Microbiocidal pyridazine dihydrooxadiazine derivatives

Abstract

Disclosed is a compound having the formula (I) wherein R1, R2, and G are as defined in claim 1, which is useful as a pesticidal agent, in particular a fungicide. # imgabs0 #

Description

[0001] The present invention relates to pyridazine dihydrooxadiazines which, as active ingredients, have microbicidal activity, especially fungicidal activity. The invention also relates to agrochemical compositions comprising at least one of the pyridazine 5,6-dihydro-4H-1,2,4-oxadiazine derivatives, to methods for the preparation of these compounds, and to the use of the pyridazine 5,6-dihydro-4H-1,2,4-oxadiazine derivatives or compositions for controlling or preventing infestation of plants, harvested food crops, seeds or inanimate materials by phytopathogenic microorganisms, preferably fungi, in agriculture or horticulture.

[0002] Many plant protection compounds have been developed to prevent or reduce plant diseases caused by microorganisms such as fungi. For example, WO 2020 / 109391 discloses pyridazine (thio)amide derivatives. WO 2020 / 127780 discloses pyridazine oxadiazine derivatives.

[0003] Accordingly, the present invention provides in a first aspect a compound of formula (I)

[0004]

[0005] or an agrochemically acceptable salt, stereoisomer, enantiomer, or N-oxide thereof, wherein:

[0006] R 1 is phenyl which is unsubstituted or substituted by:

[0007] - a single substituent selected from hydroxy, nitro, halogen, mercapto, amino, cyano, NHMe, N(Me)2, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C2 fluoroalkyl, C1-C4 alkoxy, C1-C2 fluoroalkoxy, C3-C4 alkenyloxy, C3-C4 alkenyloxy, C3-C6 cycloalkyl, C3-C6 cycloalkoxy, C3-C6 cycloalkyl C1-C2 alkyloxy, C1-C3 alkylthio, and C1-C3 alkylsulfonyl; or

[0008] - 1, 2 or 3 substituents independently selected from hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, methylthio, methylsulfonyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl; or

[0009] - R 1is a 5- or 6-membered monocyclic heteroaryl ring containing 1, 2 or 3 heteroatoms each independently selected from N, O and S, provided that no more than one is O or S; wherein said heteroaryl ring is unsubstituted or substituted with:

[0010] - a single substituent selected from hydroxy, nitro, halogen, mercapto, amino, cyano, NHMe, N(Me)2, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C2 fluoroalkyl, C1-C4 alkoxy, C1-C2 fluoroalkoxy, C3-C4 alkenyloxy, C3-C4 alkenyloxy, C3-C6 cycloalkyl, C3-C6 cycloalkoxy, C3-C6 cycloalkyl C1-C2 alkyloxy, C1-C3 alkylthio, and C1-C3 alkylsulfonyl; or

[0011] - 1 or 2 substituents independently selected from hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, methylthio, methylsulfonyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl;

[0012] R 2 is hydrogen, hydroxy, nitro, halogen, mercapto, amino, cyano, C1-C6 alkyl, C1-C2 fluoroalkyl, C3-C5 alkenyl, C3-C5 alkynyl, C1-C3 alkoxy C2-C3 alkyl, C3-C6 cycloalkyl, or C3-C6 cycloalkyl C 1-2 alkyl, C1-C4 alkoxy, C1-C2 fluoroalkoxy, C3-C5 alkenyloxy, C3-C5 alkenyloxy, C3-C6 cycloalkyl, C3-C6 cycloalkoxy, C3-C6 cycloalkyl C1-C2 alkyloxy, C1-C4 alkylamino, di-C1-C4 alkylamino, C3-C5 alkenylamino, C3-C5 alkynylamino, C1-C3 alkylthio, or C1-C3 alkylsulfonyl; or

[0013] R 2 is phenyl, phenyl C1-C2 alkyl, heteroaryl, heteroaryl C1-C2 alkyl, heterocyclic, heterocyclic C1-C2 alkyl, C3-C6 cycloalkyl, or C3-C6 cycloalkyl C 1-2 alkyl; wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring containing 1, 2 or 3 heteroatoms independently selected from N, O and S, provided that no more than one is O or S; wherein the heterocyclic moiety is a 4- to 6-membered non-aromatic ring containing 1 or 2 heteroatoms independently selected from N, O and S, provided that no more than one is O or S; and wherein any of said cycloalkyl, phenyl, heteroaryl and heterocyclic moieties is unsubstituted or substituted with:

[0014] - a single substituent selected from hydroxy, nitro, halogen, mercapto, amino, cyano, NHMe, N(Me)2, C1-C4 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, C1-C2 fluoroalkyl, C1-C4 alkoxy, C1-C2 fluoroalkoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, C3-C6 cycloalkyl, C1-C3 alkylthio, and C1-C3 alkylsulfonyl; or

[0015] - one or two substituents independently selected from hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, methylthio, methylsulfonyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl;

[0016] G is selected from G-1, G-2, G-3, and G-4, wherein:

[0017] G-1 is phenyl or phenoxy, wherein the phenyl or phenoxy is unsubstituted or substituted with:

[0018] - a single substituent selected from hydroxy, nitro, halogen, mercapto, amino, cyano, NHMe, N(Me)2, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C2 fluoroalkyl, C1-C4 alkoxy, C1-C2 fluoroalkoxy, C3-C4 alkenyloxy, C3-C4 alkenyloxy, C3-C6 cycloalkyl, C3-C6 cycloalkyloxy, C3-C6 cycloalkyl C1-C2 alkyloxy, C1-C3 alkylthio, and C1-C3 alkylsulfonyl; or

[0019] - one or two substituents independently selected from hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, methylthio, methylsulfonyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl;

[0020] - G-2 is a 5- or 6-membered monocyclic heteroaryl or heteroaryloxy; wherein the heteroaryl contains 1, 2 or 3 heteroatoms each independently selected from N, O and S, provided that no more than one is O or S; and wherein the heteroaryl or heteroaryloxy is unsubstituted or substituted with:

[0021] - a single substituent selected from hydroxy, nitro, halogen, mercapto, amino, cyano, NHMe, N(Me)2, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C2 fluoroalkyl, C1-C4 alkoxy, C1-C2 fluoroalkoxy, C3-C4 alkenyloxy, C3-C4 alkenyloxy, C3-C6 cycloalkyl, C3-C6 cycloalkyloxy, C3-C6 cycloalkyl C1-C2 alkyloxy, C1-C3 alkylthio, and C1-C3 alkylsulfonyl; or

[0022] - 1 or 2 substituents independently selected from hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, methylthio, methylsulfonyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl;

[0023] G-3 is a 9- or 10-membered heterobicyclic system containing 1, 2 or 3 heteroatoms each independently selected from N, O and S, provided that no more than one is O or S; wherein said heterobicyclic system is saturated, partially unsaturated, or aromatic; and wherein said heterobicyclic system is unsubstituted or substituted with: a single substituent selected from hydroxy, nitro, halogen, mercapto, amino, cyano, NHMe, N(Me)2, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C2 fluoroalkyl, C1-C4 alkoxy, C1-C2 fluoroalkoxy, C3-C4 alkenyloxy, C3-C4 alkenyloxy, C3-C6 cycloalkyl, C3-C6 cycloalkyloxy, C3-C6 cycloalkyl C1-C2 alkyloxy, C1-C3 alkylthio, and C1-C3 alkylsulfonyl;

[0024] G-4 is a 9- or 10-membered carbobicyclic system; wherein said carbobicyclic system is saturated, partially unsaturated, or aromatic; and wherein said carbobicyclic system is unsubstituted or substituted with: a single substituent selected from hydroxy, nitro, halogen, mercapto, amino, cyano, NHMe, N(Me)2, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C2 fluoroalkyl, C1-C4 alkoxy, C1-C2 fluoroalkoxy, C3-C4 alkenyloxy, C3-C4 alkenyloxy, C3-C6 cycloalkyl, C3-C6 cycloalkyloxy, C3-C6 cycloalkyl C1-C2 alkyloxy, C1-C3 alkylthio, and C1-C3 alkylsulfonyl.

[0025] The present invention also provides a method for preparing a compound of formula (I) and intermediate compounds useful for preparing a compound of formula (I).

[0026] Surprisingly, for practical purposes, it has been found that the novel compounds of formula (I) have a very advantageous level of biological activity for protecting plants against diseases caused by fungi.

[0027] According to a second aspect of the invention, there is provided an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I). Such an agricultural composition may further comprise at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

[0028] According to a third aspect of the invention, there is provided a method for controlling or preventing useful plants from being infested by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I), or a composition comprising such a compound as an active ingredient, is applied to these plants, parts thereof or the sites thereof.

[0029] According to a fourth aspect of the invention, there is provided the use of a compound of formula (I) as a fungicide. According to this particular aspect of the invention, the use may exclude methods for treating the human or animal body by surgery or therapy.

[0030] According to a fifth aspect, the invention makes it possible to obtain a plant propagation material, such as seeds, which contain a compound of formula (I) or a composition comprising such a compound, or are treated with such a compound or composition, or to which such a compound or composition is attached.

[0031] As used herein, the term "hydroxyl" or "hydroxy" means an -OH group.

[0032] As used herein, the term "mercapto" means an -SH group.

[0033] As used herein, the term "cyano" means a -CN group.

[0034] As used herein, amino means an -NH2 group.

[0035] As used herein, nitro means a -NO2 group.

[0036] As used herein, oxo means a =O group (for example, as in a carbonyl (C=O) group).

[0037] As used herein, the term "halogen" or "halo" refers to fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. This also applies mutatis mutandis to halogen in combination with other meanings, such as haloalkyl.

[0038] As used herein, the term "C1-C6 alkyl" refers to a straight-chain or branched-chain hydrocarbon chain group consisting only of carbon and hydrogen atoms, having no unsaturation, having one to six carbon atoms, and attached to the remainder of the molecule by a single bond. C1-C4 alkyl shall be construed accordingly. Examples of C1-C6 alkyl include, but are not limited to, methyl, ethyl, isopropyl.

[0039] As used herein, the term "C2-C4 alkenyl" refers to a straight-chain or branched-chain hydrocarbon chain group consisting only of carbon and hydrogen atoms, having at least one double bond which may have the (E) or (Z) configuration, having two or four carbon atoms, and attached to the remainder of the molecule by a single bond. Examples of C2-C4 alkenyl include, but are not limited to, vinyl (or ethenyl), prop-1-enyl, allyl (prop-2-enyl).

[0040] As used herein, the term "C2-C4 alkynyl" refers to a straight-chain or branched-chain hydrocarbon chain group consisting only of carbon and hydrogen atoms, having at least one triple bond, having two or four carbon atoms, and attached to the remainder of the molecule by a single bond. Examples of C2-C4 alkynyl include, but are not limited to, prop-1-ynyl and propargyl (prop-2-ynyl).

[0041] As used herein, the term "C1-C2 fluoroalkyl" refers to a C1-C2 alkyl group as generally defined above which is substituted by one or more fluorine atoms. Examples of C1-C2 fluoroalkyl include, but are not limited to, difluoromethyl and trifluoromethyl.

[0042] As used herein, the term "C1-C4 alkoxy" refers to a group having the formula R a O-, where R a is a C1-C4 alkyl group as generally defined above. Examples of C1-C4 alkoxy include, but are not limited to, methoxy, ethoxy, isopropoxy.

[0043] As used herein, the term "C1-C2 fluoroalkoxy" refers to a C1-C2 alkoxy group as generally defined above which is substituted by one or more fluorine atoms. Examples of C1-C2 fluoroalkoxy include, but are not limited to, difluoromethoxy or trifluoromethoxy.

[0044] As used herein, the term "C3-C6 cycloalkyl" refers to a stable monocyclic group which is saturated and contains 3 to 6 carbon atoms.

[0045] As used herein, the term "C3-C4 alkenyloxy" refers to a group having the formula R a O-, where R a is a C3-C4 alkenyl group as generally defined above. Examples of C3-C4 alkenyloxy include, but are not limited to, allyloxy.

[0046] As used herein, the term "C3-C4 alkynyloxy" refers to a group having the formula R a O-, where R a is a C3-C4 alkynyl group as generally defined above. Examples of C3-C4 alkynyloxy include, but are not limited to, propargyloxy

[0047] As used herein, the term "C3-C6 cycloalkyloxy" refers to a group having the formula R a O-, where R a is a C3-C6 cycloalkyl group as generally defined above. Examples of C3-C6 cycloalkyloxy include, but are not limited to, cyclopropoxy.

[0048] As used herein, the term "C3-C6 cycloalkyl C1-C2 alkyl" refers to a group having the formula R a O-, where R a is a C3-C6 cycloalkyl C1-C2 alkyl group as generally defined above. Examples of C3-C6 cycloalkyl C1-C2 alkyloxy include, but are not limited to, cyclopropylmethyl.

[0049] As used herein, the term "C3-C6 cycloalkyl C1-C2 alkoxy" refers to a group having the formula R a O-, where R a is a C3-C6 cycloalkyl C1-C2 alkyl group as generally defined above. Examples of C3-C6 cycloalkyl C1-C2 alkoxy include, but are not limited to, cyclohexylmethoxy.

[0050] As used herein, the term "C1-C3 alkylthio" refers to a group having the formula -SR a where R a is a C1-C3 alkyl group as generally defined above.

[0051] As used herein, the term "C1-C3 alkylsulfonyl" refers to a group having the formula -S(O)2R a where R a is a C1-C3 alkyl group as generally defined above.

[0052] As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic ring having 1 to 3 heteroatoms independently selected from N, O, and S. Examples of heteroaryl include J-1 to J-43 shown in Table J below. The cross-hatched lines in heteroaryl J-1 to J-39 represent the point of attachment to the remainder of the compound. Preferred heteroaryls include pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, and thiazolyl; preferably, pyridyl and thiazolyl.

[0053] Table J: Heteroaryls J-1 to J-39:

[0054]

[0055]

[0056] As used herein, the term "heterocyclic group" refers to a 3-, 4-, 5-, and 6-membered saturated monocyclic ring having 1 or 2 heteroatoms independently selected from nitrogen and oxygen. Examples of heterocyclic groups include K-1 to K-26 shown in Table K below. The wavy lines in heterocyclic groups K-1 to K-26 represent the point of attachment to the remainder of the compound. Some of the heterocyclic groups shown below contain asymmetric carbons, which means that compounds containing them can exist in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. Preferred heterocyclic groups include pyrrolidinyl, piperidinyl, piperazinyl, and tetrahydropyranyl; preferably, pyrrolidinyl, piperazinyl, and tetrahydropyranyl.

[0057] Table K: Heterocyclic groups K-1 to K-26:

[0058]

[0059]

[0060] As used herein, the term "optionally substituted" means that the group mentioned is unsubstituted or substituted with the designated substituents. For example, "phenyl is optionally substituted with 1 or 2 halogen atoms" means phenyl substituted with 1 halogen atom and phenyl substituted with 2 halogen atoms. The term "optionally substituted" can be used interchangeably with "unsubstituted or substituted".

[0061] As used herein, the term "control" means reducing the number of pests, eliminating pests, and / or preventing further pest damage, such that damage to plants or plant-derived products is reduced.

[0062] As used herein, the term "pest" refers to insects and mollusks present in agriculture, horticulture, forestry, and the storage of plant-derived products (such as fruits, grains, and wood); and those pests related to the damage of man-made structures. The term pest encompasses all stages of the pest life cycle.

[0063] As used herein, the term "effective amount" means the amount of a compound or its salt that provides the desired effect upon single or multiple applications.

[0064] The effective amount can be readily determined by those skilled in the art using known techniques and by observing the results obtained in similar situations. When determining the effective amount, many factors are considered, including but not limited to the type of plant or plant-derived product to be applied; the pest to be controlled and its life cycle; the specific compound to be applied; the type of application; and other relevant circumstances.

[0065] As used herein, the term "room temperature" or "RT" or "rt" or "ambient temperature" refers to a temperature of from about 15°C to about 35°C. For example, rt can refer to a temperature of from about 20°C to about 30°C.

[0066] As used herein, the wavy lines, for example in the heteroaryl shown in Table J and the heterocyclic group shown in Table K, represent the point of attachment / connection to the remainder of the compound.

[0067] The presence of one or more possible asymmetric carbon atoms in the compounds of formula (I) means that these compounds can exist in chiral isomeric forms, i.e., in the form of enantiomers or diastereoisomers. Also, as a result of restricted rotation about a single bond, atropisomers may exist. Formula (I) is intended to embrace all those possible isomeric forms and mixtures thereof. The present invention embraces all those possible isomeric forms and mixtures of the compounds of formula (I). Similarly, formula (I) is intended to embrace all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism) (when present). The present invention embraces all possible tautomeric forms of the compounds of formula (I).

[0068] Compounds of formula (I) having at least one basic center can, for example, form acid addition salts with, for example: strong inorganic acids (such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrohalic acids), strong organic carboxylic acids (such as unsubstituted or, for example, halogen-substituted C1-C4 alkanoic acids, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid), or organic sulfonic acids (such as unsubstituted or, for example, halogen-substituted C1-C4 alkanesulfonic acids or arylsulfonic acids, for example methanesulfonic acid or p-toluenesulfonic acid). Compounds of formula (I) having at least one acidic group can, for example, form salts with bases, for example mineral salts, such as alkali metal or alkaline earth metal salts, for example sodium salts, potassium salts or magnesium salts; or with ammonia or organic amines (such as morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, for example ethylamine, diethylamine, triethylamine or dimethylpropylamine, or mono-, di- or tri-hydroxy-lower alkylamines, for example monoethanolamine, diethanolamine or triethanolamine).

[0069] Compounds of formula (I) according to the invention also include hydrates that may form during salt formation.

[0070] In each case, the compounds of formula (I) according to the invention are in free form, oxidized form (as N-oxides), covalently hydrated form, or salt form (for example, in an agronomically useful or agrochemically acceptable salt form).

[0071] N-oxides are the oxidized forms of tertiary amines or the oxidized forms of nitrogen-containing heteroaromatic compounds. For example, they are described in the book "Heterocyclic N-oxides" published by A. Albini and S. Pietra in 1991 by CRC Press in Boca Raton.

[0072] The following list provides the definitions of the substituents R 1 , R 2 , and G of the compounds of formula (I) of the present invention, including preferred definitions. For any one of these substituents, any definition given below can be combined with any definition of any other substituent given below or elsewhere in this document.

[0073] In embodiments of various aspects of the present invention, R 1 is:

[0074] A. phenyl, pyridine, pyrazine, pyrimidine, or pyridazine, wherein the phenyl, pyridine, pyrazine, pyrimidine, or pyridazine is unsubstituted or substituted by one or two substituents, such as a single substituent, which is independently selected from hydroxy, halogen, mercapto, amino, nitro, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, isopropoxy, tert-butoxy, propargyloxy, NHMe, N(Me)2, methylthio, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy; or

[0075] B. phenyl, pyridine, pyrazine, pyrimidine, or pyridazine, wherein the phenyl, pyridine, pyrazine, pyrimidine, or pyridazine is unsubstituted or substituted by one or two substituents, such as a single substituent, which is independently selected from hydroxy, halogen, mercapto, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, methylthio, methylsulfonyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl; or

[0076] C. phenyl, pyridine, pyrazine, pyrimidine or pyridazine, wherein the phenyl, pyridine, pyrazine, pyrimidine or pyridazine is unsubstituted or substituted by one or two substituents, such as one substituent, which is independently selected from hydroxy, chlorine, fluorine, cyano, methyl, difluoromethyl, trifluoromethyl, methoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclopropyloxy; or

[0077] D. pyridine, pyrazine, pyrimidine or pyridazine, wherein the pyridine, pyrazine, pyrimidine or pyridazine is unsubstituted or substituted by one or two substituents, for example one substituent, which is independently selected from hydroxy, chloro, fluoro, cyano, methyl, difluoromethyl, trifluoromethyl, methoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclopropyloxy; or

[0078] E. phenyl substituted by one or two substituents, for example one substituent, which is independently selected from hydroxy, chloro, fluoro, cyano, methyl, difluoromethyl, trifluoromethyl, methoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclopropyloxy; or

[0079] F. phenyl substituted by a single substituent selected from hydroxy, chloro, fluoro, cyano, methyl, difluoromethyl, trifluoromethyl, methoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclopropyloxy; or

[0080] G. 2-fluoro-3-cyclopropylphenyl, 2-fluoro-3-methylphenyl, 2-fluorophenyl, 3-(difluoromethoxy)phenyl, 3-(trifluoromethoxy)phenyl, 2-(trifluoromethyl)pyridin-4-yl, 3-ethoxyphenyl, 3-ethylphenyl, 3-ethynylphenyl, 3-fluorophenyl, 4-(difluoromethoxy)phenyl, 4-(trifluoromethoxy)phenyl, 4-chlorophenyl, 4-cyanophenyl, 4-ethoxyphenyl, 4-ethylphenyl, 4-fluorophenyl, 3-methoxyphenyl, 3,4-dichlorophenyl, 3,4-difluorophenyl, 3,4-dimethoxyphenyl, 3,5-dichlorophenyl, 3,5-difluorophenyl, 3-cyanophenyl, 3,4-difluorophenyl, 3,4-dimethoxyphenyl, 3,5-dichlorophenyl, 3,5-difluorophenyl, 3-cyanophenyl, 2-methylpyrimidin-4-yl, 2-(trifluoromethyl)pyridin-4-yl, 3-(trifluoromethyl)pyridin-2-yl, 3-methoxypyridin-2-yl, 3-methylpyridin-2-yl, 2-chloropyridin-3-yl, 2-chloropyridin-4-yl, 2-cyanopyridin-3-yl, 2-fluoropyridin-3-yl, 2-methoxypyridin-4-yl, 2-methylpyridin-3-yl, 5-(trifluoromethyl)pyridin-3-yl, 5-chloropyridin-3-yl, 5-cyanopyridin-3-yl, 5-cyclopropylpyridin-3-yl, 5-methylpyridin-3-yl, 5-pyridazin-4-yl, 6-(trifluoromethyl)pyridin-3-yl, 6-chloropyridin-2-yl, 6-cyanopyridin-3-yl, 6-cyclopropylpyridin-2-yl, 6-methoxypyridin-3-yl, 6-methyl-2-pyridinyl, 6-methylpyridazin-3-yl, 6-methylpyridin-2-yl, 6-methylpyridin-3-yl, pyridin-3-yl, pyridin-4-yl or phenyl; or

[0081] H. 3 - cyclopropyl - 2 - fluorophenyl, 3 - (trifluoromethyl)phenyl, 3 - chloro - 2 - fluorophenyl, 3 - chlorophenyl, 5 - cyanopyridin - 3 - yl, 3 - methylphenyl, phenyl, 3 - cyclopropylphenyl, 3 - (difluoromethyl)phenyl, 3 - (difluoromethoxy)phenyl, 3 - (trifluoromethyl)-2 - fluorophenyl, 3 - methoxyphenyl, or 2,3 - difluorophenyl; or

[0082] I. phenyl, 3 - (trifluoromethyl)phenyl, 3 - methoxyphenyl, 3 - cyclopropylphenyl, 3 - cyclopropyl - 2 - fluorophenyl, or 5 - cyanopyridin - 3 - yl; or

[0083] J. 3 - cyclopropylphenyl.

[0084] For example, in embodiments of various aspects of the present invention, R 1 is:[[]]

[0085] A. phenyl which is unsubstituted or substituted with 1 or 2 substituents, each of which is independently selected from hydroxy, halogen, mercapto, amino, nitro, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, prop - 2 - ynyloxy, prop - 1 - ynyloxy, isopropoxy, tert - butoxy, propargyloxy, NHMe, N(Me)2, methylthio, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy; or

[0086] B. phenyl which is unsubstituted or substituted with 1 or 2 substituents, each of which is independently selected from hydroxy, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, prop - 2 - ynyloxy, prop - 1 - ynyloxy, difluoromethoxy, trifluoromethoxy, and cyclopropyl; or

[0087] C. phenyl which is unsubstituted or substituted with 1 or 2 substituents, each of which is independently selected from chlorine, fluorine, cyano, methyl, methoxy, difluoromethoxy, and cyclopropyl; or

[0088] D. phenyl which is unsubstituted or substituted with 1 or 2 substituents, each of which is independently selected from fluorine, chlorine, cyano, methyl, and cyclopropyl; or

[0089] E. phenyl which is unsubstituted or substituted with a single substituent selected from fluorine, chlorine, methyl, and cyclopropyl.

[0090] Additionally, for example, in embodiments of various aspects of the present invention, R 1 is:[[]]

[0091] A. A 5- or 6-membered monocyclic heteroaryl ring containing 1, 2 or 3 heteroatoms independently selected from N, O and S, which may be the same or different, provided that no more than one is O or S; wherein said heteroaryl ring is unsubstituted or substituted with 1 or 2 substituents each independently selected from hydroxy, halogen, mercapto, amino, nitro, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, isopropoxy, tert-butoxy, propargyloxy, NHMe, N(Me)2, methylthio, methylsulfonyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl; or

[0092] B. Pyridine, pyrimidine, or pyridazine, wherein said pyridine, pyrimidine, or pyridazine is unsubstituted or substituted with 1 or 2 substituents independently selected from hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, methylthio, methylsulfonyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl; or

[0093] C. Pyridine substituted with 1 or 2 substituents each independently selected from hydroxy, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, difluoromethoxy, and cyclopropyl; or

[0094] D. Pyridine substituted with a single substituent selected from chlorine, fluorine, cyano, methyl, methoxy, difluoromethoxy, and cyclopropyl; or

[0095] E. Pyridine substituted with a single substituent selected from chlorine, cyano, methyl, and cyclopropyl.

[0096] In embodiments of various aspects of the present invention, R 2 is:

[0097] A. Hydrogen, hydroxy, halogen, mercapto, amino, cyano, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkoxy, C1-C4-fluoroalkyl, C1-C4-fluoroalkoxy, or C3-C4-cycloalkyl; or

[0098] B. Hydrogen, hydroxy, halo, amino, cyano, C1-C4-alkyl, C1-C4-alkoxy, C3-C4-cycloalkyl, C2-C4-alkenyl, C1-C4-alkyl ethynyl, C3-C4-cycloalkyl ethynyl, or C2-C4-alkenyloxy; or

[0099] C. hydrogen, hydroxy, chloro, methyl, ethyl, isopropyl, methoxy, cyclopropyl, isoprenyl, 2-cyclopropylethynyl, 2-methylallyloxy, or isopropoxy; or

[0100] D. hydrogen, hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, isopropoxy, propargyloxy, NHMe, N(Me)2, methylthio, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, or cyclopropyloxy; or

[0101] E. hydrogen, hydroxy, halogen, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, methoxy, ethoxy, difluoromethoxy, or cyclopropyl; or

[0102] F. hydrogen, hydroxy, fluoro, chloro, bromo, cyano, methyl, ethyl, propyl, isopropyl, or cyclopropyl; or

[0103] G. hydrogen, hydroxy, cyano, alkyl mercaptyl, fluoro, chloro, methyl, or ethyl; or

[0104] H. hydrogen, hydroxy, chloro, cyano, methyl, ethyl, methoxy, or cyclopropyl; or

[0105] I. hydrogen, methyl, ethyl, or cyclopropyl.

[0106] In embodiments of various aspects of the present invention, G is G-1:

[0107] A. unsubstituted or substituted with 1 or 2 substituents phenyl or phenoxy, the substituents each independently selected from hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, methylthio, methylsulfonyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl; or

[0108] B. unsubstituted or substituted with 1 or 2 substituents phenyl or phenoxy, the substituents each independently selected from hydroxy, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, difluoromethoxy, trifluoromethoxy, and cyclopropyl; or

[0109] C. unsubstituted or substituted with 1, 2 or 3 substituents, such as 2 or 3 substituents phenyl, the substituents each independently selected from chloro, fluoro, bromo, methyl, methoxy, and cyclopropyl; or

[0110] D. phenyl substituted by 1 or 2 substituents, such as one substituent, and the substituents are each independently selected from chlorine and methyl; or

[0111] E. 2,4-dichlorophenyl.

[0112] In embodiments of various aspects of the present invention, G is G-2:

[0113] A. pyridine, pyrimidine, pyridazine, pyridine-oxy, pyrimidine-oxy, pyridazine-oxy, wherein the pyridine, pyrimidine, or pyridazine ring is unsubstituted or substituted by 1 or 2 substituents, and the substituents are each independently selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, methylthioalkyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl; or

[0114] B. pyridine that is unsubstituted or substituted by 1 or 2 substituents, and the substituents are each independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, difluoromethoxy, and cyclopropyl; or

[0115] C. pyrimidine or pyridazine, wherein the pyrimidine or pyridazine is unsubstituted or substituted by 1 or 2 substituents, and the substituents are each independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, difluoromethoxy, and cyclopropyl; or

[0116] D. pyridine that is unsubstituted or substituted by 1 or 2 substituents, and the substituents are each independently selected from chlorine, fluorine, cyano, methyl, and methoxy; or

[0117] E. pyridine or pyridine-oxy that is unsubstituted or substituted by a single substituent selected from chlorine and methyl.

[0118] In embodiments of various aspects of the present invention, G is G-3:

[0119] A. A chroman-4-yl, isochroman-4-yl, 4H-chromen-4-yl, 2,3-dihydrobenzofuran-2-yl, 2,3-dihydrobenzofuran-3-yl, 1,3-benzodioxol-5-yl, benzothiazol-2-yl, benzothiazol-5-yl, benzothiazol-6-yl, benzoxazol-2-yl, benzoxazol-5-yl, benzoxazol-6-yl, benzofuran-2-yl, benzofuran-3-yl, benzofuran-5-yl, benzofuran-6-yl, benzothiophen-2-yl, benzothiophen-3-yl, benzothiophen-5-yl, or benzothiophen-6-yl that is unsubstituted or substituted with 1 or 2 substituents each independently selected from chlorine, fluorine, cyano, methyl, and methoxy, such as a single substituent; or

[0120] B. A chroman-4-yl, isochroman-4-yl, 4H-chromen-4-yl, 2,3-dihydrobenzofuran-2-yl, 2,3-dihydrobenzofuran-3-yl, 1,3-benzodioxol-5-yl, benzothiazol-2-yl, benzothiazol-5-yl, benzothiazol-6-yl, benzoxazol-2-yl, benzofuran-2-yl, benzofuran-3-yl, benzothiophen-2-yl, or benzothiophen-3-yl that is unsubstituted or substituted with a single substituent selected from chlorine, fluorine, cyano, methyl, and methoxy

[0121] C. A chroman-4-yl, isochroman-4-yl, 4H-chromen-4-yl, 2,3-dihydrobenzofuran-2-yl, or 2,3-dihydrobenzofuran-3-yl that is unsubstituted or substituted with a single substituent selected from chlorine, fluorine, cyano, methyl, and methoxy; or

[0122] D. 1,3-benzodioxol-5-yl, benzothiazol-2-yl, benzothiazol-5-yl, benzothiazol-6-yl, benzoxazol-2-yl, benzofuran-2-yl, benzofuran-3-yl, benzothiophen-2-yl, or benzothiophen-3-yl.

[0123] In embodiments of various aspects of the present invention, G is G-4:

[0124] A. A naphthalen-2-yl, tetralin-1-yl, tetralin-2-yl, tetralin-6-yl, indan-1-yl, indan-2-yl, or indan-5-yl that is unsubstituted or substituted with 1 or 2 substituents each independently selected from chlorine, fluorine, cyano, methyl, and methoxy, such as a single substituent; or

[0125] B. Or a tetralin-1-yl, tetralin-2-yl, indan-1-yl, or indan-2-yl that is unsubstituted or substituted with one or two substituents each independently selected from chlorine, fluorine, cyano, methyl, and methoxy, such as a single substituent.

[0126] For example, in various aspects of the present invention, G is

[0127] A. 2,4-dimethylphenyl, 2,4-dichlorophenyl, 4-bromo-2-methylphenyl, 4-bromo-2-chlorophenyl, 2,6-dichloro-3-pyridyl, 4,6-dichloro-3-pyridyl, 3,5-dichloro-2-pyridyl, 3,4-dimethylphenyl, 2-chloro-4-methylphenyl, 2-methyl-4-bromophenyl, 2-methyl-4-chlorophenyl, or 2,4-difluorophenyl; or

[0128] B. 2,4-dimethylphenyl, 2,4-dichlorophenyl, 4-bromo-2-methylphenyl, 4-bromo-2-chlorophenyl, 2,6-dichloro-3-pyridyl, 4,6-dichloro-3-pyridyl, 3,5-dichloro-2-pyridyl, 3,4-dimethylphenyl, 2-chloro-4-methylphenyl, 2-methyl-4-bromophenyl, or 2-methyl-4-chlorophenyl; or

[0129] C. 2,4-dimethylphenyl, 2,4-dichlorophenyl, 4-bromo-2-methylphenyl, 4-bromo-2-chlorophenyl, 3,4-dimethylphenyl, 2-chloro-4-methylphenyl, 2-methyl-4-bromophenyl, 2-methyl-4-chlorophenyl, or 2,4-difluorophenyl; or

[0130] D. 2,6-dichloro-3-pyridyl, 4,6-dichloro-3-pyridyl, or 3,5-dichloro-2-pyridyl; or

[0131] E. 2,4-dichlorophenyl.

[0132] The compounds having formula (I) may contain stereogenic centers, indicated by an asterisk in formula (I*), where R 1 , R 2 and G are as defined in the first aspect, each having the corresponding embodiments as described above.

[0133]

[0134] The compounds of the present invention may be enantiomers of the compounds having formula (I) represented by formula (I-1) or formula (I-2):

[0135]

[0136] The compounds having formula (I)

[0137]

[0138] can be prepared by those skilled in the art as shown in Schemes 1 to 32 below, where G, R 1 and R 2As defined above. The compound having formula (I) can be depicted by the following formula (Ia):

[0139]

[0140] Where G and R 1 As defined above for compounds of formula (I), and wherein (A) represents a pyridazinyl moiety:

[0141]

[0142] The ## mark and -OR 1 The bond to the -5,6-dihydro-4H-1,2,4-oxadiazin-3-yl moiety is indicated by % and R 2 As defined above for compounds of formula (I), unless otherwise indicated. The same definition of (A) applies to certain intermediate compounds shown in Schemes 1 to 32, particularly compounds of formula (I), (II), (III), (IV), (VIII), (IX), (X), (XI), (XIII), (XIV), (XV), (XVI), (XVII), (XVIII), (XIX), (XX), (XXI), (XXII), (XXIV), (XXV), (XXVI), (XXVII), (XXVIII), (XXIX), (XXX), (XXXI), (XXXII), (XXXIII), and (XXXIV). For clarity, certain stereocenters are not specified, and it is not intended to limit the teachings of these schemes in any way.

[0143] As shown in Scheme 1 below, a compound having formula (I) (wherein G and R 1 As defined for the compound of formula (I), a chlorinating agent may be used, for example by using POCl, PCl, (COCl) or SOCl, optionally in the presence of dimethylformamide, preferably at a temperature between 0°C and 80°C, more preferably between 25°C and 60°C, in a suitable solvent or solvent mixture (e.g. dichloromethane, dimethylformamide, 2-methyltetrahydrofuran, tetrahydrofuran, diethyl ether, toluene, ethyl acetate) by reacting a compound of formula (II) (wherein G and R 1 As defined for compounds of formula (I)) by intramolecular cyclization. For example, see Heterocycles [Heterocycles] 2016, 92, 2166-2200 or CN 114437077.

[0144]

[0145] As shown in Scheme 2 below, a compound of formula (II) (wherein G and R 1 are as defined for a compound of formula (I)) can be obtained by amine deprotection of a compound of formula (III), wherein G and R 1 are as defined for a compound of formula (I), and wherein X 1 is H and X 2 is a protecting group, or X 1 and X 2 are the same or different protecting groups, or X 1 and X 2 together with the nitrogen to which they are attached form a protecting group. Examples of protecting groups include, for example, tert-butoxycarbonyl, benzylcarbonyl, 9-fluorenylmethylcarbonyl, trifluoroacetyl, benzyl, triphenylmethyl, benzylidene, p-toluenesulfonyl, phthalimide, or succinimide. Protecting groups can be removed using standard techniques; see Greene’s Protective Groups in Organic Synthesis, 4th Edition, Wiley-Interscience.

[0146]

[0147] As shown in Scheme 3 below, a compound of formula (III) (wherein G and R 1 are as defined for a compound of formula (I), and wherein X 1 and X 2 are as defined for a compound of formula (III) in Scheme 2) can be obtained by activating the carboxylic acid functional group of a compound of formula (IV), a compound of formula (IV) (wherein G is as defined for a compound of formula (I)) and an amine compound of formula (V) (wherein is as defined for a compound of formula (I), and wherein X 1 and X 2 are as defined for a compound of formula (III) in Scheme 2) are subjected to an amide coupling transformation, which is a process that typically occurs by converting the -OH of the carboxylic acid into a good leaving group (such as a chloride group), for example by using (COCl)2 or SOCl2, and then treating with a compound of formula (IV), preferably in a suitable solvent (e.g., N-methylpyrrolidone, acetonitrile, dimethylacetamide, dichloromethane or tetrahydrofuran), preferably at a temperature between 25 °C and 60 °C, and optionally in the presence of a base (such as triethylamine or N,N-diisopropylethylamine).

[0148] Alternatively, the compound of formula (III) can be obtained using an amidation coupling reagent (such as 1-propane phosphonic anhydride (T3P)) in a suitable solvent (e.g., acetonitrile), optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine), under the conditions described in the literature for amide coupling. See, for example, Chem. Soc. Rev. 2009, 38, 606 and Chem. Soc. Rev. 2011, 40, 5084.

[0149]

[0150] As shown in Scheme 4 below, the compound of formula (II) in which G and R 1 as defined for the compound of formula (I) can also be obtained by activating the carboxylic acid functional group of the compound of formula (IV), the compound of formula (IV) in which R 1 as defined for the compound of formula (I) and an amine compound of formula (VI) in which G is as defined for the compound of formula (I) are subjected to an amide coupling transformation, which is a process that typically occurs by converting the -OH of the carboxylic acid into a good leaving group (such as a chloride group), for example by using (COCl)2 or SOCl2, and then treating with the compound of formula (IV), preferably in a suitable solvent (e.g., N-methylpyrrolidone, acetonitrile, dimethylacetamide, dichloromethane, or tetrahydrofuran), preferably at a temperature between 25 °C and 60 °C, and optionally in the presence of a base (such as triethylamine or N,N-diisopropylethylamine).

[0151] Alternatively, the compound of formula (II) can be obtained using an amidation coupling reagent (such as 1-propane phosphonic anhydride (T3P)) in a suitable solvent (e.g., acetonitrile), optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine), under the conditions described in the literature for amide coupling. See, for example, Chem. Soc. Rev. 2009, 38, 606 and Chem. Soc. Rev. 2011, 40, 5084.

[0152]

[0153] As shown respectively in Schemes 5a, 5b and 5c below, the compounds having formula (I), (III) or (II) as defined in Schemes 1, 2, 3 and 4 above can also be prepared by reacting a nucleophilic compound having formula (VII) (wherein R 1 as defined for the compound having formula (I)) with an electrophilic compound having formula (VIII), (IX) or (X) (wherein G is as defined for the compound having formula (I), wherein X 1 and X 2 as defined for the compound having formula (III) in Scheme 2, and X 3 is a suitable leaving group such as fluorine, chlorine, bromine, iodine, BF3K, B(OH)2, or B(pinacol)) in the presence of a base (e.g., KO-t-Bu, K3PO4, K2CO3, triethylamine, or Cs2CO3), in a suitable solvent (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, or dimethyl sulfoxide), at a temperature between 10 °C and 90 °C and preferably using a metal catalyst complex (e.g., Cu or Pd). For relevant examples, see Eur. J. Org. Chem. [Journal of Organic Chemistry] 2011, 18, 3353; J. Org. Chem. [Journal of Organic Chemistry] 2009, 74, 7951; Tetrahedron Lett. [Tetrahedron Letters], 2012, 53, 5318. Compounds having formula (VII) are known or commercially available.

[0154]

[0155] As shown in Scheme 6 below, the compound having formula (VIII) (wherein G is as defined for the compound having formula (I), and X 3 is a suitable leaving group such as fluorine, chlorine, bromine, iodine, BF3K, B(OH)2, or B(pinacol)) can be prepared from a compound having formula (X) (wherein G is as defined for the compound having formula (I), and X 3Obtained by intramolecular cyclization as defined for compounds of formula (VIII). For example, see Chem. Soc. Rev. 2009, 38, 606 and Chem. Soc. Rev. 2011, 40, 5084.

[0156]

[0157]

[0158] As shown in Scheme 7 below, a compound of formula (X) (wherein G is as defined for compounds of formula (I) and X 3 is a suitable leaving group such as fluorine, chlorine, bromine, iodine, BF3K, B(OH)2, or B(pinacol)) can be obtained by deprotection of the amine of a compound of formula (IX), where in conjunction with Scheme 2, G is as defined for compounds of formula (I) and X 3 is as defined for compounds of formula (X), and wherein X 1 and X 2 are as defined for compounds of formula (III). The protecting group can be removed using standard techniques; see Greene’s Protective Groups in Organic Synthesis, 4th Edition, Wiley - Interscience.

[0159]

[0160] As shown in Scheme 8 below, a compound of formula (IX) (wherein in conjunction with Scheme 2, G is as defined for compounds of formula (I), X 1 and X 2 are as defined for compounds of formula (III), and X 3 is a suitable leaving group such as fluorine, chlorine, bromine, iodine, BF3K, B(OH)2 or B(pinacol)) can be prepared by activating the carboxylic acid functional group of a compound of formula (XI), a compound of formula (XI) (wherein X 3 is as defined for compounds of formula (IX)) and an amine compound of formula (V) (wherein in conjunction with Scheme 2, G is as defined for compounds of formula (I), X 1 and X 2For amide coupling transformation (as defined for compounds of formula (III)), it is a process that typically occurs by converting the -OH of the carboxylic acid into a good leaving group (such as a chloride group), for example by using (COCl)2 or SOCl2, and then treating with a compound of formula (V), preferably in a suitable solvent (e.g., N-methylpyrrolidone, dimethylacetamide, dichloromethane or tetrahydrofuran), preferably at a temperature between 25 °C and 60 °C, and optionally in the presence of a base (such as triethylamine or N,N-diisopropylethylamine).

[0161] Alternatively, the compound of formula (IX) can be obtained using an amidation coupling reagent (such as 1-propane phosphonic anhydride (T3P)) in a suitable solvent (e.g., acetonitrile), optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine), under the conditions described in the literature for amide coupling. See, for example, Chem. Soc. Rev. [Chemical Society Reviews] 2009, 38, 606 and Chem. Soc. Rev. [Chemical Society Reviews] 2011, 40, 5084.

[0162] Compounds of formula (V) are known, commercially available or readily accessible to experts in the field.

[0163]

[0164] As shown in Scheme 9 below, a compound of formula (X) (where G is as defined for compounds of formula (I) and X 3 is a suitable leaving group such as fluorine, chlorine, bromine, iodine, BF3K, B(OH)2 or B(pinacol)) can also be obtained by activating the carboxylic acid functional group of a compound of formula (XI), a compound of formula (XI) (where X 3 is as defined for compounds of formula (X)) and an amine compound of formula (VI) (where G is as defined for compounds of formula (I)) for amide coupling transformation, which is a process that typically occurs by converting the -OH of the carboxylic acid into a good leaving group (such as a chloride group), for example by using (COCl)2 or SOCl2, and then treating with a compound of formula (VI), preferably in a suitable solvent (e.g., N-methylpyrrolidone, dimethylacetamide, dichloromethane or tetrahydrofuran), preferably at a temperature between 25 °C and 60 °C, and optionally in the presence of a base (such as triethylamine or N,N-diisopropylethylamine).

[0165] Alternatively, the compound of formula (X) can be obtained using an amidation coupling reagent (such as 1-propane phosphonic acid cyclic anhydride (T3P)) in a suitable solvent (e.g., acetonitrile), optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine), under the conditions described in the literature for amide coupling. For example, see: Chem. Soc. Rev. 2009, 38, 606 and Chem. Soc. Rev. 2011, 40, 5084. Compounds of formula (VI) are known or commercially available.

[0166]

[0167] As shown in Schemes 10a and 10b below, the compounds of formulas (I) and (III) as defined in Schemes 1, 2, and 3 above can also be prepared by reacting a nucleophilic compound of formulas (XIII) and (XIV) (wherein, with reference to Scheme 2, G is as defined for the compound of formula (I) and X 1 and X 2 is as defined for the compound of formula (III)) with an electrophilic compound of formula (XII) (wherein R 1 is as defined for the compound of formula (I), X 3 is a suitable leaving group such as fluorine, chlorine, bromine, iodine, BF3K, B(OH)2, or B(pinacolato)) in the presence of a base (e.g., KO-t-Bu, K3PO4, K2CO3, triethylamine, or Cs2CO3) in a suitable solvent (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, or dimethyl sulfoxide) at a temperature between 10 °C and 90 °C and preferably using a metal catalyst complex (e.g., Cu or Pd). For relevant examples, see Eur. J. Org. Chem. 2011, 18, 3353; J. Org. Chem. 2009, 74, 7951; Tetrahedron Lett., 2012, 53, 5318. Compounds of formula (XII) are known or commercially available.

[0168]

[0169] As shown in Scheme 11 below, a compound of formula (XIII) (wherein G is as defined for the compound of formula (I)) can be obtained by using a chlorinating agent, for example, by using POCl3, PCl5, (COCl)2 or SOCl2, optionally in the presence of dimethylformamide, preferably at a temperature between 0 °C and 80 °C, more preferably between 25 °C and 60 °C, in a suitable solvent or solvent mixture (e.g., dichloromethane, dimethylformamide, 2-methyltetrahydrofuran, tetrahydrofuran, diethyl ether, toluene, ethyl acetate) by intramolecular cyclization of a compound of formula (XV) (wherein G is as defined for the compound of formula (I)). For example, see Chem. Soc. Rev. 2009, 38, 606 and Chem. Soc. Rev. 2011, 40, 5084.

[0170]

[0171] As shown in Scheme 12 below, a compound of formula (XV) (wherein G is as defined for the compound of formula (I)) can be obtained by amine deprotection of a compound of formula (XIV), wherein G is as defined for the compound of formula (I), and X 1 and X 2 are as defined for the compound of formula (III) in Scheme 2. The protecting group can be removed using standard techniques, see Greene’s Protective Groups in Organic Synthesis, 4th Edition, Wiley-Interscience.

[0172]

[0173] As shown in Scheme 13 below, a compound of formula (XVII) (wherein G is as defined for the compound of formula (I), and X 4 is OH or OR 1 , R 1 is as defined for the compound of formula (I)) can be obtained by reacting a compound of formula (VI) (wherein G is as defined for the compound of formula (I)) with a compound of formula (XVI) (wherein X 4 is OH or OR 1 , R 1 is as defined for the compound of formula (I), and X 5 is C1-C 4-The cyclization can be obtained by coupling with an alkoxy group such as methoxy or ethoxy. The subsequent cyclization can be achieved using an acid, typically acetic acid, at a temperature between 20°C and 120°C, preferably between 80°C and 120°C. For relevant examples, see: Heterocycles [heterocycles] 2016, 92, 2166 and WO 2017 / 031325. Compounds of formula (VI) are known or can be readily obtained by an expert in the field.

[0174]

[0175] As shown in Scheme 14 below, a compound having formula (XVI) (wherein X 4 Is OH or OR 1 , R 1 As defined for compounds of formula (I), and X 5 It is C1-C 4- Alkoxy groups, such as methoxy or ethoxy) can be obtained by reacting a compound of formula (XVIII) using an alkoxide, typically in solution, in the corresponding alcohol (e.g. sodium methoxide, sodium methoxide or potassium tert-butoxide) or in excess alcohol (e.g. methanol or ethanol) and an alkali metal at a temperature between -30°C and 20°C.

[0176] Alternatively, the compound of formula (XVI) can be obtained by hydrolyzing the compound of formula (XVIII) in the presence of an acid (preferably but not limited to hydrochloric acid) in a suitable solvent or solvent mixture (such as methanol, ethanol, dichloromethane, or 1,4-dioxane) at a temperature between -30°C and 40°C. For relevant examples, see: WO 2012178015, JP2014037370 or Angew.Chem.Int.Ed. [German Applied Chemistry International Edition] 2020, 59, 23306.

[0177]

[0178] As shown in Scheme 15 below, a compound having the formula (XX) (wherein R 1 As defined for compounds of formula (I), and X 5 is C1-C4-alkoxy, such as methoxy or ethoxy) can be prepared by reacting a compound of formula (XIX) (wherein R 1 Prepared by reacting the following:

[0179] For related examples, see: J. Med. Chem. 2012, 55, 10118.

[0180]

[0181] As shown in Scheme 15a below, a compound of formula (IV) (wherein R 1 as defined for the compound of formula (I)) can be prepared by hydrolyzing a compound of formula (XIX) (wherein R 1 as defined for the compound of formula (I)) in an aqueous solvent, a solvent mixture such as tetrahydrofuran, optionally in a basic medium, at a temperature between 60 °C and 110 °C. For relevant examples, see: J. Med. Chem. [Journal of Medicinal Chemistry] 2012, 55, 10118.

[0182]

[0183] A compound of formula (XIX) (wherein R 1 as defined for the compound of formula (I)) is known, or as shown in Scheme 16 below, can be obtained from a compound of formula (XX) (wherein R 1 as defined for the compound of formula (I), and X 7 is chlorine, bromine, iodine, or O-trifluoromethanesulfonyl) in the presence of a metal source such as XPhos Pd G1, a cyanide source such as potassium ferrocyanide, copper cyanide, zinc cyanide, or potassium cyanide, and a base (e.g., KOAc), at a temperature between 50 °C and 120 °C, preferably between 80 °C and 110 °C, in a suitable solvent or solvent mixture (e.g., dioxane, water, toluene, tetrahydrofuran, 2-methyl-tetrahydrofuran, xylene). For relevant examples, see: J. Org. Chem. [Journal of Organic Chemistry] 2018, 83, 4922 and Org. Let. [Organic Letters] 2006, 8, 1189. Compounds of formula (XX) are known or can be readily prepared by those skilled in the art.

[0184]

[0185] As shown in Scheme 17 below, a compound of formula (XVII) (wherein G is as defined for the compound of formula (I), X 4 is OH or OR 1 , R 1 as defined for the compound of formula (I)) can be prepared by using an acid (e.g., acetic acid, pure or in a suitable solvent such as methanol or ethanol), at a temperature between 20 °C and 75 °C, to react a compound of formula (XXI) (wherein G is as defined for the compound of formula (I), and X 4Cyclization, as defined for compounds of formula (XVII), followed by reduction in the presence of a hydride (e.g., sodium cyanoborohydride, sodium borohydride, sodium triacetoxyborohydride, or lithium borohydride) in a solvent or solvent mixture (such as tetrahydrofuran, toluene, or methanol) to obtain. For relevant examples, see: WO 2016201168.

[0186]

[0187] As shown in Scheme 18 below, a compound of formula (XXI) (wherein G is as defined for compounds of formula (I), and X 4 is OH or OR 1 and R 1 is as defined for compounds of formula (I)) can be obtained by optionally reacting a compound of formula (XXIII) (wherein G is as defined for compounds of formula (I), and X 8 is a leaving group such as chlorine, bromine, iodine, mesyl, tosyl, or O-trifluoromethanesulfonyl) with a compound of formula (XXII) (wherein X 4 is OH or OR 1 and R 1 is as defined for compounds of formula (I)) in a suitable solvent or solvent mixture (such as benzene, toluene, tetrahydrofuran, chloroform, acetonitrile, or 2-methyl-tetrahydrofuran) in the presence of a base (e.g., pyridine, triethylamine, potassium carbonate, sodium carbonate) at a temperature between 0 °C and 110 °C, more preferably between 20 °C and 80 °C. For relevant examples, see: J. Med. Chem. [Journal of Medicinal Chemistry] 2011, 54, 8407; WO 2002051811 or WO 2010078867. Compounds of formula (XXIII) are known or readily available to those skilled in the art.

[0188]

[0189] As shown in Scheme 19 below, a compound of formula (XXII) (wherein X 4 is OH or OR 1 and R 1As defined for the compounds of formula (I), can be prepared by reacting a compound of formula (XVIII) with hydroxylamine or a hydroxylamine salt (such as hydrochloride), optionally in the presence of a base (such as potassium carbonate or sodium carbonate), in a suitable solvent or solvent mixture (such as methanol, ethanol, 2-methyl-2-butanol, water, or 1-butyl-3-methylimidazolium acetate). For relevant examples, see: Org. Biomol. Chem. [Organic and Biomolecular Chemistry] 2014, 12, 8036; WO 2016143655 or WO2019224743. Compounds of formula (XVIII) are known, commercially available, or readily accessible to those skilled in the art. Compounds of formula (XXII) may also be known.

[0190]

[0191] As shown in Scheme 20 below, a compound of formula (XXV) in which R 1 As defined for the compounds of formula (I), and X 5 is a C1-C4-alkoxy group, such as methoxy or ethoxy) can be prepared by reacting a nucleophilic compound of formula (VII) in which R 1 As defined for the compounds of formula (I)) with an electrophilic compound of formula (XXIV) in which X 5 is a C1-C4-alkoxy group, such as methoxy or ethoxy, and X 3 is a suitable leaving group, such as fluorine, chlorine, bromine, iodine, BF3K, B(OH)2, or B(pinacol)), in the presence of a base (such as KO-t-Bu, K3PO4, K2CO3, triethylamine, or Cs2CO3), in a suitable solvent or solvent mixture (such as N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, or dimethyl sulfoxide), at a temperature between 20 °C and 110 °C and preferably using a metal catalyst complex (such as Cu or Pd). For relevant examples, see Eur. J. Org. Chem. [Journal of Organic Chemistry] 2011, 18, 3353; J. Org. Chem. [Journal of Organic Chemistry] 2009, 74, 7951; Tetrahedron Lett. [Tetrahedron Letters] 2012, 53, 5318; WO 2008110313 and WO 2012136604. Compounds of formula (VII) are known or commercially available.

[0192] A compound of formula (IV) in which R 1(as defined for the compounds of formula (I)) can then be obtained by hydrolyzing the compound of formula (XXV) (wherein X 5 is a C1-C4 alkoxy group, such as a methoxy or ethoxy group) with an alkali metal hydroxide (such as lithium hydroxide, sodium hydroxide, potassium hydroxide, or barium hydroxide) in a suitable solvent or solvent mixture (e.g., methanol, acetonitrile, ethanol, water, tetrahydrofuran, or 2-methyl-tetrahydrofuran) at a temperature between 0 °C and 80 °C. Alternatively, the ester can be cleaved using, for example, hydrochloric acid under acidic conditions. For relevant examples, see: WO2021086879 or Org. Biomol. Chem. [Organic & Biomolecular Chemistry] 2015, 13, 7928.

[0193]

[0194] As shown in Scheme 21 below, the compound of formula (XXV) (wherein R 1 is as defined for the compounds of formula (I), and X 5 is a C1-C4 alkoxy group, such as a methoxy or ethoxy group) can also be prepared by reacting a nucleophilic compound of formula (XXVI) (wherein X 5 is a C1-C4 alkoxy group, such as a methoxy or ethoxy group) with an electrophilic compound of formula (XII) (wherein R 1 is as defined for the compounds of formula (I), and X 3 is a suitable leaving group, such as chlorine, bromine, iodine, BF3K, B(OH)2, or B(pinacolato)) in a suitable solvent (e.g., dichloromethane, 1,2-dichloromethane, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, N-methylpyrrolidone, or dimethylacetamide) at a temperature between 40 °C and 80 °C and using a metal source (e.g., Cu(OAc)2), and preferably in the presence of an oxidant such as O2 or a suitable palladium precatalyst such as RockPhos Pd G3, in the presence of a base (e.g., K3PO4) and a suitable solvent (e.g., dimethyl ether or toluene) at a temperature between 20 °C and 80 °C. For relevant examples, see Org. Lett. [Organic Letters] 2003, 5, 1381; Tetrahedron Lett. [Tetrahedron Letters] 1998, 39, 2933; Tetrahedron Lett. [Tetrahedron Letters] 2003, 44, 3863 and Org. Lett. [Organic Letters] 2013, 15, 2876. Compounds of formula (XII) are known or commercially available.

[0195]

[0196] As shown in Scheme 22 below, a compound of formula (XXIX) (where X 9 is OH or halogen) can be obtained from a compound of formula (XXVIII) as follows: by hydrolysis in a similar manner to that described for the conversion of the compound of formula (XXVI) to the compound of formula (XXV) in Scheme 21. A compound of formula (XXVIII) (where X 5 is C1-C4-alkoxy, such as methoxy or ethoxy, and X 9 is OH or halogen) can be obtained from a compound of formula (XXVII) (where X 9 is OH or halogen) via an oxidation method using a suitable oxidizing agent (such as KMnO4 or a cobalt(II) salt and trihydroxyisocyanuric acid (THICA)) in a suitable solvent (e.g., acetic acid) at a temperature between 25 °C and 200 °C. For relevant examples, see: Can. J. Chem. [Canadian Journal of Chemistry] 1978, 56, 1273 and WO 2021160470. Compounds of formula (XXVII) are known or can be prepared as described in Bulletin de la Société Chimique de France [Bulletin of the Chemical Society of France] 1972, 8, 3198.

[0197]

[0198] As shown in Scheme 23 below, a compound of formula (XXV) (where X 5 is C1-C4-alkoxy, such as methoxy or ethoxy) can be obtained from a compound of formula (XXXI) via an oxidation method using a suitable oxidizing agent (such as KMnO4 or a suitable cobalt(II) salt and trihydroxyisocyanuric acid (THICA)) in a suitable solvent (e.g., acetic acid) at a temperature between 25 °C and 200 °C. For relevant examples, see: Can. J. Chem. [Canadian Journal of Chemistry] 1978, 56, 1273 and WO 2021 / 160470. Compounds of formula (XXV) can be prepared as described in Bulletin de la Société Chimique de France [Bulletin of the Chemical Society of France] 1972, 8, 3198.

[0199] In addition, the compound having formula (XXXI) can be prepared by reacting a nucleophilic compound having formula (VII) (wherein R 1 is as defined for the compound having formula (I)) with an electrophilic compound having formula (XXX) (wherein X 3 is a suitable leaving group such as fluorine, chlorine, bromine, iodine, BF3K, B(OH)2 or B(pinacol)) in the presence of a base (e.g., KO-t-Bu, K3PO4, K2CO3, triethylamine, or Cs2CO3), in a suitable solvent (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, dimethyl sulfoxide), at a temperature between 25 °C and 120 °C, and optionally using a metal catalyst and ligand complex (e.g., CuI, N,N-dimethylglycine). For relevant examples, see Eur. J. Org. Chem. [Journal of Organic Chemistry] 2011, 18, 3353; J. Org. Chem. [Journal of Organic Chemistry] 2009, 74, 7951; Tetrahedron Lett. [Tetrahedron Letters] 2012, 53, 5318; WO 2008110313 and WO 2012 / 136604. Compounds having formula (XXX) are known or commercially available.

[0200]

[0201] As shown in Scheme 24 below, the compound having formula (XXV) (wherein R 1 is as defined for the compound having formula (I), and X 5 is OH or C1-C4-alkoxy) can also be obtained from the compound having formula (XX) (wherein R 1 is as defined for the compound having formula (I), and X 7 is chlorine, bromine, iodine, or trifluoromethanesulfonyl-O-) at a temperature between 20 °C and 130 °C, preferably between 70 °C and 110 °C, using a metal source (such as XPhos Pd G1), in a pressure vessel loaded with carbon monoxide, typically a stainless steel autoclave, at a pressure typically between 1 and 50 bar, preferably between 5 and 15 bar, in the presence of an organic base (e.g., triethylamine or diisopropylethylamine) and a suitable solvent (e.g., methanol or ethanol). For relevant examples, see: J. Med. Chem. [Journal of Medicinal Chemistry] 2014, 57, 2692 and Adv. Synth. Catal. [Advanced Synthesis & Catalysis] 2006, 348, 1255.

[0202]

[0203] Alternatively, as shown in Scheme 25 below, a compound of formula (IV) (wherein R 1 is defined as for the compound of formula (I)) can also be obtained by reacting a compound of formula (XXXII) (wherein R 1 is defined as for the compound of formula (I), and X 10 is chlorine, bromine or iodine) with a lithium reagent (such as n-butyllithium, sec-butyllithium, tert-butyllithium or lithium diisopropylamide) in a suitable solvent (e.g., hexane, diethyl ether or tetrahydrofuran) at a temperature between -78 °C and -30 °C, followed by addition of carbon dioxide. For relevant examples, see: J. Am. Chem. Soc. 2018, 140, 9140 and J. Am. Chem. Soc. 2021, 143, 1539.

[0204]

[0205] As shown in Scheme 26 below, a compound of formula (XXXII) (wherein R 1 is defined as for the compound of formula (I), and X 10 is chlorine, bromine or iodine) is known or can be prepared as follows: reacting a compound of formula (XXXIII) (wherein R 1 is defined as for the compound of formula (I)) with an electrophilic halogen reagent (such as bromine, dibromohydantoin, N-bromo- or N-chloro-succinimide) at a temperature between -78 °C and 10 °C, optionally with a base (typically lithium diisopropylamide or n-butyllithium), in a suitable solvent (e.g., chloroform, 2-methyltetrahydrofuran or dimethylformamide). For relevant examples, see: Tetrahedron Lett. 2003, 44, 823; J. Am. Chem. Soc. 2010, 132, 8858 and Synthesis 2005, 16, 2782.

[0206]

[0207] As shown in Scheme 27 below, a compound of formula (IV) (wherein R 1 is defined as for the compound of formula (I)) can also be obtained by reacting a compound of formula (XXXIV) (wherein R 1Prepared by reaction with a base (typically lithium diisopropylamide or n-butyllithium) as defined for compounds having formula (I), followed by addition of carbon dioxide. Compounds having formula (XXXIV) are known, commercially available or readily prepared by those skilled in the art. For relevant examples, see: Bioorg. Med. Chem. [Bioorganic & Medicinal Chemistry Letters] 2004, 12, 5579; J. Am. Chem. Soc. [Journal of the American Chemical Society] 2010, 132, 8858 and Synthesis [Synthesis] 2005, 16, 2782.

[0208]

[0209] As shown in Scheme 28 below, compounds having formula (V) can be obtained by treating a compound having formula (XXXV), where X 1 is H and X 2 is a protecting group, or X 1 and X 2 are the same or different protecting groups, or X 1 and X 2 together with the nitrogen to which they are attached form a protecting group, and where X 1a is H and X 2a is a protecting group, or X 1a and X 2a are the same or different protecting groups, or X 1a and X 2a together with the nitrogen to which they are attached form a protecting group; and X 2 is different from X 2a . X 1 and X 1a can both be hydrogen. Additionally, if on the one hand X 1 and X 2 and on the other hand X 1a and X 2a together with the nitrogen to which they are attached form a protecting group, then the protecting groups should be different. Examples of protecting groups include, for example, tert-butoxycarbonyl, benzylcarbonyl, 9-fluorenylmethylcarbonyl, trifluoroacetyl, benzyl, triphenylmethyl, benzylidene, p-toluenesulfonyl, phthalimide, or succinimide.

[0210] The treatment of the compound of formula (XXXV) is optionally carried out with an acid (e.g., hydrochloric acid, trifluoroacetic acid) at a temperature between 0 °C and 50 °C in a suitable solvent or solvent mixture (e.g., dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran or diethyl ether). For relevant examples, see: ChemBioChem. [Biochemistry] 2009, 10, 323 and Org. Process Res. Dev. [Organic Process Research and Development] 2002, 6, 520. The compounds of formula (XXXV) are known or readily accessible to those skilled in the art.

[0211]

[0212] As shown in Scheme 29 below, a compound of formula (XXXVI) in which X 8 is OH, halogen, O-R 1 , R 1 as defined for the compound of formula (I), X 9 is halogen, methyl, trifluoromethanesulfonyloxy-, cyano, COOH, or -C(O)C1-C4 alkoxy, and R 2 is as described below) is prepared by reacting a compound of formula (XXXVII) in which X 8 and X 9 are as defined for the compound of formula (XXXVI) and Z is as described below) with a reagent of formula (XXXVIII) R 2 -X 11 . Suitable reaction conditions for the compounds of formula R 2 -X 11 (XXXVIII) and various substituents R 2 and Z are described below.

[0213] For example, a compound of formula (XXXVI) in which R 2 is cyano, C1-C6 alkyl, C3-C5 alkenyl, C3-C5 alkynyl, C1-C3 alkoxyC2-C3 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkylC 1-2 alkyl, cycloalkyl, phenyl, heteroaryl or heterocyclic group) can be prepared by reacting a compound of formula (XXXVII) in which Z is chlorine, bromine, or iodine) with a suitable cross-coupling reagent of formula (XXXVIII) in which R 2is cyano, C1-C6 alkyl, C3-C5 alkenyl, C3-C5 alkynyl, C1-C3 alkoxy C2-C3 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C 1-2 alkyl, cycloalkyl, phenyl, heteroaryl, or heterocyclic group, and X 11 is prepared by reacting with a metal, metalloid (e.g., Zn(CN), cyclopropylMgBr, MeZnCl, or AlMe3) or organometalloid (e.g., trimethylcyclotriboroxane) reagent). For examples, see J. Org. Chem. [Journal of Organic Chemistry] 1987, 52, 3847; WO 2006 / 045514; WO 2004 / 080998.

[0214] A compound having formula (XXXVI) wherein R 2 is C1-C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, phenoxy, heteroaryloxy, or C3-C6 cycloalkyloxy) can be prepared by treating a compound having formula (XXXVII) (wherein Z is a suitable leaving group such as halogen) in the presence of a base (such as NaH, KO-t-Bu, K3PO4, K2CO3, triethylamine, or Cs2CO3), optionally in the presence of an additional solvent (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, or dimethyl sulfoxide), at a temperature between 25 °C and the reflux temperature, with a suitable nucleophilic compound having formula (XXXVIII) wherein R 2 is C1-C6 alkyl, C3-C4 alkenyl, C3-C4 alkynyl, C1-C3 alkoxy C2-C3 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C 1-2 alkyl, phenyl, heteroaryl, or C3-C6 cycloalkyl, and X 11 is selected from -OH, NH, SH, or C1-C4 alkylamino). For relevant examples, see: F. Terrier, Modern Nucleophilic Aromatic Substitution [Modern Nucleophilic Aromatic Substitution], Wiley-VCH [Wiley-VCH Verlag GmbH & Co. KGaA], Weinheim, 2013.

[0215] A compound having formula (XXXVI) wherein R 2is a C1-C4-alkoxy, C3-C4-vinyloxy, C3-C4-alkynyloxy, C1-C2-fluoroalkoxy, or C3-C6-cycloalkyloxy) is readily obtained from a compound of formula (XXXVII) (wherein Z is OH or SH) using a suitable alkylating reagent of formula (XXXVIII) (such as a C1-C6-alkyl halide, C3-C5-alkenyl halide, C3-C5-alkynyl halide, C1-C3-alkoxy-C2-C3-alkyl halide, C3-C5-alkynyl halide, C1-C3-alkoxy-C2-C3-alkyl halide, C3-C6-cycloalkyl halide, and C3-C6-cycloalkyl-C 1-2 alkyl halide) or reagents such as ClF2COOH and Me2SO4 under known conditions described in the literature.

[0216]

[0217]

[0218] As shown in Scheme 30 below, the related compound of formula (XXXIX) (wherein X 7 is chlorine, bromine, or iodine) is prepared by reacting a compound of formula (XL) (wherein X 7 is identically selected from chlorine, bromine, and iodine) with a cyanide salt (such as sodium cyanide or potassium cyanide) in a suitable solvent or solvent mixture (such as dimethylformamide, tetrahydrofuran, 2-methyl-tetrahydrofuran) at a temperature between 50 °C and 120 °C, preferably between 80 °C and 100 °C, optionally in the presence of a copper salt (such as copper cyanide). For related examples, see: WO 199507264.

[0219]

[0220] As shown in Scheme 31 below, the related compound of formula (XLI) (wherein X 7 is chlorine, bromine, or iodine) is prepared by reacting a compound of formula (XLII) (wherein X 7 is identically selected from chlorine, bromine, and iodine) with methylmagnesium halide (wherein the halide is bromide or chloride) in a suitable solvent or solvent mixture (such as diethyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyl-tetrahydrofuran, tert-butyl methyl ether) at a temperature between -20 °C and 10 °C, optionally in the presence of a copper salt (such as copper iodide, copper cyanide, copper chloride, copper acetate). For related examples, see: WO 199507264.

[0221]

[0222] As shown in Scheme 32 below, a compound of formula (XLIII) wherein X 8 is OH, O-R 1 , or a halogen, wherein R 1 is as defined for the compound of formula (I), and R 2 is as described below) is prepared by reacting a compound of formula (XLIV) wherein X 8 and R 1 are as defined for the compound of formula (XLIII), and Z is as described below) with a reagent of formula (XLV) R 2 -X 11 . The compounds of formula R 2 -X 11 (XLV) and suitable reaction conditions for the various substituents R 2 and Z are described below.

[0223] For example, a compound of formula (XLIII) wherein R 2 is cyano, C1-C6 alkyl, C3-C5 alkenyl, C3-C5 alkynyl, C1-C3 alkoxy C2-C3 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C 1-2 alkyl, cycloalkyl, phenyl, heteroaryl or heterocyclic group, and wherein X 8 is as generally defined above for the compound of formula (XLIII)) can be prepared by preferably in the presence of a suitable metal (e.g., CuBr) or catalyst complex (e.g., 1,1'-bis(diphenylphosphino)ferrocene-palladium(II) dichloride), optionally in the presence of a base (e.g., K2CO3), and in an inert solvent (such as toluene or 2-methyltetrahydrofuran), at a temperature between 25 °C and the reflux temperature, reacting a compound of formula (XLIV) wherein Z is chlorine, bromine, or iodine) with a suitable cross-coupling reagent of formula (XLV) wherein R 2 is cyano, C1-C6 alkyl, C3-C5 alkenyl, C3-C5 alkynyl, C1-C3 alkoxy C2-C3 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C 1-2 alkyl, cycloalkyl, phenyl, heteroaryl or heterocyclic group, and X 11 is a metal, metalloid (e.g., Zn(CN), cyclopropylMgBr, MeZnCl, AlMe3) or organometalloid (e.g., trimethylcyclotriboroxane) reagent). For examples, see J. Org. Chem. [Journal of Organic Chemistry] 1987, 52, 3847; WO2006 / 045514; WO 2004 / 080998.

[0224] A compound of formula (XLIII) wherein R 2is a C1-C4 alkoxy group, C3-C4 alkenyloxy group, C3-C4 alkynyloxy group, phenoxy group, heteroaryloxy group, or C3-C6 cycloalkyloxy group) by reacting in the presence of a base (such as NaH, KO-t-Bu, K3PO4, K2CO3, triethylamine, or Cs2CO3), optionally in the presence of an additional solvent (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, dimethyl sulfoxide), at a temperature between 25 °C and the reflux temperature, with a suitable nucleophilic compound of formula (XLV) (where R 2 is a C1-C6 alkyl group, C3-C4 alkenyl group, C3-C4 alkynyl group, C1-C3 alkoxy C2-C3 alkyl group, C3-C6 cycloalkyl group, C3-C6 cycloalkyl C 1-2 alkyl group, phenyl group, heteroaryl group, or C3-C6 cycloalkyl group, and X 11 is selected from -OH, NH, SH, or C1-C4 alkylamino) to treat a compound of formula (XLIV) (where Z is a suitable leaving group such as a halogen). For relevant examples, see: F. Terrier, Modern Nucleophilic Aromatic Substitution [Modern Nucleophilic Aromatic Substitution], Wiley-VCH [Wiley-VCH Verlag GmbH & Co. KGaA], Weinheim, 2013.

[0225] In addition, a compound of formula (XLIII) (where R 2 is a C1-C4-alkoxy group, C3-C4 alkenyloxy group, C3-C4 alkynyloxy group, C1-C2 fluoroalkoxy group, or C3-C6 cycloalkyloxy group) is readily obtained from a compound of formula (XLIV) (where Z is OH or SH) using a suitable alkylating reagent of formula (XLV) (where R 2 is a C1-C6 alkyl group, C3-C4 alkenyl group, C3-C4 alkynyl group, C1-C3 alkoxy C2-C3 alkyl group, C3-C6 cycloalkyl group, C3-C6 cycloalkyl C 1-2 alkyl group, phenyl group, heteroaryl group, or C3-C6 cycloalkyl group, and X 11 is a suitable leaving group such as chlorine, bromine, iodine, trifluoromethanesulfonyl-O-, and methanesulfonyl-O-) or known reagents such as ClF2COOH and Me2SO4 under known conditions described in the literature.

[0226]

[0227] Depending on the reaction conditions suitable for each case and the choice of starting materials, it is possible, for example, to replace only one substituent with another substituent according to the present invention in a single reaction step, or multiple substituents can be replaced with other substituents according to the present invention in the same reaction step.

[0228] Salts of the compounds of formula (I) can be prepared in a manner known per se. Thus, for example, acid addition salts of the compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion-exchange reagent, and salts with bases are obtained by treatment with a suitable base or a suitable ion-exchange reagent. All other compounds mentioned in Schemes 1 to 16 are readily preparable by those skilled in the art or are commercially available.

[0229] Salts of the compounds of formula (I) can be converted in a conventional manner into the free compound (I), acid addition salts (e.g., by treatment with a suitable basic compound or a suitable ion-exchange reagent), and salts with bases (e.g., by treatment with a suitable acid or a suitable ion-exchange reagent).

[0230] Salts of the compounds of formula (I) can be converted in a manner known per se into other salts of the compounds of formula (I), acid addition salts, for example into other acid addition salts, for example by treatment of a salt of an inorganic acid (such as a hydrochloride) with a suitable metal salt of an acid (such as a salt of sodium, barium or silver, for example silver acetate) in a suitable solvent, in which the inorganic salt formed (such as silver chloride) is insoluble and thus precipitates from the reaction mixture.

[0231] Depending on the procedure or reaction conditions, the compounds of formula (I) having salt-forming properties can be obtained in free form or in the form of a salt.

[0232] The compounds of formula (I) and, where appropriate, their tautomers (in each case in free form or in salt form) can exist in the form of one of the possible isomers or as a mixture of these isomers, for example in the form of pure isomers (such as enantiomers and / or diastereoisomers) or as a mixture of isomers (such as a mixture of enantiomers, for example a racemate; or a mixture of diastereoisomers), depending on the number of asymmetric carbon atoms present in the molecule, the absolute and relative configuration and / or depending on the configuration of the non-aromatic double bonds present in the molecule; the present invention relates to the pure isomers as well as to all possible mixtures of isomers, and in each case in the context, even in each case where no stereochemical details are specifically mentioned, should be understood in this sense.

[0233] Mixtures of diastereoisomers or racemates of the compounds of formula (I) in free form or in salt form (the obtaining of which can depend on the starting materials and procedures chosen) can be separated in a known manner into the pure diastereoisomers or racemates on the basis of the physicochemical differences of these components, for example by fractional crystallization, distillation and / or chromatography.

[0234] Racemic mixtures of enantiomers, such as racemates, which can be obtained in a similar manner, can be resolved into the optical enantiomers by known methods, for example by recrystallization from an optically active solvent; by chromatography on a chiral adsorbent, for example high performance liquid chromatography (HPLC) on acetyl cellulose; by cleavage with a specific immobilized enzyme with the aid of a suitable microorganism; via formation of inclusion compounds, for example using a chiral crown ether, in which only one enantiomer is complexed; or by conversion into diastereomeric salts, for example by reacting a 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 mixture obtainable in this way, for example by fractional crystallization based on their different solubilities, to give diastereomers, from which the desired enantiomer can be liberated by the action of a suitable reagent (such as a basic reagent).

[0235] Pure diastereomers or enantiomers can be obtained according to the invention, not only by separating suitable mixtures of isomers, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process with starting materials having the appropriate stereochemistry according to the invention.

[0236] If the individual components have different biological activities, it is advantageous in each case to separate or synthesize the biologically more active isomers, such as enantiomers or diastereomers or mixtures of isomers, such as mixtures of enantiomers or diastereomers.

[0237] As an example, compounds having more than one asymmetric carbon atom can exist in diastereomeric forms, which can optionally be separated by chromatography, for example supercritical fluid chromatography (SFC) with a chiral column. Such diastereomers can exhibit different fungicidal activity profiles, but all isomers and diastereomers form part of the invention.

[0238] The compounds of formula (I) and, where appropriate, their tautomers (in each case in free form or in salt form) can, where appropriate, also be obtained in the form of hydrates and / or include other solvents, such as those which can be used to crystallize the compounds present in solid form.

[0239] As already indicated, unexpectedly, it has now been found that, for practical purposes, the compounds of formula (I) according to the invention have a very advantageous level of biological activity for protecting plants against diseases caused by fungi.

[0240] Compounds having formula (I) can be used in the agricultural sector and related fields of use as, for example, active ingredients for controlling phytopathogens, or on inanimate materials for controlling spoilage microorganisms or organisms potentially harmful to humans. These novel compounds are characterized by excellent activity at low application rates, good plant tolerance and environmental safety. They have very useful therapeutic, prophylactic and systemic properties and can be used to protect many cultivated plants. Compounds having formula (I) can be used to inhibit or destroy pests occurring on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of different useful plant crops, while also protecting, for example, those later-growing plant parts from infestation by phytopathogenic microorganisms.

[0241] The present invention further relates to a method for controlling or preventing infestation of plants or plant propagation materials and / or harvested food crops susceptible to microbial attack by treating the plants or plant propagation materials and / or harvested food crops, wherein an effective amount of a compound having formula (I) is applied to these plants, their parts or their sites.

[0242] Compounds having formula (I) can also be used as fungicides. As used herein, the term "fungicide" means a compound that controls, modifies, or prevents fungal growth. The term "fungicidally effective amount" when used means an amount of such a compound or combination of such compounds that is capable of having an effect on fungal growth. Controlling or modifying effects include all deviations from natural development, such as killing, arresting, etc., and preventing includes creating a barrier or other defense against fungal infection within or on the plant.

[0243] Compounds having formula (I) can also be used as seed dressings for treating plant propagation materials (e.g., seeds, fruits, tubers or grains) or plant cuttings, for protecting against fungal infection as well as against phytopathogenic fungi present in the soil. The propagation materials can be treated with a composition comprising a compound having formula (I) before planting: for example, seeds can be dressed before sowing. The active compound having formula (I) can also be applied to the grains (coating) by impregnating the seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the planting site when planting the propagation materials, for example, applied to the furrow of the seeds during sowing. The present invention also relates to such methods for treating plant propagation materials, and to plant propagation materials so treated.

[0244] In addition, compounds having formula (I) can be used in related fields for controlling fungi, for example, for the protection of industrial materials (including wood and wood-related industrial products), food storage, and hygiene management.

[0245] Furthermore, the present invention can be used to protect inanimate materials (e.g., wood, wall panels and coatings) from fungal attack.

[0246] Compounds having the formula (I) are effective, for example, against the fungi and fungal vectors of diseases and phytopathogenic bacteria and viruses. The fungi and fungal vectors of these diseases and phytopathogenic bacteria and viruses are, for example:

[0247] Absidia corymbifera, Alternaria spp., Aphanomyces spp., Ascochyta spp., Aspergillus spp. (including Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans, Aspergillus niger, Aspergillus terreus), Aureobasidium spp. (including Aureobasidium pullulans), Blastomyces dermatitidis, Blumeria graminis f. sp. tritici, Bremia lactucae, Botryosphaeria spp. (including Botryosphaeria dothidea, Botryosphaeria obtusa), Botrytis spp. (including Botrytis cinerea), Candida spp. (including Candida albicans, Candida glabrata, Candida krusei, Candida lusitaniae, Candida parapsilosis, Candida tropicalis), Cephaloascus fragrans, Ceratocystis spp., Cercospora spp. (including Cercospora arachidicola), Cercosporidium personatum, Cladosporium spp., Claviceps purpurea, Coccidioides immitis, Cochliobolus spp., Colletotrichum spp. (including Colletotrichum musae), Cryptococcus neoformans, Diaporthe spp., Didymella spp., Drechslera spp., Elsinoë spp., Epidermophyton spp., Erwinia amylovora, Erysiphe spp. (including Erysiphe cichoracearum), Eutypa lata, Fusarium spp. (including Fusarium culmorum, Fusarium graminearum, Fusarium langsethiae, Fusarium moniliforme, Fusarium subglutinans, Fusarium oxysporum, Fusarium proliferatum), Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulata, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium spp., Hyalopsora spp., Histoplasma spp. (including Histoplasma capsulatumcapsulatum), red thread blight fungus, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum species, Monilinia species, Mucor species, Mycosphaerella species (including Mycosphaerella graminicola, M. pomi), twig blight fungus, spruce pathogen, Paracoccidioides species, Penicillium species (including Penicillium digitatum, Penicillium italicum), Graphium species, Sclerospora species (including Sclerospora maydis, Sclerospora philippinensis, Sclerospora sorghi), Peronospora species, Septoria nodorum, Phakopsora pachyrhizi, Phellinus igniarius, Geniculosporium species, Phoma species, Phomopsis viticola, Phytophthora species (including Phytophthora infestans), Plasmopara species (including Plasmopara halstedii, Plasmopara viticola), Pleospora species, Podosphaera species (including Podosphaera leucotricha), Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas species, Pseudoperonospora species (including Pseudoperonospora cubensis, Pseudoperonospora humuli), Pseudopeziza tracheiphila, Puccinia species (including Puccinia hordei, Puccinia recondita, Puccinia striiformis, Puccinia triticina), Sclerotinia species, Pyrenophora species, Pyricularia species (including Pyricularia oryzae), Pythium species (including Pythium ultimum), Ramularia species, Rhizoctonia species, Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium species, Scedosporium species (including Scedosporium apiospermum, Scedosporium prolificans), Schizothyrium pomi, Sclerotinia species, Sclerotium species, Septoria species (including Septoria nodorum, Septoria tritici)Tritici)), strawberry powdery mildew pathogen (Sphaerotheca macularis), Sphaerotheca fusca (cucumber powdery mildew pathogen (Sphaerotheca fuliginea)), Sporothorix species, Stagonospora nodorum, Stemphylium species, Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia species, Trichoderma species (including Trichoderma harzianum, Trichoderma pseudokoningii, Trichoderma viride), Trichophyton species, Typhula species, Uncinula necator, Urocystis species, Ustilago species, Venturia species (including Venturia inaequalis), Verticillium species, and Xanthomonas species.

[0248] The compounds of formula (I) can be used, for example, for lawns, ornamental plants such as flowers, shrubs, broad-leaved trees or evergreen plants, such as conifers, and tree injections, pest management, etc.

[0249] Within the scope of the present invention, the target crops and / or useful plants to be protected typically include perennial and annual crops, such as berry plants, such as blackberries, blueberries, cranberries, raspberries, and strawberries; cereals, such as barley, corn (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 beet and fodder beet, coffee beans, hops, mustard, rapeseed (canola), poppy, sugar cane, sunflower, tea, and tobacco; fruit trees, such as apples, apricots, avocados, bananas, cherries, citrus fruits, nectarines, peaches, pears, and plums; grasses, such as Bermuda grass, bluegrass, bent grass, centipede grass, foxtail grass, ryegrass, St. Augustine grass, and zoysia grass; herbs, such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage, and thyme; legumes, such as kidney beans, lentils, peas, and soybeans; nuts, such as almonds, cashews, groundnuts, hazelnuts, peanuts, pecans, pistachios, and walnuts; palm plants, such as oil palm; ornamental plants, such as flowers, shrubs, and trees; other trees, such as cocoa trees, coconut trees, olive trees, and rubber trees; vegetables, such as asparagus, eggplant, broccoli, cabbage, carrots, cucumbers, garlic, lettuce, zucchini, melons, okra, onions, peppers, potatoes, pumpkins, rhubarb, spinach, and tomatoes; and grapevines, such as grapes.

[0250] The term "useful plant" should be understood to also include useful plants which have been made tolerant to herbicides (such as bromoxynil) or classes of herbicides (such as HPPD inhibitors, ALS inhibitors such as flupyrsulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enolpyruvylshikimate-3-phosphate synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen oxidase) inhibitors) by conventional breeding methods or genetic engineering. Examples of crops which have been made tolerant to imidazolinones (such as imazamox) by conventional breeding methods (mutation) are summer rape (Canola). Examples of crops which have been made tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate-resistant and glufosinate-resistant maize varieties which are commercially available under the Herculex and trade names.

[0251] The term "useful plant" should be understood to also include useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesizing one or more selectively acting toxins, such as those known, for example, from toxin-producing bacteria, in particular bacteria of the genus Bacillus.

[0252] Examples of such plants are: (maize variety expressing the CryIA(b) toxin); YieldGard (maize variety expressing the CryIIIB(b1) toxin); YieldGard (maize variety expressing the CryIA(b) and CryIIIB(b1) toxins); (maize variety expressing the Cry9(c) toxin); Herculex (maize variety expressing the CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) conferring tolerance to the herbicide glufosinate); NuCOTN (cotton variety expressing the CryIA(c) toxin); Bollgard (cotton variety expressing the CryIA(c) toxin); Bollgard (cotton variety expressing the CryIA(c) and CryIIA(b) toxins); (cotton variety expressing the VIP toxin); (potato variety expressing the CryIIIA toxin); GT Advantage (GA21 glyphosate tolerance trait), CB Advantage (CB trait of Ostrinia nubilalis), RW (western corn rootworm trait) and

[0253] The term "crop" shall be understood to also include crop plants that have been so transformed by the use of recombinant DNA techniques that they are capable of synthesizing one or more selectively acting toxins, which are, for example, known from toxin-producing bacteria, in particular those of the genus Bacillus.

[0254] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A; or insecticidal proteins of nematode-parasitic bacteria, for example of the genus Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; 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, lectins, such as pea lectin, barley lectin or snowdrop lectin; agglutinins; protease inhibitors, such as trypsin inhibitors, serine protease inhibitors, potato protease inhibitor, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid-metabolizing enzymes, such as 3-hydroxy-steroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysis inhibitors, HMG-COA-reductase, ion channel blockers such as sodium or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptors, stilbene synthases, bibenzyl synthases, chitinases and glucanases.

[0255] Furthermore, in the context of the present invention, δ-endotoxins (such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C) or vegetative insecticidal proteins (Vips) (such as Vip1, Vip2, Vip3 or Vip3A) should be understood to clearly also include hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are recombinantly produced by new combinations of different domains of those 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 naturally occurring toxin are replaced. In such amino acid replacements, preferably a protease recognition sequence that does not occur naturally is inserted into the toxin, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence was inserted into the Cry3A toxin (see WO 03 / 018810).

[0256] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-A-0 374 753, WO 93 / 07278, WO 95 / 34656, EP-A-0 427 529, EP-A-451 878 and WO 03 / 052073.

[0257] Methods for preparing such transgenic plants are generally known to those skilled in the art and are described, for example, in the above-mentioned publications. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP-A-0 367474, EP-A-0 401 979 and WO 90 / 13651.

[0258] The toxins contained in transgenic plants render the plants tolerant to harmful insects. Such insects can be present in any insect taxon, but are particularly common among beetles (Coleoptera), dipterous insects (Diptera) and moths (Lepidoptera).

[0259] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known and some of them are commercially available. Examples of such plants are: (maize variety expressing Cry1Ab toxin); YieldGard (maize variety expressing Cry3Bb1 toxin); YieldGard (maize variety expressing Cry1Ab and Cry3Bb1 toxins); (maize variety expressing Cry9C toxin); Herculex (Maize variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) conferring tolerance to the herbicide glufosinate); NuCOTN (Cotton variety expressing the Cry1Ac toxin); Bollgard (Cotton variety expressing the Cry1Ac toxin); Bollgard (Cotton variety expressing the Cry1Ac and Cry2Ab toxins); (Cotton variety expressing the Vip3A and Cry1Ab toxins); (Potato variety expressing the Cry3A toxin); GT Advantage (GA21 glyphosate tolerance trait), CB Advantage (Bt11 European corn borer (CB) trait) and

[0260] Additional examples of such genetically modified crops are:

[0261] 1. Bt11 maize from Syngenta Seeds SAS, Chemindel'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified maize expressing a truncated Cry1Ab toxin by genetic modification, making it resistant to the attack of European corn borer (Ostrinia nubilalis and Sesamia nonagrioides). Bt11 maize also expresses the PAT enzyme by genetic modification to obtain tolerance to the herbicide glufosinate.

[0262] 2. Bt176 maize from Syngenta Seeds, Chemindel'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified maize expressing the Cry1Ab toxin by genetic modification, making it resistant to the attack of European corn borer (Ostrinia nubilalis and Sesamia nonagrioides). Bt176 maize also expresses the PAT enzyme by genetic modification to obtain tolerance to the herbicide glufosinate.

[0263] 3. MIR604 maize from Syngenta Seeds, Chemindel'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Maize with insect resistance by expressing a modified Cry3A toxin by genetic modification. This toxin is Cry3A055 modified by inserting a cathepsin-G protease recognition sequence. The preparation of such genetically modified maize plants is described in WO 03 / 018810.

[0264] 4. MON 863 maize, from Monsanto Europe S.A., 270 - 272 Avenue de Tervuren, B - 1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses the Cry3Bb1 toxin and is resistant to certain Coleoptera insects.

[0265] 5. IPC 531 cotton, from Monsanto Europe, 270 - 272 Avenue de Tervuren, B - 1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0266] 6. 1507 maize, from Pioneer Overseas Corporation, Avenue Tedesco, 7B - 1160 Brussels, Belgium, registration number C / NL / 00 / 10. Genetically modified maize that expresses the protein Cry1F to obtain resistance to certain Lepidoptera insects and expresses the PAT protein to obtain tolerance to the herbicide glufosinate.

[0267] 7. NK603×MON 810 maize, from Monsanto Europe, 270 - 272 Avenue de Tervuren, B - 1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. Constituted from a conventionally bred hybrid maize variety by crossing the genetically modified varieties NK603 and MON 810. NK603×MON 810 maize transgenically expresses the protein CP4 EPSPS obtained from Agrobacterium sp. strain CP4, making it tolerant to the herbicide (containing glyphosate), and also expresses the Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki, making it tolerant to certain Lepidoptera, including Ostrinia nubilalis.

[0268] The compound having the formula (I) can be used to control or prevent phytopathogenic diseases, especially diseases caused by phytopathogenic fungi, such as Botrytis cinerea on Rosaceae, Vitaceae, Solanaceae, Cucurbitaceae and Leguminosae; Glomerella lagenarium on Cucurbitaceae; Blumeria graminis on Gramineae (such as wheat).

[0269] As used herein, the term "site" means the place where a plant grows in or on, or the place where the seeds of a cultivated plant are sown, or the place where the seeds are to be placed in the soil. It includes the soil, seeds and seedlings, together with the established vegetation.

[0270] The term "plant" refers to all the tangible parts of plants, including seeds, seedlings, young trees, roots, tubers, stems, stalks, leaves and fruits.

[0271] The term "plant propagation material" shall be understood to mean the reproductive parts of plants, such as seeds, which can be used for the propagation of plants, as well as vegetative material, such as cuttings or tubers (e.g. potatoes). Seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants can be mentioned, for example. Germinated plants and young plants which are to be transplanted after germination or after emergence can also be mentioned. These young plants can be protected before transplantation by being treated completely or partially by drenching. Preferably, "plant propagation material" shall be understood to mean seeds.

[0272] The compounds of formula (I) can be used in unmodified form or, preferably, together with auxiliaries conventionally employed in the art of formulation. For this purpose, they can be conveniently formulated in known manner as emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granules and also encapsulations, for example in polymeric substances. For the type of composition, the method of application, such as spraying, atomizing, dusting, broadcasting, spreading or watering, is chosen according to the intended purpose and the circumstances at the time. The compositions can also contain further auxiliaries, such as stabilizers, defoamers, viscosity regulators, binders or tackifiers, together with fertilizers, micronutrient donors or other formulations for obtaining special effects.

[0273] Suitable carriers and auxiliaries, for example for agricultural use, can be solid or liquid and are substances useful in the art of formulation, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are described, for example, in WO 97 / 33890.

[0274] Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations contain anti-settling agents and dispersants and can further contain wetting agents to enhance activity, as well as defoamers and crystal growth inhibitors. When in use, these concentrates are diluted in water and are generally applied as sprays to the area to be treated. The amount of active ingredient can range from 0.5% to 95% of the concentrate.

[0275] Wettable powders are in the form of finely divided particles which are readily dispersible in water or other liquid carriers. These particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller's earth, kaolin, silica and other readily wettable organic or inorganic solids. Wettable powders generally contain from 5% to 95% of the active ingredient plus small amounts of wetting agents, dispersants or emulsifiers.

[0276] An emulsifiable concentrate is a homogeneous liquid composition that is dispersible in water or other liquids and can consist entirely of the active compound and a liquid or solid emulsifier, or it can also contain a liquid carrier such as xylene, heavy aromatic naphtha, isophorone, and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquids and are typically applied as sprays to the area to be treated. The amount of the active ingredient can range from 0.5% to 95% of the concentrate.

[0277] Granular formulations include both extrudates and coarser granules and are typically applied to the area to be treated without dilution. Typical carriers for granular formulations include sand, bleaching earth, attapulgite clay, bentonite, montmorillonite, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, stucco, wood flour, ground corn cobs, ground peanut hulls, sugar, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesium oxide, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate, and other organic or inorganic materials that absorb the active compound or can be coated with the active compound. Granular formulations typically contain 5% to 25% of the active ingredient, which can include surfactants such as heavy aromatic naphtha, kerosene, and other petroleum fractions, or vegetable oils; and / or adhesives such as dextrin, gum, or synthetic resins.

[0278] Dusts are free-flowing mixtures of the active ingredient and finely divided solids such as talc, clay, flour, and other organic and inorganic solids that act as dispersants and carriers.

[0279] Microcapsules are typically microdroplets or granules of the active ingredient encapsulated within an inert porous shell that allows the enclosed material to escape into the environment at a controlled rate. The diameter of the encapsulated microdroplets is typically 1 to 50 microns. The enclosed liquid typically accounts for 50% to 95% of the weight of the capsule and can contain a solvent in addition to the active compound. The encapsulated granules are typically porous granules in which a porous membrane seals the granule orifice, retaining the active species in liquid form within the granule pores. The diameter of the granules typically ranges from 1 mm to 1 cm and preferably 1 mm to 2 mm. The granules are formed by extrusion, coagulation, or spheronization, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust, and carbonaceous granules. The shell or membrane materials include natural and synthetic rubbers, fibrous materials, styrene-butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes, and starch xanthate.

[0280] Other useful formulations for agrochemical applications include simple solutions of the active ingredient in solvents such as acetone, alkylated naphthalenes, xylenes, and other organic solvents, in which the active ingredient is completely dissolved at the desired concentration. Pressurized sprays can also be used, in which the active ingredient is dispersed in a finely divided form due to the evaporation of a low-boiling dispersant solvent carrier.

[0281] Suitable agricultural adjuvants and carriers useful for formulating the compositions of the present invention in the above types of formulations are well known to those skilled in the art.

[0282] Liquid carriers that can be utilized include, for example, water, toluene, xylene, naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol rosin acid ester, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol (diproxitol), alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, α-pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, cumene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isopentanone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, dichloromethane, m-xylene, n-hexane, n-octylamine, stearic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin wax, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as pentanol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerol, and N-methyl-2-pyrrolidone. Water is usually the preferred carrier for diluting concentrates.

[0283] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite, fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, and lignin.

[0284] A wide range of surfactants can be advantageously employed in the liquid and solid compositions, especially those designed to be diluted with a carrier prior to application. These agents typically comprise from 0.1% to 15% by weight of the formulation when used. They can be anionic, cationic, nonionic or polymeric in nature and can be used as emulsifiers, wetting agents, suspending agents or for other purposes. Typical surfactants include alkyl sulfates such as diethanolammonium lauryl sulfate; alkyl aryl sulfonates such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide adducts such as nonylphenol-C18 ethoxylate; alcohol-alkylene oxide adducts such as tridecanol-C16 ethoxylate; soaps such as sodium stearate; alkylnaphthalenesulfonates such as sodium dibutylnaphthalenesulfonate; salts of dialkyl esters of sulfosuccinic acid such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitan esters such as sorbitan oleate; quaternary amines such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and dialkyl phosphates.

[0285] Other adjuvants commonly used in agricultural compositions include crystallization inhibitors, viscosity regulators, suspending agents, spray droplet regulators, pigments, antioxidants, foaming agents, defoaming agents, light blockers, compatibility agents, defoamers, masking agents, neutralizing agents and buffers, corrosion inhibitors, dyes, flavorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.

[0286] In addition, further, other biocidal active ingredients or compositions can be combined with the compositions of the present invention and used in the methods of the present invention and applied simultaneously or sequentially with the compositions of the present invention. When applied simultaneously, these additional active ingredients can be formulated together with the compositions 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.

[0287] The pesticidal agents mentioned herein by their common names are known, for example, from "The Pesticide Manual", 15th Edition, British Crop Protection Council 2009.

[0288] In addition, the compositions of the present invention can also be applied together with one or more systemic acquired resistance inducers ("SAR" inducers). SAR inducers are known and described, for example, in U.S. Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.

[0289] Compounds of formula (I) are generally used in the form of agrochemical compositions and can be applied to the crop area or plant to be treated simultaneously or successively with other compounds. For example, these other compounds can be fertilizers or micronutrient donors or other preparations that affect plant growth. They can also be selective or non-selective herbicides, together with insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or adjuvants promoting application that are commonly used in the field of formulations.

[0290] Compounds of formula (I) can be used in the form of compositions for controlling or protecting against phytopathogenic microorganisms, which compositions comprise 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 an agrochemically acceptable salt form) and at least one of the above-mentioned adjuvants.

[0291] Accordingly, the present invention provides a composition, preferably a fungicidal composition, which comprises at least one compound of formula (I), an agriculturally acceptable carrier and optionally an adjuvant. An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural carriers are well known in the art. Preferably, in addition to comprising a compound of formula (I), the composition may comprise at least one or more pesticidal active compounds, for example, further fungicidal active ingredients.

[0292] The compound of formula (I) can be the sole active ingredient of the composition, or, where appropriate, it can be mixed with one or more further active ingredients such as pesticidal agents, fungicides, synergists, herbicides or plant growth regulators. In some cases, the further active ingredients can produce unexpected synergistic activities.

[0293] Examples of suitable additional active ingredients include the following: acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, aniline fungicides, antibiotic fungicides, aromatic fungicides, arsenic-containing fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzoyl aniline fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged biphenyl fungicides, carbamate fungicides, phenylcarbamate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furanamide fungicides, furan aniline fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine fungicides, organophosphorus fungicides, organotin fungicides, oxathiin fungicides, oxazole fungicides, phenylthioamide 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, triazolo pyrimidine fungicides, urea fungicides, valinamide fungicides, and zinc fungicides.

[0294] Specific examples of suitable additional active ingredients also include compounds selected from the group consisting of: petroleum, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenyl benzenesulfonate, 2-fluoro-N-methyl-N-1-naphthalenacetamide, 4-chlorophenyl phenyl sulfone, acetoprole, aldoxycarb, amidithion, amidothioate, amiton, amiton hydrogen oxalate, amitraz, bromopropylate, arsenic trioxide, azobenzene, azinphos, benomyl, benoxa-fos, benzyl benzoate, bixafen, brofluthrinate, bromocyclen, bromophos, bromopropylate, buprofezin, butocarboxim, butoxycarboxim, butylpyridaben, calcium polysulfide, camphechlor, carbaryl, carbophenothion, cycloheximide, chinomethionat, chlorbenside, chlordimeform, chlordimeform hydrochloride, chlorobenzilate, chlormebuform, chloromethiuron, chloropropylate, chlorthiophos, cinerin I, cinerin II, cinerins, closantel, coumaphos, crotamiton, crotoxyphos, cyhexatin, cyanthoate, DCPM, DDT, demephion, demephion-O, demephion-S, demeton, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulfon, dichlofluanid, dichlorvos, dicliphos, dicofol, dimefox, dinex, dinex-diclexine, dinocap-4, dinocap-6, dinoseb, dinoseb pentanoate, dinoseb octanoate, dinoseb butyrate, dioxathion, diphenyl sulfone, disulfiram, DNOC, dofenapyn, doramectin, endothion, eprinomectin, ethion, etrimfos, fenazaflor, fenbutatin oxide, fenothiocarb,fenpyrad, fenpyroximate, fenpyrazamine, fenson, fentrifanil, flubenzimine, flucycloxuron, fluenetil, fluorbenside, FMC 1137, formetanate, formetanate hydrochloride, formparanate, γ-HCH, guazatine, bifenazate, hexadecyl cyclopropanecarboxylate, isocarbophos, pyrethrins I, pyrethrins II, iodofenphos, lindane, propargite, phorate, dioxathion, methiophanate, methacrifos, methyl bromide, metolcarb, promecarb, milbemycin, propamocarb, monocrotophos, phenthoate, moxidectin, naled, 4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodopyridin-3-yl)methoxy]pyridazin-3-one, hexaflumuron, nikkomycin, penthiocarb, penthiocarb 1:1 zinc chloride complex, omethoate, isoxathion, sulfotep, pp'-DDT, parathion, permethrin, phenkapton, phosalone, phosfolan, phosphamidon, polychloroterpenes, polynactins, pronethalol, pirimicarb, propoxur, ethoprophos, phenthoate, pyrethrins I, pyrethrins II, pyrethrins, pyridaphenthion, pyrimithione, quinalphos, quintiofos, R-1492, glyphosate, rotenone, schradan, cadusafos, selamectin, sulprofos, SSI-121, sulfenuron, flufenerim, tepp, tert-butylcarb, tetradifon, tetrasul, thiafenox, pirimicarb, thiofanox, methiocarb, methomyl, methyl disulfoton, chlorobenzilate, thuringiensin, triazophos, triazuron, trichlorfon, trichodermin, formothion, vaniliprole, bethoxazin, copper dioctanoate, copper sulfate, cybutryne, dichlone, dichlorophen, indoleacetic acid, triphenyltin, slaked lime, sodium thiosulfate, quinoclamine, simazine, triphenyltin acetate, triphenyltin hydroxide, cyanofenphos, piperazine, thiophanate-methyl, chloralose, fenthion, pyridin-4-amine, strychnine, 1-hydroxypyridine-2-thione, 4-(quinoxalin-2-ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, copper hydroxide, cresol, bipyrithione, dodine, sodium thiram, formaldehyde, mercuric chloride, kasugamycin, kasugamycin hydrochloride hydrate, nickel bis(dimethyldithiocarbamate), 3,5,6-trichloro-2-pyridinol, octhilinone, oxolinic acid, oxytetracycline, potassium 8-hydroxyquinoline sulfate, thiabendazole, streptomycin, streptomycin sesquisulfate, tetrachloroisophthalonitrile, thimerosal, Adoxophyes orana granulovirusAgrobacterium radiobacter, Amblyseius spp., Autographa californica nucleopolyhedrovirus, Anagrus atomus, Aphelinus abdominalis, Aphidius colemani, Aphidoletes aphidimyza, Autographa gamma nucleopolyhedrovirus, Bacillus sphaericus Neide, Beauveria brongniartii, Chrysoperla carnea, Cryptolaemus montrouzieri, Cydia pomonella granulovirus, Dacnusa sibirica, Diglyphus isaea, Encarsia formosa, Eretmocerus eremicus, Heterorhabditis bacteriophora and H. megidis, Hippodamia convergens, Leptomastix dactylopii, Macrolophus caliginosus, Mamestra brassicae nucleopolyhedrovirus, Metaphycus helvolus, Metarhizium anisopliae var. acridum, Metarhizium anisopliae var. anisopliae, Neodiprion sertifer nucleopolyhedrovirus and N. lecontei nucleopolyhedrovirus, Orius spp., Paecilomyces fumosoroseus, Phytoseiulus persimilis, Steinernema bibionis, Steinernema carpocapsae, Steinernema feltiae, Steinernema glaseri, Steinernema riobrave, Steinernema riobravis, Steinernema scapterisci, Steinernema spp.,Species of Trichogramma, Typhlodromus occidentalis, Verticillium lecanii, apholate, bisazir, busulfan, dimatif, hemel, hempa, metepa, methiotepa, methyl apholate, morzid, penfluron, tepa, thiohempa, thiotepa, trimetrexate, urethane imide acetate, (E)-dec-5-en-1-yl ester 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)-heneicos-13-en-10-one, (Z)-tetradec-7-en-1-al, (Z)-tetradec-9-en-1-ol, (Z)-tetradec-9-en-1-yl acetate, (7E,9Z)-dodec-7,9-dien-1-yl acetate, (9Z,11E)-tetradec-9,11-dien-1-yl acetate, (9Z,12E)-tetradec-9,12-dien-1-yl acetate, 14-methyloctadec-1-ene, 4-methylnon-5-ol and 4-methylnon-5-one, α-polygodial, western pine beetle aggregation pheromone, codlelure, codlemone, cuelure, epoxy nonadecane, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodec-8,10-dien-1-yl acetate, dominicalure, ethyl 4-methylcaprylate, eugenol, frontalin, grandlure, grandlure I, grandlure II, grandlure III, grandlure IV, hexalure, ipsdienol, ipsenol, japonilure, lineatin, litlure, looplure, medlure, megatomoic acidmethyl eugenol, muscalure, octadeca-2,13-dien-1-yl acetate, octadeca-3,13-dien-1-yl acetate, orfralure, oryctalure, ostramone, siglure, sordidin, 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, diethyltoluamide, dimethylcarbate, dimethyl phthalate, 2-ethylhexanediol, hexamide, methoquin-butyl, methylneodecanamide, oxamate, picaridin, 1,1-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-ethylsulfinylethyl methylphosphonothioate 2,2-dichlorovinyl ester, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate, 2-(2-butoxyethoxy)ethyl thiocyanate, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate, 2-(4-chloro-3,5-dimethylphenoxy)ethanol, 2-chlorovinyldiethyl phosphate, 2-imidazolidinone, 2-isovalerylindane-1,3-dione, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate, 2-cyanothioethyl laurate, 3-bromo-1-chloroprop-1-ene, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate, 4-methyl(prop-2-ynyl)amino-3,5-dimethylphenyl methylcarbamate, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate, acephate, acrylonitrile, aldrin, allomurin, asana, alpha-ecdysone, aluminium phosphide, aminocarb, neonicotinoid, athidathion, pirimiphos-methyl, Bacillus thuringiensis delta-endotoxin, barium hexafluorosilicate, barium polysulfide, bioallethrin, Bayer 22 / 190, Bayer 22408, beta-cyfluthrin, beta-cypermethrin, bioethanomethrin, bioallethrin,Bis(2-chloroethyl) ether, borax, bromophos-ethyl, bromo-DDT, bufencarb, butacarb, butathiofos, butonate, calcium arsenate, calcium cyanide, carbon disulfide, carbon tetrachloride, cartap hydrochloride, cevadine, chlorthiophos, chlordane, chlordecone, chloroform, chloropicrin, cyanofenphos, chlorprazophos, cis-resmethrin, cismethrin, clocythrin, copper acetoarsenite, copper arsenate, copper oleate, coumithoate, cryolite, CS 708, cyanofenphos, cyanophos, cycloprothrin, cythioate, d-tetramethrin, DAEP, dazomet, decarbofuran, diamidafos, dicapthon, dichlofenthion, dicresyl, cyenopyrafen, dieldrin, 5-methylpyrazol-3-yl diethyl phosphate, dior, dimefluthrin, dimethiocarb, dimethylvinphos, dinocap, dinoterb, ethofenprox, esfenvalerate, etaphos, ethiofencarb, ethyl formate, dibromoethane, dichloroethane, ethylene oxide, EXD, fenthion, ethiofencarb, fenitrothion, fenoxacrim, flumethrin, fosthiazate, flucofuron, butathiofos, fosthietan, furathiocarb, pyrethrum, guazatine, guazatine acetate, sodium tetrathiocarbonate, halfenprox, HCH, HEOD, heptachlor, formothion, HHDN, hydrogen cyanide, imidacloprid, isazofos, isobenzan, isofenphos, imazalil, isoprothiolane, isoxathion, juvenile hormone I, juvenile hormone II, juvenile hormone III, chlorethoxyfos, kinoprene, lead arsenate, bromfenvinfos, acetamiprid, thiazophos, m-tolyl methylcarbamate, magnesium phosphide, azinphos-methyl, metam-sodium, methidathion, mercurous chloride, methylsulfotep, metam, metam-potassium, metam-sodium, methylsulfonyl fluoride, butamiphos, methoprene, methothrin, methoxychlor, methyl isothiocyanate, methyl chloroform, dichloromethane, insectozide, mirex, naled, naphthalene, NC-170, nicotine, nicotine sulfate, nithiazine, nor-nicotine, O-ethyl O-5-dichloro-4-iodophenyl ethylphosphonothioate, O-4-methyl-2-oxo-2H-chromen-7-yl O,O-diethyl phosphorothioate, O-6-methyl-2-propylpyrimidin-4-yl O,O-diethyl phosphorothioate, O,O,O',O'-tetrapropyl pyrophosphate, oleic acid, p-dichlorobenzene, methyl parathion, pentachlorophenol, pentachlorophenyl laurate, PH 60-38, fensulfothion, p-chlorothion, phosphinePhoxim-methyl, methamidophos, polychlorinated dicyclopentadiene isomers, potassium arsenite, potassium thiocyanate, precocious hormone I, precocious hormone II, precocious hormone III, amidophos, profluthrin, fenvalerate, prothiophos, pyraclostrobin, anti-pyrethroid, quassia, quinalphos-methyl, fenvalerate, iodophos, resmethrin, rotenone, thiamethoxam, ryanodine, sabadilla, octamidine, clostridium, SI-0009, thiamethoxam, sodium arsenite, sodium cyanide, sodium fluoride, sodium hexafluorosilicate, sodium pentachlorophenol, sodium selenate, sodium thiocyanate, sulcofuron, sulcofuron sodium salt uron-sodium), sulfuryl fluoride, thiopromide, tar, thiabendazole, TDE, butylpyrimidinphos, dimethoate, cyclopentylthrin, tetrachloroethane, thiochlorvos, cyclohexane, cyclohexane oxalate, cypermethrin, cypermethrin monosodium, tralomethrin, trans-permethrin, trichlormetaphos-3, chlorpyrifos, tolprocarb, chlorpyrifos-butyl, methoprene, veratridine, veratridine, XMC, zetamethrin, zinc phosphide, tolfenphos, cyfluthrin, tetrafluthrin, bis(tributyltin)oxide, bromoacetamide, iron phosphate, niclosamide-ethanolamine, Tributyltin oxide, pyromorph, snail killer, 1,2-dibromo-3-chloropropane, 1,3-dichloropropylene, 3,4-dichlorotetrahydrothiophene 1,1-dioxide, 3-(4-chlorophenyl)-5-methylrhodanine, 5-methyl-6-thioxo-1,3,5-thiadiazin-3-yl acetic acid, 6-isopentenylaminopurine, anisiflupurin, benclothiaz, cytokinin, DCIP, furfural, isamidophos, kinetin, verrucospore mycorrhizal composition, tetrachlorothiophene, xylenol, zeatin, potassium ethylxanthate, acibenzolar, acibenzolar-S-methyl, Reynoutriasachalinensis extract, α-chloroalcohol, antu, barium carbonate, bifenthion, brodifacoum, bromadiolone, brofenthion, chlorfenthion, cholecalciferol, chlorfenthion, chlorfenthion, chlorfenthion, chlorfenthion, chlorfenthion, chlorfenthion, calciferol, flufenthion, fluoroacetamide, flufenthion, flufenthion hydrochloride, flufenthion, flufenthion, phosphorus, flufenthion, flufenthion, chlorfenthion, chlorfenthion, scilia glycoside, sodium fluoride-acetate, thallium sulfate, flufenthion, 2-(2-butoxyethoxy)-ethyl piperate, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, farnesol with nerolidol, synergistic acetic ether, MGK 264, propylisomer, propylisomer, S421, propylisomer, sesasmolin, sulfoxide, anthraquinone, copper cyclohexane, copper oxychloride,Dicyclopentadiene, Selenium, Zinc naphthenate, Ziram, Imazinil, Ribavirin, Chloroinconazide, Mercuric oxide, Thiophanate-methyl, Azaconazole, Bitertanol, Bromuconazole, Cyproconazole, Difenoconazole, Diniconazole, Epoxiconazole, Fenbuconazole, Fluquinconazole, Flusilazole, Flutriafol, Furametpyr, Hexaconazole, Imazalil, Imibenconazole, Ipconazole, Metconazole, Myclobutanil, Paclobutrazol, Pyrazophos, Penconazole, Prothioconazole, Pyrifenox, Prochloraz, Propiconazole, Pyributicarb, Simeconazole, Tebuconazole, Fluconazole, Triadimefon, Triadimenol, Triflumizole, Tricyclazole, Dimethirimol, Ethirimol, Dodemorph, Fenpropidin, Fenpropimorph, Spiroxamine, Tridemorph, Cyprodinil, Cymoxanil, Pyrimethanil, Fenpiclonil, Fludioxonil, Benalaxyl, Furalaxyl, Metalaxyl, R-Metalaxyl, Furalaxyl, Oxadixyl, Carbendazim, Debacarb, Fuberidazole, Thiabendazole, Chlozolinate, Dichlozoline, Myclozoline, Procymidone, Vinclozoline, Boscalid, Carboxin, Methfuroxam, Flutolanil, Mepronil, Oxathiin, Penthiopyrad, Thifluzamide, Doramectin, Guazatine, Azoxystrobin, Kresoxim-methyl, Enestroburin, Enestrobin, Fluoxastrobin, Fluoxastrobin, Trifloxystrobin, Metominostrobin, Trifloxystrobin, Trifloxystrobin, Ferbam, Mancozeb, Maneb, Metiram, Zineb, Ziram, Captafol, Captan, Flufenpyr-ethyl, Folpet, Tolylfluanid, Bordeaux mixture, Copper oxide, Copper mancozeb, Copper quinolate, Phthalide, EBP, IBP, Blasticidin-S, Chloroneb, Chlorothalonil, Cyflufenamid, Cymoxanil, Cyclobutrifluram, Diclocymet, Diclomezine, Dicloran, Diethofencarb, Dimethomorph, Flumorph, Dithianon, Ethaboxam, Etridiazole, Oxazolinone,Fenamidone, fenoxanil, ferimzone, fluazinam, flumetylsulforim, fluopicolide, fluoxytioconazole, flusulfamide, fluxapyroxad, fenhexamid, fosetyl-aluminium, hymexazol, propineb, cyazofamid, methasulfocarb, metrafenone, pencycuron, phthalide, polyoxins, propamocarb, pyribencarb, proquinazid, pyroquilon, pyriofenone, quinoxyfen, quintozene, tiadinil, triazoxide, tricyclazole, triforine, validamycin, valifenalate, zoxamide, mandipropamid, flubeneteram, isopyrazam, sedaxane, benzovindiflupyr, fluxametamide, 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid (3’,4’,5’-trifluoro-biphenyl-2-yl)-amide, isoflucypram, isofetamid, dipymetitrone, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithieno[1,2-c]isothiazole-3-carbonitrile, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-2,5-dimethyl-pyrazol-3-amine, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, fluindapyr, Jiaxiangjunzhi, lvbenmixianan, dichlobentiazox, 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-oloxathiapiprolin, tert-butyl N-[6-[[[(1-methyl-1H-tetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamate, pyraziflumid, inpyrfluxam, trolprocarb, trifloxystrobin, ipfentrifluconazole, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-inden-4-yl]pyridine-3-carboxamide, N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylformamidine, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethylphenyl]-N-ethyl-N-methylformamidine, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chlorophenyl]methanesulfonate, but-3-ynyl N-[6-[[(Z)-[(1-methyl-1H-tetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamate, methyl N-[[5-[4-(2,4-dimethylphenyl)-1,2,3-triazol-2-yl]-2-methylphenyl]methyl]carbamate, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine, pyridachlometyl, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylinden-4-yl]pyrazole-4-carboxamide, 1-[2-[[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxymethyl]-3-methylphenyl]-4-methyl-1H-tetrazol-5-one, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethyl-1H-pyrazol-1-yl)phenoxy]methyl]phenyl]-1H-tetrazol-5-one, aminopyrifen, amisulbrom, zoxamide, fluxapyroxad, (Z,2E)-5-[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethylpent-3-enamide, florylpicoxamid, fenpicoxamid, metarylpicoxamid, isobutyl ethyoximate, ipflufenoquin, quinofumelin, isopropylthianil, 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-trifluoroprop-1-enoxy]phenyl]methyl]pyrazole-3-carboxylate (which can be prepared by the method described in WO 2020 / 056090)N-[[4-[1-(4-cyclopropyl-2,6-difluorophenyl)pyrazol-4-yl]-2-methylphenyl]methyl]carbamic acid methyl ester (which can be prepared by the method described in WO 2020 / 097012), N-[[4-[1-(2,6-difluoro-4-isopropylphenyl)pyrazol-4-yl]-2-methylphenyl]methyl]carbamic acid methyl ester (which can be prepared by the method described in WO 2020 / 097012), 6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoroethyl]-5-methyl-pyridazine-4-carboxamide (which can be prepared by the method described in WO 2020 / 109391), 6-chloro-N-[2-(2-chloro-4-methylphenyl)-2,2-difluoroethyl]-3-(3-cyclopropyl-2-fluorophenoxy)-5-methyl-pyridazine-4-carboxamide (which can be prepared by the method described in WO 2020 / 109391), 6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoroethyl]-5-methyl-pyridazine-4-carboxamide (which can be prepared by the method described in WO 2020 / 109391), N-[2-[2,4-dichlorophenoxy]phenyl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide, benzothiazole, cyanofenphos, zinc salt of 5-amino-1,3,4-thiadiazole-2-thiol (2:1), fluopyram, flufenoxadiazam, fluoxastrobin, fluoxastrobin, pyrapropoyne, picarbutrazox, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethylinden-4-yl)pyridine-3-carboxamide, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylinden-4-yl)pyridine-3-carboxamide, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, metyltetraprole, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylinden-4-yl)pyridine-3-carboxamide, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidine methanol, fluoxapiprolin, enoxastrobin, (Z)-methyl 3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop-2-enoate,(Z)-Methyl 3-methoxy-2-[2-methyl-5-(4-propyl-1,2,4-triazol-2-yl)phenoxy]prop-2-enoate, (Z)-methyl 2-[5-(3-isopropyl-1H-pyrazol-1-yl)-2-methylphenoxy]-3-methoxyprop-2-enoate, (Z)-methyl 3-methoxy-2-[2-methyl-5-(3-propyl-1H-pyrazol-1-yl)phenoxy]prop-2-enoate, (Z)-methyl 3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)-1H-pyrazol-1-yl]phenoxy]prop-2-enoate (these compounds can be prepared by the methods described in WO 2020 / 079111), (Z)-methyl 2-(5-cyclohexyl-2-methylphenoxy)-3-methoxyprop-2-enoate, (Z)-methyl 2-(5-cyclopentyl-2-methylphenoxy)-3-methoxyprop-2-enoate (these compounds can be prepared by the methods 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-pyridinyl]oxy]benzonitrile, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridinyl]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-pyridinyl]oxy]benzonitrile, trinexapac-ethyl, pyribencarb, zhongshengmycin, thiodiazole copper, thiazole zinc, amectotractin, iprodione, octhilinone (seboctylamine), N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxyethoxy]-3-pyridinyl]-N-ethyl-N-methylformamidine, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxyethoxy]-3-pyridinyl]-N-ethyl-N-methylformamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridinyl]-N-ethyl-N-methylformamidine, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridinyl]-N-ethyl-N-methylformamidine,N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-isopropyl-N-methyl-formamidine (these compounds can be prepared by the methods described in WO2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared by the methods described in IPCOM000249876D); N-isopropyl-N’-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine, N’-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine (these compounds can be prepared by the methods 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 methods described in WO 2019 / 110427); N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide,N-((1S)-1-benzyl-3-chloro-1-methylbut-3-en-1-yl)-8-fluoroquinoline-3-carboxamide (these compounds can be prepared by the methods described in WO 2017 / 153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethylisoquinoline, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 1-(6-chloro-7-methylpyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethylisoquinoline (these compounds can be prepared by the methods described in WO 2017 / 025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethylisoquinoline, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline, 4,4-difluoro-1-(5-fluoro-4-methylbenzimidazol-1-yl)-3,3-dimethylisoquinoline, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolinyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole (these compounds can be prepared by the methods described in WO 2016 / 156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]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 by the methods described in WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 093348 and WO 2017 / 118689); 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared by the method described in WO 2017 / 029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared by the method described in WO 2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile (this compound can be prepared by the method described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile (this compound can be prepared by the method described in WO 2016 / 156290); (4-phenoxyphenyl)methyl 2-amino-6-methylpyridine-3-carboxylate (this compound can be prepared by the method described in WO 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']bipyrrole-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-phenoxyphenyl)-N-ethyl-N-methyl-formamidine; N'-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-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 by the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone (these compounds can be prepared by the method described in WO 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide (this compound can be prepared by the method described in WO2018 / 065414); ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate (this compound can be prepared by the method described in WO 2018 / 158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, 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-carbodiimido]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (these compounds can be prepared by the method described in WO 2018 / 202428).、

[0295] The following mixtures of the compound of formula (I) with active ingredients are preferred. The abbreviation "TX" means a compound selected from the group consisting of: the compounds shown in Tables A-1 to A-13, compound 1.1 listed in Table T1 (below):

[0296] Compounds selected from the group consisting of: petroleum + TX, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX, 2,4-dichlorophenyl benzenesulfonate + TX, 2-fluoro-N-methyl-N-1-naphthalenylacetamide + TX, 4-chlorophenyl phenyl sulfone + TX, acetamiprid + TX, oxamyl + TX, cythioate + TX, amidothioate + TX, prothoate + TX, ammonium hydrogen prothoate + TX, amitraz + TX, aramite + TX, arsenic trioxide + TX, azobenzene + TX, azinphos + TX, benomyl + TX, benoxa-fos + TX, benzyl benzoate + TX, bixafen + TX, brofluthrinate + TX, bromocyclen + TX, bromophos + TX, bromopropylate + TX, buprofezin + TX, butocarboxim + TX, butoxycarboxim + TX, butylpyridaben + TX, calcium polysulfide + TX, camphechlor + TX, carbaryl + TX, carbophenothion + TX, cycloheximide + TX, chinomethionat + TX, chlorbenside + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorobenzilate + TX, chlorfenson + TX, chlorfensulfide + TX, chlorobenzilate + TX, chloromebuform + TX, chloromethiuron + TX, chloropropylate + TX, chlorthiophos + TX, cinerin I + TX, cinerin II + TX, cinerins + TX, closantel + TX, coumaphos + TX, crotamiton + TX, crotoxyphos + TX, dithianon + TX, cyanthoate + TX, DCPM + TX, DDT + TX, demephion + TX, demephion-O + TX, demephion-S + TX, demeton + TX, demeton-O + TX, demeton-O-methyl + TX, demeton-S + TX, demeton-S-methyl + TX, demeton-S-methylsulfon + TX, dichlofluanid + TX, dichlorvos + TX, dicliphos + TX, dicofol + TX, dimefox + TX, dinocap + TX, dinocap + TX, dinocap-4 + TX, dinocap-6 + TX, dinoseb + TX, dinoseb pentanoate + TX,Dinosulfon + TX, Dinoterbon + TX, Dichlorvos + TX, Diphenyl Sulfone + TX, Disulfiram + TX, DNOC + TX, Dofenapyn + TX, Doramectin + TX, Endothion + TX, Eprinomectin + TX, Ethoate-methyl + TX, Etrimfos + TX, Fenazaflor + TX, Fenbutatin Oxide + TX, Fenothiocarb + TX, Fenpyrad + TX, Fenpyroximate + TX, Fenpyrazamine + TX, Fenson + TX, Fentrifanil + TX, Flubenzimine + TX, Flucycloxuron + TX, Fluenetil + TX, Fluorbenside + TX, FMC 1137 + TX, Formetanate + TX, Formetanate Hydrochloride + TX, Formparanate + TX, γ-HCH, Guazatine, Bifenazate, Hexadecyl Cyclopropanecarboxylate, Isocarbophos, Pyrethrins I, Pyrethrins II, Iodofenphos, Lindane, Propargite, Aphidiphos, Dithicrofos, Methiocarb, Methacrifos, Methyl Bromide, MTMC, Promecarb, Milbemectin, Propanil, Monocrotophos, Phosalone, Moxidectin, Naled, 4-Chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one, Flumethrin, Nikkomycin, Phenothrin, Phenothrin 1:1 Zinc Chloride Complex, Omethoate, Isoxathion, Oxydemeton-methyl, pp'-DDT, Parathion, Permethrin, Fenthion, Phosalone, Phosfolan, Phosphamidon, Polychloroterpenes, Polynactins, Propiconazole, Pyridaphenthion, Propoxur, Ethoprophos, Prothoate, Pyrethrins I, Pyrethrins II, Pyrethrins, Pyridaphenthion, Pyrimiphos-methyl, Quinalphos, Quintiofos, R-1492, Glyphosate, RotenoneAcephate + TX, Cadusafos + TX, Selamectin + TX, Sulfotep + TX, SSI-121 + TX, Sufentanil + TX, Flufenoxuron + TX, TEPP + TX, BPMC + TX, Tetradifon + TX, Chlorbenside + TX, Thiafenox + TX, Bendiocarb + TX, Monocrotophos + TX, Dimethoate + TX, Chlordimeform + TX, Bacillus thuringiensis + TX, Triamiphos + TX, Triazuron + TX, Trichlorfon + TX, Streptomyces griseochromogenes + TX, Oxamyl + TX, Vaniliprole + TX, Bethoxazin + TX, Copper dicaprylate + TX, Copper sulfate + TX, Cybutryne + TX, Dichlone + TX, Dichlorophen + TX, Iminodiacetic acid + TX, Triphenyltin + TX, Calcium hydroxide + TX, Sodium thiram + TX, Mexacarbate + TX, Quinonamid + TX, Simazine + TX, Triphenyltin acetate + TX, Triphenyltin hydroxide + TX, Crufomate + TX, Piperazine + TX, Thiophanate-methyl + TX, Chloralose + TX, Fenthion + TX, Pyridin-4-amine + TX, Strychnine + TX, 1-Hydroxy-1H-pyridine-2-thione + TX, 4-(Quinoxalin-2-ylamino)benzenesulfonamide + TX, 8-Hydroxyquinoline sulfate + TX, Bronopol + TX, Copper hydroxide + TX, Cresol + TX, Pyritinol + TX, Dodine + TX, Sodium phtalimide + TX, Formaldehyde + TX, Mercuric chloride + TX, Kasugamycin + TX, Kasugamycin hydrochloride hydrate + TX, Nickel dimethyldithiocarbamate + TX, 3,5,6-Trichloro-2-pyridinol + TX, Octhilinone + TX, Oxolinic acid + TX, Oxytetracycline + TX, Potassium hydroxyquinoline sulfate + TX, Thiabendazole + TX, Streptomycin + TX, Streptomycin sesquisulfate + TX, Tricyclazole + TX, Thimerosal + TX, Adoxophyes orana granulovirus + TX, Agrobacterium radiobacter + TX, Amblyseius spp. + TX, Autographa gamma nuclear polyhedrosis virus + TX, Anagrus atomus + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, Autographa californica nuclear polyhedrosis virus + TX, Bacillus sphaericus Neide + TX, Beauveria brongniartii + TX, Chrysoperla carnea + TX, Cryptolaemus montrouzieri + TXCydia pomonella GV + TX, Dacnusasibirica + TX, Diglyphus isaea + TX, Encarsia formosa + TX, Eretmocerus eremicus + TX, Heterorhabditis bacteriophora and H. megidis + TX, Hippodamia convergens + TX, Leptomastix dactylopii + TX, Macrolophus caliginosus + TX, Mamestra brassicae NPV + TX, Metaphycus 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, apholate + TX, bisazir + TX, busulfan + TX, dimatif + TX, hemel + TX, hempa + TX, metepa + TX, methiotepa + TX,methyl apholate + TX, morzid + TX, penfluron + TX, tepa + TX, thiohempa + TX, thiotepa + TX, tritac + TX, urethanimine acetate + TX, (E)-dec-5-en-1-yl ester and (E)-dec-5-en-1-ol + TX, (E)-tridec-4-en-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E,Z)-tetradec-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-heneicos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, (7E,9Z)-dodec-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradec-9,12-dien-1-yl acetate + TX, 14-methyloctadec-1-ene + TX, 4-methylnon-5-ol and 4-methylnon-5-one + TX, α-multistriatin + TX, western pine beetle aggregation pheromone + TX, codlelure + TX, codlemone + TX, cuelure + TX, epoxy nonadecane + TX, dodec-8-en-1-yl acetate + TX, dodec-9-en-1-yl acetate + TX, dodec-8,10-dien-1-yl acetate + TX, dominicalure + TX, ethyl 4-methylcaprylate + TX, eugenol + TX, southern pine beetle aggregation pheromone (frontalin) + TX, grandlure + TX, grandlure I + TX, grandlure II + TX, grandlure III + TX, grandlure IV + TX, hexalure + TX, ipsdienol + TX, ipsenol + TX, japonilure + TX, lineatin + TX, litlure + TX, looplure + TX, medlure + TX, megatomoic acid + TX, methyleugenol + TX,Muscalure + TX, Octadeca-2,13-dien-1-yl acetate + TX, Octadeca-3,13-dien-1-yl acetate + TX, Orfralure + TX, Oryctalure (rhinoceros beetle aggregation pheromone) + TX, Ostramone + TX, Siglure + TX, Sordidin + TX, Sulcatol + TX, Tetradec-11-en-1-yl acetate + TX, Trimedlure (Mediterranean fruit fly attractant) + TX, Mediterranean fruit fly attractant A + TX, Mediterranean fruit fly attractant B1 + TX, Mediterranean fruit fly attractant B2 + TX, Mediterranean fruit fly attractant C + TX, Trunc-call + TX, 2-(Octylthio)-ethanol + TX, Butopyronoxyl + TX, Butoxy(polypropylene glycol) + TX, Dibutyl adipate + TX, Dibutyl phthalate + TX, Dibutyl succinate + TX, DEET + TX, Dimethylcarbate + TX, Dimethyl phthalate + TX, 2-Ethylhexyl diol + TX, Hexamide + TX, Methoquin-butyl + TX, Methylneodecanamide + TX, Oxamate + TX, Picaridin + TX, 1-Dichloro-1-nitroethane + TX, 1,1-Dichloro-2,2-bis(4-ethylphenyl)ethane + TX, 1,2-Dichloropropane and 1,3-dichloropropene + TX, 1-Bromo-2-chloroethane + TX, 2,2,2-Trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2-Ethylsulfinylethyl methylphosphonothioate, 2,2-dichlorovinyl ester + TX, 2-(1,3-Dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-(2-Butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-Dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate + TX, 2-(4-Chloro-3,5-dimethylphenoxy)ethanol + TX, 2-Chlorovinyl diethyl phosphate + TX, 2-Imidazolidinone + TX, 2-Isovalerylindane-1,3-dione + TX, 2-Methyl(prop-2-ynyl)aminophenyl methylcarbamate + TX, 2-Cyanothioethyl laurate + TX, 3-Bromo-1-chloroprop-1-ene + TX, 3-Methyl-1-phenylpyrazol-5-yl dimethylcarbamate + TX, 4-Methyl(prop-2-ynyl)amino-3,5-dimethylphenyl methylcarbamate + TX, 5,5-Dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate + TX, Acephate + TX, Acrylonitrile + TX, Aldrin + TX, Allomurin + TX,Asana + TX, α-Ecdysone + TX, Aluminium phosphide + TX, Aminocarb + TX, Neonicotinoid + TX, Aathidathion + TX, Pirimiphos-methyl + TX, Bacillus thuringiensis δ-endotoxin + TX, Barium hexafluorosilicate + TX, Barium polysulfide + TX, Resmethrin + TX, Bayer 22 / 190 + TX, Bayer 22408 + TX, Beta-cyfluthrin + TX, Beta-cypermethrin + TX, Bioethanomethrin + TX, Bioallethrin + TX, Bis(2-chloroethyl) ether + TX, Borax + TX, Bromfenvinfos + TX, Bromo-DDT + TX, Bendiocarb + TX, Butacarb + TX, Butathiofos + TX, Butonate + TX, Calcium arsenate + TX, Calcium cyanide + TX, Carbon disulfide + TX, Carbon tetrachloride + TX, Cartap hydrochloride + TX, Cevadine + TX, Cinerin I + TX, Chlordane + TX, Chlordecone + TX, Chloroform + TX, Chloropicrin + TX, Cyanofenphos + TX, Chlorprazophos + TX, Cis-resmethrin + TX, Cismethrin + TX, Clocythrin + TX, Cupric acetoarsenite + TX, Cupric arsenate + TX, Cupric oleate + TX, Coumithoate + TX, Cryolite + TX, CS 708 + TX, Cyanofenphos + TX, Cyanophos + TX, Cycloprothrin + TX, Cythioate + TX, d-Amtim + TX, DAEP + TX, Dazomet + TX, Decarbofuran + TX, Diamidafos + TX, Isochlorphos + TX, Dichlofenthion + TX, Dicresyl + TX, Cyclaniliprole + TX, Dieldrin + TX, 5-Methylpyrazol-3-yl diethyl phosphate + TX, Dior + TX, Transfluthrin + TX, Dimethacarb + TX, Permethrin + TX, Methyldichlorvos + TX, Dimetilan + TX, Butaphenphos + TX, Pentachlorophenol + TX, Dinoseb + TX, Phenthoate + TX, Thiodicarb + TX, DSP + TX, Ecdysterone + TX, EI 1642 + TX, EMPC + TX, EPBP + TX, Etaphos + TX, Ethiofencarb + TX, Ethyl formate + TX, Ethylene dibromide + TX, Ethylene dichloride + TX, Ethylene oxide + TX, EXD + TX, Fenchlorphos + TX, Ethylphencarb + TX, Fenitrothion + TX, Fenoxacrim + TX, Cyhalothrin + TX, Fensulfothion + TX, Ethyl fenthion + TX, Flucofuron + TX, Butylphos + TX, Phosphamidon + TX, Butocarboxim + TX, Furathiocarb + TX, Pyrethrum + TX, Guazatine + TX,Guazatine + TX, Sodium tetrathiocarbonate + TX, Halfenprox + TX, HCH + TX, HEOD + TX, Heptachlor + TX, Sumithion + TX, HHDN + TX, Hydrogen cyanide + TX, Quinocarb + TX, IPSP + TX, Isazofos + TX, Carbophenothion + TX, Isodrin + TX, Isofenphos + TX, Methabenzthiazuron + TX, Isoprothiolane + TX, Oxydemeton-methyl + TX, Juvenile hormone I + TX, Juvenile hormone II + TX, Juvenile hormone III + TX, Chlorcyclaniliprole + TX, Kinoprene + TX, Lead arsenate + TX, Bromfenvinfos + TX, Acetamiprid + TX, Thiazophos + TX, MPMC + TX, Magnesium phosphide + TX, Azinphos + TX, Metolcarb + TX, Methidathion + TX, Mercurous chloride + TX, Methoxysulfenphos + TX, Metam-sodium + TX, Metam-potassium + TX, Metam-sodium + TX, Methylsulfonyl fluoride + TX, Butamifos + TX, Methoprene + TX, Allethrin + TX, Methoxychlor + TX, Methyl isothiocyanate + TX, Methyl chloroform + TX, Methylene chloride + TX, Oxythioquinox + TX, Mirex + TX, Naled + TX, Naphthalene + TX, NC-170 + TX, Nicotine + TX, Nicotine sulfate + TX, Nithiazine + TX, Nor nicotine + TX, O-ethyl O-(5-dichloro-4-iodophenyl) ethylphosphonothioate + TX, O,O-diethyl O-(4-methyl-2-oxo-2H-chromen-7-yl) phosphorothioate + TX, O,O-diethyl O-(6-methyl-2-propylpyrimidin-4-yl) phosphorothioate + TX, O,O,O',O'-tetrapropyl pyrophosphorodithioate + TX, Oleic acid + TX, p-Dichlorobenzene + TX, Methyl parathion + TX, Pentachlorophenol + TX, Pentachlorophenyl laurate + TX, PH 60-38 + TX, Fenthion + TX, Parathion + TX, Phosphine + TX, Phoxim + TX, Methamidophos + TX, Polychlorinated bicyclopentadiene isomers + TX, Potassium arsenite + TX, Potassium thiocyanate + TX, Precocene I + TX, Precocene II + TX, Precocene III + TX, Amidithion + TX, Profluthrin + TX, BPMC + TX, Prothiofos + TX, Pyrazophos + TX, Transfluthrin + TX, Quassia extract + TX, Quinalphos-methyl + TX, Chlorthiophos + TX, Iodamoctone + TX, Resmethrin + TX, Rotenone + TX, Tefluthrin + TX, Ryanodine + TX, Ryania + TX, Sabadilla + TX, Schradan + TX, Nemacur + TX, SI-0009 + TX, Thiophenecarbonitrile + TX, Sodium arsenite + TX, Sodium cyanide + TX, Sodium fluoride + TX, Sodium hexafluorosilicate + TX, Sodium pentachlorophenate + TX, Sodium selenate + TX, Sodium thiocyanate + TX, Sulcofuron + TX, Sulcofuron-sodium + TX,Sulphuryl fluoride + TX, profenofos + TX, tar + TX, pyridaben + TX, TDE + TX, butylpyrimiphos + TX, temephos + TX, allethrin + TX, tetrachloroethane + TX, thichlorphon + TX, thiocyclam + TX, thiocyclam oxalate + TX, thionazin + TX, monosultap + TX, monosultap sodium + TX, tralomethrin + TX, transfluthrin + TX, triazamate + TX, trichlormetaphos-3 + TX, trichloronate + TX, promecarb + TX, tolprocarb + TX, picoxystrobin + TX, methoprene + TX, veratridine + TX, veratrine + TX, XMC + TX, zetamethrin + TX, zinc phosphide + TX, azinphos + TX, meperfluthrin + TX, dimefluthrin + TX, bis(tributyltin) oxide + TX, bromoacetamide + TX, iron phosphate + TX, niclosamide ethanolamine + TX, tributyltin oxide + TX, pyrimorph + TX, nicobifen + 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, anisiflupurin + TX, benclothiaz + TX, cytokinin + TX, DCIP + TX, furfural + TX, isamidofos + TX, kinetin + TX, Myrothecium verrucaria composition + TX, tetrachlorothiophene + TX, xylenol + TX, zeatin + TX, potassium ethylxanthate + TX, benalaxyl + TX, benalaxyl-M + TX, Reynoutria sachalinensis extract + TX, α-chloroalcohol + TX, alpha-naphthylthiourea + TX, barium carbonate + TX, bromodialuron + TX, bromadiolone + TX, bromethalin + TX, chlorophacinone + TX, cholecalciferol + TX, chlorophacinone + TX, coumatetralyl + TX, coumatetralyl + TX, coumatetralyl + TX, difenacoum + TX, thiacoumone + TX, diphacinone + TX, calciferol + TX, flocoumafen + TX, fluoroacetamide + TX, flupropadine + TX, flupropadine hydrochloride + TX, norbormide + TX, phosacetim + TX, phosphorus + TX, pindone + TX, pyrinuron + TX, scilliroside + TX, sodium fluoroacetate + TX, thallium sulfate + TX, warfarin + TX, 2-(2-butoxyethoxy)ethyl piperate + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, farnesol with nerolidol + TX, piperonyl butoxide + TX, MGK 264 + TX, piperonyl ether + TX, piperonal + TX,Propyl isomer + TX, S421 + TX, synergistic powder + TX, sesasmolin + TX, sulfoxide + TX, anthraquinone + TX, copper cyclohexane + TX, copper oxychloride + TX, dicyclopentadiene + TX, salen + TX, zinc cyclohexane + TX, zinc thiram + TX, imanin + TX, ribavirin + TX, chloroinconazide + TX, mercuric oxide + TX, thiophanate methyl + TX, azaconazole + TX, bifenthrin + TX, oxadiazole + TX, cyproconazole + TX, difenoconazole + TX, diniconazole- + TX, fluoxepiconazole + TX, fenbuconazole + TX, fluquinconazole + TX, flusilazole + TX, flutriafol + TX, furopyramide Amine + TX, hexaconazole + TX, imazalil-+TX, imidazole + TX, cyproconazole + TX, metconazole + TX, myclobutrazol + TX, paclobutrazol + TX, pyrifenox + TX, prochloraz + TX, propiconazole + TX, pyraclostrobin + TX, simeconazole + TX, tebuconazole + TX, fluconazole + TX, triadimefon + TX, triadimenol + TX, triflumizole + TX, trichlorfon + TX, pyrimidine + TX, chlorfenapyr + TX, flufenapyr + TX, bupirimate + TX, dimethirimol + TX , ethirimol + TX, dodecacyclic morpholine + TX, fenpropidin + TX, fenpropimorph + TX, spiroxafil + TX, tridecafil + TX, cyprodinil + TX, pyraclostrobin + TX, pyrimethanil + TX, fenpiclonil + TX, fludioxonil + TX, benalaxyl + TX, furalaxyl + TX, metalaxyl + TX, R-metalaxyl + TX, furamide + TX, oxadixyl + TX, carbendazim + TX, debacarb + TX, oxadixyl + TX, thiabendazole + TX, chlo zolinate + TX, dichlozoline + TX, myclozoline - + TX, procymidone + TX, vinclozoline + TX, boscalid + TX, carboxin + TX, furamide + TX, flutolanil + TX, oxacarb + TX, penthiopyrad + TX, thiofuran + TX, docodine + TX, biguanide + TX, myclozolin + TX, etherstroburin + TX, enestroburin + TX,Enestroburin + TX, Fluopyram + TX, Fluoxastrobin + TX, Kresoxim-methyl + TX, Metominostrobin + TX, Trifloxystrobin + TX, Trifloxystrobin + TX, Picoxystrobin + TX, Pyraoxystrobin + TX, Pyraclostrobin + TX, Ferric dimethyldithiocarbamate + TX, Mancozeb + TX, Manganese ethylenebisdithiocarbamate + TX, Metiram + TX, Zineb methyl + TX, Zineb + TX, Captafol + TX, Captan + TX, Pyrazolynate + TX, Folpet + TX, Tolyfluanid + TX, Bordeaux mixture + TX, Copper oxide + TX, Copper mancozeb + TX, Oxine copper + TX, Phthalide + TX, EPN + TX, IBP + TX, Kitazin-P + TX, Pyrazophos + TX, Tolclofos-methyl + TX, Anilazine + TX, Benzothiazole + TX, Blasticidin-S + TX, Chloroneb + TX, Chlorothalonil + TX, Cyflufenamid + TX, Cymoxanil + TX, Cyclobutrifluram + TX, Diclocymet + TX, Diclomezine + TX, Dicloran + TX, Diethofencarb + TX, Dimethomorph + TX, Flumorph + TX, Dithianon + TX, Ethaboxam + TX, Etridiazole + TX, Oxadixyl + TX, Fenamidone + TX, Fenoxanil + TX, Ferimzone + TX, Fluazinam + TX, Flumetylsulforim + TX, Fluopicolide + TX, Fluoxytioconazole + TX, Flusulfamide + TX, Fluxapyroxad + TX, Carboxin + TX, Fosetyl-aluminium + TX, Hymexazol + TX, Propineb + TX, Cyazofamid + TX, Methasulfocarb + TX, Metrafenone + TX, Pencycuron + TX, Phthalide + TX, Polyoxins + TX, Propamocarb + TX, Pyribencarb + TX, Proquinazid + TX, Pyroquilon + TX, Pyriofenone + TX, Quinoxyfen + TX, Quintozene + TX, Tiadinil + TX, Triazoxide + TX, Tricyclazole + TX, Triforine + TX, Validamycin + TX, Valifenalate + TX, Zoxamide + TX,mandipropamid + TX, flubeneteram + TX, isopyrazam + TX, sedaxane + TX, benzovindiflupyr + TX, fluxapyroxad + TX, 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid (3’,4’,5’-trifluoro-biphenyl-2-yl)-amide + TX, isoflucypram + TX, isofetamid + TX, dipymetitrone + TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithieno[1,2-c]isothiazole-3-carbonitrile + TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-2,5-dimethyl-pyrazol-3-amine + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine + TX, fluindapyr + TX, jiaxiangjunzhi, lvbenmixianan, dichlobentiazox, 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, oxathiapiprolin, N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamic acid tert-butyl ester, pyraziflumid, inpyrfluxam, trolprocarb, cyflufenamid, ipfentrifluconazole, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide, N'-(2,5-dimethyl-4-phenoxyphenyl)-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-piperidinyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl]methanesulfonate + TX, N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]but-3-ynyl carbamate + TX, N-[[5-[4-(2,4-dimethylphenyl)-1,2,3-triazol-2-yl]-2-methyl-phenyl]methyl]methyl carbamate + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, pyridachlometyl + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylinden-4-yl]pyrazole-4-carboxamide + TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-1H-tetrazol-5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]-1H-tetrazol-5-one + TX, aminopyrifen + TX, amisulbrom + TX, zoxamide + TX, fluxapyroxad + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX, florylpicoxamid + TX, fenpicoxamid + TX, metarylpicoxamid + TX, isobutyl ethoxyquinoline + TX, ipflufenoquin + TX, quinofumelin + TX, isopropylthianil + TX, ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate + TX (which can be prepared by the method described in WO 2020 / 056090), ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enoxy]phenyl]methyl]pyrazole-3-carboxylate + TX (which can be prepared by the method described in WO 2020 / 056090), methyl N-[[4-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate + TX (which can be prepared by the method described in WO 2020 / 097012), methyl N-[[4-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate + TX (which can be prepared by the method described in WO 2020 / 097012)6-Chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide + TX (which can be prepared by the method described in WO 2020 / 109391), 6-chloro-N-[2-(2-chloro-4-methyl-phenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide + TX (which can be prepared by the method described in WO 2020 / 109391), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide + TX (which can be prepared by the method described in WO 2020 / 109391), N-[2-[2,4-dichlorophenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, benzothiazole + TX, cyanofenphos + TX, zinc 5-amino-1,3,4-thiadiazole-2-thiolate (2:1) + TX, fluopyram + TX, flufenoxadiazam + TX, fluopyram + TX, fluopyram + TX, pyrapropoyne + TX, picarbutrazox + TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, metyltetraprole + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidine methanol + TX, fluoxapiprolin + TX, enoxastrobin + TX, (Z)-methyl 3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)-1,2,4-triazol-2-yl]phenoxy]prop-2-enoate + TX, (Z)-methyl 3-methoxy-2-[2-methyl-5-(4-propyl-1,2,4-triazol-2-yl)phenoxy]prop-2-enoate + TX, (Z)-methyl 2-[5-(3-isopropyl-1H-pyrazol-1-yl)-2-methylphenoxy]-3-methoxyprop-2-enoate + TX,(Z)-Methyl 3-methoxy-2-[2-methyl-5-(3-propyl-1H-pyrazol-1-yl)phenoxy]acrylate + TX, (Z)-Methyl 3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)-1H-pyrazol-1-yl]phenoxy]acrylate + TX (these compounds can be prepared by the methods described in WO 2020 / 079111), (Z)-Methyl 2-(5-cyclohexyl-2-methylphenoxy)-3-methoxyacrylate + TX, (Z)-Methyl 2-(5-cyclopentyl-2-methylphenoxy)-3-methoxyacrylate + TX (these compounds can be prepared by the methods 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-pyridinyl]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-pyridinyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridinyl]oxy]benzonitrile + TX, trinexapac-ethyl + TX, pyraoxystrobin + TX, zhongshengmycin + TX, thiodiazole copper + TX, thiazole zinc + TX, amectotractin + TX, iprodione + TX, octhilinone (seboctylamine) + TX; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxyethoxy]-3-pyridinyl]-N-ethyl-N-methylformamidine + TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxyethoxy]-3-pyridinyl]-N-ethyl-N-methylformamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridinyl]-N-ethyl-N-methylformamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridinyl]-N-ethyl-N-methylformamidine + TX,N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-isopropyl-N-methyl-formamidine + TX (These compounds can be prepared by the methods described in WO 2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX (This compound can be prepared by the methods described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine + TX, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine + TX (These compounds can be prepared by the methods described in WO 2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine + TX (These compounds can be prepared by the methods 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-methylbut-3-en-1-yl)-8-fluoroquinoline-3-carboxamide + TX (These compounds can be prepared by the methods described in WO 2017 / 153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethylisoquinoline + 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-dimethylisoquinoline + TX (These compounds can be prepared by the methods described in WO 2017 / 025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline + TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethylisoquinoline + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline + TX, 4,4-difluoro-1-(5-fluoro-4-methylbenzimidazol-1-yl)-3,3-dimethylisoquinoline + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolinyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole + TX (These compounds can be prepared by the methods described in WO 2016 / 156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX,4,4-Dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate + TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine + TX. The compounds in this paragraph can be obtained from WO 2017 / 055473, WO 2017 / 055469,Prepared by the methods described in WO 2017 / 093348 and WO 2017 / 118689; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound can be prepared by the method described in WO 2017 / 029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound can be prepared by the method described in WO2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate + TX (this compound can be prepared by the method described in WO2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithieno[2,3-c:5,6-c']bipyrrole-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]thiobenzamide + TX; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX (this compound can be prepared by the method described in WO 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methyl-formamidine + TX; N'-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared by the method described in WO 2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX (this compound can be prepared by the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX,(3-Methylisoxazol-5-yl)[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX (These compounds can be prepared by the methods described in WO2017 / 220485); 2-Oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX (This compound can be prepared by the methods described in WO 2018 / 065414); Ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate + TX (This compound can be prepared by the methods described in WO 2018 / 158365); 2,2-Difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX, N-[(E)-Methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[(Z)-Methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[N-Methoxy-C-methyl-carbamimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX (These compounds can be prepared by the methods described in WO 2018 / 202428).

[0297] References in brackets after the active ingredient, e.g., [3878-19-1], refer to Chemical Abstracts Registry Numbers. The mixing combinations described above are known. Where the active ingredient is included in "The Pesticide Manual", they are described therein by the entry numbers given in parentheses above for the particular compound; for example, the compound "abamectin" is described by the entry number (1). Where "[CCN]" is added above to a particular compound, the said compound is included in "Compendium of Pesticide Common Names", which can be found on the Internet [A. Wood; Compendium of Pesticide Common Names , Copyright obtained in [1995 - 2004]; for example, the compound "acetoprole" is described at the Internet address http: / / www.alanwood.net / pesticides / acetoprole.html.

[0298] Most of the above - mentioned active ingredients are referred to by the so - called "common name" described above, and in individual cases, the relevant "ISO common name" or another "common name" is used. If the name is not a "common name", the type of name used is replaced by the name given in parentheses for the particular compound; in this case, the IUPAC name, IUPAC / Chemical Abstracts name, "chemical name", "trivial name", "compound name", or "development code" is used, or if neither one of those names nor the "common name" is used, the "alias" is used. "CAS Registry Number" means the Chemical Abstracts Registry Number.

[0299] The active ingredient mixture of the compound of formula (I) (selected from one of the compounds shown in Tables A - 1 to A - 13 (below) or compound 1.1 listed in Table T1 (below)) preferably has a mixing ratio ranging from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially from 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5:1 and 1:5, particularly preferably from 2:1 to 1:2, and a ratio from 4:1 to 2:1 is also preferred, especially at 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. Those mixing ratios are by weight.

[0300] The mixture as described above can be used in a method for controlling pests, which method comprises applying a composition comprising the mixture as described above to the pests or their environment, except for methods used in surgery or therapy for treating the human or animal body and diagnostic methods carried out on the human or animal body.

[0301] Mixtures comprising the compounds shown in Tables A-1 to A-13 (below), or compound 1.1 listed in Table T1 (below), and one or more of the active ingredients as described above can be applied, for example, in a single "ready-to-use" form, applied as a combined spray mixture (which consists of separate formulations of the individual active ingredient components) (such as a "tank mix"), and the individual active ingredients are used in combination when applied in a sequential manner (i.e., one after another at a moderately short interval, such as a few hours or days). The order of applying the compounds shown in Tables A-1 to A-13 (below), or compound 1.1 listed in Table T1 (below), and one or more of the active ingredients as described above is not critical for carrying out the present invention.

[0302] The compounds of the present invention can also be used in combination with anthelmintics. Such anthelmintics include compounds selected from macrolide compounds, such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin, and milbemycin derivatives, as described in EP-357460, EP-444964, and EP-594291. Further anthelmintics include semi-synthetic and biosynthetic avermectin / milbemycin derivatives, such as those described in US-5015630, WO-9415944, and WO-9522552. Further anthelmintics include benzimidazoles, such as albendazole, cambendazole, 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 trematocides (such as triclabendazole and clorsulon) and cestocides (such as praziquantel and niclosamide).

[0303] The compounds of the present invention can be used in combination with derivatives and analogs of paraherquamide / marcfortine anthelmintics and anti-parasitic oxazolines (such as those disclosed in US-5478855, US-4639771, and DE-19520936).

[0304] The compounds of the present invention can be used in combination with derivatives and analogs of the general class of dioxomopholine antiparasitic agents as described in WO 96 / 15121, and also with cyclic depsipeptides having anthelmintic activity (such as those described in WO 96 / 11945, WO 93 / 19053, WO 93 / 25543, EP 0 626 375, EP 0 382 173, WO 94 / 19334, EP 0 382 173, and EP 0 503 538).

[0305] The compounds of the present invention can be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide, etc.; neonicotinoids such as imidacloprid, etc.

[0306] The compounds of the present invention can be used in combination with terpenoid alkaloids, such as those described in International Patent Application Publication No. WO 95 / 19363 or WO 04 / 72086, especially the compounds disclosed therein.

[0307] Other examples of such bioactive compounds that can be used in combination with the compounds of the present invention include, but are not limited to, the following:

[0308] Organophosphates: acephate, pyraclofos, ethion, methyl parathion, bromophos, bromophos-ethyl, cadusafos, chlorethoxyphos, chlorpyrifos, chlorethoxyfos, chlormephos, demeton, demeton-S-methyl, demeton-S-methyl sulfone, dialifos, diazinon, dichlorvos, dimefox, dimethoate, disulfoton, ethoprophos, etrimfos, famphur, fenamiphos, fenthion, flupyrazofos, fonofos, formothion, fosthiazate, heptenophos, isazofos, isofenphos, isothioate, malathion, methacrifos, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, paraoxon, parathion, parathion-methyl, phenthoate, phosalone, phosfolan, phosmet, phosphamidon, phorate, pirimiphos-methyl, profenofos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulprofos, temephos, terbufos, tetraconazole, thimeton, triazophos, trichlorfon, vamidothion.

[0309] Carbamates: alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenoxycarb, fenthion, furathiocarb, HCN-801, isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-isopropylphenyl butynyl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717.

[0310] Pyrethroids: acrinathrin, allethrin, beta-cypermethrin, 5-benzyl-3-furfuryl (E)-(1R)-cis-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl) cyclopropanecarboxylate, bifenthrin, beta-cyfluthrin, cyfluthrin, alpha-cypermethrin, beta-cypermethrin, bioallethrin, bioallethrin ((S)-cyclopentyl isomer), bioresmethrin, biphenthrin, NCI-85193, cycloprothrin, cyhalothrin, cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, flufenprox, flumethrin, lambda-cyhalothrin, permethrin, phenothrin, propargite, pyrethrum (natural product), resmethrin, tetramethrin, theta-cypermethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, zetacypermethrin.

[0311] Arthropod growth regulators: a) Chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, flonicamid, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triazamate; b) Ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) Juvenile hormone analogs: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) Lipid biosynthesis inhibitors: spirodiclofen.

[0312] Other anti-parasitic drugs: acequinocyl, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorbenside, chlordimeform, chlorfenapyr, chromafenozide, clothianidin, cyanazine, diacloden, diafenthiuron, DBI-3204, diomycin, dihydroxymethyl dihydroxypyrrolidine, dienochlor, dinocap, endosulfan, ethiprole, etofenprox, fenazaquin, flumite, MTI-800, fenpyroximate, fluacrypyrim, flufenerim, flubroxyfen, halofenprox, hydramethylnon, IKI-220, hydrocerussite, NC-196, neem guard, nidinorterfuran, nitenpyram, SD-35651, WL-108477, pyridalyl, propargite, protrifenbute, pymetrozine, pyridaben, pyrimidifen, NC-1111, R-195, RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601, silafluofen, silomadine, spinosad, tebufenpyrad, tetradifon, tetra-antibiotic, thiacloprid, thiosultap, thiamethoxam, tolfenpyrad, triazamate, triethylspinosad, triomycin, synergistic alkynyl ether, vertalec, YI-5301.

[0313] Biological agents: Bacillus thuringiensis ssp aizawai, Bacillus thuringiensis ssp kurstaki, Bacillus thuringiensis δ-endotoxin, baculovirus, entomopathogenic bacteria, viruses and fungi.

[0314] Bactericides: chlortetracycline, oxytetracycline, streptomycin.

[0315] Other biological agents: enrofloxacin, febantel, penethamate, meloxicam, cefalexin, kanamycin, pimobendan, clenbuterol, omeprazole, sulmide, benazepril, pyriprole, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, cefotaxime, carprofen, mefronil, praziquantel, triclabendazole.

[0316] The composition according to the invention may also contain other solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (such as epoxidized coconut oil, rapeseed oil or soybean oil), defoamers (such as silicone oils), preservatives, viscosity regulators, binders and / or tackifiers, fertilizers or other active ingredients for obtaining specific effects, such as bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0317] The composition according to the invention is 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 the active ingredient together with one or more auxiliaries. These methods for preparing the composition and the use of the compound (I) for preparing these compositions are also the subject of the present invention.

[0318] Another aspect of the present invention relates to the use of a compound of formula (I) or preferably a single compound as defined herein, of a composition comprising at least one compound of formula (I) or at least one single compound preferably as defined above, or of a fungicidal or insecticidal mixture comprising at least one compound of formula (I) or at least one single compound preferably as defined above (mixed with other fungicides or insecticides as described above) for controlling or preventing the infestation of plants (such as useful plants (e.g. crop plants)), their propagation material (e.g. seeds), harvested crops (e.g. harvested food crops), or non-living materials by insects or phytopathogenic microorganisms (preferably fungal organisms).

[0319] Another aspect of the present invention relates to a method for controlling or preventing the infestation of plants (such as useful plants (e.g. crop plants)), their propagation material (e.g. seeds), harvested crops (e.g. harvested food crops), or non-living materials by insects or phytopathogenic or spoilage microorganisms or organisms potentially harmful to humans (especially fungal organisms), which method comprises applying a compound of formula (I) or preferably a single compound as defined above as an active ingredient to these plants, parts of these plants or their sites, their propagation material, or any part of these non-living materials.

[0320] Controlling or preventing means reducing the infestation or spoilage by phytopathogenic microorganisms or organisms potentially harmful to humans (especially fungal organisms) to a level which has been proven to be improved.

[0321] A preferred method for controlling or preventing crop plants from being infested by phytopathogenic microorganisms, especially fungal organisms, or insects is foliar application, which comprises applying a compound of formula (I), or an agrochemical composition containing at least one such compound. The application frequency and application rate will depend on the risk of infestation by the respective pathogen or insect. However, the compound of formula (I) can also penetrate the plant via the soil through the roots (systemic action) by soaking the locus of the plant with a liquid formulation or by applying the compound in solid form, for example in the form of granules, to the soil (soil application). In rice crops, such granules can be applied to flooded paddy fields. The compound 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.

[0322] Formulations (such as compositions containing a compound of formula (I) and, if desired, solid or liquid adjuvants or monomers for encapsulating the compound of formula (I)) can be prepared in a known manner, typically by intimately mixing and / or grinding the compound with extenders such as solvents, solid carriers and optionally surface-active compounds (surfactants).

[0323] Advantageous application rates are generally from 5 g to 2 kg of active ingredient (a.i.) / hectare (ha), preferably from 10 g to 1 kg a.i. / ha, most preferably from 20 g to 600 g a.i. / ha. When used as a seed soaking agent, a suitable dose is from 10 mg to 1 g of active substance / kg of seeds.

[0324] As used herein, the term "g a.i. / ha" refers to the application rate given in grams [g] of active ingredient [a.i.] / unit surface [ha]. The unit hectare (symbol ha) is a metric unit of area equal to the area of a square with a side length of 100 m (1 hm 2 ) or 10,000 square meters. The hectare is a commonly used unit of area in the metric system.

[0325] When the combinations according to the invention are used for treating seeds, a rate of 0.001 to 50 g of the compound of formula (I) / kg of seeds, preferably from 0.01 to 10 g / kg of seeds, is generally sufficient.

[0326] Suitably, the compositions containing a compound of formula (I) according to the invention are applied prophylactically (i.e. before the development of the disease) or therapeutically (i.e. after the development of the disease).

[0327] The compositions of the present invention can be used in any conventional form, for example, in the form of a two-pack, powder for dry seed treatment (DS), emulsion for seed treatment (ES), flowable concentrate for seed treatment (FS), solution for seed treatment (LS), water dispersible powder for seed treatment (WS), capsule suspension for seed treatment (CF), gel for seed treatment (GF), emulsion concentrate (EC), suspension concentrate (SC), suspo-emulsion (SE), capsule suspension (CS), water dispersible granule (WG), emulsifiable granule (EG), water-in-oil emulsion (EO), oil-in-water emulsion (EW), microemulsion (ME), dispersible oil suspension (OD), oil suspension (OF), oil-soluble 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.

[0328] Such compositions can be produced in a conventional manner, for example, by mixing the active ingredient with suitable formulation inert agents (diluents, solvents, fillers and optionally other formulation ingredients such as surfactants, biocides, antifreeze agents, adhesives, thickeners and compounds providing auxiliary effects). Conventional slow-release formulations designed for long-term sustained efficacy can also be used. In particular, formulations to be 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) and other compounds providing auxiliary effects, for example, condensation products of formaldehyde with naphthalene sulfonates, alkyl aryl sulfonates, lignin sulfonates, fatty alkyl sulfates and ethoxylated alkyl phenols and ethoxylated fatty alcohols.

[0329] Using the combination and diluent of the present invention, in the form of a suitable seed dressing formulation, for example, in the form of an aqueous suspension or dry powder having good adhesion to seeds, the seed dressing formulation is applied to the seeds in a manner known per se. Such seed dressing formulations are known in the art. The seed dressing formulation can contain a single active ingredient or a combination of active ingredients in encapsulated form, for example, as slow-release capsules or microcapsules.

[0330] Typically, these formulations include from 0.01% to 90% by weight of an active agent, from 0 to 20% of an agriculturally acceptable surfactant, and 10% to 99.99% of a solid or liquid formulation inert agent and one or more adjuvants, and the active agent is optionally composed of at least a compound of formula (I) together with other active agents (especially microbicides or preservatives, etc.). The concentrated form of the composition usually contains from about 2% to 80% by weight, preferably from about 5% to 70% by weight of the active agent. The application form of the formulation may contain, for example, from 0.01% to 20% by weight, preferably from 0.01% to 5% by weight of the active agent. However, commercial products will preferably be formulated as concentrates, and the end user will typically use a diluted formulation.

[0331] However, it is preferred that commercial products be formulated as concentrates, and the end user will typically use a diluted formulation.

[0332] The compounds according to Tables A-1 to A-13 below can be prepared according to the above method. The following examples are intended to illustrate the invention and show preferred compounds of formula (I), where R 1 as defined in Tables A-1 to A-13; and R 2 and G are as defined in Table G below.

[0333] Table G

[0334]

[0335]

[0336] Table A-1: This table provides 48 compounds of formula (I), A-1.01 and A-1.48, where R 1 is 3-cyclopropyl-2-fluorophenyl, and the substituents R 2 and G are as defined in Table G above.

[0337] For example, compound A-1.02 is:

[0338]

[0339] Table A-2: This table provides 48 compounds of formula (I), A-2.01 and A-2.48, where R 1 is 3-(trifluoromethyl)phenyl, and the substituents R 2 and G are as defined in Table G above.

[0340] Table A-3: This table provides 48 compounds of formula (I), A-3.01 and A-3.48, where R 1is 3-chloro-2-fluorophenyl, and the substituent R 2 and G are as defined in Table G above.

[0341] Table A-4: This table provides 48 compounds of formula (I), A-4.01 and A-4.48, wherein R 1 is 3-chlorophenyl, and the substituent R 2 and G are as defined in Table G above.

[0342] Table A-5: This table provides 48 compounds of formula (I), A-5.01 and A-5.48, wherein R 1 is 5-cyanopyridin-3-yl, and the substituent R 2 and G are as defined in Table G above.

[0343] Table A-6: This table provides 48 compounds of formula (I), A-6.01 and A-6.48, wherein R 1 is 3-methylphenyl, and the substituent R 2 and G are as defined in Table G above.

[0344] Table A-7: This table provides 48 compounds of formula (I), A-7.01 and A-7.48, wherein R 1 is phenyl, and the substituent R 2 and G are as defined in Table G above.

[0345] Table A-8: This table provides 48 compounds of formula (I), A-8.01 and A-8.48, wherein R 1 is 3-cyclopropylphenyl, and the substituent R 2 and G are as defined in Table G above.

[0346] Table A-9: This table provides 48 compounds of formula (I), A-9.01 and A-9.48, wherein R 1 is 3-(difluoromethyl)phenyl, and the substituent R 2 and G are as defined in Table G above.

[0347] Table A-10: This table provides 48 compounds of formula (I), A-10.01 and A-10.48, wherein R 1 is 3-(difluoromethoxy)phenyl, R 2 is methyl, and the substituent R 2 and G are as defined in Table G above.

[0348] Table A-11:This table provides 48 compounds of formula (I), A-11k.01 and A-11.48, where R 1 is 3-(trifluoromethyl)-2-fluorophenyl, and the substituents R 2 and G are as defined in Table G above.

[0349] Table A-12: This table provides 48 compounds of formula (I), A-12.01 and A-12.48, where R 1 is 3-methoxyphenyl, and the substituents R 2 and G are as defined in Table G above.

[0350] Table A-13: This table provides 48 compounds of formula (I), A-13.01 and A-13.48, where R 1 is 2,3-difluorophenyl, and the substituents R 2 and G are as defined in Table G above

[0351] Also made available are certain intermediate compounds of formula (II-i), (IV-i), (VIII-i), (X-i), (XIII-i), (XX-i), (XXI-i), (XXXVI-i) and (XLIV-i), some of which are novel. For example:

[0352] - A compound of formula (II-i), where R 1 , R 2 and G are as defined for the compounds of formula (I); as where R 1 is as defined in Tables A-1 to A-13 above, and R 2 and G are as defined in Table G above:

[0353]

[0354] - A compound of formula (IV-i), where R 1 and R 2 are as defined for the compounds of formula (I); as where R 1 is as defined in Tables A-1 to A-13 above, and R 2 is as defined in Table G above:

[0355]

[0356] - A compound of formula (VIII-i), where R 2 and G are as defined for the compounds of formula (I), and X 3 is a suitable leaving group, such as fluorine, chlorine, bromine, iodine, BF3K, B(OH)2 or B(pinacol); as where R2 and G are as defined in Table G above:

[0357]

[0358] - a compound having the formula (X-i), wherein R 2 and G are as defined for the compound having the formula (I), and X 3 is a suitable leaving group, such as fluorine, chlorine, bromine, iodine, BF3K, B(OH)2 or B(pinacol); wherein R 2 and G are as defined in Table G above:

[0359]

[0360] - a compound having the formula (XIII-i), wherein R 2 and G are as defined for the compound having the formula (I); wherein R 2 and G are as defined in Table G above:

[0361]

[0362] - a compound having the formula (XX-i), wherein R 1 and R 2 are as defined for the compound having the formula (I), and X 7 is chlorine, bromine, iodine or O-trifluoromethanesulfonyl; wherein R 1 is as defined in Tables A-1 to A-13 above, and R 2 is as defined in Table G above:

[0363]

[0364] - a compound having the formula (XXI-i), wherein R 2 and G are as defined for the compound having the formula (I), and X 4 is OH, halogen, or OR 1 , R 1 is as defined for the compound having the formula (I); wherein R 1 is as defined in Tables A-1 to A-13 above, and R 2 and G are as defined in Table G above:

[0365]

[0366] - a compound having the formula (XXXVI-i), wherein R 2 is as defined for the compound having the formula (I), X 8 is OH, halogen, or O-R 1 , R 1As defined for compounds of formula (I), and X 9 is halogen, methyl, trifluoromethanesulfonyl - O -, cyano, COOH, or - C(O)C1 - C4 alkoxy; wherein R 1 is as defined in Tables A - 1 to A - 13 above, and R 2 and G are as defined in Table G above:

[0367]

[0368] - Compounds of formula (XLIV - i), wherein G is as defined for compounds of formula (I), Z is OH, SH, chlorine, bromine, or iodine, and X 8 is OH, halogen, or O - R 1 , R 1 is as defined for compounds of formula (I); wherein R 1 is as defined in Tables A - 1 to A - 13 above, and G is as defined in Table G above:

[0369]

[0370] Examples

[0371] The following examples are used to illustrate the invention and are not meant to limit the invention in any way.

[0372] The compounds of the invention may differ from known compounds in having greater efficacy at low application rates, which can be confirmed by those skilled in the art using the experimental procedures outlined in the examples, using lower application rates (if necessary), for example, 60 ppm, 20 ppm, or 2 ppm.

[0373] Compounds of formula (I) can have any number of benefits, including in particular a favorable level of biological activity for protecting plants against diseases caused by fungi or superior properties for use as an agrochemical active ingredient (e.g., higher biological activity, favorable activity spectrum, increased safety (including improved crop tolerance), improved physico - chemical properties, or increased biodegradability).

[0374] Throughout this specification, temperatures are given in degrees Celsius (°C), and "m.p." means melting point. LC / MS or LC - MS or LCMS means liquid chromatography - mass spectrometry, and the apparatus and methods are described below.

[0375] Unless otherwise stated, recorded on a Bruker 400 MHz spectrometer 1 1H NMR and 19 19F NMR measurements, chemical shifts relative to TMS ( 1 1H) and CFCl3 (19 F) Standards are given in ppm. Spectra were measured in the deuterated solvents as indicated. The following abbreviations were used: s = singlet; br s = broad singlet; d = doublet; br d = broad doublet; dd = double doublet; dt = double triplet; t = triplet, tt = triple triplet, q = quartet, quin = quintet, sept = septet; m = multiplet.

[0376] These compounds were characterized using any of the following LCMS methods. The characteristic LCMS values obtained for each compound were the retention time (“Rt”, recorded in minutes) and the measured molecular ion (M+H) + or (M-H) - .

[0377] Method B (LCMS): Spectra were recorded on a mass spectrometer from Agilent Technologies (6410 triple quadrupole mass spectrometer) equipped with an electrospray source (positive and negative polarity switching, capillary voltage (kV) 7.00, scan type MS2 scan, fragmentation voltage (V) 120.00, gas temperature (°C): 350, gas flow (L / min): 11, nebulizer gas (psi): 40, mass range: 110 Da to 650 Da) and an Agilent 1200 series HPLC: DAD wavelength: 254 nm, column: KINETEX EVO C18, column length: 50 mm, column inner diameter: 4.6 mm, particle size: 2.6 μm, column oven temperature: 40 °C

[0378] Gradient conditions:

[0379] Solvent A: Water containing 0.1% formic acid: acetonitrile: 95:5 v / v

[0380] Solvent B: Acetonitrile containing 0.1% formic acid

[0381]

[0382] If necessary, the final compounds that are enantiomerically pure can be obtained from the racemic materials via standard physical separation techniques (e.g., reverse phase chiral chromatography) or by stereoselective synthesis techniques (e.g., by using chiral starting materials) when appropriate.

[0383] Method C (LCMS):Spectra were recorded on a mass spectrometer (Acquity QDA mass spectrometer) from Waters, equipped with an electrospray source (positive and negative polarity switching, capillary voltage (kV) 0.8, cone voltage (V) 25.00, full scan, source temperature (°C): 120, desolvation gas flow rate (L / Hr): 1000, desolvation temperature (°C): 600, cone gas flow rate (L / Hr): 50, mass range: 110 Da to 850 Da) and HPLC: DAD wavelength range: 230 to 400 nm, column Acquity UPLC HSS T3 C18, column length: 30 mm, column inner diameter: 2.1 mm, particle size: 1.8 μm, column oven temperature: 40 °C

[0384] Gradient conditions:

[0385] Solvent A: Water containing 0.1% formic acid: acetonitrile: 95:5 v / v

[0386] Solvent B: Acetonitrile containing 0.05% formic acid

[0387]

[0388] When necessary, the final compound that is enantiomerically pure can, where appropriate, be obtained from racemic material via standard physical separation techniques (such as reverse-phase chiral chromatography) or by stereoselective synthesis techniques (such as by using chiral starting materials).

[0389] Method D (LCMS): Spectra were recorded on a mass spectrometer (Acquity SDQ mass spectrometer) from Waters, equipped with an electrospray source (positive and negative polarity switching, capillary voltage (kV) 3.0, full scan, cone voltage (V) 41.0, source temperature (°C): 150, desolvation temperature (°C): 500, cone gas flow rate (L / Hr): 50, mass range: 110 Da to 800 Da) and HPLC 'H' grade: DAD wavelength range: 210 to 400 nm, column Acquity UPLC HSS T3 C18, column length: 30 mm, column inner diameter: 2.1 mm, particle size: 1.8 μm, column oven temperature: 40 °C

[0390] Gradient conditions:

[0391] Solvent A: Water containing 0.1% formic acid: acetonitrile: 95:5 v / v

[0392] Solvent B: Acetonitrile containing 0.05% formic acid

[0393]

[0394] When necessary, the final compounds that are pure in the enantiomeric sense can be obtained from racemic materials via standard physical separation techniques (e.g., reverse-phase chiral chromatography) or by stereoselective synthesis techniques (e.g., by using chiral starting materials) as appropriate.

[0395] Formulation examples

[0396]

[0397]

[0398] The combination is thoroughly mixed with these adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a wettable powder that can be diluted with water to give a suspension of the desired concentration.

[0399]

[0400] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a powder that can be directly used for seed treatment.

[0401] Emulsifiable concentrate

[0402]

[0403] An emulsion with any required dilution that can be used in plant protection can be obtained by diluting with water from this concentrate.

[0404]

[0405] A ready-to-use dust powder is obtained by mixing the combination with a carrier and grinding the mixture in a suitable grinder. Such dust powders can also be used for dry dressing of seeds.

[0406] Extruder granule

[0407]

[0408] The combination is mixed with these adjuvants and ground, and the mixture is moistened with water. The mixture is extruded and then dried in an air stream.

[0409] Coated granule

[0410] Active ingredient 8%

[0411] Polyethylene glycol (molar weight 200) 3%

[0412] Kaolin 89%

[0413] The finely ground combination is uniformly applied to kaolin moistened with polyethylene glycol in a mixer. In this way, dust-free coated granules are obtained.

[0414] Suspension concentrate

[0415]

[0416] The finely ground combination is intimately mixed with adjuvants to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants together with plant propagation material can be treated and protected against microbial infestation by spraying, watering or dipping.

[0417] Flowable concentrate for seed treatment

[0418]

[0419]

[0420] The finely ground combination is intimately mixed with adjuvants to give a flowable concentrate from which solutions of any desired dilution can be obtained by dilution with water, which can be used directly for seed treatment. Using such dilutions, living plants together with plant propagation material can be treated and protected against microbial infestation by spraying, watering or dipping.

[0421] Sustained-release capsule suspension

[0422] 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 part of an antifoaming agent and 51.6 parts of water until the desired particle size is reached. 2.8 parts of a 1,6-hexanediamine mixture in 5.3 parts of water are added to this emulsion. The mixture is stirred until the polymerization reaction is complete. The obtained capsule suspension is stabilized by adding 0.25 part of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% of the active ingredient. The diameter of the medium capsules is 8 - 15 microns. The resulting formulation is applied as an aqueous suspension to the seeds in a device suitable for this purpose.

[0423] Formulation types include emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifiable granules (EG), emulsions, water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oil dispersions (OD), oil suspensions (OF), oil-soluble solutions (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume solutions (UL), technical materials (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG), or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0424] Abbreviations

[0425] Abbreviations used in the synthetic schemes and preparation examples ACN Acetonitrile (or MeCN)

[0426] DCM Dichloromethane DMSO Dimethyl sulfoxide DMSO-d 6 Deuterated dimethyl sulfoxide Et3N Triethylamine (or TEA)

[0427] EtOAc Ethyl acetate HATU O-(7-Azabenzotriazol-1-yl)-N,N,N’,N’-tetramethyluronium hexafluorophosphate MeOH Methanol THF Tetrahydrofuran equiv. Equivalent h Hour LC / MS or LC-MS Liquid chromatography mass spectrometry M Mole MHz Megahertz min Minute NMR Nuclear magnetic resonance ppm Parts per million RT Room temperature Rt Retention time TLC Thin layer chromatography

[0428] Preparation examples

[0429] The following examples further illustrate (but do not limit) the invention. Those skilled in the art will readily recognize appropriate variations of the reactants and of the reaction conditions and techniques from these procedures.

[0430] Unless otherwise indicated 11H NMR spectra were recorded at 400 MHz and 19 19F NMR spectra were recorded at 377 MHz, and chemical shifts were recorded in ppm. The following abbreviations were used: s = singlet; br s = broad singlet; d = doublet; br d = broad doublet; dd = double doublet; dt = double triplet; t = triplet, tt = triple triplet, q = quartet, quin = quintet, sept = septet; m = multiplet.

[0431] Throughout this specification, temperatures are given in degrees Celsius (°C). "MP" means melting point. "Rt" means retention time. LC / MS means liquid chromatography - mass spectrometry. The LC / MS apparatus and method are:

[0432] Example P1 : 3 - [5 - (3 - cyclopropylphenoxy) - 3 - methyl - pyridazin - 4 - yl] - 5 - [(2,4 - dichlorophenyl)methyl] - 5,6 - dihydro - 4H - 1,2,4 - oxadiazine (Compound 1.1 of Table T1)

[0433]

[0434] a) Preparation of 5-bromo-4-(3-cyclopropylphenoxy)-1H-pyridazin-6-one

[0435] In a round - bottom flask, to a mixture of 4,5 - dibromopyridazin - 3 - ol (10 g, 37.4 mmol) and 3 - cyclopropylphenol (41.16 mmol) in DMSO (80 mL), cesium carbonate (93.5 mmol) was added and the mixture was purged with a nitrogen stream for 10 minutes. Copper(I) iodide (1.87 mmol) and N,N - dimethylglycine (5.61 mmol) were added, and the reaction mixture was purged with nitrogen again for 5 minutes. Then the reaction mixture was heated at 110 °C for 5 hours. The reaction progress was monitored by TLC and LCMS. The mixture was diluted with EtOAc, quenched with water and extracted with EtOAc. The organic layer was washed with water, brine, dried over sodium sulfate, filtered and evaporated under reduced pressure to obtain the crude product. The crude material was purified by combiflash column chromatography (cyclohexane / EtOAc). The desired fractions were evaporated, and the obtained solid was triturated with tert - butyl methyl ether to give pure 5 - bromo - 4 - (3 - cyclopropylphenoxy) - 1H - pyridazin - 6 - one as a white solid (6.1 g, 50%).

[0436] LCMS (Method D): Retention time 1.02 min, m / z 307,309 [M + H] + .

[0437] 11H NMR (400 MHz, CDCl3) δ ppm 11.82 (br s, 1H), 7.44 (s, 1H), 7.34 (t, 1H), 7.03 (d, 1H), 6.89 (ddd, 1H), 6.83 (t, 1H), 1.90 - 1.97 (m, 1H), 1.02 - 1.08 (m, 2H), 0.71 - 0.77 (m, 2H).

[0438] b) Preparation of methyl 4-(3-cyclopropylphenoxy)-6-oxo-1H-pyridazine-5-carboxylate

[0439] Charge a 50 mL autoclave vessel with 5-bromo-4-(3-cyclopropylphenoxy)-1H-pyridazin-6-one (3.0 g, 9.8 mmol), TEA (20 mmol), MeOH (30 mL), and Pd(dppf)Cl2·CH2Cl2 (0.98 mmol). Flush the reactor twice with carbon monoxide and load 15 bar. Heat the reaction mass to 90 °C. After 5 h, cool the reaction mass to 25 °C, release the pressure and flush the reaction mixture with nitrogen. Drain the reaction mass into a clean conical flask. Dilute the reaction mass with water and extract twice with EtOAc. Wash the combined organic layers with brine, dry over sodium sulfate, filter and concentrate under reduced pressure to obtain the crude product, which is washed with pentane to obtain methyl 4-(3-cyclopropylphenoxy)-6-oxo-1H-pyridazine-5-carboxylate (1.4 g, 45% yield).

[0440] LCMS (method C): retention time 0.98 min, m / z 287 [M + H] + 。

[0441] 1 1H NMR (400 MHz, CDCl3) δ ppm 11.16 - 11.34 (m, 1H), 7.56 (s, 1H), 7.32 (t, 1H), 7.01 (d, 1H), 6.90 (ddd, 1H), 6.81 (t, 1H), 3.88 (s, 3H), 1.89 - 1.96 (m, 1H), 0.98 - 1.11 (m, 2H), 0.68 - 0.78 (m, 2H).

[0442] c) Preparation of methyl 3-chloro-5-(3-cyclopropylphenoxy)pyridazine-4-carboxylate

[0443] Charge a round-bottom flask with methyl 5-(3-cyclopropylphenoxy)-2-methyl-3-oxopyridazine-4-carboxylate (0.8 g, 2.65 mmol), and slowly add phosphorus oxychloride (53.11 mmol) with stirring. Heat the reaction mixture at 75 °C for 2 h. Cool the resulting yellow oil to room temperature, dilute with EtOAc, and slowly pour into water (50 mL) in a conical flask, and gently shake. Separate the organic layer, wash with water, dry over sodium sulfate and evaporate to obtain methyl 3-chloro-5-(3-cyclopropylphenoxy)pyridazine-4-carboxylate (750 mg, 85% by mass, 78% yield), which is used as such without purification for the next step.

[0444] LCMS (Method 2): retention time 1.08 min, m / z 305, 307 [M+H] + 。

[0445] d) Preparation of methyl 5-(3-cyclopropylphenoxy)-3-methylpyridazine-4-carboxylate

[0446] Add potassium carbonate (11.5 mmol), Pd(dppf)Cl2·CH2Cl2 (0.287 mmol) and trimethylcyclotriboroxane (11.5 mmol) to a solution of methyl 3-chloro-5-(3-cyclopropylphenoxy)pyridazine-4-carboxylate (1.75 g, 5.74 mmol) in 2-methyl-THF (35 mL). Stir the reaction mixture at 95 °C for 3 h, and confirm the progress by TLC and LCMS. Dilute the reaction mass with water and extract with EtOAc, wash the organic layer with brine, dry over sodium sulfate and evaporate to obtain the crude product, which is purified by Combiflash (cyclohexane / EtOAc) to obtain methyl 5-(3-cyclopropylphenoxy)-3-methylpyridazine-4-carboxylate (1.2 g, 72% yield)

[0447] LCMS (Method D): retention time 1.07 min, m / z 285 [M+H] + 。

[0448] 1 1H NMR (400 MHz, CDCl3) δ ppm 8.71 (s, 1H), 7.33 (t, 1H), 7.02 (d, 1H), 6.89 (ddd, 1H), 6.81 (t, 1H), 3.97 (s, 3H), 2.76 (s, 3H), 1.84 - 2.00 (m, 1H), 0.97 - 1.09 (m, 2H), 0.69 - 0.75 (m, 1H), 0.66 - 0.78 (m, 1H).

[0449] e) Preparation of 5-(3-cyclopropylphenoxy)-3-methylpyridazine-4-carboxylic acid

[0450] To a stirred solution of methyl 5-(3-cyclopropylphenoxy)-3-methyl-pyridazine-4-carboxylate (0.65 g, 2.3 mmol) in 3:1 THF / water (20 mL) was added barium hydroxide octahydrate (6.9 mmol). The mixture was stirred at room temperature for 4 h. The reaction progress was confirmed by TLC and LCMS. The reaction mixture was acidified with 1 N HCl and extracted twice with EtOAc. The obtained organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to afford 5-(3-cyclopropylphenoxy)-3-methyl-pyridazine-4-carboxylic acid (0.423 g, 65% yield).

[0451] LCMS (Method C): retention time 0.18 min, m / z 271 [M+H] + 。

[0452] f) 5-(3-cyclopropylphenoxy)-N-[1-[(2,4-dichlorophenyl)methyl]-2-(1,3-dioxoisoindolin- 2-yl)oxy-ethyl]-3-methylpyridazine-4-carboxamide

[0453] To a mixture of 5-(3-cyclopropylphenoxy)-3-methyl-pyridazine-4-carboxylic acid (300 mg, 1.11 mmol) and 2-[2-amino-3-(2,4-dichlorophenyl)propoxy]isoindoline-1,3-dione 2,2,2-trifluoroacetate (1.33 mmol) in dimethylformamide (3 mL) was added N-ethyl-N-isopropyl-propan-2-amine (2.77 mmol) and HATU (1.22 mmol). The resulting pale yellow solution was stirred at room temperature for 16 h. The reaction progress was monitored by LCMS. The reaction mixture was diluted with water and extracted with EtOAc. The combined organic layers were washed with saturated solutions of sodium carbonate and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure to give a crude material which was purified by Combiflash chromatography (cyclohexane / EtOAc) to afford 5-(3-cyclopropylphenoxy)-N-[1-[(2,4-dichlorophenyl)methyl]-2-(1,3-dioxoisoindolin-2-yl)oxy-ethyl]-3-methyl-pyridazine-4-carboxamide (0.7 g, 70 mass%, 70% yield).

[0454] LCMS (Method B): retention time 1.67 min, m / z 617 [M+H] + 。

[0455] g) Preparation of N-[1-(aminooxymethyl)-2-(2,4-dichlorophenyl)ethyl]-5-(3-cyclopropylphenoxy)-3-methyl- pyridazine-4-carboxamide

[0456] To a solution of 5-(3-cyclopropylphenoxy)-N-[1-[(2,4-dichlorophenyl)methyl]-2-(1,3-dioxoisoindolin-2-yl)oxy-ethyl]-3-methyl-pyridazine-4-carboxamide (300 mg, 0.485 mmol) in THF (9 mL) was added hydrazine monohydrate (0.971 mmol, 97 mass %). The mixture was stirred at room temperature for 30 min. Thereafter, a solid precipitated. The solid was filtered off and the filtrate was concentrated to give N-[1-(aminooxymethyl)-2-(2,4-dichlorophenyl)ethyl]-5-(3-cyclopropylphenoxy)-3-methyl-pyridazine-4-carboxamide (260 mg, 90 mass %, 98% yield), which was used directly in the next step.

[0457] LCMS (Method C): retention time 1.21 min, m / z 487, 489 [M+H] + 。

[0458] g) 3-[5-(3-cyclopropylphenoxy)-3-methylpyridazine-4-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6- dihydro-4H-1,2,4-oxadiazine

[0459] To a solution of N-[1-(aminooxymethyl)-2-(2,4-dichlorophenyl)ethyl]-5-(3-cyclopropylphenoxy)-3-methyl-pyridazine-4-carboxamide (140 mg, 0.287 mmol) in DCM (5 mL) was added phosphorus pentachloride (0.488 mmol). The mixture was stirred at 45 °C for 2 h. The progress of the reaction was monitored by TLC and LCMS. Then the reaction mixture was cooled to room temperature and quenched slowly with saturated sodium bicarbonate solution (saturated NaHCO3 solution), diluted with water and extracted twice with EtOAc. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure to give the crude product. The crude material was initially purified by Combiflash (cyclohexane / EtOAc) and subsequently by preparative HPLC to give 3-[5-(3-cyclopropylphenoxy)-3-methyl-pyridazine-4-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (25 mg, 18%).

[0460] LCMS (Method C): retention time 1.25 min, m / z 469, 471 [M+H] + 。

[0461] 11H NMR (400 MHz, CDCl3) δ ppm 8.60 (s, 1H), 7.31 - 7.43 (m, 2H), 7.16 (d, 1H), 7.04 (dd, 2H), 6.83 - 6.91 (m, 1H), 6.80 (s, 1H), 4.97 (br s, 1H), 3.92 - 4.05 (m, 3H), 3.03 - 3.17 (m, 2H), 2.80 (s, 3H), 1.82 - 2.04 (m, 1H), 0.98 - 1.11 (m, 2H), 0.68 - 0.78 (m, 2H).

[0462] Table T1: Physical data of the compound of formula (I) - Measured [M + H]

[0463]

[0464]

[0465]

[0466] Biological examples and test methods:

[0467] The following examples are used to illustrate the present invention. The compounds of the present invention may differ from known compounds in having greater efficacy at low application rates, which can be demonstrated by those skilled in the art using the experimental procedures outlined in the examples, using lower application rates (if necessary), for example, 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

[0468] The compounds of formula (I) can have any number of benefits, including in particular favorable levels of biological activity for protecting plants against diseases caused by fungi or superior properties for use as active ingredients in agrochemicals (e.g., higher biological activity, favorable activity spectra, increased safety (including improved crop tolerance), improved physico - chemical properties, or increased biodegradability).

[0469] General description of test methods

[0470] Leaf discs or segments of different plant species are cut from plants grown in a greenhouse. The cut leaf discs or segments are placed on water agar in a multi-well plate (24-well format). Before (preventively) or after (therapeutically) inoculation, the leaf discs are sprayed with the test solution. The compound to be tested is prepared as a DMSO solution (maximum 10 mg / mL) and diluted to the appropriate concentration with 0.025% Tween20 just before spraying. Depending on the corresponding test system, the inoculated leaf discs or segments are incubated under defined conditions (temperature, relative humidity, light, etc.). Depending on the disease system, a single assessment of the disease level is made 3 to 14 days after inoculation. The percentage of disease control relative to untreated control leaf discs or segments is then calculated.

[0471] Mycelial fragments or conidial suspensions of the fungus (freshly prepared from a liquid culture of the fungus or from frozen stock) are directly mixed into nutrient broth. The DMSO solution of the test compound (maximum 10 mg / mL) is diluted 50-fold with 0.025% Tween20 and 10 μL of this solution is pipetted into a microtiter plate (96-well format). Then the nutrient broth containing the fungal spores / mycelial fragments is added thereto to obtain the final concentration of the test compound. The test plates are incubated in the dark at 24 °C and 96% relative humidity. Depending on the disease system, after 2 to 7 days, the inhibition of fungal growth is determined photometrically and the percentage of antifungal activity relative to the untreated control is calculated.

[0472] Example B1: Botryotinia fuckeliana (also known as Botrytis cinerea) (gray mold of grapes) (grape gray mold disease)

[0473] Fungal conidia from frozen stock are directly mixed into nutrient broth (Vogels broth). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24 °C and the inhibition of growth is determined photometrically 3 - 4 days after application.

[0474] When compared to untreated controls that showed extensive disease development under the same conditions, the following compounds from Table T1 gave at least 80% control of Botrytis fuckeliana at 20 ppm: 1.1, 1.2, 1.3, 1.4, 1.5, 1.6

[0476] Example B2: Glomerella lagenarium (also known as Colletotrichum lagenarium) (anthracnose of cucurbits)

[0477] Fungal conidia from frozen storage were directly mixed into nutrient broth (PDB - potato dextrose broth). After placing the (DMSO) solution of the test compound in a microtiter plate (96 - well format), nutrient broth containing the fungal spores was added. These test plates were incubated at 24 °C and growth inhibition was measured photometrically 3 - 4 days after application.

[0478] When compared to untreated controls that showed extensive disease development under the same conditions, the following compounds from Table T1 gave at least 80% control of Glomerella cingulata at 20 ppm: 1.1, 1.2, 1.3, 1.4, 1.5, 1.6

[0480] Example B3: Blumeria graminis f. sp. tritici (powdery mildew on wheat)

[0481] Wheat leaf segments of the cultivar Kanzler were placed on agar in a multi - well plate (24 - well format) and sprayed with formulated test compounds diluted in water. One day after application, leaf discs were inoculated by shaking powdery mildew - infected plants over the test plates. In a growth chamber, the inoculated leaf discs were incubated at 20 °C and 60% rh under a light regime of 24 h darkness followed by 12 h illumination / 12 h darkness, and compound activity was evaluated as the percentage of disease control compared to untreated controls when an appropriate level of disease damage appeared on the untreated control leaf segments (6 - 8 days after application).

[0482] When compared to untreated controls that showed extensive disease development under the same conditions, the following compounds from Table T1 gave at least 80% control of Glomerella cingulata at 20 ppm: 1.1, 1.2

Claims

1. A compound having the formula (I) or an agrochemically acceptable salt, stereoisomer, enantiomer, or N-oxide of the compound having the formula (I), wherein: R 1 is an unsubstituted phenyl or a phenyl substituted with the following: - A single substituent selected from hydroxy, nitro, halogen, mercapto, amino, cyano, NHMe, N(Me)2, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C2 fluoroalkyl, C1-C4 alkoxy, C1-C2 fluoroalkoxy, C3-C4 alkenyloxy, C3-C4 alkenyloxy, C3-C6 cycloalkyl, C3-C6 cycloalkyloxy, C3-C6 cycloalkyl C1-C2 alkyloxy, C1-C3 alkylthio, and C1-C3 alkylsulfonyl; or - 1, 2 or 3 substituents independently selected from hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, methylthio, methylsulfonyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl; or R 1 is a 5- or 6-membered monocyclic heteroaryl ring containing 1, 2 or 3 heteroatoms each independently selected from N, O and S, provided that no more than one is O or S; wherein said heteroaryl ring is unsubstituted or substituted with the following: - A single substituent selected from hydroxy, nitro, halogen, mercapto, amino, cyano, NHMe, N(Me)2, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C2 fluoroalkyl, C1-C4 alkoxy, C1-C2 fluoroalkoxy, C3-C4 alkenyloxy, C3-C4 alkenyloxy, C3-C6 cycloalkyl, C3-C6 cycloalkyloxy, C3-C6 cycloalkyl C1-C2 alkyloxy, C1-C3 alkylthio, and C1-C3 alkylsulfonyl; or - 1 or 2 substituents independently selected from hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, methylthio, methylsulfonyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl; R 2 is hydrogen, hydroxy, nitro, halogen, mercapto, amino, cyano, C1-C6 alkyl, C1-C2 fluoroalkyl, C3-C5 alkenyl, C3-C5 alkynyl, C1-C3 alkoxy C2-C3 alkyl, C3-C6 cycloalkyl, or C3-C6 cycloalkyl C 1-2 alkyl, C1-C4 alkoxy, C1-C2 fluoroalkoxy, C3-C5 alkenyloxy, C3-C5 alkenyloxy, C3-C6 cycloalkyl, C3-C6 cycloalkyloxy, C3-C6 cycloalkyl C1-C2 alkyloxy, C1-C4 alkylamino, di-C1-C4 alkylamino, C3-C5 alkenylamino, C3-C5 alkynylamino, C1-C3 alkylthio, or C1-C3 alkylsulfonyl; or R 2 is phenyl, phenyl C1-C2 alkyl, heteroaryl, heteroaryl C1-C2 alkyl, heterocyclic group, heterocyclic group C1-C2 alkyl, C3-C6 cycloalkyl, or C3-C6 cycloalkyl C 1-2 alkyl; wherein the heteroaryl moiety is a 5- or 6-membered monocyclic aromatic ring containing 1, 2 or 3 heteroatoms independently selected from N, O and S, provided that no more than one is O or S; wherein the heterocyclic moiety is a 4- to 6-membered non-aromatic ring containing 1 or 2 heteroatoms independently selected from N, O and S, provided that no more than one is O or S; and wherein any of the cycloalkyl, phenyl, heteroaryl and heterocyclic moieties is unsubstituted or substituted with the following: - A single substituent selected from hydroxy, nitro, halogen, mercapto, amino, cyano, NHMe, N(Me)2, C1-C4 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, C1-C2 fluoroalkyl, C1-C4 alkoxy, C1-C2 fluoroalkoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, C3-C6 cycloalkyl, C1-C3 alkylthio, and C1-C3 alkylsulfonyl; or - 1 or 2 substituents independently selected from hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, methylthio, methylsulfonyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl; G is selected from G-1, G-2, G-3, and G-4, wherein: G-1 is phenyl or phenoxy, wherein the phenyl or phenoxy is unsubstituted or substituted by the following: - A single substituent selected from hydroxyl, nitro, halogen, mercapto, amino, cyano, NHMe, N(Me)2, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C2 fluoroalkyl, C1-C4 alkoxy, C1-C2 fluoroalkoxy, C3-C4 alkenyloxy, C3-C4 alkenyloxy, C3-C6 cycloalkyl, C3-C6 cycloalkyloxy, C3-C6 cycloalkyl C1-C2 alkyloxy, C1-C3 alkylthio, and C1-C3 alkylsulfonyl; or - 1 or 2 substituents independently selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, methylthio, methylsulfonyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl; G-2 is a 5- or 6-membered monocyclic heteroaryl or heteroaryloxy; wherein the heteroaryl contains 1, 2 or 3 heteroatoms each independently selected from N, O and S, provided that no more than one is O or S; and wherein the heteroaryl or heteroaryloxy is unsubstituted or substituted with: - A single substituent selected from hydroxyl, nitro, halogen, mercapto, amino, cyano, NHMe, N(Me)2, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C2 fluoroalkyl, C1-C4 alkoxy, C1-C2 fluoroalkoxy, C3-C4 alkenyloxy, C3-C4 alkenyloxy, C3-C6 cycloalkyl, C3-C6 cycloalkyloxy, C3-C6 cycloalkyl C1-C2 alkyloxy, C1-C3 alkylthio, and C1-C3 alkylsulfonyl; or - 1 or 2 substituents independently selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, methylthio, methylsulfonyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl; G-3 is a 9- or 10-membered heterobicyclic system containing 1, 2 or 3 heteroatoms each independently selected from N, O and S, provided that no more than one is O or S; wherein the heterobicyclic system is saturated, partially unsaturated, or aromatic; and wherein the heterobicyclic system is unsubstituted or substituted with: a single substituent selected from hydroxyl, nitro, halogen, mercapto, amino, cyano, NHMe, N(Me)2, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C2 fluoroalkyl, C1-C4 alkoxy, C1-C2 fluoroalkoxy, C3-C4 alkenyloxy, C3-C4 alkenyloxy, C3-C6 cycloalkyl, C3-C6 cycloalkyloxy, C3-C6 cycloalkyl C1-C2 alkyloxy, C1-C3 alkylthio, and C1-C3 alkylsulfonyl; G-4 is a 9- or 10-membered carbobicyclic system; wherein said carbobicyclic system is saturated, partially unsaturated, or aromatic; and wherein said carbobicyclic system is unsubstituted or substituted with: a single substituent selected from hydroxy, nitro, halogen, mercapto, amino, cyano, NHMe, N(Me)2, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C2 fluoroalkyl, C1-C4 alkoxy, C1-C2 fluoroalkoxy, C3-C4 alkenyloxy, C3-C4 alkenyloxy, C3-C6 cycloalkyl, C3-C6 cycloalkyloxy, C3-C6 cycloalkyl C1-C2 alkyloxy, C1-C3 alkylthio, and C1-C3 alkylsulfonyl.

2. The compound according to claim 1, wherein R 1 is phenyl, pyridine, pyrazine, pyrimidine, or pyridazine, wherein the phenyl, pyridine, pyrazine, pyrimidine, or pyridazine is unsubstituted or substituted by one or two substituents, such as a single substituent, and the substituents are independently selected from hydroxy, halogen, mercapto, amino, nitro, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, isopropoxy, tert-butoxy, propargyloxy, NHMe, N(Me)2, methylthio, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy.

3. The compound according to claim 1 or claim 2, wherein R 1 is 3-cyclopropyl-2-fluorophenyl, 3-(trifluoromethyl)phenyl, 3-chloro-2-fluorophenyl, 3-chlorophenyl, 5-cyanopyridin-3-yl, 3-methylphenyl, phenyl, 3-cyclopropylphenyl, 3-(difluoromethyl)phenyl, 3-(difluoromethoxy)phenyl, 3-(trifluoromethyl)-2-fluorophenyl, 3-methoxyphenyl, or 2,3-difluorophenyl.

4. The compound according to any one of claims 1 to 3, wherein R 2 is hydrogen, hydroxy, halogen, mercapto, amino, cyano, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkoxy, C1-C4-fluoroalkyl, C1-C4-fluoroalkoxy, or C3-C4-cycloalkyl.

5. The compound according to any one of claims 1 to 4, wherein R 2 is hydrogen, methyl, ethyl, or cyclopropyl.

6. The compound according to any one of claims 1 to 5, wherein G is an unsubstituted or 1- or 2-substituted phenyl or phenoxy, and the substituents are each independently selected from hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, methylthio, methylsulfonyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl; or wherein G is an unsubstituted or 1- or 2-substituted pyridine, and the substituents are each independently selected from hydroxy, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, prop-2-ynyloxy, prop-1-ynyloxy, difluoromethoxy, and cyclopropyl.

7. The compound according to any one of claims 1 to 6, wherein G is 2,4-dimethylphenyl, 2,4-dichlorophenyl, 4-bromo-2-methylphenyl, 4-bromo-2-chlorophenyl, 2,6-dichloro-3-pyridyl, 4,6-dichloro-3-pyridyl, 3,5-dichloro-2-pyridyl, 3,4-dimethylphenyl, 2-chloro-4-methylphenyl, 2-methyl-4-bromophenyl, 2-methyl-4-chlorophenyl, or 2,4-difluorophenyl.

8. An agrochemical composition comprising a fungicidally effective amount of the compound according to any one of claims 1 to 7.

9. The composition according to claim 8, further comprising at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

10. A method for controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of the compound according to any one of claims 1 to 7, or the composition according to claim 8 or 9, is applied to the plants, parts thereof, or the locus thereof.

11. Use of the compound according to any one of claims 1 to 7 as a fungicide.

12. A plant propagation material, such as a seed, comprising the compound according to any one of claims 1 to 7 or the composition according to claim 8 or 9, or treated with the compound or the composition, or having the compound or the composition attached thereto.

13. A compound having the formula (II-i), (X-i), or (XXI-i): wherein X 3 is a leaving group selected from fluorine, chlorine, bromine, iodine, BF3K, B(OH)2, and B(pinacol); X 4 is OH, a halogen, or OR 1 ; and R 1 、R 2 and G are as defined in any one of claims 1 to 7.

14. A compound having the formula (IV-i), (XX-i), or (XXXVI-i): wherein X 7 is chlorine, bromine, iodine, or O-trifluoromethanesulfonyl; X 8 is OH, a halogen, or O-R 1 ; X 9 is halogen, methyl, trifluoromethanesulfonyl - O -, cyano, COOH, or - C(O)C1 - C4 alkoxy; and R 1 and R 2 is as defined in any one of claims 1 to 5.

15. A compound having the formula (VIII-i), (XV-i), or (XLIV-i): wherein X 3 is a leaving group selected from fluorine, chlorine, bromine, iodine, BF3K, B(OH)2, and B(pinacol); X 8 is OH, a halogen, or O-R 1 ; Z is OH, SH, chlorine, bromine, or iodine; and R 1 、R 2 and G are as defined in any one of claims 1 to 7.

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