirred overnight at room temperature in EtOAc (5 mL). The reaction mixture was diluted with water and EtOAc, and the organic layer was removed. The aqueous layer was back-extracted three times with EtOAc, and the combined organic layers were dried over Na2SO4, filtered, and concentrated in vacuo to give the crude product. This was purified by silica gel dichromatography to give [2-(2,4-difluorophenyl)tetrazol-5-yl]-[6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone as a racemic mixture of syn and anti isomers in an 82:18 ratio, respectively.

[0333] The racemic mixture was further purified by chromatography on a chiral phase and the major syn isomer was isolated: Chiralpak-IG (250 x 20 mm, 5 µm), mobile phase A: TBME (97%), mobile phase B: EtOH (3%) isocratic, flow rate: 17 mL / min, DAD detection: DAD, run time: 40 min, sample preparation: 350 mg in 6 mL of EtOH + 4 mL of TBME, the syn isomer in rotamer form was obtained.

[0334] Isomer 1: [2-(2,4-difluorophenyl)tetrazol-5-yl]-[(1S,4S)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-38, Table P) [ka] LCMS (Method D): m / z 466 [M+H], retention time 1.50 min. 1 H NMR (400MHz, CDCl3) δ ppm (rotamer ratio 65:35)7.87-7.97(m,1H),7.39-7.43(m,1H),7.31(s,1H),7.11-7.20(m ,3H),6.84(dd,J=8.57,2.19Hz,1H),6.60(d,J=2.50Hz,1H),5.85(q,J= 6.67Hz,1H),4.47(dd,J=11.63,5.13Hz,1H),4.25-4.37(m,1H),3.91(s,3H),3.71(s,3H),3.53(dd,J=13.6,11.7Hz,1H),1.68(d,J=6.75Hz,3H) 19 F NMR(376MHz,CDCl3)δ -103.71(s,1 F),-115.07(s,1 F)

[0335] Isomer 2: [2-(2,4-difluorophenyl)tetrazol-5-yl]-[(1R,4R)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (compound P-39, Table P) [ka] (Compound P-39, Table P) LCMS (Method D): m / z 466 [M+H], retention time 1.50 min. NMR identical to isomer 1

[0336] Example P7: Preparation of [6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone (compound P-35, Table P) Prepared similarly to Example 5. Thus, a mixture of 6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline (0.55 g, 2.14 mmol), 2-phenyltetrazole-5-carboxylic acid (0.45 g, 2.35 mmol), N,N-diisopropylethylamine (1.17 mL, 6.41 mmol), and T3P (50% by weight) in EtOAc (4.08 g, 3.78 mL, 6.41 mmol) was stirred overnight at room temperature in ethyl acetate (11 mL). LCMS after this time indicated product formation. The reaction mixture was diluted with water and EtOAc. The EtOAc was decanted, and the aqueous layer was back-extracted with EtOAc. The combined organic layers were dried over Na2SO4, filtered, and concentrated in vacuo. The crude product was purified by column chromatography to give the title compound as a white solid, a diastereomeric mixture (syn:anti 63:37 ratio).

[0337] The racemic mixture was further purified by column: Chiralpak-IG (250x20mm, 5µm), mobile phase A: TBME (80%), mobile phase B: EtOH (20%) isocratic, flow rate: 17mL / min, DAD detection: DAD, run time: 45min, sample preparation: 580mg in 10mL EtOH + 4mL THF + 1mL TBME to give the syn isomer in rotamer form.

[0338] Isomer 1: [(1R,4R)-6-Methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone (Compound P-36, Table P) [ka] (Compound P-36, Table P) LCMS (Method D): m / z 430 [M+H], retention time 1.50 minutes. 1 H NMR (400MHz, CDCl3) δ ppm (rotamer ratio 64:36)8.16-8.22(m,2H),7.53-7.62(m,3H),7.40-7.44(m,1H),7.32(s,1 H),7.12-7.20(m,1H),6.84(dd,J=8.57,2.19Hz,1H),6.58-6.61(m,1H),5. 89-5.80(m,1H),4.47(dd,J=11.57,5.19Hz,1H),4.33-4.40(m,1H),3.91(s ,3H),3.72(s,3H),3.53(dd,J=13.63,11.76Hz,1H),1.68(d,J=6.75Hz,3H)

[0339] Isomer 2: [(1S,4S)-6-Methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone (Compound P-36, Table P) [ka] (Compound P-36, Table P) LCMS (Method D): m / z 430 [M+H], retention time 1.50 min. 1 H NMR (400 MHz, CDCl3) δ ppm (rotation isomer ratio 61:39) 8.16-8.22 (m, 2H), 7.53-7.62 (m, 3H), 7.40-7.44 (m, 1H), 7.32 (s, 1H), 7.12-7.20 (m, 1H), 6.84 (dd, J=8.57, 2.19 Hz, 1H), 6.58-6.61 (m, 1H), 5.89-5.80 (m, 1H), 4.47 (dd, J=11.57, 5.19 Hz, 1H), 4.33-4.40 (m, 1H), 3.91 (s, 3H), 3.68 (s, 3H), 3.53 (dd, J=13.63, 11.76 Hz, 1H), 1.68 (d, J=6.75 Hz, 3H).

[0340] An example of the synthesis of a compound of formula (I) is shown in Table P.

[0341]

Table 8-1

[0342]

Table 8-2

[0343]

Table 8-3

[0344]

Table 8-4

[0345]

Table 8-5

[0346]

Table 8-6

[0347] [Table 8-7]

[0348] Example B1: Alternaria solani / Tomato / Leaf disc (Summer blight) Tomato leaf segments (cv. Baby) were placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaves were inoculated with a fungal spore suspension two days after application. The inoculated leaf segments were incubated in a climate cabinet under a 12 / 12 h light / dark light regime at 23 / 21 °C (day / night) and 80% relative humidity. When an appropriate level of disease damage had developed on the untreated test leaf segments (5-7 days after application), the efficacy of the compound was evaluated as the percentage of disease control compared to the untreated ones.

[0349] The following compounds provided at least 80% control of Alternaria solani at 200 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-14, P-31, P-41, P-42, P-43, P-48, P-49, P-51, P-53, P-54, P-56, P-57.

[0350] Example B2: Botryotinia fuckeliana (Botrytis cinerea) / liquid culture (gray mold) Fungal conidia stored at low temperature are mixed directly into a nutrient broth (Vogels broth). A solution of the test compound (DMSO) is placed in a microtiter plate (96-well format), followed by the addition of nutrient broth containing fungal spores. The test plates are incubated at 24°C, and growth inhibition is measured photometrically 3-4 days after application.

[0351] The following compounds provided at least 80% control of Botryotinia fuckeliana at 20 ppm compared to untreated controls that showed significant disease infestation under identical conditions: P-14, P-31, P-35, P-37, P-41, P-42, P-43, P-48, P-49, P-51, P-53, P-54, P-56.

[0352] Example B3: Glomerella lagenarium (Colletotrichum lagenarium) / liquid culture (anthrax) Fungal conidia from cryogenic storage are mixed directly into nutrient broth (PDB potato dextrose broth). A solution of the test compound (DMSO) is placed in a microtiter plate (96-well format), followed by the addition of the nutrient broth containing the fungal spores. The test plates are incubated at 24°C, and growth inhibition is measured photometrically 3-4 days after application.

[0353] The following compounds at 20 ppm provided at least 80% control of Glomerella lagenarium compared to untreated controls which experienced significant disease development under identical conditions: P-11, P-14, P-31, P-35, P-41, P-42, P-43, P-44, P-48, P-49, P-51, P-53, P-54, P-56.

[0354] Example B4: Blumeria graminis f.sp. tritici (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.

[0355] The following compounds provided at least 80% control of Blumeria graminis f.sp. tritici at 200 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-37, P-42, P-43, P-48, P-49, P-51, P-53, P-54, P-56.

[0356] Example B5: Fusarium culmorum / liquid culture (blight) Fungal conidia from cryogenic storage are mixed directly into nutrient broth (PDB potato dextrose broth). A solution of the test compound (DMSO) is placed in a microtiter plate (96-well format), followed by the addition of the nutrient broth containing the fungal spores. The test plates are incubated at 24°C, and growth inhibition is measured photometrically 3-4 days after application.

[0357] The following compounds provided at least 80% control of Fusarium culmorum at 20 ppm compared to untreated controls that showed significant disease incidence under identical conditions: P-42, P-43, P-48, P-53, P-54.

[0358] Example B6: 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. The day after application, the spikelets are inoculated with a fungal spore suspension. The inoculated test leaf discs are incubated in a climate chamber under 72 hours of semi-darkness followed by a 12-hour light / 12-hour dark photoperiod 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.

[0359] The following compounds provided at least 80% control of Gibberella zeae at 200 ppm when compared to untreated controls under the same conditions that showed widespread disease development: P-54.

[0360] Example B7: Phaeosphaeria nodorum (Septoria nodorum) / Wheat / Leaf blight prevention (Septoria nodorum) 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. The leaves were inoculated with a fungal spore suspension two days after application. The inoculated test leaf segments were 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 had developed on the untreated test leaf segments (5-7 days after application), the efficacy of the compound was evaluated as the percentage of disease control compared to the untreated ones.

[0361] The following compounds provided at least 80% control of wheat leaf spot (Phaeosphaeria nodorum) at 200 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-14, P-31, P-37, P-41, P-42, P-43, P-48, P-49, P-51, P-53, P-54, P-56, P-57.

[0362] Example B8: Monographella nivalis (Microdochium nivale) / liquid culture (cereal root rot) Fungal conidia from cryogenic storage are mixed directly into nutrient broth (PDB potato dextrose broth). A solution of the test compound (DMSO) is placed in a microtiter plate (96-well format), followed by the addition of the nutrient broth containing the fungal spores. The test plates are incubated at 24°C, and growth inhibition is measured photometrically 4-5 days after application.

[0363] The following compounds provided at least 80% control of Monographella nivalis at 20 ppm compared to untreated controls that showed significant disease infestation under identical conditions: P-14, P-18, P-31, P-34, P-35, P-36, P-37, P-38, P-41, P-42, P-43, P-48, P-49, P-51, P-53, P-54, P-56.

[0364] Example B9: Mycosphaerella arachidis (Cercospora arachidicola) / liquid culture (early leaf spot) Fungal conidia from cryogenic storage are mixed directly into nutrient broth (PDB potato dextrose broth). A solution of the test compound (DMSO) is placed in a microtiter plate (96-well format), followed by the addition of the nutrient broth containing the fungal spores. The test plates are incubated at 24°C, and growth inhibition is measured photometrically 4-5 days after application.

[0365] The following compounds provided at least 80% control of Mycosphaerella arachidis at 20 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-7, P-14, P-31, P-34, P-35, P-36, P-37, P-38, P-41, P-42, P-43, P-44, P-47, P-48, P-49, P-51, P-53, P-54, P-56

[0366] Example B10: Puccinia recondita f.sp. tritici / wheat / leaf disc therapeutic (leaf 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 at 19°C and 75% relative humidity under a 12-hour light / 12-hour dark photoperiod. When an appropriate level of disease damage appears on untreated test leaf segments (6-8 days after application), the efficacy of the compounds is evaluated as the percentage of disease control compared to the untreated.

[0367] The following compounds at 200 ppm provided at least 80% control of Puccinia recondita f.sp. tritici compared to untreated controls which showed significant disease development under identical conditions: P-42.

[0368] Example B11: Puccinia recondita f.sp. tritici / wheat / leaf disc preventative (leaf rust) 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, the leaves were inoculated with a fungal spore suspension. The inoculated leaf segments were incubated in a climate cabinet at 19°C and 75% relative humidity under a 12-hour light / 12-hour dark photoperiod. When an appropriate level of disease damage appeared on the untreated test leaf segments (7-9 days after application), the efficacy of the compounds was evaluated as the percentage of disease control compared to the untreated control.

[0369] The following compounds at 200 ppm provided at least 80% control of Puccinia recondita f.sp. tritici compared to untreated controls which showed significant disease development under identical conditions: P-37, P-41, P-42, P-49.

[0370] Example B12: Pyrenophora teres / barley / leaf spot prevention (net blotch) Barley leaf discs (cv. Hasso) placed on agar in multiwell plates (24-well format) are sprayed with the formulated test compounds diluted in water. The leaf discs are inoculated with a fungal spore suspension two days after application. The inoculated leaf discs are incubated in a climate cabinet under a 12-hour light / 12-hour dark photoperiod at 20°C and 65% relative humidity until an appropriate level of disease damage has developed on the untreated test leaf discs (5-7 days after application), at which point the efficacy of the compound is assessed as disease control compared to the untreated control.

[0371] The following compounds provided at least 80% control of Pyrenophora teres at 200 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-8, P-14, P-31, P-35, P-37, P-40, P-41, P-42, P-43, P-48, P-49, P-51, P-53, P-54, P-56, P-57.

[0372] Example B13: Sclerotinia sclerotiorum / liquid culture (sclerotinia rot) Mycelial fragments from freshly cultured fungal liquid cultures are directly mixed into nutrient broth (PDB potato dextrose broth). A DMSO solution of the test compound is placed in a 96-well microtiter plate, and the nutrient broth containing the fungal material is added. The test plate is incubated at 24°C, and growth inhibition is measured photometrically 3-4 days after application.

[0373] The following compounds provided at least 80% control of Sclerotinia sclerotiorum at 20 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-42, P-48.

[0374] Example B14: Wheat leaf blight fungus (Mycosphaerella graminicola) (Septoria tritici) / liquid culture (leaf blight) Fungal conidia from cryogenic storage are mixed directly into nutrient broth (PDB potato dextrose broth). A solution of the test compound (DMSO) is placed in a microtiter plate (96-well format), followed by the addition of the nutrient broth containing the fungal spores. The test plates are incubated at 24°C, and growth inhibition is measured photometrically 4-5 days after application.

[0375] The following compounds provided at least 80% control of Mycosphaerella graminicola at 20 ppm compared to untreated controls that showed significant disease infestation under identical conditions: P-7、P-11、P-14、P-18、P-31、P-32、P-34、P-35、P-36、P-37、P-38、P-40、P-41、P-42、P-43、P-44、P-45、P-47、P-48、P-49、P-50、P-51、P-53、P-54、P-56、P-57。

Claims

1. Compounds of formula (I): 【Chemical 1】 (In the formula, R 1 But hydrogen, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl, C 2 ~C 4 Alkynyl, or C 3 ~C 6 cycloalkyl; R 2 But hydrogen, halogen, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl, C 2 ~C 4 Alkynyl, C 1 ~C 4 Haloalkyl, C 3 ~C 6 Cycloalkyl, C 1 ~C 4 Alkylcarbonyl, N—C 1 ~C 4 Alkoxy-C-C 1 ~C 4 Alkyl-carbonimidoyl, N-hydroxy-C-C 1 ~C 4 Alkyl-carbonimidoyl, or C 1 ~C 4 alkoxycarbonyl; R 3 and R 4 are independently hydrogen, halogen, or C 1 ~C 4 alkyl, R 5 and R 6 are independently hydrogen or C 1 ~C 4 alkyl, R 7 But hydrogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Alkylcarbonyl, N—C 1 ~C 4 Alkoxy-C-C 1 ~C 4 Alkyl-carbonimidoyl, N-hydroxy-C-C 1 ~C 4 Alkyl-carbonimidoyl, C 1 ~C 4 Alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C 1 ~C 4 Alkylaminocarbonyl, di(C 1 ~C 6 alkylamino)carbonyl, phenyl, 5- to 6-membered heteroaryl, or C 3 ~C 6 cycloalkyl, wherein said 5- to 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms individually selected from N, O or S, and said phenyl and 5- to 6-membered heteroaryl are unsubstituted or selected from halogen, C 1 ~C 4 Haloalkyl, cyano, carboxy, C 1 ~C 4 Alkyl or C 1 ~C 4 substituted with 1, 2, or 3 substituents independently selected from alkoxy; 3 ~C 6 Cycloalkyl is unsubstituted or is selected from the group consisting of halogen, C 1 ~C 4 Haloalkyl, cyano, C 1 ~C 4 Alkyl or C 1 ~C 4 substituted with 1, 2, or 3 substituents independently selected from alkoxy; B 1 But, CR 10 , or N; B 2 But, CR 11 , or N; R 8 , R 9 , R 10 and R 11 are independently hydrogen, halogen, 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-diC 1~4 Alkylamino, C 1 ~C 6 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, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, amino, 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 individually selected from N, O, or S; and wherein said phenyl, 5- to 6-membered heteroaryl, and C 3 ~C 6 - any of the cycloalkyl is unsubstituted or is selected from 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; A 1 But, CR 12a , or N; A 2 But, CR 13a , or N; A 3 But, CR 14a , or N; R 12a , R 13a and R 14a are independently hydrogen, halogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 2 ~C 4 Alkenyl, or C 2 ~C 4 alkynyl, Z 1 But C 1 ~C 4 alkyl, 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 individually selected from N, O, or S, and wherein any of said phenyl, 5-, or 6-membered heteroaryl is unsubstituted or is selected from halogen, cyano, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl, C 1 ~C 4 Haloalkyl, C 1 ~C 4 Alkoxy, C 1 ~C 4 Haloalkoxy, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, or C 2 ~C 4 alkynyl, wherein the C 3 ~C 6 Cycloalkyl is unsubstituted or 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; or an agrochemically acceptable salt, stereoisomer, or N-oxide thereof.

2. R 1 is methyl, and R 2 2. A compound of formula (I) according to claim 1, wherein is selected from hydrogen or methyl.

3. R 3 is hydrogen, and R 4 3. A compound of formula (I) according to claim 1 or 2, wherein is selected from hydrogen or methyl.

4. R 5 and R 6 A compound of formula (I) according to any one of claims 1 to 3, wherein is independently selected from hydrogen or methyl.

5. R 7 But hydrogen, C 1 ~C 4 Alkyl, or C 3 ~C 6 A compound of formula (I) according to any one of claims 1 to 4, which is cycloalkyl.

6. A 1 But, CR 12a or N, 2 But, CR 13a or N, 3 But, CR 14a or N, 1 , A 2 and A 3 At least two of are selected from N, and R 12a , R 13a and R 14a A compound of formula (I) according to any one of claims 1 to 5, wherein is hydrogen.

7. B 1 But, CR 10 and B 2 But, CR 11 A compound of formula (I) according to any one of claims 1 to 6, wherein

8. R 8 and R 9 are independently hydrogen, halogen, cyano, C 1 ~C 4 Alkyl, or C 1 ~C 4 alkoxy; R 10 and R 11 are independently hydrogen, halogen, C 1 ~C 3 Alkyl, or C 1 ~C 4 selected from alkoxy, A compound of formula (I) according to any one of claims 1 to 7.

9. R 10 and R 11 9. The compound of formula (I) according to claim 8, wherein is hydrogen.

10. The compound of formula (I) is a compound of formula (II): 【Chemistry 2】 (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B 2 and Z 1 is as defined for compounds of formula (I) according to any one of claims 1 to 9, and A is 【Chemistry 3】 is selected from: 【Chemistry 4】 indicates a bond to a C(=O) group, and an asterisk ( * ) but Z 1 represents a nitrogen having a bond to a group, R 12a , R 13a and R 14a are independently selected from hydrogen, halogen, methyl, cyclopropyl, or trifluoromethyl. A compound of formula (I) according to any one of claims 1 to 9, wherein

11. A is, 【Chemistry 5】 is selected from: 【Chemistry 6】 indicates a bond to a C(=O) group, and an asterisk ( * ) but Z 1 11. A compound of formula (II) according to claim 10, showing a nitrogen having a bond to a group.

12. Z 1 is selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 3,5-difluoro-2-pyridyl, 2,4-difluorophenyl, 2-fluorophenyl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, cyclobutyl, cyclohexyl, cyclopentyl, or phenyl.

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

14. A method for controlling or preventing damage to useful plants caused by plant pathogenic microorganisms, comprising applying a fungicidally effective amount of a compound of formula (I) according to any one of claims 1 to 12, or a composition comprising the compound of formula (I), to the plant, a part thereof or its habitat.

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

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