Oxadiazinylpyridazines as novel fungicides.

Abstract

The present invention relates to oxadiazinylpyridazine compounds and their use for controlling plant pathogenic microorganisms, such as plant pathogenic fungi. The present invention also relates to processes and intermediates for making these compounds.

Description

[Technical Field]

[0001] The present invention relates to oxadiazinylpyridazine compounds and their use for controlling plant pathogenic microorganisms, such as plant pathogenic fungi. The invention also relates to processes and intermediates for making these compounds.

[0002] A large number of crop protection agents have been developed to combat or prevent the spread of microorganisms.However, there is still a need to develop new compounds themselves, in order to provide compounds that have low toxicity, high selectivity, improved physicochemical properties, or can be used at low application rates while enabling effective pest control, and are effective against a wide range of plant pathogenic microorganisms such as fungi.It is also desirable to provide new compounds to prevent the development of resistance.

[0003] In accordance with the present invention, there are provided novel compounds for controlling plant pathogenic microorganisms, such as fungi, which are superior in at least some of their aspects to known compounds and compositions.

[0004] WO2007 / 031213 describes dioxazine- and oxadiazine-substituted arylamides for controlling pests. WO2008 / 009406 discloses heteroaryl-substituted pyridazines as fungicides. WO2020 / 127780 discloses heterocyclyl-substituted pyridazines as fungicides. Detailed Description of the Invention

[0005] Compounds of formula (I) The present invention provides a compound of formula (I-1): [ka] [In the formula, R 3 and R 4 is hydrogen, R 5 is hydrogen, L is methylene, R 6 is phenyl, the phenyl is substituted with two substituents independently selected from chloro, bromo, and methyl; R 7 is chloro, methyl, ethyl or ethenyl; the methyl, ethyl, and ethenyl are optionally substituted with one or two substituents independently selected from the group consisting of fluoro, chloro, hydroxy, methoxy, and ethoxy; R 8 is hydrogen, R 9 is hydrogen or formyl, Q is phenyl; the phenyl is substituted with one or two substituents independently selected from fluoro, chloro, methyl, ethyl, and cyclopropyl; wherein the cyclopropyl is optionally substituted with one or two substituents independently selected from the group consisting of fluoro and chloro; It relates to its N-oxides, salts, hydrates, and hydrates of salts and N-oxides.

[0006] The present invention relates to compositions comprising at least one compound of formula (I) as defined herein and at least one agriculturally suitable adjuvant.

[0007] The present invention also relates to the use of a compound of formula (I) as defined herein or a composition as defined herein for controlling phytopathogenic fungi.

[0008] The present invention relates to a method for controlling plant pathogenic fungi, which method comprises applying to plants, plant parts, seeds, fruits or the soil in which the plants grow at least one compound of formula (I) as defined herein or a composition as defined herein.

[0009] The present invention also relates to processes and intermediates for preparing compounds of formula (I).

[0010] Unless otherwise stated, the following definitions apply to the substituents and radicals used.

[0011] As used herein, the term "halogen" refers to a fluorine, chlorine, bromine or iodine atom.

[0012] The term "C1-C6 alkoxy" as used herein refers to a group of formula (C1-C6 alkyl)-O-, where the term "C1-C6 alkyl" is as defined herein. Examples of C1-C6 alkoxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, n-hexyloxy, 1-methylpentoxy, Examples include 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy, and 1-ethyl-2-methylpropoxy. This definition also applies to alkoxy as part of a compound substituent, such as alkoxyalkyl, alkoxyalkoxy, unless otherwise defined.

[0013] The term "leaving group," as used herein, is understood to mean a group that leaves a compound in a substitution or elimination reaction, such as a halogen atom, a trifluoromethanesulfonate ("triflate") group, an alkoxy, methanesulfonate, p-toluenesulfonic acid, and the like.

[0014] Variable R 3 , R 4 , R 5 , R 6 , R 7, R 8 The term "as described herein" when referring to and Q includes by reference the broad definition of the variable, as well as the preferred, more preferred, and even more preferred definitions, if any.

[0015] Compounds resulting from combinations that violate the laws of nature and would therefore be excluded by a person skilled in the art based on their specialized knowledge are not encompassed herein, for example, ring structures having three or more adjacent oxygen atoms are excluded.

[0016] The compounds of formula (I) may suitably be in their free form, in the form of a salt, an N-oxide or in the form of a solvate (eg a hydrate).

[0017] Depending on the nature of the substituents, the compound of formula (I) can exist in different stereoisomeric forms.These stereoisomers are, for example, enantiomers, diastereomers, atropisomers or geometric isomers.Therefore, the present invention encompasses both pure stereoisomers and any mixtures of these isomers.When a compound can exist in two or more tautomeric forms in equilibrium, the reference to the compound by describing one tautomer is considered to include all tautomeric forms.

[0018] Any compound of the present invention can exist in one or more geometric isomeric forms depending on the number of double bonds in the compound. Geometric isomers due to the nature of the substituents on the double bond or ring can exist in cis (=Z-) or trans (=E-) form. Therefore, the present invention equally relates to all geometric isomers and all possible mixtures in all ratios.

[0019] Depending on the nature of the substituents, the compounds of formula (I) may exist in the form of the free compound and / or its salts, eg pesticidal active salts.

[0020] Pesticide active salts include acid addition salts of inorganic and organic acids, as well as salts of conventional bases. Examples of inorganic acids are hydrohalic acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide, sulfuric acid, phosphoric acid, and nitric acid, as well as acid salts such as sodium bisulfate and potassium bisulfate. Useful organic acids include, for example, formic acid, carbonic acid, alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, and propionic acid, as well as glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, saturated, monounsaturated, or diunsaturated fatty acids having 6 to 20 carbon atoms, alkyl sulfate monoesters, alkyl sulfonic acids (sulfonic acids having linear or branched alkyl groups having 1 to 20 carbon atoms), aryl sulfonic acids, or aryl disulfonic acids (sulfonic acids having one or two sulfonic groups). Examples of suitable phosphonic acids include aromatic phosphonic acids (phenyl and naphthyl groups having one or two phosphonic acid groups), alkylphosphonic acids (phosphonic acids having a linear or branched alkyl group having 1 to 20 carbon atoms), arylphosphonic acids, and aryldiphosphonic acids (phenyl and naphthyl groups having one or two phosphonic acid groups), and the alkyl and aryl groups may have further substituents such as p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, and 2-acetoxybenzoic acid.

[0021] Solvates of the compounds of the invention or their salts are stoichiometric compositions of the compound and a solvent.

[0022] The compounds of the present invention may exist in multiple crystalline and / or amorphous forms. Crystalline forms include non-solvated crystalline forms, solvates and hydrates.

[0023] The present invention provides compounds of formula (I): [ka] [In the formula, R 3 and R 4 is hydrogen, R 5 is hydrogen, L is methylene; R 6 is phenyl, the phenyl is substituted with two substituents independently selected from chloro, bromo, and methyl; R 7 is chloro or methyl, R 8 is hydrogen, Q is phenyl; the phenyl is substituted with one or two substituents independently selected from fluoro, chloro, methyl, ethyl, and cyclopropyl; wherein the cyclopropyl is optionally substituted with one or two fluoro substituents; It also relates to the N-oxides, salts, hydrates, and hydrates of the salts and N-oxides.

[0024] The present invention provides R 3 and R 4 is hydrogen, R 5 is hydrogen, L is methylene; R 6 is the formula [ka] [In the formula, § 1 is the bond to L, R 6S1 is chloro, bromo or methyl, R 6S2 is chloro or methyl] is the basis of R 7 is chloro, methyl, dichloromethyl, 1-fluoroethyl, 1-hydroxyethyl or 1-ethoxyethen-1-yl; R 8 is hydrogen, R 9 is hydrogen or formyl, Q is the formula [ka] [In the formula, § 2 is the bond to the oxygen atom, Q S1 is hydrogen or fluoro, Q S2 is chloro, methyl, ethyl, cyclopropyl, 1-fluorocyclopropyl, or 1-chlorocyclopropyl] The present invention also relates to compounds of formula (I-1), the N-oxides, salts, hydrates, and hydrates of the salts and N-oxides thereof, which are groups of the formula (I-1)

[0025] Preferably, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis. R 3 and R 4 is hydrogen, R 5 is hydrogen, L is methylene; R 6 is the formula [ka] [In the formula, § 1 is the bond to L, R 6S1 is chloro, bromo or methyl, R 6S2 is chloro or methyl] is the basis of R 7 is chloro or methyl, R 8 is hydrogen, Q is the formula [ka] [In the formula, § 2 is the bond to the oxygen atom, Q S1 is hydrogen or fluoro, Q S2 is chloro, methyl, ethyl, or 1-fluorocyclopropyl] The present invention also relates to compounds of formula (I), the N-oxides, salts, hydrates and hydrates of the salts and N-oxides thereof, wherein

[0026] The present invention relates to a compound of formula (I-1-A): [ka] [In the formula, R 6 is phenyl, the phenyl is substituted with two substituents independently selected from chloro, bromo, and methyl; R 7 is chloro, methyl, ethyl or ethenyl; the methyl, ethyl, and ethenyl are optionally substituted with one or two substituents independently selected from the group consisting of fluoro, chloro, hydroxy, methoxy, and ethoxy; R 8 is hydrogen, R 9 is hydrogen or formyl, Q is phenyl; the phenyl is substituted with one or two substituents independently selected from fluoro, chloro, methyl, ethyl, and cyclopropyl; wherein the cyclopropyl is optionally substituted with one or two substituents independently selected from the group consisting of fluoro and chloro; It relates to its N-oxides, salts, hydrates, and hydrates of salts and N-oxides.

[0027] Most preferably, the present invention relates to a compound of formula (I-1), which is one of the following: (I-001) (5RS)-5-(2-bromo-4-methylbenzyl)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I-002) (5RS)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5-(2,4-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-003) (5RS)-5-(2-chloro-4-methylbenzyl)-3-[3-(2-fluoro-3-methylphenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I-004) (5RS)-5-(2-chloro-4-methylbenzyl)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I-005) (5RS)-3-[6-chloro-3-(2-fluoro-3-methylphenoxy)pyridazin-4-yl]-5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-006) (5RS)-5-(2-bromo-4-methylbenzyl)-3-[3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I-007) (5RS)-5-(2,4-dichlorobenzyl)-3-[3-(2-fluoro-3-methylphenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I-008) (5RS)-5-(3,5-dimethylbenzyl)-3-[3-(2-fluoro-3-methylphenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I-009) (5RS)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5-(3,5-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-010) (5RS)-3-[3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5-(3,5-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-011) (5RS)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5-(2,5-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-012) (5RS)-3-[3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5-(2,5-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-013) (5RS)-5-(2,5-dimethylbenzyl)-3-[3-(2-fluoro-3-methylphenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I-014) (5RS)-5-(2,4-dimethylbenzyl)-3-[3-(3-ethyl-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I-015) (5RS)-5-(2,4-dimethylbenzyl)-3-{3-[3-(1-fluorocyclopropyl)phenoxy]-6-methylpyridazin-4-yl}-5,6-dihydro-4H-1,2,4-oxadiazine, (I-016) 1-{6-(3-cyclopropylphenoxy)-5-[5-(2,4-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazin-3-yl]pyridazin-3-yl}ethanol, (I-017) (5RS)-3-[6-chloro-3-(3-chlorophenoxy)pyridazin-4-yl]-5-(2-chloro-4-methylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-018) (5RS)-3-{3-(3-cyclopropyl-2-fluorophenoxy)-6-[(1RS)-1-fluoroethyl]pyridazin-4-yl}-5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-019) (5RS)-3-[3-(3-cyclopropylphenoxy)-6-(1-ethoxyvinyl)pyridazin-4-yl]-5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-020) (5RS)-3-[3-(3-cyclopropyl-2-fluorophenoxy)-6-(1-ethoxyvinyl)pyridazin-4-yl]-5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-021) (5S)-3-[3-(3-cyclopropyl-2-fluorophenoxy)-6-(dichloromethyl)pyridazin-4-yl]-5-(2,4-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-022) (5RS)-3-{3-[3-(1-chlorocyclopropyl)phenoxy]-6-methylpyridazin-4-yl}-5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-023) 1-{6-(3-cyclopropyl-2-fluorophenoxy)-5-[5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazin-3-yl]pyridazin-3-yl}ethanol, (I-024) (5RS)-3-{6-chloro-3-[3-(1-chlorocyclopropyl)phenoxy]pyridazin-4-yl}-5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-025) (5RS)-3-[6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)pyridazin-4-yl]-5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine-4-carbaldehyde.

[0028] Most preferably, the present invention relates to compounds of formula (I) and salts, hydrates and hydrates of salts thereof, wherein the compound of formula (I) is one of the following: (I.001) (5RS)-5-(2-bromo-4-methylbenzyl)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I.002) (5RS)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5-(2,4-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-003) (5RS)-5-(2-chloro-4-methylbenzyl)-3-[3-(2-fluoro-3-methylphenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I.004) (5RS)-5-(2-chloro-4-methylbenzyl)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I.005) (5RS)-3-[6-chloro-3-(2-fluoro-3-methylphenoxy)pyridazin-4-yl]-5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I.006) (5RS)-5-(2-bromo-4-methylbenzyl)-3-[3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I.007) (5RS)-5-(2,4-dichlorobenzyl)-3-[3-(2-fluoro-3-methylphenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I.008) (5RS)-5-(3,5-dimethylbenzyl)-3-[3-(2-fluoro-3-methylphenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I.009) (5RS)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5-(3,5-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I.010) (5RS)-3-[3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5-(3,5-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I.011) (5RS)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5-(2,5-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I.012) (5RS)-3-[3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5-(2,5-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I.013) (5RS)-5-(2,5-dimethylbenzyl)-3-[3-(2-fluoro-3-methylphenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I.014) (5RS)-5-(2,4-dimethylbenzyl)-3-[3-(3-ethyl-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I.015) (5RS)-5-(2,4-dimethylbenzyl)-3-{3-[3-(1-fluorocyclopropyl)phenoxy]-6-methylpyridazin-4-yl}-5,6-dihydro-4H-1,2,4-oxadiazine.

[0029] The compounds of formula (I) are a subgroup of the compounds of formula (I-1).

[0030] Compounds resulting from combinations that violate the laws of nature and would therefore be excluded by a person skilled in the art based on their specialized knowledge are not encompassed herein, for example, ring structures having three or more adjacent oxygen atoms are excluded.

[0031] The compounds of formula (I) may suitably be in their free form, in the form of a salt, an N-oxide or in the form of a solvate (eg a hydrate).

[0032] Depending on the nature of substituents, compounds of formula (I) can exist in different stereoisomeric forms.These stereoisomers are, for example, enantiomers, diastereomers, atropisomers or geometric isomers.Therefore, the present invention encompasses both pure stereoisomers and any mixtures of these isomers.When a compound can exist in two or more tautomeric forms in equilibrium, the description of one tautomer of the compound is considered to include all tautomeric forms.

[0033] Any compound of the present invention can exist in one or more geometric isomeric forms depending on the number of double bonds in the compound. Geometric isomers due to the nature of the substituents on the double bond or ring can exist in cis (=Z-) or trans (=E-) form. Therefore, the present invention equally relates to all geometric isomers and all possible mixtures in all ratios.

[0034] Depending on the nature of the substituents, the compounds of formula (I) may exist in the form of the free compound and / or its salts, eg pesticidal active salts.

[0035] Pesticide active salts include acid addition salts of inorganic and organic acids, as well as salts of conventional bases. Examples of inorganic acids are hydrohalic acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide, sulfuric acid, phosphoric acid, and nitric acid, as well as acid salts such as sodium bisulfate and potassium bisulfate. Useful organic acids include, for example, formic acid, carbonic acid, alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, and propionic acid, as well as glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, saturated, monounsaturated, or diunsaturated fatty acids having 6 to 20 carbon atoms, alkyl sulfate monoesters, alkyl sulfonic acids (sulfonic acids having linear or branched alkyl groups having 1 to 20 carbon atoms), aryl sulfonic acids, or aryl disulfonic acids (sulfonic acids having one or two sulfonic groups). Examples of suitable phosphonic acids include aromatic phosphonic acids (phenyl and naphthyl groups having one or two phosphonic acid groups), alkylphosphonic acids (phosphonic acids having a linear or branched alkyl group having 1 to 20 carbon atoms), arylphosphonic acids, and aryldiphosphonic acids (phenyl and naphthyl groups having one or two phosphonic acid groups), and the alkyl and aryl groups may have further substituents such as p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, and 2-acetoxybenzoic acid.

[0036] Solvates of the compounds of the invention or their salts are stoichiometric compositions of the compound and a solvent.

[0037] The compounds of the present invention may exist in multiple crystalline and / or amorphous forms. Crystalline forms include non-solvated crystalline forms, solvates and hydrates.

[0038] Non-limiting examples of suitable Q groups include those Q groups listed in the "Q" column of Table 1.

[0039] The R identified above 3 , R 4 , R 5 , R 6 , R 7 , R8 , R 9 The definitions of L and Q (both broad and preferred, more preferred, and even more preferred) can be combined in various ways, and thus combinations of these definitions provide subclasses of compounds of the invention, such as those disclosed below.

[0040] The present invention also relates to any compound of formula (I) disclosed in Table 1.

[0041] The compounds of formula (I) can be used as fungicides (for controlling phytopathogenic fungi), in particular in methods for controlling phytopathogenic fungi which comprise applying one or more compounds of formula (I) to plants, plant parts, seeds, fruit or the soil in which the plants grow.

[0042] Methods for preparing compounds of formula (I) and intermediates The present invention relates to methods for preparing compounds of formula (I-1), formula (I), and intermediates thereof. The methods described herein can be applied, mutatis mutandis, to the preparation of compounds of formula (I) and (I-1). Unless otherwise indicated, the group R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , L and Q have the meanings given above for compounds of formula (I). These definitions apply not only to the final product of formula (I) but also to all intermediates.

[0043] The compounds of formula (Ia) are various subsets of formula (I). The compounds of formulas (Ia-1) through (Ia-6) are various subsets of formula (Ia). All substituents of formulas (Ia) and (Ia-1) through (Ia-6) are as defined above for formula (I) unless otherwise specified.

[0044] The compounds of formula (I) can be prepared by a variety of routes analogous to known methods (see the Examples and references therein). Non-limiting examples of suitable methods are described herein.

[0045] A compound of formula (I) can be obtained directly by carrying out Processes A through E, or can be obtained by converting or derivatizing another compound of formula (I) prepared according to the processes described herein. For example, a compound of formula (I) can be converted to another compound of formula (I) by replacing one or more substituents of the starting compound of formula (I) with other substituents.

[0046] The processes described herein can be suitably carried out using one or more inert organic solvents customarily used for the reactions under consideration. Suitable inert organic solvents can be selected from the following: aliphatic, alicyclic or aromatic hydrocarbons (e.g., petroleum ether, pentane, hexane, heptane, cyclohexane, methylcyclohexane, ligroin, benzene, toluene, xylene or decalin), halogenated aliphatic, alicyclic or aromatic hydrocarbons (e.g., chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or trichloroethane), ethers (e.g., diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole), ketones (e.g., acetone, methyl ethyl ether, methyl ketone ... methyl isopropyl ketone and methyl isobutyl ketone, etc.), esters (e.g., methyl acetate, ethyl acetate or butyl acetate), alcohols (e.g., methanol, ethanol, propanol, isopropanol, butanol, tert-butanol), nitriles (e.g., acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile), amides (e.g., N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-1-formanilide, N-methylpyrrolidone or hexamethylphosphoric triamide), sulfoxides (e.g., dimethyl sulfoxide) or sulfones (e.g., sulfolane), ureas (e.g., 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone) or mixtures thereof.

[0047] Some processes described herein require or can optionally employ one or more inorganic or organic bases conventionally used in such reactions. Examples of suitable inorganic and organic bases include, but are not limited to, alkaline earth or alkali metal carbonates (e.g., sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, or cesium carbonate), alkali metal hydrides (e.g., sodium hydride), alkaline earth or alkali metal hydroxides (e.g., sodium hydroxide, calcium hydroxide, potassium hydroxide, or other ammonium hydroxide derivatives), alkaline earth, alkali, or ammonium fluorides (e.g., potassium fluoride, cesium fluoride, or tetrabutylammonium fluoride), alkali or alkaline earth metal acetates (e.g., sodium acetate, lithium acetate, potassium acetate, or calcium acetate), and alkali metal hydrides (e.g., sodium hydroxide, calcium hydroxide, potassium hydroxide, or other ammonium hydroxide derivatives). Examples of suitable bases include amines such as methylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dicyclohexylmethylamine, N,N-diisopropylethylamine, N-methylpiperidine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN), diazabicycloundecene (DBU), quinuclidine, 3-acetoxyquinuclidine, guanidine, or aromatic bases such as pyridine, picoline, lutidine, or collidine.

[0048] Some of the processes described herein can optionally be carried out in the presence of a transition metal catalyst, such as a salt or complex of a metal (e.g., copper or palladium), and, where appropriate, in the presence of a ligand.

[0049] Suitable copper salts or complexes and hydrates thereof include, but are not limited to, copper metal, copper(I) iodide, copper(I) chloride, copper(I) bromide, copper(II) chloride, copper(II) bromide, copper(II) oxide, copper(I) oxide, copper(II) acetate, copper(I) acetate, copper(I) thiophene-2-carboxylate, copper(I) cyanide, copper(II) sulfate, copper(II) bis(2,2,6,6-tetramethyl-3,5-heptanedionate), copper(II) trifluoromethanesulfonate, tetrakis(acetonitrile)copper(I) hexafluorophosphate, tetrakis(acetonitrile)copper(I) tetrafluoroborate.

[0050] Ethylenediamine, N,N'-dimethylethylenediamine, N,N'-dimethylethylenediamine, rac-trans-1,2-diaminocyclohexane, rac-trans-N,N'-dimethylcyclohexane-1,2-diamine, 1,1'-binaphthyl-2,2'-diamine, N,N,N',N'-tetramethylethylenediamine, proline, N,N-dimethylglycine, quinolin-8-ol, pyridine, 2-aminopyridine, 4- (Dimethylamino)pyridine, 2,2'-bipyridyl, 2,6-di(2-pyridyl)pyridine, 2-picolinic acid, 2-(dimethylaminomethyl)-3-hydroxypyridine, 1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, 2,9-dimethyl-1,10-phenanthroline, 4,7-dimethoxy-1,10-phenanthroline, N,N'-bis[(E)-pyridin-2-ylmethylidene]cyclohexyl It is also possible to generate the appropriate copper complex in situ in the reaction mixture by separately adding a copper salt and a ligand or salt to the reaction, such as 1H-pyrrole-2-carboxylic acid, 1,1,1-tris(hydroxymethyl)ethane, n-butylimidazole, ethylene glycol, 2,2,6,6-tetramethylheptane-3,5-dione, 2-(2,2-dimethylpropanoyl)cyclohexanone, acetylacetone, dibenzoylmethane, 2-(2-methylpropanoyl)cyclohexanone, biphenyl-2-yl(di-tert-butyl)phosphane, ethylenebis(diphenylphosphine), N,N-diethylsalicylamide, 2-hydroxybenzaldehyde oxime, oxo[(2,4,6-trimethylphenyl)amino]acetic acid, or 1H-pyrrole-2-carboxylic acid.

[0051] Suitable palladium salts or complexes include, but are not limited to, palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium(0), bis(dibenzylideneacetone)palladium(0), tris(dibenzylideneacetone)dipalladium(0), bis(triphenylphosphine)palladium(II) dichloride, [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II), bis(cinnamyl)dichlorodipalladium(II), bis(allyl)-dichlorodipalladium(II) or [1,1′-bis(di-tert-butylphosphino)ferrocene]dichloropalladium(II).

[0052] Triethylphosphine, tri-tert-butylphosphine, tri-tert-butylphosphonium tetrafluoroborate, tricyclohexylphosphine, 2-(dicyclohexylphosphino)biphenyl, 2-(di-tert-butylphosphino)biphenyl, 2-(dicyclohexylphosphino)-2'-(N,N-dimethylamino)biphenyl, 2-(tert-butylphosphino)-2'-(N,N-dimethylamino)biphenyl, 2-di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2,6'-dimethoxybiphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, triphenylphosphine, tris-(o-tolyl)phosphine, 3-(diphenylphosphine Sodium 2-(dicyclohexylphosphino)benzenesulfonate, tris-(2-methoxyphenyl)phosphine, 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)ethane, 1,4-bis(dicyclohexylphosphino)butane, 1,2-bis(dicyclohexylphosphino)ethane, 2-(dicyclohexylphosphino)-2'-(N,N-di (methylamino)-biphenyl, 1,1'-bis(diphenylphosphino)-ferrocene, (R)-(-)-1-[(S)-2-diphenylphosphino)ferrocenyl]ethyldicyclohexylphosphine, tris-(2,4-tert-butyl-phenyl)phosphite, di(1-adamantyl)-2-morpholinophenylphosphine or 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride.

[0053] Suitable catalysts and / or ligands can be selected from commercial catalogs such as "Metal Catalysts for Organic Synthesis" by Strem Chemicals, or from review articles (Chemical Society Reviews (2014), 43, 3525, Coordination Chemistry Reviews (2004), 248, 2337 and references therein).

[0054] Some of the processes described herein have been previously described in the literature (Nature chemistry review, (2017) 0052 and references therein; Science (2016) 352, 6291, 1304; Org. Lett. 2016, 18, 4012; J. Org. Chem 2016, 81, 6898; J. Am. Chem. Soc. 2016, 138, 12715; J. Am. Chem. Soc. 2016, 138, 13862; J. Am. Chem. Soc. 2016, 138, 8034; J. Org. Chem. 2016, 81, 12525; J. Org. Chem. 2015, 80, This can be carried out by metallaphotoredox catalysis according to the method reported in [Publication ID No. 7642]. This process is then carried out in the presence of a photosensitizer, such as an Ir or Ru complex or an organic dye, and a metal catalyst, such as a Ni complex. This reaction can be carried out in the presence of a ligand, and, if appropriate, a base, under irradiation with blue or white light.

[0055] Suitable photosensitizers include, but are not limited to, [Ir(dFCF3ppy)2(bpy)]PF6 (dFCF3ppy = 2-(2,4-difluorophenyl)-5-trifluoromethylpyridine, bpy = 2,2'-bipyridine), [Ir(dFCF3ppy)2(dtbbpy)]PF6 (dtbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine), Ir(ppy)2(dtbbpy)PF6 (ppy = 2-phenylpyridine), Ir(ppy)2(bpy)PF6, Ir(dFppy)3PF6 (dFCF3ppy = 2-(2,4-difluorophenyl)pyridine), fac-Ir(ppy)3, (Ir[diF(5- Examples include Ir(III) photocatalysts such as [diF(5-Me)ppy]2(tetraMePhen)PF6 (diF(5-Me)ppy = 2-(2,4-difluorophenyl)-5-methylpyridine, tetraMePhen = 3,4,7,8-tetramethyl-1,10-phenanthroline), Ru(II) photocatalysts such as Ru(bpy)3Cl2 or Ru(bpy)3(PF6)2, or organic dyes such as 9-mesityl-10-acridinium perchlorate or tetrafluoroborate, or 2,4,5,6-tetra-9H-carbazol-9-yl-1,3-benzenedicarbonitrile, 9-fluorenone, and 9,10-phenanthrenequinone.

[0056] Suitable nickel catalysts include, but are not limited to, bis(1,5-cyclooctadiene)nickel(0), in anhydrous or hydrated form or as a dimethoxyethane complex, nickel(II) chloride, nickel(II) bromide, nickel(II) iodide, nickel(II) acetylacetonate, and nickel(II) nitrate hexahydrate. These nickel catalysts can be used in combination with ligands such as 2,2'-bipyridine, 4,4'-di-tert-butyl-2,2'-bipyridine, 4,4'-dimethoxy-2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, or phenanthrolines such as 1,10-phenanthroline, 4,7-dimethyl-1,10-phenanthroline, or 4,7-dimethoxy-1,10-phenanthroline, or diamines such as N,N,N',N'-tetramethylethylenediamine, or diones such as tetramethylheptanedione.

[0057] The processes described herein can be carried out at temperatures ranging from -105°C to 250°C, preferably from -78°C to 185°C.

[0058] The reaction time varies as a function of the scale of the reaction and the reaction temperature, but is generally between a few minutes and 48 hours.

[0059] The processes described herein are generally carried out under normal pressure, however, it is also possible to operate under elevated or reduced pressure.

[0060] The processes described herein can optionally be carried out under microwave irradiation at normal or elevated pressure.

[0061] In the processes described herein, the starting materials are generally used in approximately equimolar amounts, however, it is also possible to use one of the starting materials in a relative excess.

[0062] Methods for preparing compounds of formula (I) Process A R 3 , R 4 , R 5, R 6 , R 7 , R 8 Compounds of formula (Ia), wherein L and Q are defined as above, are When W is hydrogen, the compound of formula (4) 3 , R 4 , R 5 , R 6 , R 7 , R 8 , L and Q are as defined above) with a dehydrating agent, optionally in the presence of a base, to give the compound of formula (Ia) directly, or or When W is an amino protecting group such as tert-butoxycarbonyl, benzyl, allyl, or (4-methoxyphenyl)methyl, compounds of formula (4) can be treated with a dehydrating agent, optionally in the presence of a base, followed by a deprotection step, as shown in Scheme 1, to give compounds of formula (Ia). It can be produced by

[0063] [ka]

[0064] Compounds of formula (Ia) can be obtained by treating compounds of formula (4) with a dehydrating agent such as POCl3, PO5, or triflic anhydride, optionally in the presence of a base. Such methods for forming the oxadiazine ring are known and are described in the literature (J. Med. Chem. 2017, 60, 2383-2400). The reaction can be carried out in a conventional inert organic solvent. It is preferable to use optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; ethers such as diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; nitriles such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; alcohols such as ethanol or isopropanol.

[0065] If W represents an amino-protecting group, step 3 is followed by an additional deprotection step using reaction conditions described in the literature (Greene's Protective Groups in Organic Synthesis; Peter GM Wuts; Wiley; Fifth Edition; 2014; 895-1194). For example, a tert-butoxycarbonyl group can be removed in an acidic medium such as hydrochloric acid or trifluoroacetic acid.

[0066] The compound of formula (4) - reacting a compound of formula (1) with an amine of formula (2) or one of its salts to obtain a compound of formula (3); - Removal of the phthalimide group of compound (3) to obtain a compound of formula (4) It can be obtained by

[0067] The reaction conditions for removing the phthalimide group are well known and reported in the literature (Greene's Protective Groups in organic Synthesis; Peter GM Wuts; Wiley; Fifth Edition; 2014; 1012-1014).

[0068] Compounds of formula (1) may be prepared by one or more of the processes described herein (see Process F).

[0069] Amines of formula (2) can be prepared by process G described herein.

[0070] U 1 Compounds of formula (1) in which is a hydroxyl group can be reacted with amines of formula (2) in the presence of a condensing reagent by methods described in the literature (e.g., Tetrahedron 2005, 61, 10827-10852). Examples of suitable condensing reagents include, but are not limited to, halogenating reagents (e.g., phosgene, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, phosphorus trichloride oxide, oxalyl chloride, or thionyl chloride), dehydrating reagents (e.g., ethyl chloroformate, methyl chloroformate, isopropyl chloroformate, isobutyl chloroformate, or methanesulfonyl chloride), carbodiimides (e.g., N,N'-dicyclohexylcarbodiimide (DCC)), or other conventional condensing (or peptide coupling) reagents (e.g., phosphorus pentoxide, polyphosphoric acid, bis(2-oxo-3-oxazolidinyl)phosphinic acid chloroformate, or methanesulfonyl chloride). methylmorpholinium chloride hydrate, 4-(4,6-dimethoxy[1.3.5]-triazin-2-yl)-4-methylmorpholinium chloride hydrate, bromotripyrrolidinophosphonium hexafluorophosphate, or propanephosphonic anhydride (T3P).

[0071] U 1 Compounds of formula (1) in which is a halogen atom can be reacted with amines of formula (2) in the presence of an acid scavenger by well-known methods. Suitable acid scavengers include any inorganic and organic bases commonly used in such reactions, as described herein. Alkali metal carbonates, alkaline earth metal acetates, tertiary amines, or aromatic bases are preferred.

[0072] U 1 A compound of formula (1) where is a C1-C6 alkoxy group can be reacted with an excess of an amine of formula (2), optionally in the presence of a Lewis acid such as trimethylaluminum.

[0073] Process B R 3 , R 4 , R 5 , R 6 , R 7 , R 8 Compounds of formula (Ia), wherein L and Q are defined as above, can be reacted with R in the presence of a base (e.g., an organic or inorganic base), and optionally in the presence of a suitable copper salt or complex, as shown in Scheme 2. 3 , R 4 , R 5 , R 6 , R 7 , R 8 The compound of formula (7), wherein L and Q are defined as above and X is halogen, preferably chlorine, can be prepared by reacting a compound of formula (8), wherein Q is defined as above.

[0074] [ka]

[0075] Compounds of formula (7) can be prepared by first reacting R 7 , R 8 and X is defined as above, and U1 is hydroxy, halogen or C1-C6 alkoxy; and 3 , R 4 , R 5 , R 6 and L is defined as above, and W is hydrogen, tert-butoxycarbonyl, benzyl, allyl, or (4-methoxyphenyl)methyl, by reacting with an amine of formula (2) or one of its salts to form R 3 , R 4 , R 5 , R 6 , R 7 , R 8 to obtain a compound of formula (6a), wherein L, Q and W are as defined above, The phthalimide group of compound (6a) is then removed to form R 3 , R 4 , R 5 , R 6 , R 7 , R 8 to obtain a compound of formula (6b), wherein L, Q and W are as defined above, When W is hydrogen, the compound of formula (6b) is treated with a dehydrating agent, optionally in the presence of a base, to directly obtain a compound of formula (7); When W is an amino protecting group, the compound of formula (6b) is treated with a dehydrating agent, optionally in the presence of a base, followed by a deprotection step to give a compound of formula (7). It can be produced by

[0076] The reaction of a compound of formula (7) with a compound of formula (8) can be carried out in the presence of a transition metal catalyst, such as a copper salt or complex, and, where appropriate, in the presence of a ligand as described herein.

[0077] Compounds of formula (5) are commercially available.

[0078] Compounds of formula (8) are commercially available or can be obtained by converting or derivatizing other compounds of formula (8) according to well-known methods.

[0079] Process C R 3 , R 4 , R 5 , R 6 , R 7 , R 8 Compounds of formula (Ia), wherein L and Q are defined as above, can be prepared by the reaction of R 3 , R 4 , R 6 , R 7 , R 8 The compound of formula (Ia) can be prepared by adding a reducing agent to a compound of formula (12) in which L and Q are defined as above to give a compound of formula (Ia).

[0080] [ka]

[0081] Compounds of formula (12) can be cyclized under acidic conditions in the presence of a reducing agent such as sodium cyanoborohydride to give compounds of formula (Ia). The reaction conditions for forming the oxadiazine ring in this manner are known and are described in the literature (Heterocycles 2016, 92, 2166-2200).

[0082] The compound of formula (12) can be prepared by reacting R 7 , R 8 and Q are defined as above, and a compound of formula (10) 3 , R 4 , R 6 and a compound of formula (11) in which L is defined as above. Suitable bases can be alkali metal hydrides such as sodium hydride, alkali metal carbonates such as potassium carbonate, alkali metal hydroxides such as potassium hydroxide, or phosphazene bases such as BEMP, as described in the literature (Heterocycles 2016, 92, 2166-2200).

[0083] The compound of formula (10) is R 7 , R 8and Q as defined above, by reacting a compound of formula (9) with hydroxylamine or one of its salts. The reaction conditions for such a transformation are known and reported in the literature (WO2010 / 138600).

[0084] Compound of formula (9) [ka] [In the formula, R 7 , R 8 and X is defined as above by the means described for step 3 of Process B. can be prepared from a compound of formula (18).

[0085] Compounds of formula (11) are commercially available or can be prepared by processes described in the literature (Eur. J. Med. Chem. 2014, 84, 302; Eur. J. Med. Chem. 2015, 100, 18-23; WO2017 / 031325).

[0086] Process D R 3 , R 4 , R 5 , R 6 , R 7 , R 8 Compounds of formula (Ia), wherein L and Q are defined as above, can be prepared as shown in Scheme 4: - under conditions similar to those described in Process A, R 7 , R 8 and Q are defined as above, and R 3 , R 4 , R 5 , R 6 and L is defined as above, and E 1 is hydroxyl or halogen, with an amine of formula (13) or one of its salts to form a compound 3 , R 4 , R 5 , R 6 , R7 , R 8 , E 1 obtaining a compound of formula (14) in which L and Q are defined as above and W is hydrogen, tert-butoxycarbonyl, benzyl, allyl or (4-methoxyphenyl)methyl, Compounds of formula (14) are treated with a dehydrating agent followed by hydroxylamine to give R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , E 1 , forming a compound of formula (15) wherein L, Q and W are defined as above; -E 1 is hydroxyl, converting the compound of formula (15) to a compound of formula (Ia) using Mitsunobu reaction conditions; -E 1 is a halogen, converting the compound of formula (15) to a compound of formula (Ia) in the presence of a base. It can be produced by a process including:

[0087] [ka]

[0088] Steps 2 and 3 of Process D can be carried out using reaction conditions similar to those described in Process E.

[0089] Equation (13-a, E 1 = hydroxyl) are commercially available or can be prepared by methods described in the literature (Molecules, 9 (6), 405-426; 2004; WO2017 / 203474). 1 = halogen) or one of its salts can be obtained from the corresponding amino alcohol by well-known methods.

[0090] Process E R3 , R 4 , R 5 , R 6 , R 7 , R 8 Compounds of formula (Ia), wherein L and Q are defined as above, can be prepared as shown in Scheme 5: - under conditions similar to those described in Process A, R 7 and R 8 is defined as above, X is a halogen, preferably chlorine, and U 1 a compound of formula (5) wherein is hydroxy, halogen, or C1-C6 alkoxy; -R 3 , R 4 , R 5 , R 6 and L is defined as above, and E 1 is hydroxyl or halogen, with an amine of formula (13) or one of its salts to form 3 , R 4 , R 5 , R 6 , R 7 , R 8 , E 1 obtaining a compound of formula (16), wherein L and X are as defined above and W is hydrogen, tert-butoxycarbonyl, benzyl, allyl or (4-methoxyphenyl)methyl, Compounds of formula (16) are treated with a dehydrating agent followed by hydroxylamine to give R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , E 1 forming a compound of formula (17) wherein L and X are as defined above, -E 1 is hydroxyl, converting the compound of formula (17) to a compound of formula (7) using Mitsunobu reaction conditions; -E 1 When is a halogen, converting the compound of formula (17) to a compound of formula (7) in the presence of a base; in the presence of a base (e.g., an organic or inorganic base), and optionally in the presence of a suitable copper salt or complex, R 3 , R 4 , R 5 , R 6 , R 7 , R 8 a compound of formula (7) wherein L and X are defined as above; - a compound of formula (8) in which Q is defined as above, to obtain a compound of formula (Ia) It can be produced by a process including:

[0091] [ka]

[0092] Method for producing the compound of formula (1) The compounds of formula (1) described herein can be obtained directly by carrying out process F below, or can be obtained by conversion or derivatization of another compound of formula (1) prepared according to the processes described herein.

[0093] Process F As shown in Scheme 6, R 7 and R 8 The compound of formula (1) wherein R is as defined above can be reacted with R 7 and R 8 is defined as above, X is a halogen, and U 1 The compound of formula (5) wherein Q is C1-C6 alkoxy can be prepared by reacting the compound of formula (5) wherein Q is C1-C6 alkoxy with a reagent of formula (8) wherein Q is defined as above.

[0094] [ka]

[0095] Process F can be carried out in the presence of a salt or complex of a suitable transition metal catalyst, and where appropriate in the presence of a ligand.

[0096] Compounds of formula (5) are commercially available.

[0097] Compounds of formula (8) are commercially available or can be obtained by converting or derivatizing other compounds of formula (8) according to well-known methods.

[0098] U 1 Compounds of formula (1) where U is C1-C6 alkoxy can be converted to U by well-known functional group interconversion methods, for example, by hydrolysis of the ester group with LiOH in THF / water. 1 can be converted to a compound of formula (1) in which

[0099] U 1 Compounds of formula (1) where is hydroxyl can be prepared by the reaction of U in the presence of a halogenating agent by well-known methods. 1 is a halogen. Suitable halogenating reagents include, but are not limited to, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, phosphorus trichloride, oxalyl chloride, or thionyl chloride.

[0100] Process G As shown in Scheme 7, R 8 and Q are defined as above, and R 7a is chloro and U 1 Compounds of formula (1-b) where R is C1-C6 alkoxy can be prepared by known methods in one or more steps by converting R 8 , U 1 and Q are defined as above, and R 7b can be converted to the corresponding compound of formula (1-c) wherein is methyl.

[0101] [ka]

[0102] Non-limiting examples of conversions can be performed according to the description provided in Process H.

[0103] Method for preparing compounds of formula (2) and (13) Process H As shown in Scheme 9, R 3 , R 4 , R 5 , R 6 and L as defined above, can be prepared by methods described in the literature in one or more steps by the addition of R 3 , R 4 , R 5 , R 6 and L are defined as above, and W is hydrogen, tert-butoxycarbonyl, benzyl, allyl, or (4-methoxyphenyl)methyl, and can be converted to the corresponding compounds (2), (13-a).

[0104] [ka]

[0105] Amino alcohols are commercially available or can be prepared by methods described in the literature (Molecules, 9 (6), 405-426; 2004, WO2017 / 203474).

[0106] The amino functionality of compound (18) is protected according to known methods to give a compound of formula (13-a).

[0107] Compounds of formula (13-a) can then be converted to compounds of formula (2) via step 2 of process H using standard Mitsunobu reaction conditions known to those skilled in the art (Strategic Applications of Named Reactions in Organic Synthesis; Laszlo Kurti, Barbara Czako; Elsevier; 2005; 294-295 and references therein).

[0108] Process I As shown in Scheme 9, L, Q, and R 3 , R4 , R 5 , R 6 and R 8 is defined as above, and R 9 is H and R 7a Compounds of formula (Ia) where L, Q, T, R are chloro can be prepared in one or more steps by methods described in the literature. 3 , R 4 , R 5 , R 6 and R 8 is defined as above, and R 7b is methyl, or ethenyl, C1-C6-alkenyloxy substituted with one substituent methoxy or ethoxy, and The compound of formula (Ib) is a compound of formula (Ib) in which L, Q, T, R 3 , R 4 , R 5 , R 6 and R 8 is defined as above, and R 7c can be converted to a compound of formula (Ic) wherein:

[0109] [ka]

[0110] Non-limiting examples of transformations that can be carried out according to Scheme 9 are shown below.

[0111] R 7a Compounds of formula (Ia) where R is chlorine can be prepared by the transition metal catalyzed process or the Metallaphotoredox catalyzed process described herein, or by methods known to those skilled in the art. 7b can be converted to a compound of formula (Ib) wherein is methyl.

[0112] R 7bCompounds of formula (Ib) where R is C2-C6 alkenyl substituted with C1-C3 alkoxy can be prepared by the method described in the literature (e.g., J. Org. Chem. 1993, 55, 3114). 7c can be converted to a compound of formula (Ic) wherein

[0113] R 7c Compounds of formula (Ic) where R is a C1-C5 alkylcarbonyl can be obtained by standard functional group interconversions such as reduction of the ketone to an alcohol in the presence of NaBH4 in methanol. 7c can be further converted to a compound of formula (Ic) wherein is C1-C6 hydroxyalkyl.

[0114] R 7c is C2-C6 hydroxyalkyl, the compound of formula (Ic) can be prepared by the reaction of R 7c can be further converted to compound (Ic), wherein is C2-C6 fluoroalkyl. Non-limiting examples of fluorinating agents include sulfur fluorides such as sulfur tetrafluoride, diethylaminosulfuric acid trifluoride, morpholinosulfuric acid trifluoride, bis(2-methoxyethyl)aminosulfur trifluoride, 2,2-difluoro-1,3-dimethylimidazolidine, or 4-tert-butyl-2,6-dimethylphenylsulfur trifluoride.

[0115] Compounds of formula (Ia) may be prepared by one or more of the processes described herein.

[0116] Process J As shown in Scheme 10, L, Q, and R 3 , R 4 , R 5 , R 6 and R 8 is defined as above, and R 9 Compounds of formula (Id) where R is formyl can be prepared by reacting compounds of formula (Ia) with R 9wherein R is as defined above and W is halogen, C-C alkoxycarbonyloxy, C-C haloalkoxycarbonyloxy, C-C alkylcarbonyloxy, C-C haloalkylcarbonyloxy, C-C haloalkylsulfonyloxy, or C-C alkylsulfonyloxy.

[0117] [ka]

[0118] Process M can be carried out by methods described in the literature (e.g., Tetrahedron Lett. 1995, 36, 8949; Greene's Protective Groups in organic Synthesis; Peter GM Wuts; Wiley; Fifth Edition; 2014; 1174-1175).

[0119] Compounds of formula (19) are commercially available.

[0120] Compounds of formula (Ia) may be prepared by one or more of the processes described herein.

[0121] Compositions and Formulations The present invention further relates to compositions, particularly compositions for controlling unwanted microorganisms, which can be applied to the microorganisms and / or their habitat.

[0122] composition comprises at least one compound of formula (I) and at least one agriculturally suitable adjuvant, such as a carrier and / or surfactant.

[0123] Carrieris generally an inert, solid or liquid, natural or synthetic, organic or inorganic substance. The carrier generally improves the application of the compound to, for example, plants, plant parts or seeds. solid support Examples of suitable carriers include, but are not limited to, ammonium salts, especially ammonium sulfate, ammonium phosphate, and ammonium nitrate, kaolin, clay, talc, chalk, quartz, natural rock flours such as attapulgite, montmorillonite, and diatomaceous earth, silica gel, and synthetic rock flours such as finely divided silica, alumina, and silicates. Examples of typically useful solid carriers for preparing granules include, but are not limited to, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, and dolomite, synthetic granules of inorganic and organic powders, and granules of organic materials such as paper, sawdust, coconut shells, corn cobs, and tobacco stalks. Suitable carriers include, but are not limited to, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, and dolomite, synthetic granules of inorganic and organic powders, and granules of organic materials such as paper, sawdust, coconut shells, corn cobs, and tobacco stalks. Liquid Carrier Examples of suitable solvents include, but are not limited to, water, organic solvents, and combinations thereof. solvent Examples of suitable solvents include, for example, aromatic and non-aromatic hydrocarbons (such as chlorinated aromatic or chlorinated aliphatic hydrocarbon classes as cyclohexane, paraffins, alkylbenzenes, xylenes, toluene, tetrahydronaphthalene, alkylnaphthalenes, chlorobenzene, chloroethylene or methylene chloride), alcohols and polyols (optionally substituted, etherified and / or esterified, such as ethanol, propanol, butanol, benzyl alcohol, cyclohexanol or glycols), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanol), and the like. Examples include polar and non-polar organic chemical liquids from vegetable or animal oils, such as hydroxybenzoates, amines, amines, amine derivatives, amine esters (including fats and oils), amine derivatives, ...

[0124] Preferred solid carriers are selected from clay, talc and silica.

[0125] Preferred liquid carriers are selected from water, fatty acid amides and esters thereof, aromatic and non-aromatic hydrocarbons, lactams and carbonate esters.

[0126] The amount of carrier will typically range from 1 to 99.99%, preferably from 5 to 99.9%, more preferably from 10 to 99.5%, and most preferably from 20 to 99% by weight of the composition.

[0127] The liquid carrier will typically be present in the range 20 to 90% by weight of the composition, for example 30 to 80%.

[0128] The solid carrier will typically be present in the range 0 to 50% by weight of the composition, preferably 5 to 45% by weight, for example 10 to 30% by weight.

[0129] If the composition includes two or more carriers, the ranges outlined refer to the total amount of carriers.

[0130] surfactantsThe surfactant may be an ionic (cationic or anionic), amphoteric, or nonionic surfactant, such as an ionic or nonionic emulsifier, foaming agent, dispersant, wetting agent, penetration enhancer, and any mixture thereof. Examples of suitable surfactants include, but are not limited to, salts of polyacrylic acid, salts of lignosulfonic acid (such as sodium lignosulfonate), salts of phenolsulfonic acid or naphthalenesulfonic acid, polycondensates of ethylene oxide and / or propylene oxide with fatty alcohols, fatty acids, or fatty amines (e.g., polyoxyethylene fatty acid esters such as castor oil ethoxylate, polyoxyethylene fatty alcohol ethers, e.g., alkylaryl polyglycol ethers), substituted phenols (preferably alkylphenols or arylphenols) and their ethoxylates. Examples of suitable salts include esters of phenols such as tristyrylphenol ethoxylates, sulfosuccinates, taurine derivatives (preferably alkyl taurates), phosphates of polyethoxylated alcohols or phenols, fatty esters of polyols (such as fatty acid esters of glycerol, sorbitol, or sucrose), sulfates (such as alkyl sulfates and alkyl ether sulfates), sulfonates (e.g., alkyl sulfonates, aryl sulfonates, and alkyl benzene sulfonates), phosphates, protein hydrolysates, lignosulfite waste liquor, and methylcellulose. References to salts in this paragraph preferably refer to the respective alkali, alkaline earth, and ammonium salts.

[0131] Preferred surfactants are selected from polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty acid esters, alkylbenzene sulfonates such as calcium dodecylbenzene sulfonate, castor oil ethoxylates, sodium lignosulfonates, and arylphenol ethoxylates such as tristyrylphenol ethoxylate.

[0132] The amount of surfactant will typically range from 5 to 40%, for example from 10 to 20% by weight of the composition.

[0133] Suitable auxiliariesFurther examples include water repellents, desiccants, binders (adhesives, tackifiers, fixatives such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latexes such as gum arabic, polyvinyl alcohol and polyvinyl acetate, natural and synthetic phospholipids such as cephalin and lecithin, polyvinylpyrrolidone and tylose), thickeners and secondary thickeners (cellulose ethers, acrylic acid derivatives, xanthan gum, modified clays, such as the products available under the name Bentone, and finely divided silica), stabilizers (e.g. low temperature stabilizers, preservatives (e.g. dichlorophen and benzyl alcohol hemiformal), antioxidants, light stabilizers, especially UV stabilizers, or other agents which improve chemical and / or physical stability), dyes or pigments (inorganic pigments such as iron oxides, titanium oxide, and Prussian blue; organic pigments such as alizarin, azo, metal phthalocyanine dyes, etc., antifoaming agents (e.g., silicone antifoams and magnesium stearate), antifreeze, tackifiers, gibberellins and processing aids, mineral and vegetable oils, fragrances, waxes, nutrients (including micronutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum, and zinc), protective colloids, thixotropic substances, penetrating agents, sequestering agents, and complexing agents.

[0134] The choice of auxiliary agent depends on the intended application mode of the compound of formula (I) and / or the physical properties of such compound.In addition, auxiliary agent can be selected to impart specific properties (technical, physical and / or biological properties) to the composition or the use form prepared therefrom.By selecting auxiliary agent, the composition can be customized to meet specific needs.

[0135] The compositions of the present invention can be provided to the end user as ready-to-use formulations, i.e., they can be applied directly to plants or seeds by means of suitable equipment, such as spraying or dusting equipment. Alternatively, the compositions can be provided to the end user in the form of a concentrate, which must be diluted, preferably with water, before use.

[0136] The compositions of the present invention may be prepared by conventional methods, for example by mixing a compound of formula (I) with one or more suitable auxiliaries as described herein above.

[0137] The composition contains a fungicidally effective amount of a compound of formula (I). The term "effective amount" refers to an amount sufficient to control harmful fungi on cultivated plants or to protect the material, without causing substantial damage to the treated plants. Such an amount can vary widely and depends on various factors, such as the fungal species to be controlled, the cultivated plants or material being treated, climatic conditions, and the particular compound of formula (I) used. Typically, the composition of the present invention contains 0.01 to 99% by weight, preferably 0.05 to 98% by weight, more preferably 0.1 to 95% by weight, even more preferably 0.5 to 90% by weight, and most preferably 1 to 80% by weight of a compound of formula (I). The composition may contain two or more compounds of the present invention. In such cases, the ranges mentioned above refer to the total amount of the compounds of the present invention.

[0138] The compositions of the present invention may be in the form of conventional formulations such as solutions (e.g., aqueous solutions), emulsions, aqueous and oily suspensions, powders (e.g., wettable powders, soluble powders), dusts, pastes, granules (e.g., soluble granules, dusting granules), suspoemulsion concentrates, natural or synthetic products impregnated with a compound of formula (I), fertilizers, and microencapsulations in polymeric materials. Composition TypeThe compound of formula (I) may be in a suspended, emulsified or dissolved form. Examples of specific suitable composition types are solutions, water-soluble concentrates (e.g., SL, LS), dispersible concentrates (DC), suspensions and suspension concentrates (e.g., SC, OD, OF, FS), emulsifiable concentrates (e.g., EC), emulsions (e.g., EW, EO, ES, ME, SE), capsules (e.g., CS, ZC), pastes, lozenges, wettable powders or dusts (e.g., WP, SP, WS, DP, DS), pressings (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), insecticides (e.g., LN), and gel formulations (e.g., GW, GF) for treating plant propagation materials such as seeds. These and other composition types are defined by the Food and Agriculture Organization of the United Nations (FAO). An overview is provided in “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6th Ed. May 2008, Croplife International.

[0139] Preferably, the composition of the present invention is in the form of one of the following types: EC, SC, FS, SE, OD and WG, more preferably EC, SC, OD and WG.

[0140] Examples of composition types and further details about their preparation are provided below. When two or more compounds of the present invention are included, the amount of the compounds of the present invention mentioned above refers to the total amount of the compounds of the present invention. When two or more representatives of such components, such as wetting agents, binders, etc., are present, this applies mutatis mutandis to other additional components of the composition.

[0141] i) Water-soluble concentrates (SL, LS) 10 to 60% by weight of at least one compound of formula (I) and 5 to 15% by weight of a surfactant (e.g., a polyoxyethylene fatty alcohol ether) are dissolved in water and / or a water-soluble solvent (e.g., an alcohol such as propylene glycol, or a carbonate such as propylene carbonate) in an amount such that the total amount is 100% by weight. The concentrate is diluted with water before application.

[0142] ii) Dispersible Concentrate (DC) 5 to 25% by weight of at least one compound of formula (I) and 1 to 10% by weight of a surfactant and / or binder (e.g., polyvinylpyrrolidone) are dissolved in an organic solvent (e.g., cyclohexanone) in an amount such that the total amount becomes 100% by weight. A dispersion is obtained by diluting with water.

[0143] iii) Emulsifiable concentrate (EC) 15 to 70% by weight of at least one compound of formula (I) and 5 to 10% by weight of a surfactant (e.g., a mixture of calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in a water-insoluble organic solvent (e.g., an aromatic hydrocarbon or a fatty acid amide) in an amount such that the total amount becomes 100% by weight, and additional water-soluble solvent is added as needed. An emulsion is obtained by diluting with water.

[0144] iv) Emulsions (EW, EO, ES) 5-40% by weight of at least one compound of formula (I) and 1-10% by weight of a surfactant (e.g., a mixture of calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40% by weight of a water-insoluble organic solvent (e.g., an aromatic hydrocarbon). This mixture is added to water in an amount sufficient to make the total amount 100% by weight using an emulsifier. The resulting composition is a homogeneous emulsion. The emulsion can be further diluted with water before application.

[0145] v) Suspensions and suspension concentrates v-1) Aqueous (SC, FS) In a suitable grinding device, such as a stirred ball mill, 20-60% by weight of at least one compound of formula (I) is ground with 2-10% by weight of surfactants (e.g., sodium lignosulfonate and polyoxyethylene fatty alcohol ether), 0.1-2% by weight of a thickener (e.g., xanthan gum), and water to obtain a fine suspension of the active substance. Water is added in an amount such that the total amount is 100% by weight. Dilution with water results in a stable suspension of the active substance. In FS-type compositions, up to 40% by weight of a binder (e.g., polyvinyl alcohol) is added.

[0146] v-2) Oil-based (OD, OF) In a suitable mill, such as a stirred ball mill, 20-60% by weight of at least one compound of formula (I) is mixed with 2-10% by weight of a surfactant (e.g., sodium lignosulfonate and polyoxyethylene fatty alcohol ether), 0.1-2% by weight of a thickener (e.g., modified clay, especially bentone, or silica), and an organic carrier to obtain a fine oil suspension of the active substance. The organic carrier is added in an amount such that the total amount is 100% by weight. Dilution with water results in a stable dispersion of the active substance.

[0147] vi) Water-dispersible granules and water-soluble granules (WG, SG) 50-80% by weight of at least one compound of formula (I) is finely ground with the addition of surfactants (e.g., sodium lignosulfonate and polyoxyethylene fatty alcohol ether) and converted into water-dispersible or water-soluble granules using technical equipment (e.g., extruders, spray towers, fluidized beds). The surfactants are used in an amount such that the total amount is 100% by weight. Dilution with water results in a stable dispersion or solution of the active substance.

[0148] vii) Water-dispersible and water-soluble powders (WP, SP, WS) 50-80% by weight of at least one compound of formula (I) is milled in a rotor-stator mill with 1-8% by weight of a surfactant (e.g., sodium lignosulfonate, polyoxyethylene fatty alcohol ether), and a solid carrier such as silica gel in an amount sufficient to bring the total to 100% by weight. Dilution with water results in a stable dispersion or solution of the active substance.

[0149] viii) Gel (GW, GF) In a stirred ball mill, 5-25% by weight of at least one compound of formula (I) is milled with 3-10% by weight of a surfactant (e.g., sodium lignosulfonate), 1-5% by weight of a binder (e.g., carboxymethylcellulose), and an amount of water to bring the total to 100% by weight. This results in a fine suspension of the active substance. Dilution with water results in a stable suspension of the active substance.

[0150] ix) Microemulsion (ME) 5-20% by weight of at least one compound of formula (I) is added to 5-30% by weight of an organic solvent mixture (e.g., fatty acid dimethylamide and cyclohexanone), 10-25% by weight of a surfactant mixture (e.g., polyoxyethylene fatty alcohol ether and arylphenol ethoxylate), and an amount of water such that the total amount becomes 100% by weight. The mixture is stirred for 1 hour to spontaneously form a thermodynamically stable microemulsion.

[0151] x) Microcapsules (CS) An oil phase containing 5 to 50% by weight of at least one compound of formula (I), 0 to 40% by weight of a water-insoluble organic solvent (e.g., aromatic hydrocarbon), and 2 to 15% by weight of an acrylic monomer (e.g., methyl methacrylate, methacrylic acid, and di- or triacrylate) is dispersed in an aqueous solution of a protective colloid (e.g., polyvinyl alcohol). Poly(meth)acrylate microcapsules are formed by radical polymerization initiated by a radical initiator. Alternatively, an oil phase containing 5 to 50% by weight of at least one compound of formula (I), 0 to 40% by weight of a water-insoluble organic solvent (e.g., aromatic hydrocarbon), and an isocyanate monomer (e.g., diphenylmethene-4,4'-diisocyanate) is dispersed in an aqueous solution of a protective colloid (e.g., polyvinyl alcohol). Polyurea microcapsules are formed by adding a polyamine (e.g., hexamethylenediamine). The monomer accounts for 1 to 10% by weight of the total CS composition.

[0152] xi) Dust (DP, DS) 1 to 10% by weight of at least one compound of formula (I) is finely ground and thoroughly mixed with a solid carrier, such as finely divided kaolin, in an amount to bring the total to 100% by weight.

[0153] xii) Granules (GR, FG) 0.5 to 30% by weight of at least one compound of formula (I) is finely ground and combined with a solid carrier (e.g., silicate) in an amount that brings the total to 100% by weight. Granulation is achieved by extrusion, spray drying, or fluidized bed.

[0154] xiii) Ultra-trace liquid (UL) 1 to 50% by weight of at least one compound of formula (I) is dissolved in an organic solvent, such as an aromatic hydrocarbon, in an amount such that the total amount is 100% by weight.

[0155] The compositions of types i) to xiii) may optionally further comprise 0.1 to 1 wt. % of a preservative, 0.1 to 1 wt. % of an antifoaming agent, 0.1 to 1 wt. % of a dye and / or pigment, and 5 to 10 wt. % of an antifreeze.

[0156] Mixtures / Combinations The compounds of formula (I) and compositions of the present invention can be mixed with other active ingredients, such as fungicides, bactericides, acaricides, nematicides, insecticides, biological control agents, or herbicides. Mixtures with fertilizers, growth regulators, safeners, nitrification inhibitors, semiochemicals, and / or other agriculturally beneficial agents are also possible. This can broaden the spectrum of activity or prevent the development of resistance. Examples of known fungicides, insecticides, acaricides, nematicides, and bactericides are disclosed in the Pesticide Manual, 17th Edition.

[0157] Examples of fungicides that may be mixed with the compounds of formula (I) and compositions of the present invention are: 1) Inhibitors of ergosterol biosynthesis, for example: (1.001) cyproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) fenhexamid, (1.005) fenpropidin, (1.006) fenpropimorph, (1.007) fenpyrazamine, (1.008) fluquinconazole, (1.009) flutriafol, (1.010) imazalil, (1.011) imazalil sulfate, (1.012) ipconazole, (1.013) metconazole, (1.01 4) Myclobutanil, (1.015) Paclobutrazol, (1.016) Prochloraz, (1.017) Propiconazole, (1.018) Prothioconazole, (1.019) Pyrisoxazole, (1.020) Spiroxamine, (1.021) Tebuconazole, (1.022) Tetraconazole, (1.023) Triadimenol, (1.024) Tridemorph, (1.025) Triticonazole, (1.026) (1R,2S,5S)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1 (1.027) (1S,2R,5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.028) (2R)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.029) (2R)-2-(1-chlorocyclopropyl) -4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.030)(2R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.031)(2S)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.032) (2S)-2-(1-chlorocyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.033) (2S)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.034) (R)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl) (1.035)(S)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.036)[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.037) 1-({(2R,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl )-1H-1,2,4-triazole, (1.038) 1-({(2S,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl)-1H-1,2,4-triazole, (1.039) 1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.040) 1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate (1.041) 1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.042) 2-[(2R,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.043) 1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.044) 2-[(2R,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.045) 1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.046) 1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.047) 1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-tri043) 2-[(2R,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.044) 2-[(2R,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.045) 2-[(2R,4S,5S)-1-(2,4-dichlorophenyl) )-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.046) 2-[(2S,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.047) 2-[(2S,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2 ,4-Dihydro-3H-1,2,4-triazole-3-thione, (1.048) 2-[(2S,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.049) 2-[(2S,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1. 050) 2-[1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.051) 2-[2-chloro-4-(2,4-dichlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.052) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.053) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.054) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)pentan-2-ol, (1.055) Mefentrifluconazole, (1.056) 2-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2, 4-Triazole-3-thione, (1.057) 2-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.058) 2-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.059) 5-(4-chlorobenzyl)-2-(chloromethyl)-2- Methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.060) 5-(allylsulfanyl)-1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.061) 5-(allylsulfanyl)-1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.062) 5-(allylsulfanyl)- 1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.063) N'-(2,5-dimethyl-4-{[3-(1,1,2,2-tetrafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.064) N'-(2,5-dimethyl-4-{[3-(2,2,2-trifluoroethoxy)phenyl]sulfanyl}phenyl)N-ethyl-N-methylimidoformamide, (1.065) N'-(2,5-dimethyl-4-{[3-(2,2,3,3-tetrafluoropropoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methyl-imidoformamide, (1.066) N'-(2,5-dimethyl-4-{[3-(pentafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methyl-imidoformamide, (1.067) N'-(2,5-dimethyl-4-{3-[(1,1,2,2-tetrafluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methyl imidoformamide, (1.068) N'-(2,5-dimethyl-4-{3-[(2,2,2-trifluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.069) N'-(2,5-dimethyl-4-{3-[(2,2,3,3-tetrafluoropropyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.070) N'-(2,5-dimethyl-4-{3-[(pentafluoroethyl)sulfanyl]phenoxy}phenyl)- N-ethyl-N-methylimidoformamide, (1.071) N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylimidoformamide, (1.072) N'-(4-{[3-(difluoromethoxy)phenyl]sulfanyl}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (1.073) N'-(4-{3-[(difluoromethyl)sulfanyl]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (1.074) N'-[ 5-Bromo-6-(2,3-dihydro-1H-inden-2-yloxy)-2-methylpyridin-3-yl]-N-ethyl-N-methylimidoformamide, (1.075)N'-{4-[(4,5-dichloro-1,3-thiazol-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methylimidoformamide, (1.076)N'-{5-bromo-6-[(1R)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.077) N'-{5-bromo-6-[(1S)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.078) N'-{5-bromo-6-[(cis-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.079) N'-{5-bromo-6-[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.080) N'-{5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide. (1.081) Ipfentifluconazole, (1.082) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.083) 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl) Propan-2-ol, (1.084) 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, (1.085) 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile, (1.086) 4-[[6-[rac-(2R) -2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, (1.087) N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenylethyl)phenyl]-N-methylimidoformamide, (1.088) N'- {5-bromo-2-methyl-6-[(1-propoxypropan-2-yl)oxy]pyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.089) hexaconazole, (1.090) penconazole, (1.091) fenbuconazole, (1.092) methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propanoate, 2) Inhibitors of the respiratory chain at complex I or II, such as (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapyroxad, (2.008) furametpyr, (2.009) isofetamide, (2.010) isopyrazam (antiepimeric enantiomer 1R,4S,9S), (2.011) isopyrazam (antiepimeric enantiomer 1S,4R ,9R), (2.012) Isopyrazam (antiepimeric racemic 1RS,4SR,9SR), (2.013) Isopyrazam (mixture of syn-epimeric racemic 1RS,4SR,9RS and anti-epimeric racemic 1RS,4SR,9SR), (2.014) Isopyrazam (syn-epimeric enantiomer 1R,4S,9R), (2.015) Isopyrazam (syn-epimeric enantiomer 1S,4R,9S), (2.016) Isopyrazam (syn-epimeric racemic 1RS,4SR ,9RS), (2.017) Penflufen, (2.018) Penthiopyrad, (2.019) Pydiflumetofen, (2.020) Pyraziflumide, (2.021) Sedaxane, (2.022) 1,3-dimethyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.023) 1,3-dimethyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide amide, (2.024) 1,3-dimethyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.025) 1-methyl-3-(trifluoromethyl)-N-[2'-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (2.026) 2-fluoro-6-(trifluoromethyl)-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)benzamide, (2.027) 3-(Difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.028) Inpirfluxam, (2.029) 3-(Difluoromethyl)-1-methyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.030) Fluindapyr, (2.031) 3-(Difluoromethyl)-N-[(3R)-7-fluindapyr

[00130] 3-(difluoromethyl)-N-[(3S)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.032) 3-(difluoromethyl)-N-[(3S)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.033) 5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazoline -4-amine, (2.034) N-(2-cyclopentyl-5-fluorobenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.035) N-(2-tert-butyl-5-methylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.036) N-(2-tert-butylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (2.037) N-(5-chloro-2-ethylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.038) isoflucipram, (2.039) N-[(1R,4S)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.040)040) N-[(1S,4R)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.041) N-[1-(2,4-dichlorophenyl)-1-methoxypropan-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.042) N-[2-chloro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5- Fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.043) N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.044) N-[5-chloro-2-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.045) N-cyclopropyl-3-(difluoro Methyl)-5-fluoro-1-methyl-N-[5-methyl-2-(trifluoromethyl)benzyl]-1H-pyrazole-4-carboxamide, (2.046) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-fluoro-6-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.047) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropyl-5-methylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.048) ) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carbothioamide, (2.049) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.050) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(5-fluoro-2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.051) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-4,5-dimethylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.052) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-fluorobenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.053) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-methylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.054) N-cyclopropyl-N-(2-cyclopropyl-5-fluorobenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide N-cyclopropyl-N-(2-cyclopropyl-5-methylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.055) N-cyclopropyl-N-(2-cyclopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.056) N-cyclopropyl-N-(2-cyclopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.057) pyrapropoin, (2.058) N-[rac-(1S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)nicotinamide, (2.059) N-[(1S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)nicotinamide, (2.060) fulveneteram. 3) Inhibitors of the respiratory chain at complex III, such as (3.001) ametoctrazine, (3.002) amisulbrom, (3.003) azoxystrobin, (3.004) methoxystrobin, (3.005) cumoxystrobin, (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) enoxastrobin, (3.009) famoxadone, (3.010) fenamidone, (3.011) flufenoxystrobin, (3.012) fluoxastrobin, (3.013) kresoxim-methyl, (3 014) Metominostrobin, (3.015) Orysastrobin, (3.016) Picoxystrobin, (3.017) Pyraclostrobin, (3.018) Pyrametstrobin, (3.019) Pyraoxystrobin, (3.020) Trifloxystrobin, (3.021) (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylvinyl])oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylacetamide, (3.022) (2E ,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.023) (2R)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.024) (2S)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.025) fenpicoxamide, (3.026) mandestrobin, (3.027) N-( 3-Ethyl-3,5,5-trimethylcyclohexyl)-3-formamido-2-hydroxybenzamide, (3.028) (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.029) Methyl {5-[3-(2,4-dimethylphenyl)-1H-pyrazol-1-yl]-2-methylbenzyl}carbamate, (3.030) Methyltetraprole, (3.031) Florylpicoxamide, (3.032) (2S,3S)-3-(o-Tolyl)butan-2-yl N-{[4-methoxy-3-(propanoyloxy)-2-pyridyl]carbonyl}-L-alaninate. 4) Inhibitors of mitosis and cell division, for example (4.001) carbendazim, (4.002) diethofencarb, (4.003) ethaboxam, (4.004) fluopicolide, (4.005) pencycuron, (4.006) thiabendazole, (4.007) thiophanate-methyl, (4.008) zoxamide, (4.009) pyridaclomethyl, (4.010) 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, (4.011) 3-chloro-5-(6-chloropyridine- 3-yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine, (4.012) 4-(2-bromo-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.013) 4-(2-bromo-4-fluorophenyl)-N-(2-bromo-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.014) 4-(2-bromo-4-fluorophenyl)-N-(2-bromophenyl)-1,3-dimethyl-1H-pyrazol-5-amine amine, (4.015) 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.016) 4-(2-bromo-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.017) 4-(2-bromo-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.018) 4-(2-chloro-4-fluorophenyl)-N-(2,6- difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.019) 4-(2-chloro-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.020) 4-(2-chloro-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.021) 4-(2-chloro-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.022) 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, (4.023) N-(2-bromo-6-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.024) N-(2-bromophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.025) N-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.026) Fluopimomide. 5) Compounds with multi-site action, for example (5.001) Bordeaux mixture, (5.002) captafol, (5.003) captan, (5.004) chlorothalonil, (5.005) copper hydroxide, (5.006) copper naphthenate, (5.007) copper oxide, (5.008) copper oxychloride, (5.009) copper(2+) sulfate, (5.010) dithianon, (5.011) dodine, (5.012) folpet, (5.013) mancozeb, (5.014) maneb, (5.015 ) Metiram, (5.016) Metiram zinc, (5.017) Oxine copper, (5.018) Propineb, (5.019) Sulfur preparations containing sulfur and calcium polysulfide, (5.020) Thiram, (5.021) Zineb, (5.022) Ziram, (5.023) 6-ethyl-5,7-dioxo-6,7-dihydro-5H-pyrrolo[3',4':5,6][1,4]dithiino[2,3-c][1,2]thiazole-3-carbonitrile, (6.001) Acibenzolar-S-methyl, 6) Compounds capable of inducing host defense, such as (6.001) acibenzolar-S-methyl, (6.002) isotianil, (6.003) probenazole, (6.004) tiadinil, 7) Inhibitors of amino acid and / or protein biosynthesis, for example (7.001) cyprodinil, (7.002) kasugamycin, (7.003) kasugamycin hydrochloride hydrate, (7.004) oxytetracycline, (7.005) pyrimethanil, (7.006) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinoline, 8) Inhibitors of ATP production, for example (8.001) silthiofam, 9) Inhibitors of cell wall synthesis, for example (9.001) benthiavalicarb, (9.002) dimethomorph, (9.003) flumorph, (9.004) iprovalicarb, (9.005) mandipropamide, (9.006) pyrimorph, (9.007) valifenalate, (9.008) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one, (9.009) (2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one, 10) Inhibitors of lipid and membrane synthesis, for example (10.001) propamocarb, (10.002) propamocarb hydrochloride, (10.003) tolclofos-methyl, 11) Inhibitors of melanin biosynthesis, for example (11.001) tricyclazole, (11.002) tolprocarb, 12) Inhibitors of nucleic acid synthesis, for example (12.001) benalaxyl, (12.002) benalaxyl-M (chiralaxyl), (12.003) metalaxyl, (12.004) metalaxyl-M (mefenoxam), 13) Signal transduction inhibitors, for example (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) proquinazide, (13.005) quinoxyfen, (13.006) vinclozolin, 14) Compounds capable of acting as uncouplers, for example (14.001) fluazinam, (14.002) meptyldinocap, 15) (15.001) Abscisic acid, (15.002) Benthiazole, (15.003) Bethoxadin, (15.004) Capsimycin, (15.005) Carvone, (15.006) Chinomethionate, (15.007) Kufuraneb, (15.008) Cyflufenamid, (15.009) Cymoxanil, (15.010) Cyprosulfamide, (15.011) Flutianil, (15.012) Fosetyl aluminum, (15.013) Fosetyl calcium, (15.014) Fosetyl sodium, (15.015) Methyl isothiocyanate , (15.016) Metrafenone, (15.017) Milidiomycin, (15.018) Natamycin, (15.019) Nickel dimethyldithiocarbamate, (15.020) Nitrotarisopropyl, (15.021) Oxamocarb, (15.022) Oxathiapiproline, (15.023) Oxyfenthiin, (15.024) Pentachlorophenol and its salts, (15.025) Phosphorous acid and its salts, (15.026) Propamocarb-focetylate, (15.027) Pyriophenone (Clazafenone), (15.028 ) Tebufloquine, (15.029) Tecloftalam, (15.030) Tolnifanide, (15.031) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.032) 1-(4-{4-[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazole -2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.033) 2-(6-benzylpyridin-2-yl)quinazoline, (15.034) dipimethitrone, (15.035) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.036) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.037) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone 2-[6-(3-fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazoline, (15.039) 2-{(5R)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenylmethane sulfonate, (15.040) 2-{(5S)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (15.041) ipflufenoquin, (15.042) 2-{2-fluoro-6-[(8-fluoro-2-methylquinolin-3-yl)oxy]phenyl}propan-2-ol, (15.043) fluo xapiproline, (15.044) 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}phenyl methanesulfonate, (15.045) 2-phenylphenol and its salts, (15.046) 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline, (15.047) quinofumeline, (15.048) 4-Amino-5-fluoropyrimidin-2-ol (tautomer: 4-amino-5-fluoropyrimidin-2(1H)-one), (15.049) 4-oxo-4-[(2-phenylethyl)amino]butanoic acid, (15.050) 5-amino-1,3,4-thiadiazole-2-thiol, (15.051) 5-chloro-N'-phenyl-N'-(prop-2-yn-1-yl)thiophene-2-sulfonohydrazide, (15.052) 5-fluoro-2-[(4-fluorobenzyl)oxy]pyrimidin-4-amine , (15.053) 5-Fluoro-2-[(4-methylbenzyl)oxy]pyrimidin-4-amine, (15.054) 9-Fluoro-2,2-dimethyl-5-(quinolin-3-yl)-2,3-dihydro-1,4-benzoxazepine, (15.055) But-3-yn-1-yl {6-[({[(Z)-(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.056) Ethyl (2Z)-3-amino-2-cyano-3-phenylacrylic acid ester ethyl, (15.057) phenazine-1-carboxylic acid, (15.058) propyl 3,4,5-trihydroxybenzoate, (15.059) quinolin-8-ol, (15.060) quinolin-8-ol sulfate (2:1), (15.061) tert-butyl {6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.062) 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4- Dihydropyrimidin-2(1H)-one, (15.063) aminopyrifen, (15.064) (N'-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylimidoformamide), (15.065) (N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methylimidoformamide), (15.066) (2-{2-[(7,8-difluoro-2-methylquinolin-3-yl)oxy]-6-fluorophenyl}propan-2-ol), (15.067) (5-Bromo-1-(5,6-dimethylpyridin-3-yl)-3,3-dimethyl-3,4-dihydroisoquinoline), (15.068) (3-(4,4-difluoro-5,5-dimethyl-4,5-dihydrothieno[2,3-c]pyridin-7-yl)quinoline), (15.069) (1-(4,5-dimethyl-1H-benzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline), (15.070) 8-Fluoro-3-(5-fluoro-3,3-dimethyl-3,4-dihydroisoquinoline-1- yl) quinolone, (15.071) 8-fluoro-3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl) quinolone, (15.072) 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)-8-fluoroquinoline, (15.073) (N-methyl-N-phenyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide), (15.074) {4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]furan phenyl}methylcarbamate, (15.075) (N-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}cyclopropanecarboxamide), (15.076) N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.077) N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.078) N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (15.079) N-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]cyclopropanecarboxamide, (15.080) N-(2-fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.081) 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, (15.082) N-Allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]methyl]acetamide, (15.083) N-[(E)-N-Methoxy-C-methyl-carbonimidoyl]-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.084) N-[(Z)-N-Methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.085) N-Allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]methyl]acetamide N-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.086) 4,4-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, (15.087) N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide, (15.088) 5-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, 1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, (15.089) N-((2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl)-3,3,3-trifluoro-propanamide, (15.090) 1-methoxy-1-methyl-3-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.091) 1,1-diethyl-3-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, (15.092) N-((2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl)-3,3,3-trifluoro-propanamide, (15.093) 1-methoxy-1-methyl-3-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.094) 1-methoxy-1-methyl-3-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1-Methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.092) N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.093) N-Methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, (15.094) 1-Methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.095) N-Methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl)cyclopropanecarboxamide, (15.096) N,2-Dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.097) N-Ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]methyl]propanamide, (15.098) 1-Methoxy-3-methyl-1-[[4-[. 5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.099) 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.100) 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.101) 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl nyl]methyl]piperidin-2-one, (15.102) 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]]phenyl]methyl]isoxazolidin-3-one, (15.103) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.104) 3,3-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl ]methyl]piperidin-2-one, (15.105) 1-[[3-fluoro-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]azepan-2-one, (15.106) 4,4-dimethyl-2-[[4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.107) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one Sazolidin-3-one, (15.108) ethyl 1-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}-1H-pyrazole-4-carboxylate, (15.109) N,N-dimethyl-1-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}-1H-1,2,4-triazol-3-amine, (15.110) N-{2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}butanamide, (15.111) N-(1-methylcyclopropyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.112) N-(2,4-difluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.113) 1-(5,6-dimethylpyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.114) 1-(6-(difluoromethyl)-5-methyl-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline (15.115) 1-(5-(fluoromethyl)-6-methyl-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.116) 1-(6-(difluoromethyl)-5-methoxy-pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.117) 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-2-yl]-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline 1,5-dihydro-2,4-benzodioxepin-6-yl]methanesulfonate, (15.116) 3-[2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.117) 3-[2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.118) N-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}propanamide, (15.119) 3-[2-(1-{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.120) 9-fluoro-3-[2-(1 -{[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.121) 3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.122) 3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-9-fluoro-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.123) 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.124) 8-fluoro-N-(4,4,4-trifluoro-2-methyl-1-phenylbutane-2- (15.125) 8-fluoro-N-[(2S)-4,4,4-trifluoro-2-methyl-1-phenylbutan-2-yl]quinoline-3-carboxamide, (15.126) N-(2,4-dimethyl-1-phenylpentan-2-yl)-8-fluoroquinoline-3-carboxamide, (15.127) N-[(2S)-2,4-dimethyl-1-phenylpentan-2-yl]-8-fluoroquinoline-3-carboxamide, and (15.128) D-tagatose. is.

[0158] All of the listed mixing partners of the above categories (1) to (15) can be present in the form of free compounds or, if their functional groups allow it, in the form of their pesticidal active salts.

[0159] The compounds of formula (I) and compositions of the present invention can also be combined with one or more biological control agents.

[0160] As used herein, the term "biological control" is defined as the control of pests, such as plant pathogenic fungi and / or insects and / or mites and / or nematodes, by the use or employment of biological control agents.

[0161] As used herein, the term "biological control agent" is defined as an organism other than a pest and / or a protein or secondary metabolite produced by such an organism for biological control. Mutants of a second organism are included in the definition of a biological control agent. The term "mutant" refers to a variant of a parent strain and methods for obtaining such a mutant or variant in which the insecticidal activity is greater than that expressed by the parent strain. "Parent strain" is defined herein as the original strain prior to mutagenesis. To obtain such mutants, the parent strain can be treated with chemicals such as N-methyl-N'-nitro-N-nitrosoguanidine, ethyl methanesulfone, or by irradiation with gamma rays, X-rays, UV radiation, or other means known to those skilled in the art. Known mechanisms of biological control agents include enterobacteria, which control root rot by outcompeting fungi for space on the root surface. Bacterial toxins, such as antibiotics, have been used to control pathogens. The toxin can be isolated and applied directly to the plant, or a bacterial species can be administered to produce the toxin in situ.

[0162] A "variant" is a strain that has all the distinguishing characteristics of the NRRL or ATCC accession number set forth herein and can be identified as having a genome that hybridizes under high stringency conditions to the genome of the NRRL or ATCC accession number.

[0163] "Hybridization" refers to the reaction of one or more polynucleotides to form a complex stabilized through hydrogen bonding between the bases of the nucleotide residues. Hydrogen bonding can occur through Watson-Crick base pairing, Hoogstein binding, or other sequence-specific methods. The complex can contain two strands forming a duplex structure, three or more strands forming a multi-stranded complex, a single self-hybridizing strand, or any combination thereof. Hybridization reactions can be performed under conditions of varying "stringency." Generally, low-stringency hybridization reactions are performed in 10x SSC at 40°C or in solutions of equivalent ionic strength / temperature. Moderate-stringency hybridization reactions are typically performed at approximately 50°C in 6x SSC, and high-stringency hybridization reactions are typically performed at approximately 60°C in 1x SSC.

[0164] A variant of a designated NRRL or ATCC accession number can also be defined as a strain having a genome sequence that has greater than 85%, more preferably greater than 90%, or more preferably greater than 95% sequence identity to the genome of the designated NRRL or ATCC accession number. When a polynucleotide or polynucleotide region (or polypeptide or polypeptide region) has a certain percentage (e.g., 80%, 85%, 90%, or 95%) of "sequence identity" to another sequence, it means that, when aligned, that percentage of bases (or amino acids) are identical when the two sequences are compared. This alignment and percent homology or sequence identity can be determined using software programs known in the art, such as those described in Current Protocols in Molecular Biology (F.M. Ausubel et al., eds., 1987).

[0165] NRRL is the abbreviation for Agricultural Research Service Culture Collection, an international depository for the purpose of depositing microbial strains under the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure, and its address is the National Center for Agricultural Utilization Research, Agricultural Research Service, US Department of Agriculture, 1815 North University Street, Peroira, Illinois 61604, USA.

[0166] ATCC is an abbreviation for American Type Culture Collection, an international depository for the purpose of depositing microbial strains under the Budapest Treaty on the International Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure, and its address is ATCC Patent Depository, 10801 University Blvd., Manassas, VA 10110 USA.

[0167] Examples of biological control agents that can be combined with the compounds of formula (I) and compositions of the present invention are: (A) an antibacterial agent selected from the group consisting of: (A1) (A1.1) Bacillus subtilis, particularly strain QST713 / AQ713 (having NRRL accession number B21661 and available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, USA, U.S. Patent No. 6,060,051); (A1.2) Bacillus species, particularly strain D747 (having accession number FERM BP-8234 and available as DOUBLE NICKEL® from Kumiai Chemical Industry Co., Ltd., USA, U.S. Patent No. 7,094,592); (A1.3) Bacillus pumilus, particularly B12161, having NRRL accession number 50185; strain F-33 (available as part of the BASF product CARTISSA®, EPA registration number 71840-19); (A1.4) Bacillus subtilis var. amyloliquefaciens strain FZB24 with accession number DSM10271 (available from Novozymes as TAEGRO® or TAEGRO® ECO (EPA registration number 70127-5)); (A1.5) strains of Paenibacillus species with accession number NRRL B-50972 or accession number NRRL B-67129, WO2016 / 154297; (A1.6) Bacillus subtilis strain BU1814 (BASF (A1.7) Bacillus mojavensis strain R3B (accession number NCAIM(P)B001389) from Certis USA LLC, a subsidiary of Mitsui & Co. (WO2013 / 034938); (A1.8) Bacillus subtilis CX-9060 from Certis USA LLC, a subsidiary of Mitsui & Co.; (A1.9) Paenibacillus polymyxa, particularly the AC-1 strain (e.g., TOPSEED® from Green Biotech Company Ltd.); (A1.10) Pseudomonas proradix (e.g., PRORADIX® from Sourcon Padena); (A1.11) Pantoea agglomerans, particularly the E325 strain (accession number NRRLB-21856) (available as BLOOMTIME BIOLOGICAL™ FD BIOPESTICIDE from Northwest Agri Products); and (A2) (A2.1) Aureobasidium pullulans, in particular blastospores of the strain DSM 14940, blastospores of the strain DSM 14941, or a mixture of blastospores of the strains DSM 14940 and DSM 14941 (e.g., Botector® and BLOSSOM PROTECT® from Bio-ferm, CH); (A2.2) Pseudozyma aphidis (disclosed in WO 2011 / 151819 by the Research Development Company of the Hebrew University of Jerusalem); Saccharomyces cerevisiae, in particular the strains CNCM No. I-3936, CNCM No. I-3937, CNCM No. I-3938 or CNCM No. I-3939 from Lesaffre et Compagnie, FR. No. I-3939 strain (WO2010 / 086790); (B) a biological fungicide selected from the group consisting of: (B1) Bacteria, such as (B1.1) Bacillus subtilis, in particular the strain QST713 / AQ713 (having NRRL accession number B21661, described in U.S. Patent No. 6,060,051, and available from Bayer CropScience LP, USA, as SERENADE OPTI or SERENADE ASO); (B1.2) Bacillus pumilus, in particular the strain QST2808 (having NRRL accession number B-30087, described in U.S. Patent No. 6,245,551, and available from Bayer CropScience LP, USA, as SONATA®); (B1.3) Bacillus pumilus, in particular the strain GB34 (available from Bayer AG, Germany, as Yield Shield®); (B1.4) Bacillus pumilus, in particular the strain BU34 (having NRRL accession number 50185) strain F-33 (available as part of the BASF product CARTISSA, EPA registration number 71840-19); (B1.5) Bacillus amyloliquefaciens, particularly strain D747 (having accession number FERM BP-8234 and available from Kumiai Chemical Industry Co., Ltd. as Double Nickel®, U.S. Patent No. 7,094,592); (B1.6) Bacillus subtilis Y1336 (registered as a biofungicide in Taiwan under registration numbers 4764, 5454, 5096, and 5277 and available from BioN-Tech, Taiwan as BIOBAC® WP); (B1.7) Bacillus subtilis strain MBI 600 (BASF) with accession number NRRL B-50595, U.S. Patent No. 5,061,495 (B1.8) Bacillus subtilis strain GB03 (available as Kodiak® from Bayer AG, Germany); (B1.9) Bacillus subtilis var. amyloliquefaciens strain FZB24 with accession number DSM 10271 (available as TAEGRO® or TAEGRO® (EPA registration number 70127-5) from Novozymes); (B1.(B1.10) Bacillus mycoides isolate J with accession number B-30890 (available from Certis USA LLC, a subsidiary of Mitsui & Co., as BMJ TGAI® or WG, and LifeGard®); (B1.11) Bacillus licheniformis, in particular strain SB3086 with accession number ATCC 55406, WO 2003 / 000051 (available from Novozymes as ECOGUARD® Biofungicide and GREEN RELEAF®); (B1.12) accession number NRRL B-50972 or accession number NRRL Paenibacillus species strain B-67129, WO2016 / 154297; (B1.13) Bacillus subtilis strain BU1814 (available as VELONDIS® PLUS, VELONDIS® FLEX, and VELONDIS® EXTRA from BASF SE); (B1.14) Bacillus subtilis CX-9060 from Certis USA LLC, a subsidiary of Mitsui & Co.; (B1.15) Bacillus amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL accession number B-50768; WO2014 / 028521) (Marrone Bio (B1.16) Bacillus amyloliquefaciens strain FZB42 (available as RHIZOVITAL® from ABiTEP GmbH, Germany); (B1.17) Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (QUARTZO® (WG) and PRESENCE® (WP) from FMC Corporation); (B1.18) Bacillus mohavensis strain R3B (accession number NCAIM(P)B001389) from Certis USA LLC, a subsidiary of Mitsui & Co. (WO2013 / 034938); (B1.19) Paenibacillus polymyxa subsp. plantarum from BASF SE (WO2016 / 020371); (B1.20) Paenibacillus epiphyticus from BASF SE (WO2016 / 020371); (B.1.21) Pseudomonas chlororaphis strain AFS009 with accession numbers NRRLB-50897, WO2017 / 019448 (e.g., HOWLER™ and ZIO™ from AgBiome Innovations, USA); (B1.22) Pseudomonas chlororaphis, in particular strain MA342 (e.g., CEDOMON™, CERALL™ and CEDRESS™ from Bioagri and Koppert); (B1.23) Streptomyces lidicus (B1.24) Agrobacterium radiobacter strain K84 (e.g., GALLTROL-A® from AgBioChem, Inc., California); (B1.25) Agrobacterium radiobacter strain K1026 (e.g., NOGALL™ from BASF SE); (B1.26) Bacillus subtilis strain KTSB (FOLIACTIVE® from Donaghys); (B1.27) Bacillus subtilis IAB / BS03 (STK Bio-Ag Technologies, Inc., AVIV®; (B1.28) Bacillus subtilis strain Y1336 (registered as a biofungicide in Taiwan under registration numbers 4764, 5454, 5096 and 5277, available as BIOBAC® WP from BioNTech, Taiwan); (B1.29) Bacillus amyloliquefaciens isolate B246 (e.g., AVOGREEN® from the University of Pretoria); (B1.30) Bacillus methylotrophicus strain BAC-9912 (from the Chinese Academy of Sciences' Institute of Applied Ecology); (B1.31) Pseudomonas proradix (e.g., PRORADIX® from Sourcon Padena); (B1.32) Streptomyces griseoviridis strain K61 (also known as Streptomyces galbus strain K61) (Accession number DSM7206) (MYCOSTOP® from Verdera; PREFENCE® from BioWorks; see Crop Protection 2006, 25, 468-475); (B1.33) Pseudomonas fluorescens fluorescens) strain A506 (e.g., NuFarm's BLIGHTBAN® A506); and (B2) Fungi, for example: (B2.1) Coniothyrium minitans, in particular the strain CON / M / 91-8 (accession number DSM-9660; e.g., Contans® from Bayer CropScience Biologics GmbH); (B2.2) Metschnikowia fructicola, in particular the strain NRRL Y-30752; (B2.3) Microsphaeropsis ochracea; (B2.5) Trichoderma atroviride, in particular the strain SC1 (accession number CBS122089, WO2009 / 116106 and U.S. Pat. No. 8,431,120 (Bi-PA)), strain 77B (Andermatt (B2.6) Trichoderma harzianum strain T-22 (e.g., Trianum-P from Andermatt Biocontrol or Koppert) or strain Cepa Simb-T5 (Simbiose Agro); (B2.14) Gliocladium roseum (also known as Clonostachys rosea f. rosea), in particular strain 321U from Adjuvants Plus, Xue (Efficacy of Clonostachys rosea strain ACM941 and fungicide seed treatments for controlling the root tot complex of field pea, Can Jour Plant Sci 83(3): 519-524), or the IK726 strain (Jensen DF, et al.Development of a biocontrol agent for plant disease control with special emphasis on the near-commercial fungal antagonist Clonostachys rosea strain 'IK726'; Australas Plant Pathol. 2007;36:95-101; (B2.35) Talaromyces flavus strain V117b; (B2.36) Trichoderma viride, in particular strain B35 (Pietr et al., 1993, Zesz. Nauk. AR w Szczecinie 161: 125-137); (B2.37) Trichoderma asperellum, in particular strain SKT-1 with accession number FERM P-16510 (e.g., ECO-HOPE® from Kumiai Chemical Industry), strain T34 (e.g., Biocontrol Technologies, Spain). (B2.38) Trichoderma atroviride strain CNCM I-1237 (e.g., Esquive® WP, Agrauxine, France); (B2.39) Trichoderma atroviride strain number V08 / 002387; (B2.40) Trichoderma atroviride strain NMI number V08 / 002388; (B2.41) Trichoderma atroviride strain NMI number V08 / 002389; (B2.42) Trichoderma atroviride strain NMI number V08 / 002390; (B2.43) Trichoderma atroviride strain LC52 (e.g., Agrimm Technologies Limited, Tenet; (B2.44) Trichoderma atroviride strain ATCC20476 (IMI206040); (B2.45) Trichoderma atroviride strain T11 (IMI352941 / CECT20498); (B2.46) Trichoderma harmatum; (B2.47) Trichoderma harzianum; (B2.48) Trichoderma harzianum Rify T39 (e.g., Trichodex® from Mactesym, USA); (B2.49) Trichoderma asperellum, in particular the kd strain (e.g., T-Gro from Andermatt Biocontrol); (B2.50) Trichoderma harzianum ITEM908 strain (e.g., Trianum-P from Koppert); (B2.51) Trichoderma harzianum TH35 strain (e.g., Root-Pro from Mycontrol); (B2.52) Trichoderma virens (also known as Gliocladium virens), in particular the GL-21 strain (e.g., SoilGard from Certis, USA); (B2.53) Trichoderma viride viride strain TV1 (e.g. Trianum-P from Koppert); (B2.54) Ampelomyces quisqualis, in particular strain AQ10 (e.g. AQ10® from IntrachemBio Italia); (B2.56) Aureobasidium pullulans pullulans, in particular strain DSM 14940; (B2.57) Aureobasidium pullulans, in particular strain DSM 14941; (B2.58) A mixture of spores of Aureobasidium pullulans, in particular strains DSM 14940 and DSM 14941 (e.g., Botector® from Bio-ferm, CH); (B2.64) Cladosporium cladosporioides strain H39 (from Stichting Dienst Landbouwkundig Onderzoek GmbH) with accession number CBS 122244, US 2010 / 0291039; (B2.69) Gliocladium catenulatum (synonym: Clonostachys rosae f. Clonostachys rosea f. catenulate) strain J1446 (e.g., Prestop® from Lallemand); (B2.70) Lecanicillium lecanii (formerly known as Verticillium lecanii) conidia strain KV01 (e.g., Vertalec® by Koppert / Arysta); (B2.71) Penicillium vermiculatum; (B2.72) Pichia anomala strain WRL-076 (NRRL Y-30842), U.S. Pat. No. 7,579,183; (B2.75) Trichoderma atroviride strain SKT-1 (FERM P-16510), JP 11-253151 A; (B2.76) Trichoderma atroviride strain SKT-2 (FERM P-16511), JP 11-253151 A; (B2.77) Trichoderma atroviride strain SKT-3 (FERM P-17021), JP 11-253151 A; (B2.78) Trichoderma gamsii (formerly T. viride) strain ICC080 (IMI CC 392151 CABI, e.g. BioDerma by AGROBIOSOL DE MEXICO, SA DE CV); (B2.79) Trichoderma harzianum strain DB103 (available as T-Gro® 7456 from Dagutat Biolab); (B2.80) Trichoderma polysporum strain IMI206039 (e.g. Binab TF from BINAB Bio-Innovation AB, Sweden). WP); (B2.81) Trichoderma stromaticum having accession number Ts3550 (e.g., Tricovab from CEPLAC, Brazil); (B2.83) Ulocladium oudemansii strain HRU3 having accession number NM99 / 06216 (e.g., BOTRY-ZEN® from Botry-Zen Ltd, New Zealand, and BOTRYSTOP® from BioWorks Inc., New Zealand); (B2.(B2.84) Verticillium albo-atrum (formerly V. dahliae), strain WCS850, having accession number WCS850 and deposited at the Central Bureau for Fugi Cultures (e.g., DUTCH TRIG® from Tree Care Innovations); (B2.86) Verticillium chlamydosporium; (B2.87) a mixture of Trichoderma asperellum strain ICC012 (also known as Trichoderma harzianum ICC012) having accession number CABI CC IMI392716 and Trichoderma gammushii (formerly T. viride) strain ICC080 having accession number IMI 392151 (e.g., BIO-TAM® and Agrobiosol® from Isagro USA, Inc.). (B2.88) Trichoderma asperelloides JM41R (accession number NRRLB-50759) (TRICHO PLUS® from BASF SE); (B2.89) Aspergillus flavus strain NRRL21882 (product known as AFLA-GUARD® from Syngenta / ChemChina); (B2.90) Chaetomium cupreum (accession number CABI353812) (e.g., BIOKUPRUUM® from AgriLife); (B2.91) cell walls of Saccharomyces cerevisiae, in particular the strain LASO2 (Agro-Levures et Derives), strain LAS117 (CEREVISANE® from Lesaffre; BASF ROMEO® from SE), strains CNCM I-3936, CNCM I-3937, CNCM I-3938, and CNCM I-3939 from Lesaffre et Compagnie, France (WO2010 / 086790); (B2.92) Trichoderma virens strain G-41 (accession number ATCC 20906), formerly known as Glocladium virens (e.g., ROOTSHIELD® PLUS WP and TURFSHIELD® PLUS WP, BioWorks, USA); (B2.93) Trichoderma hamatum, with accession number ATCC 28012; (B2.94) Ampelomyces quiskaris strain AQ10, with accession number CNCM I-807 (e.g., AQ10®, IntrachemBio Italia); (B2.95) Phlebiopsis gigantea strain VRA1992 (ROTSTOP® C, Danstar Ferment); (B2.96) BASF Penicillium steckii (DSM27859; WO2015 / 067800) from SE; (B2.97) Chaetomium globosum (available as RIVADIOM® from Rivale); (B2.98) Cryptococcus flavescens strain 3C (NRRLY-50378); (B2.99) Dactylaria candida; (B2.100) Dilophosphora alopecur (available as TWIST FUNGUS®); (B2.101) Fusarium oxysporum strain Fo47 (Natural Plant (B2.102) Pseudozyma flocculosa strain PF-A22UL (available from Plant Products Co., Canada as SPORODEX® L); (B2.103) Trichoderma gammii (formerly T. viride) strain ICC080 (IMI CC392151 CABI) (available from Agrobisol de Mexico, SA DE CV as BIODERMA®). available); (B2.104) Trichoderma fertile (e.g., the BASF product TrichoPlus); (B2.105) Muscodor roseus, in particular the strain A3-5 (accession number NRRL30548); (B2.106) Simplicillium lanosoniveum; Biological control agents that can be combined with the compound combination of the present invention and have the effect of improving plant growth and / or plant health include: (C1) Bacillus pumilus, particularly strain QST2808 (having NRRL accession number B-30087); Bacillus subtilis, particularly strain QST713 / AQ713 (having NRRL accession number B-21661 and described in U.S. Patent No. 6,060,051; available from Bayer CropScience LP, USA, as SERENADE® OPTI or SERENADE® ASO); Bacillus subtilis, particularly strain AQ30002 (having NRRL accession number B-50421 and described in U.S. Patent Application No. 13 / 330,576); Bacillus subtilis, particularly strain AQ30004 (and NRRL B-50455, described in U.S. Patent Application No. 13 / 330,576); Sinorhizobium meliloti (Sinorhizobium Bacillus meliloti strain NRG-185-1 (NITRAGIN® GOLD from Bayer CropScience); Bacillus subtilis strain BU1814 (available as TEQUALIS® from BASF SE); Bacillus subtilis rm303 (RHIZOMAX® from Biofilm Crop Protection); Bacillus amyloliquefaciens pm414 (LOLI-PEPTA® from Biofilm Crop Protection); Bacillus mycoides BT155 (NRRL B-50921), Bacillus mycoides EE118 (NRRL B-50918), Bacillus mycoides EE141 (NRRL B-50916), Bacillus mycoides BT46-3 (NRRL B-50922), Bacillus cereus cereus family member EE128 (NRRL B-50917), Bacillus thuringiensis BT013A (NRRL B-50924), also known as Bacillus thuringiensis 4Q7, Bacillus cereus family member EE349 (NRRL B-50928), Bacillus amyloliquefaciens SB3281 (ATCC# PTA-7542;WO2017 / 205258), Bacillus amyloliquefaciens TJ1000 (available as QUIKROOTS® from Novozymes); Bacillus firmus, in particular the strain CNMC I-1582 (e.g., VOTIVO® from BASF SE); Bacillus pumilus, in particular the strain GB34 (e.g., YIELD SHIELD® from Bayer CropScience, Germany); Bacillus amyloliquefaciens, in particular the strain IN937a; Bacillus amyloliquefaciens, in particular the strain FZB42 (e.g., RHIZOVITAL® from ABiTEP, Germany); Bacillus amyloliquefaciens BS27 (accession number NRRL B-5015; a mixture of Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (available from FMC Corporation as QUARTZO® (WG), PRESENCE® (WP)); Bacillus cereus, particularly strain BP01 (ATCC 55675; e.g., MEPICHLOR® from Arysta Lifesciences, USA); Bacillus subtilis, particularly MBI600 (e.g., SUBTILEX® from BASF SE); Bradyrhizobium japonicum (e.g., OPTIMIZE® from Novozymes); Mesorhizobium cicer (e.g., NODULATOR® from BASF SE); Rhizobium leguminosarium biovar viciae (e.g., BASF NODULATOR from SE; Delftia acidovorans, particularly the strain RAY209 (e.g., BIOBOOST® from Brett Young Seeds); Lactobacillus species (e.g., LACTOPLANT® from LactoPAFI); Paenibacillus polymyxa, particularly the strain AC-1 (e.g., TOPSEED® from Green Biotech Company Ltd.);Pseudomonas proradicus (e.g., PRORADIX® from Sourcon Padena); Azospirillum brasilense (e.g., VIGOR® from KALO, Inc.); Azospirillum lipoferum (e.g., VERTEX-IF® from TerraMax, Inc.); a mixture of Azotobacter vinelandii and Clostridium pasteurianum (available as INVIGORATE® from Agrinos); Pseudomonas aeruginosa, particularly the PN1 strain; Rhizobium leguminosarum, particularly bv. viseeae (bv. viceae strain Z25 (accession number CECT4585); Azorhizobium caulinodans, especially strain ZB-SK-5; Azotobacter chroococcum, especially strain H23; Azotobacter vinelandii, especially strain ATCC12837; Bacillus siamensis, especially strain KCTC13613T; Bacillus tequilensis, especially strain NII-0943; Serratia marcescens, especially strain SRM (accession number MTCC8708); Thiobacillus species (e.g., Cropay, UK) Bacteria selected from the group consisting of CROPAID® from Co., Ltd.; and (C2) Purpureocillium lilacinum (formerly known as Paecilomyces lilacinus) strain 251 (AGAL89 / 030550; e.g., BioAct from Bayer CropScience Biologics GmbH), Penicillium bilaii strain ATCC22348 (e.g., JumpStart® from Acceleron BioAg), Talaromyces flavus strain V117b; Trichoderma atroviride strain CNCM I-1237 (e.g., Esquive® WP from Agrauxine, France), Trichoderma viride, e.g., strain B35 (Pietr et al., 1993, Zesz. Nauk.AR w Szczecinie 161: 125-137); Trichoderma atroviride strain LC52 (also known as Trichoderma atroviride strain LU132; e.g., Sentinel from Agrimm Technologies Limited); Trichoderma atroviride strain SC1 described in International Application No. PCT / IT2008 / 000196; Trichoderma asperellum strain kd (e.g., T-Gro from Andermatt Biocontrol); Trichoderma asperellum strain Eco-T (Plant Health Products, South Africa); Trichoderma harzianum strain T-22 (e.g., Trianum-P from Andermatt Biocontrol or Koppert); Myrothecium verrucaria strain AARC-0255 (e.g., Valent DiTera™ from Biosciences; Penicillium virilis strain ATCC CATCC 20851; Pythium oligandrum strain M1 (ATCC 38472; e.g., Polyversum from Bioprepraty, Czech Republic); Trichoderma virens strain GL-21 (e.g., SoilGard™ from Certis, USA); Verticillium albo-atrum (formerly V. dahliae) strain WCS850 (CBS276).92; e.g., Dutch Trig from Tree Care Innovations; Trichoderma atroviride, in particular strain numbers V08 / 002387, NMI V08 / 002388, NMI V08 / 002389, and NMI V08 / 002390; Trichoderma harzianum strain ITEM908; Trichoderma harzianum strain TSTh20; Trichoderma harzianum strain 1295-22; Pythium oligandrum strain DV74; Rhizopogon amylopogon (e.g., in Myco-Sol from Helena Chemical Company); Rhizopogon fulvigleba (e.g., in Helena Chemical A fungus selected from the group consisting of Trichoderma virens strain GI-3; an insecticidal biological control agent selected from the following: (D1) Bacillus thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372; e.g., XENTARI® from Valent BioSciences); Bacillus mycoides isolate J. (e.g., BmJ from Certis USA LLC, a subsidiary of Mitsui & Co.); Bacillus sphaericus, in particular serotype H5a5b strain 2362 (ABTS-1743) (e.g., VECTOLEX® from Valent BioSciences, USA); Bacillus thuringiensis subsp. kurstaki from Becker Microbial Products, IL.kurstaki strain BMP123; Bacillus thuringiensis subsp. aizawa, in particular serotype H-7 (e.g., FLORBAC® WG, Valent BioSciences, USA); Bacillus thuringiensis subsp. kurstaki strain HD-1 (e.g., DIPEL® ES, Valent BioSciences, USA); Bacillus thuringiensis subsp. kurstaki strain BMP123, Becker Microbial Products, IL; Bacillus thuringiensis israelensis strain BMP144 (e.g., AQUABAC®, Becker Microbial Products, IL); Burkholderia species, in particular Burkholderia rinojensis strain A396 (also known as Burkholderia rinojensis strain MBI305) (accession number NRRL B-50319; WO2011 / 106491 and WO2013 / 032693; e.g., MBI-206 TGAI and ZELTO® from Marrone Bio Innovations; Chromobacterium subtsugae, particularly the strain PRAA4-1T (MBI-203; e.g., GRANDEVO® from Marrone Bio Innovations); Paenibacillus popilliae (formerly Bacillus popilliae; e.g., MILKY SPORE POWDER® and MILKY SPORE GRANULAR® from St. Gabriel Laboratories); Bacillus thuringiensis subsp. israelensis (serotype H-14) strain AM65-52 (accession number ATCC 1276) (e.g., Valentin Biosciences, USA); BioSciences' VECTOBAC®; Bacillus thuringiensis var.kurstaki) strain EVB-113-19 (e.g., BIOPROTEC® from AEF Global); Bacillus thuringiensis subsp. tenebrionis strain NB176 (SD-5428; e.g., NOVODOR® FC from BioFa, Germany); Bacillus thuringiensis var. japonensis strain Buibui; Bacillus thuringiensis subsp. kurstaki strain ABTS351; Bacillus thuringiensis subsp. kurstaki strain PB54; Bacillus thuringiensis subsp. kurstaki strain SA11; Bacillus thuringiensis subsp. kurstaki strain SA12; Bacillus thuringiensis subsp. kurstaki strain EG2348; Bacillus thuringiensis var. columelli (e.g., Changzhou Jianghai Chemical strain Aizawa GC-91; Serratia entomophila (e.g., INVADE® from Wrightson Seeds); Serratia marcescens, particularly strain SRM (accession number MTCC8708); and Wolbachia pipientis ZAP strain (e.g., ZAP MALES® from Mosquito Mate); and (D2) Isaria fumosorosea (formerly known as Paecilomyces fumosoroseus) apopka97 strain; Beauveria bassiana ATCC74040 strain (e.g., NATURALIS® from Intrachem Bio Italia); Beauveria bassiana GHA strain (accession number ATCC74250; e.g., BOTANIGUARD® ES and MYCONTROL-O® from Laverlam International Corporation); Zooftora radicans radicans; Metarhizium robertii 15013-1 (deposited as NRRL Accession No. 67073), Metarhizium robertii 23013-3 (deposited as NRRL Accession No. 67075), and Metarhizium anisopliae 3213-1 (deposited as NRRL Accession No. 67074) (WO2017 / 066094; Pioneer Hi-Bred International); Boweria bassiana strain ATP02 (accession No. DSM24665). Among these, Isaria fumosorosea (formerly Paecilomyces fumosoroseus) strain apopka97 is particularly preferred. (E) a virus selected from the group consisting of Adoxophyes orana (summer fruit tortrix moth) granulosis virus (GV), Cydia pomonella (codling moth) granulosis virus (GV), Helicoverpa armigera (cotton bollworm) nucleopolyhedrovirus (NPV), Spodoptera exigua (beet armyworm) mNPV, Spodoptera frugiperda (striped armyworm) mNPV, and Spodoptera littoralis (Egyptian armyworm) NPV; (F) Bacteria and fungi that can be added as "inoculants" to plants or plant parts or plant organs and that, by their specific properties, promote plant growth and plant health; examples include: Agrobacterium spp., Azorhizobium caulinodans, Azospirillum spp., Azotobacter spp., Bradyrhizobium spp., Burkholderia spp., especially Burkholderia cepacia (formerly known as Pseudomonas cepacia), Gigaspora spp., or Gigaspora monosporum. monosporum, Glomus spp., Laccaria spp., Lactobacillus buchneri, Paraglomus spp., Pisolithus tinctorus, Pseudomonas spp., Rhizobium spp., in particular Rhizobium trifolii, Rhizopogon spp., Scleroderma spp., Suillus spp. and Streptomyces spp.; and (G) Allium sativum, Artemisia absinthium, Azadirachtin, Biokeeper WP, Cassia nigricans, Celastrus angulatus, Chenopodium anthelminticum, Chitin, Armour-Zen, Dryopteris filix-max, Equisetum arvense, Fortune Aza, Fungastop, Heads Up (Chenopodium quinoa saponin extract), Pyrethrum / Pyrethrins, Quassia amara amara, Quercus, Quillaja, Regalia, "Requiem™ Insecticide", rotenone, ryania / ryanodine, Symphytum officinale, Tanacetum vulgare, thymol, Triact 70, TriCon, Tropaeulum majus, Urtica dioica, Veratrin, Viscum album, Brassicaceae extracts, especially rapeseed or mustard powder, and olive oil, especially C, as found, for example, in products under the trade name FLiPPER®. 16 -C 20 Bio-insecticides / acaricides active substances obtained from unsaturated fatty acids / carboxylic acids having a carbon chain length of

[0168] The compounds of formula (I) and compositions of the present invention may be combined with one or more active ingredients selected from insecticides, acaricides and nematicides.

[0169] The terms "insecticide" and "insecticidal" refer to the ability of a substance to increase mortality or inhibit growth rate of insects. As used herein, the term "insect" includes all organisms in the class "Insecta."

[0170] "Nematicide" and "nematicidal" refer to the ability of a substance to increase mortality or inhibit the growth rate of nematodes. Generally, the term "nematodes" includes eggs, larvae, juveniles and adult forms of the organisms.

[0171] "Acaricide" and "acaricidal" refer to the ability of a substance to increase mortality or inhibit the growth rate of ectoparasites belonging to the class Arachnida, subclass Acari.

[0172] Examples of insecticides, acaricides and nematicides that can be mixed with the compounds of formula (I) and compositions of the present invention are: (1) For example, carbamates, such as alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC, and xylylcarb; or organophosphates, such as acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyphos, chlorfenvinphos, chlormephos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos / DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfide Acetylcholinesterase (AChE) inhibitors such as photon, EPN, ethion, ethoprophos, famphr, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyaphos, isofenphos, isopropyl O-(methoxyaminothiophosphoryl)salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton methyl, parathion methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirinmufos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon and vamidothion; (2) GABA-gated chloride channel blockers, such as cyclodiene-organochlorine compounds, e.g., chlordane and endosulfan, or phenylpyrazoles (fiproles), e.g., ethiprole and fipronil; (3) For example, pyrethroids, such as acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin s-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin, β-cyfluthrin, cyhalothrin, λ-cyhalothrin, γ-cyhalothrin, cypermethrin, α-cypermethrin, β-cypermethrin, θ-cypermethrin, ζ-cypermethrin, cyphenothrin [(1R)-trans isomer], deltamethrin, empenthrin [(EZ)-(1R)-isomer] , esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucisrinate, flumethrin, τ-fluvalinate, halfenprox, imiprothrin, kadesrin, momfluorotrin, permethrin, fenothrin [(1R)-trans isomer], prallethrin, pyrethrins (pyrethram), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R)-isomer)], tralomethrin and transfluthrin or sodium channel modulators such as DDT or methoxychlor; (4) nicotinic acetylcholine receptor (nAChR) competitive modulators, such as neonicotinoids, e.g., acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam, or nicotine, or sulfoxaflor, or flupyradifurone; (5) nicotinic acetylcholine receptor (nAChR) allosteric modulators, such as spinosyns, e.g., spinetoram and spinosad; (6) glutamate-gated chloride channel (GluCl) allosteric modulators, such as avermectins / milbemycins, e.g., abamectin, emamectin benzoate, lepimectin, and milbemectin; (7) Juvenile hormone analogues, such as hydroprene, kinoprene and methoprene or fenoxycarb or pyriproxyfen; (8) Other nonspecific (multi-site) inhibitors such as alkyl halides, e.g., methyl bromide and other alkyl halides; or chloropicrin or sulfuryl fluoride or borax or tartar emetic or methyl isocyanate generators, e.g., diazomet and metam; (9) Chordotonal organ modulators, such as pymetrozine or flonicamide; (10) mite growth inhibitors such as clofentezine, hexythiazox and diflobidazine or etoxazole; (11) Microbial disruptors of insect gut membranes, such as Bacillus thuringiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, Bacillus thuringiensis subsp. tenebrionis, and Bacillus thuringiensis plant proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, and Cry34Ab1 / 35Ab1; (12) ATP disruptors, such as diafenthiuron or organotin compounds, such as azocyclotin, cyhexatin and fenbutatin oxide, or propargite or tetradifon, which are inhibitors of mitochondrial ATP synthase; (13) Uncouplers of oxidative phosphorylation by disrupting the proton gradient, such as chlorfenapyr, DNOC, and sulfluramide; (14) Nicotinic acetylcholine receptor channel blockers, such as bensultap, cartap hydrochloride, thiothylam, and thiosultap sodium; (15) Type 0 chitin biosynthesis inhibitors, such as bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, and triflumuron; (16) Type 1 chitin biosynthesis inhibitors, such as buprofezin; (17) Molting disruptors, such as cyromazine (especially for dipterans, i.e., dipterans); (18) Ecdysone receptor agonists, such as chromafenozide, halofenozide, methoxyfenozide, and tebufenozide; (19) Octopamine receptor agonists, such as amitraz; (20) mitochondrial complex III electron transport inhibitors, such as hydramethylnon or acequinocyl or fluacrypyrim; (21) Mitochondrial complex I electron transport inhibitors, such as, for example, those from the group of METI acaricides, such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad or rotenone (Derris); (22) Voltage-dependent sodium channel blockers, such as indoxacarb or metaflumizone; (23) Inhibitors of acetyl-CoA carboxylase, such as derivatives of tetronic and tetramic acids, for example, spirodiclofen, spiromesifen, and spirotetramat; (24) Mitochondrial complex IV electron transport inhibitors, such as phosphines, for example, aluminum phosphide, calcium phosphide, phosphine, and zinc phosphide, or cyanides, for example, calcium cyanide, potassium cyanide, and sodium cyanide; (25) Mitochondrial complex II electron transport inhibitors, such as β-ketonitrile derivatives, e.g., cyenopyrafen and cyflumetofen, and carboxanilides, e.g., piflubumid; (28) Ryanodine receptor modulators, such as diamides, e.g., chlorantraniliprole, cyantraniliprole, and flubendiamide; For example, afidopiropen, afoxolaner, azadirachtin, benclothiaz, benzoximate, bifenazate, brofuranilide, bromopropylate, quinomethionate, chlorprallethrin, cryolite, cyclaniliprole, cycloxapride, cyhalodiamide, dichloromezothiaz, dicofol, ε-metofluthrin, ε-monfluthrin, flometoquin, fluazaindolizine, fluensulfone, flufenerim, flufenoxystrobin, flufiprole, fluhexafon, fluopyram, fluralaner, and fluxamic acid. thamide, fufenozide, guadipyr, heptafluthrin, imidaclothiz, iprodione, κ-bifenthrin, κ-tefluthrin, lotilaner, meperfluthrin, paichongding, pyridalyl, pyrifluquinazone, pyriminostrobin, spirobudiclofen, tetramethylfluthrin, tetraniliprole, tetrachlorantraniliprole, tigoraner, thioxazaphen, thiofluoximate, triflumezopyrim and iodomethane; in addition, preparations based on Bacillus firmus (I-1582, BioNeem, Votivo), and the following compounds: 1-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-triazol-5-amine (known from WO 2006 / 043635) (CAS 885026-50-6), {1'-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]-5-fluorospiro[indole-3,4'-piperidine]-1(2H)-yl}(2-chloropyridin-4-yl)methanone (known from WO 2003 / 106457) (CAS S637360-23-7), 2-chloro-N-[2-{1-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]piperidin-4-yl}-4-(trifluoromethyl)phenyl]isonicotinamide (known from WO2006 / 003494) (CAS872999-66-1), 3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-methoxy-1,8-diazaspiro[4.5]dec-3-en-2-one (known from WO2010052161) (CAS1225292-17-0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-ylethyl carbonate (known from EP2647626) (CAS1440516-42-6), 4-(but-2-yn-1-yloxy)-6-(3,5-dimethylpiperidin-1-yl)-5-fluoropyrimidine (known from WO2004 / 099160) (CAS792914-58-0), PF1364 (known from JP2010 / 018586) (CAS1204 776-60-2), N-[(2E)-1-[(6-chloropyridin-3-yl)methyl]pyridin-2(1H)-ylidene]-2,2,2-trifluoroacetamide (known from WO2012 / 029672) (CAS1363400-41-2), (3E)-3-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-1,1,1-trifluoro-propan-2-one (known from WO2013 / 144213) (CAS1461743-15-6), N-[3-( benzylcarbamoyl)-4-chlorophenyl]-1-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide (known from WO2010 / 051926) (CAS 1226889-14-0), 5-bromo-4-chloro-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-2-(3-chloro-2-pyridyl)pyrazole-3-carboxamide (known from CN103232431) (CAS 1449220 -44-3), 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxide-3-thietanyl)-benzamide, 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(trans-1-oxide-3-thietanyl)-benzamide and 4-[(5S)-5-(3,5-dichlorophenyl)-4,5-Dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxide-3-thietanyl)benzamide (known from WO2013 / 050317A1) (CAS 1332628-83-7), N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]-propanamide, (+)-N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[( 3,3,3-trifluoropropyl)sulfinyl]-propanamide and (-)-N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]-propanamide A1) (CAS 1477923-37-7), 5-[[(2E)-3-chloro-2-propen-1-yl]amino]-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3- Carbonitrile (known from CN101337937A) (CAS1105672-77-2), 3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)thioxomethyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide, (Liudaibenjiaxuanan) (CAS1232543-85-9 known from CN103109816A); N-[4-chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3- N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide (known from WO2011 / 085575A1) (CAS1233882-22-8), 4-[3-[2,6-dichloro-4-[(3,3-Dichloro-2-propen-1-yl)oxy]phenoxy]propoxy]-2-methoxy-6-(trifluoromethyl)-pyrimidine (known from CN101337940A) (CAS 1108184-52-6); (2E)- and 2(Z)-2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydrazinecarboxamide (known from CN101715774A) (CAS 1232543-85-9); 3-(2,2-dichloroethenyl)-2,2-dimethyl-4-(1H-benzimidazol-2-yl)phenylcyclohexyl (4aS)-7-Chloro-2,5-dihydro-2-[[(methoxycarbonyl)[4-[(trifluoromethyl)thio]phenyl]amino]carbonyl]-indeno[1,2-e][1,3,4]oxadiazine-4a(3H)-carboxylic acid methyl ester (known from CN102391261A) (CAS1370358-69-2); 6-deoxy-3-O-ethyl-2,4-di-O-methyl-, 1-[N-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1H-1,2,4-Triazol-3-yl]phenyl]carbamate]-α-L-mannopyranose (known from US2014 / 0275503A1) (CAS 1181213-14-8); 8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-azabicyclo[3.2.1]octane (CAS 1253850-56-4), (8-anti)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-azabicyclo[3.2.1]octane (CAS 1253850-56-4), (8-syn)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-azabicyclo[3.2.1]octane (CAS 933798-27-7), (8-syn)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-azabicyclo[3.2.1]octane (known from WO2007040280A1 and WO2007040282A1) (CAS 934001-66-8), N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3 -trifluoropropyl)thio]-propanamide (known from WO2015 / 058021A1 and WO2015 / 058028A1) (CAS 1477919-27-9) and N-[4-(aminothioxomethyl)-2-methyl-6-[(methylamino)carbonyl]phenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide (known from CN103265527A) (CAS 1452877-50-7), 5-(1,3-dioxan-2-yl)-4-[[4-(trifluoromethyl) 3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-methoxy-1-methyl-1,8-diazaspiro[4.5]dec-3-en-2-one (known from WO2010 / 066780A1 and WO2011 / 151146A1) (CAS 1229023-34-0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-1,8-diazaspiro[4.5]decane-2,4-dione (known from WO2014 / 187846A1) (CAS 1638765-58-8), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl-carboxylic acid ethyl ester (WO2010 / 066780A1, WO2011151146A1 ) (CAS 1229023-00-0), N-[1-[(6-chloro-3-pyridinyl)methyl]-2(1H)-pyridinylidene]-2,2,2-trifluoroacetamide (known from DE 3639877 A1 and WO 2012029672 A1) (CAS 1363400-41-2), [N(E)]-N-[1-[(6-chloro-3-pyridinyl)methyl]-2(1H)-pyridinylidene]-2,2,2-trifluoroacetamide (known from DE 3639877 A1 and WO 2012029672 A1) (CAS 1363400-41-2), Further active compounds such as [N(Z)]-N-[1-[(6-chloro-3-pyridinyl)methyl]-2(1H)-pyridinylidene]-2,2,2-trifluoroacetamide (known from WO2016005276A1) (CAS1689566-03-7), [N(Z)]-N-[1-[(6-chloro-3-pyridinyl)methyl]-2(1H)-pyridinylidene]-2,2,2-trifluoroacetamide (CAS1702305-40-5), 3-endo-3-[2-propoxy-4-(trifluoromethyl)phenoxy]-9-[[5-(trifluoromethyl)-2-pyridinyl]oxy]-9-azabicyclo[3.3.1]nonane (known from WO2011 / 105506A1, WO2016 / 133011A1) (CAS1332838-17-1), is.

[0173] Examples of herbicides that can be mixed with the compounds of formula (I) and compositions of the present invention are: Acetochlor, acifluorfen, acifluorfen sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim sodium, ametryn, amicarbazone, amidochlor, amidosulfuron, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid, aminocyclopyrachlor, aminocyclopyrachlor potassium, aminocyclopyrachlor methyl, aminopyralid, amitrole, ammonium sulfamate, anilofos, asulam, a Thorazine, azafenidine, azimsulfuron, beflubutamid, benazolin, benazolin ethyl, benfluralin, benfuresate, bensulfuron, bensulfuron methyl, bensulide, bentazon, benzobicyclon, benzofenap, bicyclopyrone, bifenox, viranaphos, viranaphos sodium, bispyribac, bispyribac sodium, bixyllozone, bromacil, bromobutide, bromofenoxime, bromoxynil, bromoxynil butyrate, bromoxynil potassium, bromoxynil heptanoate, and bromoxynil octanoate, busoxinone, butachlor, butafenacil, butamifos, butenachlor, butralin, butroxydim, butyrate, cafenstrole, carbetamide, carfentrazone, carfentrazone-ethyl, chloramben, chlorbromuron, 1-{2-chloro-3-[(3-cyclopropyl-5-hydroxy-1-methyl-1H-pyrazol-4-yl)carbonyl]-6-(trifluoromethyl)phenyl}piperidin-2-one, 4-{2-chloro-3-[(3,5-dimethyl-1H-pyrazol-1-yl)methyl]- 4-(methylsulfonyl)benzoyl}-1,3-dimethyl-1H-pyrazol-5-yl-1,3-dimethyl-1H-pyrazole-4-carboxylate, chlorfenac, chlorfenac sodium, chlorfenprop, chlorflurenol, chlorflurenol methyl, chloridazon, chlorimuron, chlorimuron ethyl, 2-[2-chloro-4-(methylsulfonyl)-3-(morpholin-4-ylmethyl)benzoyl}-3-hydroxycyclohex-2-en-1-one, 4-{2-chloro-4-(methylsulfonyl)-3-[(2,2,2-trifluoroethoxy)methyl]benzoyl}-1-ethyl-1H-pyrazol-5-yl-1,3-dimethyl-1H-pyrazole-4-carboxylate, chlorophthalim, chlorotoluron, chlorthaldimethyl, 3-[5-chloro-4-(trifluoromethyl)pyridin-2-yl]-4-hydroxy-1-methylimidazolidin-2-one, chlorsulfuron, cinidon, cinidon ethyl, cinmethylin, cinosulfuron, clasifos, clethodim, clodinafop, clodinafop -Propargyl, clomazone, clomeprop, clopyralid, cloransulam, cloransulam-methyl, cumyluron, cyanamide, cyanazine, cycloate, cyclopyranyl, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop, cyhalofop-butyl, cyprazine, 2,4-D, 2,4-D-butotyl, -butyl, -dimethylammonium, -diolamine, -ethyl, -2-ethylhexyl, isobutyl, -isooctyl, -isopropylammonium, -potassium ammonium, -triisopropanolammonium, and -trolamine, 2,4-DB, 2,4-DB-butyl, -dimethylammonium, -isooctyl, -potassium, and -sodium, dymron (dimuron), dalapon, dazomet, n-decanol, desmedipham, detosylpyrazolate (DTP), dicamba, dichlobenil, dichlorprop, dichlorprop-P, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, difenzoquat, di Flufenican, diflufenzopyr, diflufenzopyr sodium, dimefron, dimepiperate, dimethachlor, dimethamethrin, dimethenamid, dimethenamid-P, 3-(2,6-dimethylphenyl)-6-[(2-hydroxy-6-oxocyclohex-1-en-1-yl)carbonyl]-1-methylquinazoline-2,4(1H,3H)-dione, 1,3-dimethyl-4-[2-(methylsulfonyl)-4-(trifluoromethyl)benzoyl]-1H-pyrazol-5-yl-1,3-Dimethyl-1H-pyrazole-4-carboxylate, dimetrasulfuron, dinitramine, dinoterb, diphenamide, diquat, diquat-dibromide, dithiopyr, diuron, DMPA, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsurfuron, ethametsurfuron-methyl, etiodin, ethofumesate, ethoxyfen, ethoxyfen-ethyl, ethoxysulfuron, etobenzanide, ethyl-[(3-{2-chloro-4-fluoro-5-[3-methyl-2,6-dioxo-4-(trifluoromethyl)amino]phenyl]propanol]

[0033] F-9960, F-5231, i.e., N-{2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-5-oxo-4,5-dihydro-1H-tetrazol-1-yl]phenyl}ethanesulfonamide, F-7967, i.e., 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fenquinotrione, fentrazamide, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazifop-butyl, fluazifop-P-butyl, flucarbazone, flucarbazone sodium, flucetosulfuron fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazin, fluometuron, flurenol, flurenol-butyl, dimethylammonium and methyl, fluoroglycofen, fluoroglycofen-ethyl, flupropanate, flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluridone, fluorochloridone, fluroxypyr, fluroxypyr-meptyl, flurtamone, fluthiacet, fluthiacetmethyl, fomesafen, fomesafen sodium, foramsulfuron, fosamine, glufosinate, glufosinate-ammonium, glufosinate-P-sodium, glufosinate-P-ammonium, glufosinate-P-sodium, glyphosate, glyphosate-ammonium, isopropylammonium, diammonium, dimethylammonium, potassium, sodium and trimesium, H-9 201, i.e., O-(2,4-dimethyl-6-nitrophenyl) O-ethyl isopropyl phosphoramidothioate, haloxifene, haloxifene methyl, halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfop-ethoxyethyl, haloxyfop-P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, hexazinone, HW-02, i.e., 1-(dimethoxyphosphoryl)ethyl-(2,4-Dichlorophenoxy)acetate, 4-hydroxy-1-methoxy-5-methyl-3-[4-trifluoromethyl)pyridin-2-yl]imidazolidin-2-one, 4-hydroxy-1-methyl-3-[4-trifluoromethyl)pyridin-2-yl]imidazolidin-2-one, (5-hydroxy-1-methyl-1H-pyrazol-4-yl)(3,3,4-trimethyl-1,1-dioxide-2,3-dihydro-1-benzothiophen-5-yl)methanone, 6-[(2-hydroxy-6-oxocyclohex-1-en-1-yl)carbonyl]-1,5-dimethyl-3-(2-methylphenyl)quinazoline-2,4(1H,3H)-dione, imazamethabenz, imazamethabenz methyl, imazamox, i Mazamox ammonium, imazapic, imazapic ammonium, imazapyr, imazapyr isopropylammonium, imazaquin, imazaquin ammonium, imazethapyr, imazethapyr immonium, imazosulfuron, indanofan, indaziflam, iodosulfuron, iodosulfuron methyl sodium, ioxynil, ioxynil octanoate, potassium and sodium, ipfencarbazone, isoproturon, isolone, isoxaben, isoxaflutole, carbutilate, KUH-043, i.e., 3-({[5-(difluoromethyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfonyl)-5,5-dimethyl-4,5-dihydro-1,2-Oxazole, ketospiradox, lactofen, lenacil, linuron, MCPA, MCPA-butotyl, -dimethylammonium, -2-ethylhexyl, -isopropylammonium, -potassium and -sodium, MCPB, MCPB-methyl, -ethyl and -sodium, mecoprop, mecoprop-sodium and -butotyl, mecoprop-P, mecoprop-P-butotyl, -dimethylammonium, -2-ethylhexyl and -potassium, mefenacet, mefluidide, mesosulfuron, mesosulfuron-methyl, mesotrione, methabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methiopyrsulfuron, methiozolin, 2-({2-[(2-methoxyethoxy)methyl]-6 -(trifluoromethyl)pyridin-3-yl}carbonyl)cyclohexane-1,3-dione, methyl isothiocyanate, 1-methyl-4-[(3,3,4-trimethyl-1,1-dioxide-2,3-dihydro-1-benzothiophen-5-yl)carbonyl]-1H-pyrazol-5-ylpropane-1-sulfonate, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron methyl, molinat, monolinuron, monosulfuron, monosulfuron ester, MT-5950, i.e., N-(3-chloro-4-isopropylphenyl)-2-methylpentanamide, NGGC-011, napropamide, NC-310, i.e., [5-(benzyloxy)-1-methyl-1H-pyrazol-4-yl](2,4-Dichlorophenyl)methanone, nebron, nicosulfuron, nonanoic acid (pelargonic acid), norflurazon, oleic acid (fatty acid), orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefon, oxyfluorfen, paraquat, paraquat dichloride, pebulate, pendimethalin, penoxsulam, pentachlorophenol, pentoxazone, petoxamide, petroleum, phenmedipham, picloram, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, primi Sulfuron methyl, prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propiisochlor, propoxycarbazone, propoxycarbazone sodium, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotole, pyrazolinate (pyrazolate), pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl, pyribambenz-propyl, Pyribenzoxim, pyributicarb, pyridafol, pyridate, pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, piroxsulam, quinclorac, quinomelac, quinoclamine, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, QYM-201, QYR-301, rimsulfuron, saflufenacil, sethoxydim, sizuron, shima gin, simetryn, SL-261, sulcotrione, sulfentrazone, sulfometuron, sulfometuron methyl, sulfosulfuron, SYN-523, SYP-249, i.e., 1-ethoxy-3-methyl-1-oxobut-3-en-2-yl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate, SYP-300, i.e., 1-[7-fluoro-3-oxo-4-(prop-2-yn-1-yl)-3,4-dihydro-2H-1,4-benzoxazin-6-yl]- 3-propyl-2-thioxoimidazolidine-4,5-dione, 2,3,6-TBA, TCA (trichloroacetic acid), TCA-sodium, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbumeton, terbuthylazine, terbutryn, tetflupyrrolimet, thenylchlor, thiazopyr, thiencarbazone, thiencarbazone methyl, thifensulfuron, thifensulfuron methyl, thiobencarb, thiafenacil, tolpyralate, topramezone, These are tetraalkoxydim, triafamone, triallate, triasulfuron, triaziflam, tribenuron, tribenuron methyl, triclopyr, trietazine, trifloxysulfuron, trifloxysulfuron sodium, trifludimoxazine, trifluralin, triflusulfuron, triflusulfuron methyl, tritosulfuron, urea sulfate, vernolate, and ZJ-0862, i.e., 3,4-dichloro-N-{2-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzyl}aniline.

[0174] Examples of plant growth regulators are: Acibenzolar, acibenzolar-S-methyl, 5-aminolevulinic acid, ancymidol, 6-benzylaminopurine, brassinolide, catechin, chlormequat chloride, cloprop, cycloanilide, 3-(cycloprop-1-enyl)propionic acid, daminozide, dazomet, n-decanol, dikegulac, dikegulac sodium, endothal, endothal dipotassium, disodium and mono(N,N-dimethylalkylammonium), ethephon, flumetralin, flurenol, flurenol butyl, fluprimidol, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid (IAA), 4-isopropyl methyl ... andol-3-ylbutyric acid, isoprothiolane, probenazole, jasmonic acid, hydrazide maleic acid, mepiquat chloride, 1-methylcyclopropene, methyl jasmonate, 2-(1-naphthyl)acetamide, 1-naphthylacetic acid, 2-naphthyloxyacetic acid, nitrophenolate mixture, paclobutrazol, N-(2-phenylethyl)-β-alanine, N-phenylphthalamic acid, prohexadione, prohexadione calcium, prohydrojasmone, salicylic acid, strigolactone, tecnazene, thidiazuron, triacontanol, trinexapac, trinexapac-ethyl, tositodef, uniconazole, and uniconazole-P.

[0175] Examples of safeners which may be mixed with the compounds of formula (I) and compositions of the invention are, for example, benoxacor, cloquintocet (-mexyl), cyometrinil, cyprosulfamide, dichlormid, fenchlorazole (-ethyl), fenclorim, flurazole, fluxofenim, furilazole, isoxadifen (-ethyl), mefenpyr (-diethyl), naphthalic anhydride, oxabetrinil, 2-methoxy-N-({4-[(methylcarbamoyl)amino]phenyl}sulfonyl)benzamide (CAS 129531-12-0), 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (CAS 71526-07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (CAS 52836-31-4).

[0176] Examples of nitrification inhibitors that can be mixed with the compounds of formula (I) and compositions of the invention include 2-(3,4-dimethyl-1H-pyrazol-1-yl)succinic acid, 2-(4,5-dimethyl-1H-pyrazol-1-yl)succinic acid, 3,4-dimethylpyrazolium glycolate, 3,4-dimethylpyrazolium citrate, 3,4-dimethylpyrazolium lactate, 3,4-dimethylpyrazolium mandelate, 1,2,4-triazole, 4-chloro-3-methylpyrazole, N-((3(5)-methyl-1H-pyrazol-1-yl)methyl)acetamide, N-((3(5)-methyl-1H-pyrazol-1-yl)methyl)formamide, N-((3(5),4-dimethylpyrazol-1-yl)methyl)formamide, N-((4-chloro-3(5)-methyl-pyrazol-1-yl)methyl)formamide; Reaction adducts of dicyandiamide, urea and formaldehyde, Triazonyl-dicyandiamide adduct, Formaldehyde-dicyandiamide adduct, 2-cyano-1-((4-oxo-1,3,5-triazinan-1-yl)methyl)guanidine, 1-((2-cyanoguanidino)methyl)urea element, 2-cyano-1-((2-cyanoguanidino)methyl)guanidine, 2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N-serve), dicyandiamide, 3,4-dimethylpyrazole phosphate, 4,5-dimethylpyrazole phosphate, 3,4-dimethylpyrazole, 4,5-dimethylpyrazole, ammonium thiosulfate, neem, neem-derived products, linoleic acid, α-linolenic acid, methyl p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl)propionate, karanjin, brachialactone p-Benzoquinone sorgoleone, 4-amino-1,2,4-triazole hydrochloride, 1-amido-2-thiourea, 2-amino-4-chloro-6-methylpyrimidine, 2-mercapto-benzothiazole, 5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (telazol, etridiazole), 2-sulfanilamidothiazole, 3-methylpyrazole, 1,2,4-triazole thiourea, cyanamide, melamine, zeolite powder, catechol, benzoquinone, sodium tetraborate, allyl thiourea, chlorate, and zinc sulfate.

[0177] The compounds of formula (I) and compositions of the present invention may be combined with one or more agriculturally beneficial agents.

[0178] Examples of agriculturally beneficial agents include biostimulants, plant growth regulators, plant signaling molecules, growth promoters, microbial stimulating molecules, biomolecules, soil conditioners, nutrients, plant nutrients, and the like. enhancers), such as lipochitooligosaccharides (LCOs), chitooligosaccharides (COs), chitinous compounds, flavonoids, jasmonic acid or its derivatives (e.g., jasmonates), cytokinins, auxins, gibberellins, abscisic acid, ethylene, brassinosteroids, salicylates, macronutrients and micronutrients, linoleic acid or its derivatives, linolenic acid or its derivatives, karrikins, and beneficial microorganisms (e.g., Rhizobium species, Bradyrhizobium species, Sinorhizobium species, Azorhizobium species, Glomus species, Gigaspora species, Hymenosyphos species, Oediodendron species, Laccaria species, Pisorius species, Rhizopogon species, Streptomyces species, Rhizoctonia species, Examples of suitable bacterial strains include, but are not limited to, Bacillus species, Acinetobacter species, Arthrobacter species, Arthrobotrys species, Aspergillus species, Azospirillum species, Bacillus species, Burkholderia species, Candida species, Chryseomonas species, Enterobacter species, Eupenicillium species, Exiguobacterium species, Klebsiella species, Kluyvera species, Macrobacterium species, Mucor species, Paecilomyces species, Paenibacillus species, Penicillium species, Pseudomonas species, Serratia species, Stenotrophomonas species, Streptomyces species, Streptosporangium species, Swaminatania species, Thiobacillus species, Torulospora species, Vibrio species, Xanthobacter species, Xanthomonas species, etc., and combinations thereof.

[0179] Methods and Uses The compounds of formula (I) and compositions of the present invention have strong fungicidal activity and / or plant defense regulating ability. They can be used to control undesirable microorganisms, such as undesirable fungi and bacteria, in plants. As described in more detail below, they can be particularly useful in crop protection (controlling microorganisms that cause plant diseases) or for protecting materials (e.g., industrial materials, wood, stored goods). More specifically, the compounds and compositions of formula (I) can be used to protect seeds, germinated seeds, sprouted seedlings, plants, plant parts, fruits, harvested products, and / or the soil in which plants grow from undesirable microorganisms.

[0180] As used herein Prevention or control This includes preventative, curative and eradicative treatments of unwanted microorganisms. Unwanted microorganisms The pathogen may be a pathogenic bacterium, a pathogenic virus, a pathogenic oomycete, or a pathogenic fungus, more specifically a plant pathogenic bacterium, a plant pathogenic virus, a plant pathogenic oomycete, or a plant pathogenic fungus. As described in more detail below, these plant pathogenic microorganisms are the causative agents of a wide range of plant diseases.

[0181] More specifically, the compounds of formula (I) and compositions of the present invention can be used as fungicides.For the purposes of this specification, the term "fungicide" can be used in crop protection to control undesirable fungi such as Plasmodiophoromycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes, and / or to control Oomycetes.

[0182] The compounds of formula (I) and compositions of the present invention can also be used as antibacterial agents.In particular, they can be used in crop protection to control unwanted bacteria, such as Pseudomonadaceae, Rhizobiaceae, Xanthomonadaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

[0183] The compounds of formula (I) and the compositions of the present invention can also be used as antiviral agents in crop protection. For example, the compounds of formula (I) and the compositions of the present invention can be used to treat or prevent the spread of viruses such as tobacco mosaic virus (TMV), tobacco rattle virus, tobacco dwarf virus (TStuV), tobacco leaf curl virus (VLCV), tobacco bulbil mosaic virus (TVBMV), tobacco necrotic dwarf virus (TNDV), tobacco streak virus (TSV), potato virus X (PVX), potato viruses Y, S, M and A, potato paddy mosaic virus (PAMV), potato mop top virus (PMTV), potato leaf roll virus (PLRV), alfalfa mosaic virus (AMV), cucumber mosaic virus (CMV), cucumber stalk virus (CMV ... The present invention may have an effect on plant viral diseases such as Cucurbit green mottle mosaic virus (CGMMV), Cucumber yellows virus (CuYV), Watermelon mosaic virus (WMV), Tomato spotted wilt virus (TSWV), Tomato ringspot virus (TomRSV), Sugarcane mosaic virus (SCMV), Rice dwarf virus, Rice stripe virus, Rice black streak dwarf virus, Strawberry mottle virus (SMoV), Strawberry vein green virus (SVBV), Strawberry mild yellow edge virus (SMYEV), Strawberry crinkle virus (SCrV), Broad bean wilt virus (BBWV) and Melon necrotic spot virus (MNSV).

[0184] The present invention is also a method for controlling undesirable microorganisms, such as undesirable fungi, oomycetes and bacteria in plants, comprising the step of applying at least one compound of formula (I) or at least one composition of the present invention to the microorganisms and / or their habitat (plants, plant parts, seeds, fruits or the soil in which the plants grow).

[0185] Typically, when the compounds of formula (I) and compositions of the present invention are used in curative or protective methods for controlling phytopathogenic fungi and / or phytopathogenic oomycetes, an effective and plant-compatible amount is applied to plants, plant parts, fruits, seeds, or the soil or substrate in which the plants are grown. Suitable substrates that can be used to cultivate plants include inorganic-based substrates such as mineral wool, especially stone wool, perlite, sand, or gravel; organic substrates such as peat, pine bark, and sawdust; and petroleum-based substrates such as polymer foams and plastic beads. Effective and plant-compatible amounts " refers to an amount that is sufficient to control or destroy the fungi that may exist or appear in agricultural land, and does not cause significant phytotoxicity symptoms to crops.This amount can vary within a wide range depending on the fungi to be controlled, the type of crop, the stage of growth of the crop, climatic conditions, and the compound or composition of the present invention used.This amount can be determined by systematic field tests, which is within the ability of a person skilled in the art.

[0186] Plants and plant parts The compounds of formula (I) and compositions of the present invention can be applied to any plant or plant part.

[0187] plantmeans all plants and plant populations, such as desirable and undesirable wild plants or crop plants (including naturally occurring crop plants). Crops may be plants obtained by conventional breeding and optimization methods, or by biotechnology and genetic engineering methods, or a combination of these methods, and include genetically modified plants (GMOs or transgenic plants) and plant varieties that are and are not protectable by plant breeders' rights.

[0188] plant cultivars is understood to mean plants having new properties ("traits") and obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. They may be cultivars, varieties, biotypes or genotypes.

[0189] plant parts is understood to mean all parts and organs of a plant, above and below ground, such as shoots, leaves, needles, stalks, stems, flowers, fruiting bodies, fruits, seeds, roots, tubers and rhizomes, etc. Plant parts also include harvested material, vegetative propagation material and generative propagation material, such as cuttings, tubers, rhizomes, slips and seeds.

[0190] Plants that can be treated according to the method of the invention include cotton, flax, grapevines, fruits, vegetables, such as Rosaceae species (e.g. pome fruits such as apples and pears, but also stone fruits such as apricots, cherries, almonds, peaches, and soft fruits such as strawberries), Ribesioidae species, Juglandaceae species, Birch species, Anacardiaceae species, Fagaceae species, Moraceae species, Oleaceae species, Actinidaceae species, Lauraceae species, Musaceae species. species (banana trees and plantations, etc.), Rubiaceae species (e.g., coffee), Theaceae species (e.g., tomato), Liliaceae species (e.g., lettuce), Asteraceae species (e.g., lettuce), Umbelliferae species (e.g., Cruciferae species), Chenopodiaceae species (e.g., cucurbitaceae species), Alliaceae species (e.g., leeks, onions), and Papilionaceae species (e.g., cucumber). sp.) (e.g., pea); Graminaceae species (Gramineae sp.) (e.g., maize, grass, wheat, rye, rice, barley, oats, millet, and triticale), Asteraceae species (e.g., sunflower), Brassicaceae species (e.g., white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, bok choy, kohlrabi, radish, rapeseed, mustard, horseradish, and watercress), Legume species (Fabacae sp.Major crop plants such as Fabaceae species (e.g., beans, peanuts), legume species (Papilionaceae species) (e.g., soybean), Solanaceae species (e.g., potato), and Chenopodiaceae species (e.g., sugar beet, fodder beet, Swiss chard, beetroot); useful and ornamental plants for gardens and wooded areas; and genetically modified varieties of each of these plants.

[0191] Plants and plant cultivars that may be treated by the above-mentioned methods include plants and plant cultivars that are tolerant to one or more biotic stresses, such plants exhibiting good protection against animals and microorganisms such as nematodes, insects, mites, plant pathogenic fungi, bacteria, viruses and / or viroids.

[0192] Plants and plant cultivars that can be treated by the above-mentioned methods include plants that are tolerant to one or more abiotic stress conditions, such as drought, exposure to low temperatures, exposure to heat, osmotic stress, flooding, increased soil salinity, increased mineral exposure, exposure to ozone, exposure to strong light, limited nitrogen nutrient availability, limited phosphorus nutrient availability, and shade avoidance.

[0193] Plants and plant cultivars that can be treated by the above-mentioned methods include plants characterized by improved yield characteristics. Increased yield in plants can be the result of improved plant physiology, growth, and development, such as improved water use efficiency, water retention efficiency, improved nitrogen utilization, improved carbon assimilation, improved photosynthesis, improved germination efficiency, and accelerated maturation. Yield can also be affected by improved plant architecture (under stress and non-stress conditions), including, but not limited to, early flowering, flowering control for hybrid seed production, seedling vigor, plant size, internode number and distance, root growth, seed size, fruit size, pod size, number of pods or panicles, number of seeds per pod or panicle, seed mass, increased seed filling, reduced seed dispersal, reduced pod dehiscence, and lodging resistance. Additional yield characteristics include carbohydrate content and seed composition, such as cotton or starch composition, protein content, oil content and composition, nutritional value, reduced antinutritional compounds, improved processability, and better storage stability.

[0194] Plants and plant cultivars that can be treated by the above-described methods include hybrid plants and plant cultivars that already express the characteristics of hybrid vigor, which generally result in higher yield, vigor, health and resistance to biotic and abiotic stresses.

[0195] Transgenic plants, seed treatments and integration events Compounds of formula (I) can be advantageously used to treat transgenic plants, plant cultivars, or plant parts that have received genetic material that confers advantageous and / or useful properties (traits) to these plants, plant cultivars, or plant parts. Accordingly, the present invention is intended to be combined with one or more recombinant traits or genetic recombination events, or combinations thereof. For purposes of this application, a genetic recombination event occurs when a specific recombinant DNA molecule is inserted into a specific location (locus) within a chromosome of the plant genome. The insertion creates a new DNA sequence, called an "event," characterized by the inserted recombinant DNA molecule and a certain amount of genomic DNA immediately adjacent to / flanking both ends of the inserted DNA. Such traits or genetic recombination events include, but are not limited to, pest resistance, water use efficiency, yield performance, drought tolerance, seed quality, improved nutritional value, hybrid seed production, and herbicide tolerance, as measured relative to a plant that does not possess the trait or genetic recombination event. Examples of such advantageous and / or useful properties (traits) are better plant growth, vigor, stress tolerance, erectness, host resistance, nutrient uptake, plant nutrition and / or yield, in particular improved growth, increased tolerance to high or low temperatures, increased tolerance to drought or increased tolerance to water or soil salinity levels, improved flowering performance, ease of harvesting, accelerated ripening, increased yield, higher quality and / or higher nutritional value of the harvested product, improved storage life and / or processability of the harvested product, increased resistance to harmful animals and microorganisms such as insects, arachnids, nematodes, mites, slugs and snails, etc.

[0196] Among the DNA sequences encoding proteins that confer properties of resistance to such harmful animals and microorganisms, especially insects, mention may be made in particular of the genetic material of Bacillus thuringiensis that encodes the Bt proteins, which are widely described in the literature and well known to those skilled in the art, as well as of proteins extracted from bacteria such as Photorhabdus (WO 97 / 17432 and WO 98 / 08932). In particular, Bt Cry or VIP proteins including CryIA, CryIAb, CryIAc, CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF proteins or toxic fragments thereof, as well as hybrids or combinations thereof, in particular CryIF proteins or hybrids derived from CryIF proteins (e.g., hybrid CryIA-CryIF proteins or toxic fragments thereof), CryIA type proteins or toxic fragments thereof, preferably CryIAc proteins or hybrids derived from CryIAc proteins (e.g., hybrid CryIAb-CryIAc proteins) or CryIAb or Bt2 proteins or toxic fragments thereof, Cry2Ae, Cry2Af or Cry2Ag proteins or toxic fragments thereof, CryA.105 proteins or toxic fragments thereof, VIP3Aa19 proteins, VIP3Aa20 proteins, VIP3A proteins produced in COT202 or COT203 cotton events, Estruch et al. (1996), Proc Reference is made to the VIP3Aa protein or toxic fragments thereof described in Natl Acad Sci U S A. 28;93(11):5389-94, the Cry proteins described in WO2001 / 47952, and Photorhabdus species strains such as Xenorhabdus (described in WO98 / 50427), Serratia (especially from S. entomohila), or the Tc protein from Photorhabdus described in WO98 / 08932.Also encompassed herein are variants or mutants of these proteins in which several (1 to 10, preferably 1 to 5) amino acids differ from the sequences listed above, in particular the sequences of toxic fragments thereof, or any variants or mutants fused to plastid or transport peptides such as plastid transport peptides, or fused to other proteins or peptides.

[0197] Another particularly noteworthy example of such a trait is conferring resistance to one or more herbicides, such as imidazolinones, sulfonylureas, glyphosate, or phosphinothricin. Among DNA sequences encoding proteins that confer the trait of herbicide resistance to transformed plant cells and plants, mention may be made in particular of the bar or PAT genes, or the Streptomyces coelicolor gene described in WO 2009 / 152359 that confers resistance to the herbicide glufosinate, or of genes encoding suitable EPSPS (5-enolpyruvylshikimate-3-phosphatosynthase) that confer resistance to EPSPS-targeting herbicides, particularly herbicides such as glyphosate and its salts, or of genes encoding glyphosate-n-acetyltransferase, or of genes encoding glyphosate oxidoreductase. Further suitable herbicide tolerance traits include at least one ALS (acetolactate synthase) inhibitor (e.g., WO2007 / 024782), a mutated Arabidopsis ALS / AHAS gene (e.g., U.S. Pat. No. 6,855,533), a gene encoding a 2,4-D monooxygenase that confers tolerance to 2,4-D (2,4-dichlorophenoxyacetic acid), and a gene encoding a dicamba monooxygenase that confers tolerance to dicamba (3,6-dichloro-2-methoxybenzoic acid).

[0198] Another example of such a trait is resistance to one or more plant pathogenic fungi, such as Asian soybean rust. Among DNA sequences encoding proteins that confer such disease resistance traits, mention may be made in particular of the genetic material of Glycine tomentella, such as publicly available accessions PI441001, PI483224, PI583970, PI446958, PI499939, PI505220, PI499933, PI441008, PI505256, or PI446961, as described in WO2019 / 103918.

[0199] Further particularly important examples of such properties are increased resistance to bacteria and / or viruses, e.g. due to systemic acquired resistance (SAR), systemin, phytoalexins, elicitors, as well as resistance genes and the corresponding expressed proteins and toxins.

[0200] Particularly useful genetically modified events in genetically modified plants or plant cultivars that can be preferentially treated according to the present invention include event 531 / PV-GHBK04 (cotton, insect control, described in WO2002 / 040677), event 1143-14A (cotton, insect control, not deposited, described in WO2006 / 128569); event 1143-51B (cotton, insect control, not deposited, described in WO2006 / 128570); event 1445 (cotton, herbicide resistance, not deposited, described in US-A2002-120964 or WO2002 / 034946); event 17053 (rice, herbicide resistance, deposited as PTA-9843, described in WO2010 / 117737); event 17314 (rice, herbicide resistance, PTA-9 844, described in WO2010 / 117735); Event 281-24-236 (cotton, insect control - herbicide resistance, deposited as PTA-6233, described in WO2005 / 103266 or US-A2005-216969); Event 3006-210-23 (cotton, insect control - herbicide resistance, deposited as PTA-6233, described in US-A2007-143876 or WO 2005 / 103266); Event 3272 (maize, quality traits, deposited as PTA-9972, described in WO2006 / 098952 or US-A2006-230473); Event 33391 (wheat, herbicide resistance, deposited as PTA-2347, described in WO2002 / 027004), Event 40416 (maize, insect control - herbicide resistance, ATCC PTA-11508, described in WO11 / 075593); Event 43A47 (maize, insect control - herbicide resistant, deposited as ATCC PTA-11509, described in WO2011 / 075595); Event 5307 (maize, insect control, deposited as ATCC PTA-9561, described in WO2010 / 077816); Event ASR-368 (bentgrass, herbicide resistant, deposited as ATCC PTA-4816, described in US-A2006-162007 or WO2004 / 053062); Event B16 (maize, herbicide resistant, not deposited, described in US-A2003-126634);Event BPS-KV127-9 (soybean, herbicide resistance, deposited as NCIMB number 41603, described in WO2010 / 080829); event BLR1 (oilseed rape, restoration of male sterility, deposited as NCIMB41193, described in WO2005 / 074671); event CE43-67B (cotton, insect control, DSM ACC2724, described in US-A2009-217423 or WO2006 / 128573); Event CE44-69D (cotton, insect control, not deposited, described in US-A2010-0024077); Event CE44-69D (cotton, insect control, not deposited, described in WO2006 / 128571); Event CE46-02A (cotton, insect control, not deposited, described in WO2006 / 128572); Event COT102 (cotton, insect control, not deposited, described in US-A200 6-130175 or described in WO2004 / 039986); event COT202 (cotton, insect control, not deposited, described in US-A2007-067868 or WO2005 / 054479); event COT203 (cotton, insect control, not deposited, described in WO2005 / 054480); event DAS21606-3 / 1606 (soybean, herbicide resistance, deposited as PTA-11028, described in WO2012 / 033794); event DAS40278 (maize, herbicide resistance, ATCC PTA-10244, described in WO2011 / 022469); event DAS-44406-6 / pDAB8264.44.06.1 (soybean, herbicide-resistant, deposited as PTA-11336, described in WO2012 / 075426); event DAS-14536-7 / pDAB8291.45.36.2 (soybean, herbicide-resistant, deposited as PTA-11335, described in WO2012 / 075429); event DAS-59122-7 (maize, insect control-herbicide-resistant, ATCC PTA11384, described in US-A2006-070139); event DAS-59132 (maize, insect control - herbicide resistant, not deposited, described in WO2009 / 100188); event DAS68416 (soybean, herbicide resistant, deposited as ATCC PTA-10442, described in WO2011 / 066384 or WO2011 / 066360);Event DP-098140-6 (maize, herbicide resistance, deposited as ATCC PTA-8296, described in US-A2009-137395 or WO08 / 112019); Event DP-305423-1 (soybean, quality traits, not deposited, described in US-A2008-312082 or WO2008 / 054747); Event DP-32138-1 (maize, hybridization system, deposited as ATCC PTA-9158, described in US-A2009-0210970 or WO2009 / 103049); Event DP-356043-5 (soybean, herbicide resistance, ATCC PTA-8287, described in US-A2010-0184079 or WO2008 / 002872); Event EE-I (eggplant, insect control, not deposited, described in WO07 / 091277); Event Fil 17 (maize, herbicide resistant, deposited as ATCC209031, described in US-A2006-059581 or WO98 / 044140); event FG72 (soybean, herbicide resistant, deposited as PTA-11041, described in WO2011 / 063413); event GA21 (maize, herbicide resistant, deposited as ATCC209033, described in US-A2005-086719 or WO98 / 044140); event GG25 (maize, herbicide resistant, deposited as ATCC209032, described in US-A2005-188434 or WO98 / 044140); event GHB119 (cotton, insect control - herbicide resistant, ATCC event GHB614 (cotton, herbicide resistant, deposited as ATCC PTA-6878, described in US-A2010-50282 or WO2007 / 017186); event GJ11 (maize, herbicide resistant, deposited as ATCC209030, described in US-A2005-188434 or WO98 / 044140); event GM RZ13 (sugar beet, virus resistant, deposited as NCIMB-41601, described in WO2010 / 076212); event H7-1 (sugar beet, herbicide resistant, deposited as NCIMB41158 or NCIMB41159, described in US-A2004-172669 or WO2004 / 074492);Event JOPLIN1 (wheat, disease resistant, not deposited, described in US-A2008-064032); event LL27 (soybean, herbicide resistant, deposited as NCIMB41658, described in WO2006 / 108674 or US-A2008-320616); event LL55 (soybean, herbicide resistant, deposited as NCIMB41660, described in WO2006 / 108675 or US-A2008-196127); event LLcotton25 (cotton, herbicide resistant, ATCC PTA-3343, described in WO2003 / 013224 or USA2003-097687); event LLRICE06 (rice, herbicide resistance, deposited as ATCC203353, described in US6,468,747 or WO2000 / 026345); event LLRice62 (rice, herbicide resistance, deposited as ATCC203352, described in WO2000 / 026345); event LLRICE601 (rice, herbicide resistance, deposited as ATCC PTA-2600, described in US-A2008-2289060 or WO2000 / 026356); event LY038 (maize, quality traits, ATCC PTA-5623, described in US-A2007-028322 or WO2005 / 061720); event MIR162 (corn, insect control, deposited as PTA-8166, described in US-A2009-300784 or WO2007 / 142840); event MIR604 (corn, insect control, not deposited, described in US-A2008-167456 or WO2005 / 103301); event MON15985 (cotton, insect control, deposited as ATCC PTA-2516, described in US-A2004-250317 or WO2002 / 100163); event MON810 (corn, insect control, not deposited, described in US-A2002-102582). Event MON863 (maize, insect control, deposited as ATCC PTA-2605, described in WO2004 / 011601 or US-A2006-095986); Event MON87427 (maize, pollination control, deposited as ATCC PTA-7899, described in WO2011 / 062904);Event MON87460 (maize, stress tolerance, deposited as ATCC PTA-8910, described in WO2009 / 111263 or US-A2011-0138504); event MON87701 (soybean, insect control, deposited as ATCC PTA-8194, described in US-A2009-130071 or WO2009 / 064652); event MON87705 (soybean, quality trait - herbicide tolerance, deposited as ATCC PTA-9241, described in US-A2010-0080887 or WO2010 / 037016); event MON87708 (soybean, herbicide tolerance, deposited as ATCC PTA-9670, described in WO2011 / 034704); Event MON87712 (soybean, yield, deposited as PTA-10296, described in WO2012 / 051199), event MON87754 (soybean, quality traits, deposited as ATCC PTA-9385, described in WO2010 / 024976), event MON87769 (soybean, quality traits, deposited as ATCC PTA-8911, described in US-A2011-0067141 or WO2009 / 102873). Event MON88017 (maize, insect control - herbicide resistant, deposited as ATCC PTA-5582, described in US-A2008-028482 or WO2005 / 059103); Event MON88913 (cotton, herbicide resistant, deposited as ATCC PTA-4854, described in WO2004 / 072235 or US-A2006-059590); Event MON88302 (oilseed rape, herbicide resistant, deposited as PTA-10955, described in WO2011 / 153186); Event MON88701 (cotton, herbicide resistant, deposited as PTA-11754, described in WO2012 / 134808); Event MON89034 (maize, insect control, ATCC PTA-7455, described in WO07 / 140256 or US-A2008-260932); event MON89788 (soybean, herbicide resistant, deposited as ATCC PTA-6708, described in US-A2006-282915 or WO2006 / 130436); event MSl1 (oilseed rape, pollination control - herbicide resistant, deposited as ATCC PTA-850 or PTA-2485, described in WO2001 / 031042);Event MS8 (oilseed rape, pollination control - herbicide resistance, deposited as ATCC PTA-730, described in WO2001 / 041558 or US-A2003-188347); event NK603 (maize, herbicide resistance, deposited as ATCC PTA-2478, described in US-A2007-292854); event PE-7 (rice, insect control, not deposited, described in WO2008 / 114282); event RF3 (oilseed rape, pollination control; event RT73 (oilseed rape, herbicide resistant, not deposited, described in WO2002 / 036831 or US-A2008-070260); event SYHT0H2 / SYN-000H2-5 (soybean, herbicide resistant, deposited as PTA-11226, described in WO2012 / 0 82548), event T227-1 (sugar beet, herbicide resistant, not deposited, described in WO2002 / 44407 or US-A2009-265817); event T25 (maize, herbicide resistant, not deposited, described in US-A2001-029014 or WO2001 / 051654); event T304-40 (cotton, insect control - herbicide resistant, ATCC PTA-8171, described in US-A2010-077501 or WO2008 / 122406); Event T342-142 (cotton, insect control, not deposited, described in WO2006 / 128568); Event TC1507 (maize, insect control - herbicide resistance, not deposited, described in US-A2005-039226 or WO2004 / 099447); Event VIP1034 (maize, insect control - herbicide resistance, ATCC Deposited as PTA-3925, described in WO2003 / 052073); Event 32316 (maize, insect control - herbicide resistant, deposited as PTA-11507, described in WO2011 / 084632), Event 4114 (maize, insect control - herbicide resistant, deposited as PTA-11506, described in WO2011 / 084621);Event EE-GM3 / FG72 (soybean, herbicide tolerance, ATCC accession number PTA-11041) optionally stacked with event EE-GM1 / LL27 or event EE-GM2 / LL55 (WO2011 / 063413A2), event DAS-68416-4 (soybean, herbicide tolerance, ATCC accession number PTA-10442, WO2011 / 066360A1), event DAS-68416-4 (soybean, herbicide tolerance, ATCC accession number PTA-10442, WO2011 / 066384A1), event DP-040416-8 (maize, insect control, ATCC accession number PTA-11508, WO2011 / 075593A1); event DP-043A47-3 (maize, insect control, ATCC accession number PTA-11509, WO2011 / 075595A1), event DP-004114-3 (maize, insect control, ATCC accession number PTA-11506, WO2011 / 084621A1), event DP-032316-8 (maize, insect control, ATCC accession number PTA-11507, WO2011 / 084632A1), event MON-88302-9 (oilseed rape, herbicide resistance, ATCC accession number PTA-10955, WO2011 / 153186A1), event DAS-21606-3 (soybean, herbicide resistance, ATCC accession number PTA-11028, WO2012 / 033794A2);Event MON-87712-4 (soybean, quality traits, ATCC accession number PTA-10296, WO2012 / 051199A2), Event DAS-44406-6 (soybean, layered herbicide tolerance, ATCC accession number PTA-11336, WO2012 / 075426A1), Event DAS-14536-7 (soybean, layered herbicide tolerance, ATCC accession number PTA-11335, WO2012 / 075429A1) , event SYN-000H2-5 (soybean, herbicide resistance, ATCC accession number PTA-11226, WO2012 / 082548A2), event DP-061061-7 (oilseed rape, herbicide resistance, accession number not available, WO2012 / 071039A1), event DP-073496-4 (oilseed rape, herbicide resistance, accession number not available, US20131692), event 8264.44.06.1 (soybean, stacked herbicide resistance) herbicide tolerance, accession number PTA-11336, WO2012075426A2), event 8291.45.36.2 (soybean, stacked herbicide tolerance, accession number PTA-11335, WO2012 / 075429A2), event SYHT0H2 (soybean, ATCC accession number PTA-11226, WO2012 / 082548A2), event MON88701 (cotton, ATCC accession number PTA-11754, WO20 12 / 134808A1), event KK179-2 (alfalfa, ATCC accession number PTA-11833, WO2013 / 003558A1), event pDAB8264.42.32.1 (soybean, ATCC accession number PTA-11993, WO2013 / 010094A1), and event MZDT09Y (maize, ATCC accession number PTA-13025, WO2013 / 012775A1);

[0201] Additionally, a list of such genetic modification events is provided by the Animal and Plant Health Inspection Service (APHIS) of the United States Department of Agriculture (USDA) and can be found on the World Wide Web at their website at aphis.usda.gov. The status of such list as it exists or was on the filing date of this application is relevant to this application.

[0202] The genes / events that confer the desired traits of interest can also exist in combination with each other in genetically modified plants.Examples of genetically modified plants that may be mentioned are important crop plants such as cereals (wheat, rice, triticale, barley, rye, oats), corn, soybeans, potatoes, sugar beets, sugarcane, tomatoes, peas and other types of vegetables, cotton, tobacco, rapeseed and fruit plants (apples, pears, citrus fruits and grapes), with particular emphasis on corn, soybeans, wheat, rice, potatoes, cotton, sugarcane, tobacco and rapeseed.Particular emphasis is placed on the traits that improve the resistance of plants to insects, spiders, nematodes, slugs and snails, and improve the resistance of plants to one or more herbicides.

[0203] Commercially available examples of such plants, plant parts or plant seeds that may be preferentially treated in accordance with the present invention include commercial products such as plant seeds sold or distributed under the trade names GENUITY®, DROUGHTGARD®, SMARTSTAX®, RIB COMPLETE®, ROUNDUP READY®, VT DOUBLE PRO®, VT TRIPLE PRO®, BOLLGARD II®, ROUNDUP READY 2 YIELD®, YIELDGARD®, ROUNDUP READY® 2 XTEND™, INTACTA RR2 PRO®, VISTIVE GOLD® and / or XTENDFLEX™.

[0204] pathogen Non-limiting examples of fungal disease pathogens that can be treated according to the present invention include: Diseases caused by powdery mildew pathogens, such as Blumeria species, for example Blumeria graminis; Podosphaera species, for example Podosphaera leucotricha; Sphaerotheca species, for example Sphaerotheca fuliginea; Uncinula species, for example Uncinula necator; diseases caused by rust pathogens, such as Gymnosporangium species, for example Gymnosporangium sabinae; Hemileia species, for example Hemileia vastatrix; Phakopsora species, for example Phakopsora pachyrhizi or Phakopsora meibomiae; Puccinia species, for example Puccinia recondita, Puccinia graminis or Puccinia striiformis; diseases caused by Uromyces species, for example Uromyces appendiculatus; Oomycetes, for example Albugo species, such as Albugo candida; Bremia species, such as Bremia lactucae; Peronospora species, such as Peronospora pisi or Peronospora brassicae; Phytophthora species, such as Phytophthora infestans; Plasmopara species, such as Plasmopara viticola; Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensis. cubensis); diseases caused by Pythium species, such as Pythium ultimum; Alternaria species, such as Alternaria solani; Cercospora species, such as Cercospora beticola; Cladiosporium species, such as Cladiosporium cucumerinum; Cochliobolus species, such as Cochliobolus sativus (conidial form: Drechslera, also known as Helminthosporium) or Cochliobolus miyabeanus; Colletotrichum species, such as Colletotrichum lindemtanium. lindemuthanium; Corynespora spp., for example, Corynespora cassiicola; Cycloconium spp., for example, Cycloconium oleaginum; Diaporthe spp., for example, Diaporthe citri; Elsinoe spp., for example, Elsinoe fawcettii; Gloeosporium spp., for example, Gloeosporium laeticolor; Glomerella spp., for example, Glomerella cingulata; Gignardia spp., for example, Guignardia bidwelli bidwelli); Leptosphaeria species, for example, Leptosphaeria maculans; Magnaporthe species, for example, Magnaporthe grisea;Microdochium species, such as Microdochium nivale; Mycosphaerella species, such as Mycosphaerella graminicola, Mycosphaerella arachidicola or Mycosphaerella fijiensis; Phaeosphaeria species, such as Phaeosphaeria nodorum; Pyrenophora species, such as Pyrenophora teres or Pyrenophora tritici repentis; Ramularia species, such as Ramularia colosigni collocygni or Ramularia areola; Rhynchosporium species, for example Rhynchosporium secalis; Septoria species, for example Septoria apii or Septoria lycopersici; Stagonospora species, for example Stagonospora nodorum; Typhula species, for example Typhula incarnata; leaf spot and leaf wilt caused by Venturia species, for example Venturia inaequalis; Corticium spp., for example, Corticium graminearum; Fusarium spp., for example, Fusarium oxysporum; Gaeumannomyces spp., for example, Gaeumannomyces graminis; Plasmodiophora spp., for example, Plasmodiophora brassicae; Rhizoctonia spp., for example, Rhizoctonia solani; Sarocladium spp., for example, Sarocladium oryzae; Sclerotium spp., for example, Sclerotium oryzae. oryzae; Tapesia species, e.g., Tapesia acuformis; Root and trunk diseases caused by Thielaviopsis species, e.g., Thielaviopsis basicola; For example, Alternaria spp., for example Alternaria spp.; Aspergillus spp., for example Aspergillus flavus; Cladosporium spp., for example Cladosporium cladosporioides; Claviceps spp., for example Claviceps purpurea; Fusarium spp., for example Fusarium culmorum; Gibberella spp., for example Gibberella zeae; Monographella spp., for example Monographella nivalis; Stagnospora spp., for example Stagnospora nodrum. ear and panicle diseases (including corncob) caused by Pseudomonas nodorum; Diseases caused by smut fungi, such as Sphacelotheca species, for example Sphacelotheca reiliana; Tilletia species, for example Tilletia caries or Tilletia controversa; Urocystis species, for example Urocystis occulta; Ustilago species, for example Ustilago nuda; For example, Aspergillus species, such as Aspergillus flavus; Botrytis species, such as Botrytis cinerea; Monilinia species, such as Monilinia laxa; Penicillium species, such as Penicillium expansum or Penicillium purpurogenum; Rhizopus species, such as Rhizopus stolonifer; Sclerotinia species, such as Sclerotinia sclerotiorum; Verticilium species, such as Verticilium alboatrum. alboatrum) causing fruit rot; For example, Alternaria species, such as Alternaria brassicicola; Aphanomyces species, such as Aphanomyces euteiches; Ascochyta species, such as Ascochyta lentis; Aspergillus species, such as Aspergillus flavus; Cladosporium species, such as Cladosporium herbarum; Cochliobolus species, such as Cochliobolus sativus (conidial morphology: Drechslera, bipolaris, synonym: Helminthosporium); Colletotrichum species, such as Colletotrichum cocodes coccodes; Fusarium spp., for example, Fusarium culmorum; Gibberella spp., for example, Gibberella zea; Macrophomina spp., for example, Macrophomina phaseolina; Microdochium spp., for example, Microdochium nivale; Monogramfera spp., for example, Monogramfera nivalis; Penicillium spp., for example, Penicillium expansum; Phoma spp., for example, Phoma lingam; Phomopsis spp., for example, Phomopsis sojae; Phytophthora spp., for example, Phytophthora cactrum; Pyrenophora spp., for example, Pyrenophora graminea; Pyricularia spp., for example, Pyricularia oryzae oryzae; Pythium spp., for example, Pythium ultimum; Rhizoctonia spp., for example, Rhizoctonia solani; Rhizopus spp., for example, Rhizopus oryzae;Seed-borne and soil-borne rots and seedling diseases caused by Sclerotium species, such as Sclerotium rolfsii; Septoria species, such as Septoria nodorum; Typhula species, such as Typhula incarnata; Verticillium species, such as Verticillium dahliae; Malignant tumors, galls and witch's broom caused by Nectria species, e.g., Nectria galligena; Wilt caused by Verticillium species, e.g., Verticillium longisporum; Fusarium species, e.g., Fusarium oxysporum; Deformations of leaves, flowers and fruits caused by, for example, Exobasidium species, e.g., Exobasidium vexans; Taphrina species, e.g., Taphrina deformans; Degenerative diseases of woody plants caused by, for example, Esca species, such as Phaeomoniella chlamydospora, Phaeoacremonium aleophilum or Fomitiporia mediterranea; Ganoderma species, such as Ganoderma boninense; Diseases of plant tubers caused by Rhizoctonia species, e.g., Rhizoctonia solani; Helminthosporium species, e.g., Helminthosporium solani; Bacterial pathogens, such as Xanthomonas spp., e.g., Xanthomonas campestris pv. oryzae; Pseudomonas spp., e.g., Pseudomonas syringae pv. lachrymans; Erwinia spp., e.g., Erwinia amylovora; Liberibacter spp., e.g., Liberibacter asiaticus; Xyella spp., e.g., Xylella fastidiosa; Ralstonia spp., e.g., Ralstonia solanacearum; solanacearum; Dickeya species, e.g., Dickeya solani; Clavibacter species, e.g., Clavibacter michiganensis; diseases caused by Streptomyces species, e.g., Streptomyces scabies; Soybean diseases: For example, Alternaria leaf spot (Alternaria spec. atrans tenuissima), anthracnose (Colletotrichum gloeosporoides dematium vular. truncatum), cercospora leaf spot and blight (Cercospora kikuchii), and choanephora black leaf blight (Coanephora infundibrifera trispora Syn.) (Choanephora infundibulifera trispora), Dactuliophora leaf spot (Dactuliophora glycines), Downy mildew (Peronospora manshurica), Drechslera blight (Drechslera glycini), Frogeye leaf spot (Cercospora sojina), Leptosphaerulina leaf spot (Leptosphaerulina trifolii), Phyllostica leaf spot (Phyllostica soyaecola) sojaecola, black spot (Phomopsis sojae), powdery mildew (Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines), leaf rot, foliage, and spider blight (Rhizoctonia solani), rust (Phakopsora pachyrhizi, Phakopsora meibomiae), scab (Sphaceloma glycines), stemphyllium blight (Stemphylium botryosum) Fungal diseases of leaves, stems, pods and seeds caused by Fusarium botryosum, sudden death syndrome (Fusarium virguliforme), and ring spot (Corynespora cassiicola); Black root rot (Calonectria crotalariae), charcoal rot (Macrophomina phaseolina), Fusarium wilt or dieback, root rot, and sheath and neck rot (Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti), mycoleptodiscus root rot (Mycoleptodiscus terrestris), neocosmospora (Neocosmospora basinfecta), vasinfecta), sheath blight and stem blight (Diaporthe phaseolorum), branch blight (Diaporthe phaseolorum var.caulivora), phytophthora rot (Phytophthora megasperuma), leaf drop (Phialophora gregata), pythium rot (Pythium aphanidermatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctonia root rot, stem blight, and damping-off (Rhizoctonia solani) solani), sclerotinia stem rot (Sclerotinia sclerotiorum), sclerotinia southern blight (Sclerotinia rolfsii), and thielaviopsis root rot (Thielaviopsis basicola). Examples include:

[0205] mycotoxins Additionally, the compounds of formula (I) and compositions of the present invention can reduce the mycotoxin content in harvested materials and in foods and feeds prepared therefrom. Mycotoxins include, but are not limited to, those produced by the following fungi: Fusarium spec., such as Fusarium acuminatum, Fusarium asiaticum, Fusarium avenaceum, Fusarium crookwellense, Fusarium culmorum, Fusarium graminearum (Gibberella zeae), Fusarium equiseti, Fusarium fujikoroi, Fusarium musarum, Fusarium oxysporum, Fusarium proliferatum, Fusarium poae, Fusarium spp. Fusarium species such as F. poae, F. pseudograminearum, F. sam-bucinum, F. scirpi, F. semitectum, F. solani, F. sporotrichoides, F. langsethiae, F. subglutinans, F. tricinctum, and F. verticillioides, as well as Aspergillus flavus, Aspergillus parasiticus, and Aspergillus nomius. nomius), Aspergillus ochraceus (A. ochraceus), Aspergillus clavatus (A. clavatus), Aspergillus terreus (A. terreus), Aspergillus versicolor (A.Aspergillus species such as P. versicolor, Penicillium species such as P. verrucosum, P. viridicatum, P. citrinum, P. expansum, P. claviforme, and P. roqueforti, Claviceps purpurea, C. fusiformis, C. paspali, and C. africana, These include deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac-DON, T2- and HT2-toxins, fumonisins, zearalenone, moniliformin, fusarin, diacetoxyscirpenol (DAS), beauvericin, enniatin, fusaroproliferin, fusarenol, ochratoxin, patulin, ergot alkaloids, and aflatoxins produced by Claviceps species such as Stachybotrys species, Stachybotrys species, and others.

[0206] Material Protection The compounds of formula (I) and compositions of the invention can also be used in the protection of materials, in particular industrial materials, against attack and destruction by phytopathogenic fungi.

[0207] Additionally, the compounds of formula (I) and compositions of the present invention can be used alone or in combination with other active ingredients as antifouling compositions.

[0208] In this specification industrial materials"Microbial protection" is understood to mean inanimate materials prepared for industrial use. For example, industrial materials to be protected from microbial deterioration or destruction may be adhesives, glues, paper, wallpaper and board / cardboard, textiles, carpets, leather, wood, fibers and tissues, paints and plastic products, cooling lubricants, and other materials that are infected or destroyed by microorganisms. Parts of production plants and buildings that may be damaged by microbial growth, such as cooling water circuits, cooling and heating systems, ventilation and air conditioning units, may also be mentioned within the scope of the materials to be protected. Industrial materials within the scope of the present invention preferably include adhesives, sizes, paper and card, leather, wood, paints, cooling lubricants, and heat transfer fluids, and more preferably wood.

[0209] The compounds of formula (I) and compositions of the present invention can prevent adverse effects such as rotting, decay, discolouration, bleaching or mould formation.

[0210] In the case of treating wood, the compounds of formula (I) and compositions of the present invention can also be used against fungal diseases that tend to grow on or in wood.

[0211] wood This refers to all types of wood and all types of construction wood implementations, such as solid wood, high-density wood, laminated wood and plywood.Furthermore, the compounds of formula (I) and the compositions of the present invention can be used to protect objects that come into contact with salt water or brackish water from contamination, especially ship hulls, screens, nets, buildings, moorings and signaling systems.

[0212] The compounds of formula (I) and the compositions of the present invention can also be used to protect stored goods. Stored goods are understood to mean natural substances of plant or animal origin or their processed products of natural origin that are desired to be long-term protected. Stored goods of plant origin, such as plants or plant parts such as stems, leaves, tubers, seeds, fruits, and grains, can be protected in the freshly harvested state or after processing by (pre)drying, wetting, crushing, crushing, pressing, or roasting. Stored goods also include raw wood, such as construction lumber, utility poles, and barriers, or wood in the form of finished products, such as furniture. Stored goods of animal origin are, for example, hides, leather, fur, and hair. The compounds of formula (I) and the compositions of the present invention can prevent adverse effects such as decay, rot, discoloration, bleaching, or mold formation.

[0213] Microorganisms capable of decomposing or modifying industrial materials include, for example, bacteria, fungi, yeasts, algae, and slime organisms. The compounds of formula (I) and compositions of the present invention preferably act against fungi, particularly molds, wood-discoloring and wood-destroying fungi (ascomycetes, basidiomycetes, mycomycetes, and zygomycetes), and slime organisms and algae. Examples include microorganisms of the following genera: Alternaria, such as Alternaria tenuis; Aspergillus, such as Aspergillus niger; Chaetomium, such as Chaetomium globosum; Coniophora, such as Coniophora puetana; Lentinus, such as Lentinus tigrinus; Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporus versicolor; Aureobasidium pullulans. Aureobasidium such as Sclerophoma pullulans; Sclerophoma such as Sclerophoma pityophila; Trichoderma viride Trichoderma such as Trichoderma viride; Ophiostoma species, Ceratocystis species, Humicola species, Petriella species, Trichurus species, Coriolus species, Gloeophyllum species, Pleurotus species, Poria species, Serpula species, and Escherichia such as Tyromyces species, Cladosporium species, Paecilomyces species, Mucor species, and Escherichia coli;Pseudomonas species, such as Pseudomonas aeruginosa; Staphylococcus species, such as Staphylococcus aureus, Candida species, and Saccharomyces species, such as Saccharomyces cerevisiae;

[0214] Seed treatment The compounds of formula (I) and compositions of the present invention can also be used to protect seeds from undesirable microorganisms, such as plant pathogenic fungi or plant pathogenic oomycetes. As used herein, the term seeds includes dormant seeds, primed seeds, pre-germinated seeds, and seeds with germinated roots and leaves.

[0215] Therefore, the present invention also relates to a method for protecting seeds against unwanted microorganisms, which method comprises treating the seeds with a compound of formula (I) or a composition of the present invention.

[0216] The treatment of seeds with the compound of formula (I) or the composition of the present invention protects the seeds from plant pathogenic microorganisms and also protects the germinated seeds, the emerging seedlings, and the plants that emerge from the treated seeds. Therefore, the present invention also relates to a method for protecting seeds, germinating seeds, and protecting the germinated seedlings.

[0217] Seed treatment can be carried out before sowing, at the time of sowing or immediately after sowing.

[0218] When seed treatment is carried out before sowing (for example, so-called on-seed application), seed treatment can be carried out as follows: seeds are placed in a mixture of a desired amount of the compound of formula (I) or the composition of the present invention, and the seeds and the compound of formula (I) or the composition of the present invention are mixed until a uniform distribution is achieved on the seeds.If necessary, the seeds can be dried.

[0219] The present invention also relates to seeds coated with a compound of formula (I) or a composition of the invention.

[0220] Preferably, seeds are treated in a state that is sufficiently stable so that they are not damaged during the treatment process.Generally, seeds can be treated at any time from harvesting to immediately after sowing.Seeds that are separated from plants and have been removed from cobs, husks, stems, husks, hairs or fruit flesh are usually used.For example, seeds that are harvested, washed and dried until the moisture content is less than 15% by weight can be used.Alternatively, seeds that are dried after being treated with water and then dried again can be used, or seeds that are immediately after priming, seeds that are stored in a primed state, seeds that have not yet germinated, or seeds that have been sown in seedbeds, trays, tapes or paper.

[0221] The amount of the compound of formula (I) or the composition of the present invention that is applied to seeds is typically such that the germination of seeds is not impaired or the resulting plants are not damaged.This is particularly because the compound of formula (I) exhibits phytotoxicity effects at a specific application rate.When determining the amount of the compound of formula (I) that is applied to seeds, the specific phenotype of transgenic plants should also be taken into consideration, so as to achieve optimal seed and germinating plant protection using the minimum amount of compound.

[0222] The compounds of formula (I) can be applied directly to the seeds, i.e., without other ingredients and without dilution. The compounds of the present invention can also be applied to the seeds.

[0223] The compound of formula (I) and the composition of the present invention are suitable for protecting the seeds of all plant varieties.Preferred seeds are cereals (such as wheat, barley, rye, millet, triticale, and oats), rapeseed, corn, cotton, soybean, rice, potato, sunflower, bean, coffee, pea, beet (such as sugar beet and fodder beet), peanut, vegetables (such as tomato, cucumber, onion, and lettuce), lawn and ornamental plants.More preferably are wheat, soybean, rapeseed, corn and rice seeds.

[0224] The compounds of formula (I) and compositions of the present invention can be used to treat transgenic seeds, particularly those of plants capable of expressing polypeptides or proteins that act against pests, herbicide damage, or abiotic stress, thereby enhancing protective effects. Plant seeds capable of expressing polypeptides or proteins that act against pests, herbicide damage, or abiotic stress can contain at least one heterologous gene that enables the expression of the polypeptide or protein. These heterologous genes in transgenic seeds can be derived from microorganisms such as Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus, or Gliocladium. These heterologous genes are preferably derived from Bacillus species, in which case the gene product is effective against European corn borer and / or western corn rootworm. Particularly preferably, the heterologous gene is derived from Bacillus thuringiensis.

[0225] Applicable The compounds of formula (I) can be applied as such or in the form of, for example, a ready-to-use solution, emulsion, aqueous or oily suspension, powder, wettable powder, paste, soluble powder, dust, soluble granules, dusting granules, suspoemulsion concentrates, natural products impregnated with a compound of formula (I), synthetic materials impregnated with a compound of formula (I), fertilizers in polymeric materials or microencapsulated.

[0226] Application can be achieved by conventional methods, such as watering, spraying, atomizing, spraying, dusting, foaming, or painting.The compound of formula (I) can also be applied by ultra-low volume methods, through drip irrigation systems or drench application, applied in furrows, or injected into the stem or trunk of the soil.Furthermore, the compound of formula (I) can be applied by wound seals, paints, or other wound dressings.

[0227] The effective and plant-compatible amount of a compound of formula (I) applied to a plant, plant part, fruit, seed or soil depends on various factors such as the compound / composition used, the target of treatment (plant, plant part, fruit, seed or soil), the type of treatment (dusting, spraying, seed dressing), the purpose of the treatment (treatment and protection), the type of microorganism, the developmental stage of the microorganism, the susceptibility of the microorganism, the growth stage of the crop, and the environmental conditions.

[0228] When the compounds of formula (I) are used as fungicides, the application rates can vary within a relatively wide range depending on the type of application. For the treatment of plant parts such as leaves, the application rates range from 0.1 to 10,000 g / ha, preferably from 10 to 1,000 g / ha, and more preferably from 50 to 300 g / ha (when applied by sprinkling or dropwise application; the application rates can be reduced, especially when inert materials such as rock wool or perlite are used). For seed treatment, the application rates can range from 0.1 to 200 g / 100 kg of seeds, preferably from 1 to 150 g / 100 kg of seeds, more preferably from 2.5 to 25 g / 100 kg of seeds, and even more preferably from 2.5 to 12.5 g / 100 kg of seeds. For soil treatment, the application rates to the soil can range from 0.1 to 10,000 g / ha, preferably from 1 to 5,000 g / ha.

[0229] These application rates are merely examples and are not intended to limit the scope of the invention.

[0230] The compounds of formula (I) can be used in combination with models, such as site-specific crop management, and incorporated into computer programs for satellite farming, precision farming, or precision agriculture. Such models support the operation of site-specific agricultural sites with data from various sources, such as soil, weather, crops (e.g., type, growth stage, plant health), weeds (e.g., type, growth stage), diseases, pests, nutrients, water, humidity, biomass, satellite data, yield, etc., with the aim of optimizing profitability, sustainability, and environmental conservation. In particular, such models help optimize agronomic decisions, control the accuracy of pesticide applications, and record the work performed.

[0231] As one example, a compound of formula (I) can be applied to a crop according to an appropriate dosing regimen when a model models the development of a fungal disease and calculates that a threshold has been reached at which it is recommended to apply a compound of formula (I) to the crop plant.

[0232] Commercially available systems that include agricultural models include FieldScripts™ from The Climate Corporation, Xarvio™ from BASF, and AGLogic™ from John Deere.

[0233] The compounds of formula (I) can also be used in combination with high-performance spraying devices, such as spot sprayers or precision sprayers, attached to or housed within agricultural vehicles, such as tractors, robots, helicopters, airplanes, and unmanned aerial vehicles (UAVs), including drones. Such devices typically include input sensors (e.g., cameras, etc.) and a processing unit configured to analyze input data, make decisions based on the analysis of the input data, and apply the compounds of the present invention to crop plants (respectively, weeds) in a specific and precise manner. The use of such smart spraying devices typically requires a positioning system (e.g., a GPS receiver, etc.) to locate the recorded data and guide or control the agricultural vehicle; a geographic information system (GIS) to display information on an easy-to-understand map; and an appropriate farm vehicle to perform the necessary farm tasks, such as spraying.

[0234] In one example, fungal diseases can be detected from images acquired by a camera. In one example, fungal diseases can be identified and / or classified based on the images. Such identification and / or classification can utilize image processing algorithms. Such image processing algorithms can utilize machine learning algorithms, such as trained neural networks, decision trees, and artificial intelligence algorithms. In this way, the compounds described herein can be applied only when necessary.

[0235] Certain aspects of the present teachings will be further understood in light of the following examples, which should not be construed as limiting the scope of the disclosure in any way. [Example]

[0236] A-1.General concept A-1.1. Measurement of LogP value The determination of the LogP values ​​provided herein was carried out in accordance with EEC Directive 79 / 831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a reversed phase column in the following manner: [a] LogP values ​​were determined by measuring LC-UV in the acidic range using 0.1% aqueous formic acid and acetonitrile (linear gradient from 10% acetonitrile to 95% acetonitrile) as eluents. [b] LogP values ​​were determined by measuring LC-UV in the neutral range using 0.001 molar aqueous ammonium acetate and acetonitrile (linear gradient from 10% acetonitrile to 95% acetonitrile) as eluents. [c] LogP values ​​were determined by measuring LC-UV in the acidic range using 0.1% phosphoric acid and acetonitrile as eluents (linear gradient from 10% acetonitrile to 95% acetonitrile).

[0237] If multiple LogP values ​​are obtained within the same method, all values ​​are given, separated by a "+".

[0238] Calibration was performed with linear alkanones (having 3 to 16 carbon atoms) with known LogP values ​​(measurement of LogP values ​​using retention times by linear interpolation between consecutive alkanones). λ maxima were determined using the UV spectrum and chromatographic signal peak values ​​from 200 nm to 400 nm.

[0239] A-1.2. 1 H-NMR data Of the selected examples provided herein 1 H-NMR data is 1 It is written in the form of a H-NMR peak list. For each signal peak, the δ value is given in ppm, and the signal intensity is given in parentheses. There is a semicolon as a separator between the δ value-signal intensity pairs.

[0240] Thus, an example peak list is: δ1(strength 1);δ2(strength 2);·······;δ i (strengthi );·····;δ n (strength n ) It has the form:

[0241] The intensity of the sharp signals correlates with the height in cm of the signal in the printed example NMR spectrum, showing the actual relationship of signal intensities. From the broad signals, several peaks or signal centers can be shown and their relative intensities compared to the most intense signal in the spectrum.

[0242] 1 To calibrate the chemical shifts of the H spectra, we used the chemical shifts of tetramethylsilane and / or the solvent used, especially when measuring spectra in DMSO. Therefore, in the NMR peak list, peaks from tetramethylsilane may, but do not necessarily, occur.

[0243] 1 The H-NMR peak list is a classical 1 It resembles a H-NMR print and therefore contains all the peaks that would normally be listed in a classical NMR interpretation.

[0244] Furthermore, they are based on the classical 1 1 H-NMR print signals, stereoisomers of the target compounds, which are also the subject of the present invention, and / or peaks of impurities.

[0245] To display compound signals in the δ range of the solvent and / or water, the usual peaks of the solvent, e.g., the DMSO peak and the water peak in DMSO-D6, are 1 They appear in the H-NMR peak list and usually have high intensities on average.

[0246] The peaks of stereoisomers of the target compound and / or impurity peaks typically have lower intensities on average than the peaks of the target compound (eg, purity >90%).

[0247] Such stereoisomers and / or impurities may be typical for a particular preparation method, and therefore their peaks are useful for identifying the reproduction of the preparation method via a "by-product fingerprint."

[0248] The expert calculates the peaks of the target compounds using known methods (MestreC, ACD simulation, and empirically evaluated expectation values), and can separate the peaks of the target compounds using additional intensity filters if necessary. This separation is achieved by the conventional 1 This is similar to picking relevant peaks in H-NMR interpretation.

[0249] Detailed description of NMR data including peak lists found in the publication "Citation of NMR Peaklist Data within Patent Applications" of Research Disclosure Database Number 564025.

[0250] The following examples illustrate, but are not limited to, the preparation and biological activity of the compounds of formula (I) of the present invention.

[0251] A-3. Synthesis of compounds of formula (I) and intermediates The compounds shown in Table 1 below were prepared similarly to the examples provided above or according to the methods described herein.

[0252] Synthesis of Compounds of Formula (I) and Intermediates Preparation Example 1: Preparation of (5RS)-5-(2-chloro-4-methylbenzyl)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine (Compound No. I-004) Step 1: Preparation of N-[(2RS)-1-chloro-3-(2-chloro-4-methylphenyl)propan-2-yl]-3-(3-chlorophenoxy)-6-methylpyridazine-4-carboxamide (Compound 14-03) To a solution of 3-(3-chlorophenoxy)-6-methylpyridazine-4-carboxylic acid (250 mg, 0.95 mmol) and propylphosphonic anhydride (1 mL, 3.49 mmol, 50% in THF) in dichloromethane (8 mL) under an argon atmosphere, N,N-diisopropylethylamine (0.6 mL, 3.49 mmol) and (2RS)-1-chloro-3-(2-chloro-4-methylphenyl)propan-2-aminium chloride (264.5 mg, 1.1 mmol) were added. The reaction mixture was stirred at room temperature for 1 hour, diluted with water, and extracted with dichloromethane (3 x 200 mL). The organic extract was washed with saturated aqueous sodium bicarbonate and brine, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (gradient heptane / ethyl acetate) to give, after evaporation of the solvent, 257 mg (purity, 55%) of N-[(2RS)-1-chloro-3-(2-chloro-4-methylphenyl)propan-2-yl]-3-(3-chlorophenoxy)-6-methylpyridazine-4-carboxamide as a white solid.

[0253] Step 2: Preparation of N-[(2RS)-1-chloro-3-(2-chloro-4-methylphenyl)propan-2-yl]-3-(3-chlorophenoxy)-N'-hydroxy-6-methylpyridazine-4-carboximidamide (compound 15-03) To a solution of N-[(2RS)-1-chloro-3-(2-chloro-4-methylphenyl)propan-2-yl]-3-(3-chlorophenoxy)-6-methylpyridazine-4-carboxamide (257 mg, 0.55 mmol) in toluene (11 mL) was added phosphorus pentachloride (345 mg, 1.65 mmol). The reaction mixture was stirred at 75° C. for 30 minutes and then concentrated under reduced pressure. The residue was dissolved in acetonitrile (10 mL) and added to a solution of hydroxylamine (0.68 mL, 11.1 mmol, 50% in water) in acetonitrile (10 mL). After stirring at room temperature for 1 hour, the reaction mixture was diluted with water and extracted with ethyl acetate (3×50 mL). The organic extract was washed with water and brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (gradient heptane / ethyl acetate) to give, after evaporation of the solvent, 91 mg (purity 95%, yield 32%) of N-[(2RS)-1-chloro-3-(2-chloro-4-methylphenyl)propan-2-yl]-3-(3-chlorophenoxy)-N'-hydroxy-6-methylpyridazine-4-carboximidamide.

[0254] Step 3: Preparation of (5RS)-5-(2-chloro-4-methylbenzyl)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine To a solution of N-[(2RS)-1-chloro-3-(2-chloro-4-methylphenyl)propan-2-yl]-3-(3-chlorophenoxy)-N'-hydroxy-6-methylpyridazine-4-carboximidamide (91 mg, 0.19 mmol) in tetrahydrofuran (7 mL) was added sodium tert-butoxide (18 mg, 0.19 mmol) at 0°C. The reaction mixture was stirred for 10 minutes, then diluted with water and extracted with ethyl acetate (3 x 50 mL). The organic extract was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (gradient heptane / ethyl acetate) to give, after evaporation of the solvent, 37 mg (purity 96%, yield 42%) of (5RS)-5-(2-chloro-4-methylbenzyl)-3-[3-(chlorophenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine.

[0255] Preparation Example 2: Preparation of (5RS)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5-(2,4-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine (Compound Number: I-002) Step 1: Preparation of 3-(3-chlorophenoxy)-N-{(2RS)-1-(2,4-dimethylphenyl)-3-[(1,3-dioxo-1,3-dihydro-2H-isoindol)oxy]propan-2-yl}-6-methylpyridazine-4-carboxamide (Compound 3-01) Under an argon atmosphere, to a mixture of 3-(3-chlorophenoxy)-6-methylpyridazine-4-carboxylic acid (250 mg, 0.94 mmol) and HATU (395 mg, 1.0 mmol) in DMF (6 mL) was added 2-{[(2RS)-2-amino-3-(2,4-dimethylphenyl)propyl]oxy}-1H-isoindole-1,3(2H)-dione trifluoroacetic acid (455 mg, 1.04 mmol) and N,N-diisopropylethylamine (0.49 mL, 2.83 mmol) at 0 °C. After 15 min at 0 °C, the reaction mixture was stirred at room temperature for 1 h. It was then diluted with water and extracted with ethyl acetate (2 × 200 mL). The organic extract was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (gradient heptane / ethyl acetate) to give, after evaporation of the solvent, 296 mg (purity 90%, yield 49%) of 3-(3-chlorophenoxy)-N-{(2RS)-1-(2,4-dimethylphenyl)-3-[(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)oxy]propan-2-yl}-6-methylpyridazine-4-carboxamide as a white oil.

[0256] Step 2: Preparation of N-[(2RS)-1-(aminooxy)-3-(2,4-dimethylphenyl)propan-2-yl]-3-(3-chlorophenoxy)-6-methylpyridazine-4-carboxamide (Compound 4-01) To a solution of 3-(3-chlorophenoxy)-N-{(2RS)-1-(2,4-dimethylphenyl)-3-[(1,3-dioxo-1,3-dihydro-2H-isoindole)oxy]propan-2-yl}-6-methylpyridazine-4-carboxamide (296 mg, 0.51 mmol) in dichloromethane / methanol (10 mL, 1:1) under an argon atmosphere, hydrazine monohydrate (0.09 mL, 0.55 mmol) was added. The reaction mixture was stirred at room temperature for 3 hours and concentrated. It was then diluted with water and extracted with dichloromethane (2 × 200 mL). The organic extract was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. Evaporation of the solvent gave 185 mg (85% purity, 69% yield) of N-[(2RS)-1-(aminooxy)-3-(2,4-dimethylphenyl)propan-2-yl]-3-(3-chlorophenoxy)-6-methylpyridazine-4-carboxamide as a colorless oil.

[0257] Step 3: Preparation of (5RS)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5-(2,4-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine To a solution of N-[(2RS)-1-(aminooxy)-3-(2,4-dimethylphenyl)propan-2-yl]-3-(3-chlorophenoxy)-6-methylpyridazine-4-carboxamide (135 mg, 0.31 mmol) in acetonitrile (22 mL) under an argon atmosphere was added POCl (0.09 mL, 0.92 mmol) at 85 °C. The reaction mixture was stirred at 85 °C for 2 h. After cooling to room temperature, the mixture was poured into saturated aqueous sodium bicarbonate and extracted with ethyl acetate (2 × 100 mL). The organic extract was dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (gradient heptane / ethyl acetate) to give, after evaporation of the solvent, 58 mg (purity 97%, yield 43%) of (5RS)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5-(2,4-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine as a colorless oil.

[0258] Preparation of Example 3: Preparation of (5RS)-3-[6-chloro-3-(2-fluoro-3-methylphenoxy)pyridazin-4-yl]-5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine (Compound No. I-005) To a suspension of cesium carbonate (249 mg, 0.76 mmol) in 2-methyltetrahydrofuran (1 mL) cooled to 0 °C under an argon atmosphere was added a solution of 2-fluoro-3-methylphenol (77 mg, 0.61 mmol) in 2-methyltetrahydrofuran (1 mL). After 1 h, a solution of (5RS)-5-(2,4-dichlorobenzyl)-3-(3,6-dichloropyridazin-4-yl)-5,6-dihydro-4H-1,2,4-oxadiazine (200 mg, 0.51 mmol) in 2-methyltetrahydrofuran (8 mL) was added to the reaction mixture. The reaction was heated at 55 °C for 4 h, diluted with water, and extracted with ethyl acetate (2 × 50 mL). The organic extract was washed with water and brine, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (gradient heptane / ethyl acetate) to give, after evaporation of the solvent, 161 mg (purity 90%, yield 59%) of (5RS)-3-[6-chloro-3-(2-fluoro-3-methylphenoxy)pyridazin-4-yl]-5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine as an oil.

[0259] Preparation of Example 4: Preparation of (5RS)-5-(2,4-dichlorobenzyl)-3-[3-(2-fluoro-3-methylphenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine (Compound I-007) Under an argon atmosphere, (5RS)-3-[6-chloro-3-(2-fluoro-3-methylphenoxy)pyridazin-4-yl]-5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine (130 mg, 0.27 mmol), 2,4,6-trimethyl-1,3,5,2,4,6-trioxatriborinane (110 mg, 0.88 mmol), cesium carbonate (132 mg, 0.41 mmol), and Pd(dppf)Cl (11 mg, 0.013 mmol) were suspended in dioxane / water (6 mL, 2:1) in a microwave vial. The tube was sealed, and the reaction mixture was heated at 110 °C for 30 min in a microwave oven. The reaction mixture was diluted with water and extracted with ethyl acetate (2 × 50 mL). The organic extract was washed with water and brine, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (gradient heptane / ethyl acetate) to give, after evaporation of the solvent, 70 mg (95% pure, 53% yield) of (5RS)-5-(2,4-dichlorobenzyl)-3-[3-(2-fluoro-3-methylphenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine as an oil.

[0260] Preparation of Example 5: Preparation of (5RS)-3-[3-(3-cyclopropyl-2-fluoro-phenoxy)-6-(1-ethoxyvinyl)pyridazin-4-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (compound I-020) In a sealed vial under argon, a mixture of (5RS)-3-[6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)pyridazin-4-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine [2446127-10-0] (1.4 g, 2.75 mmol), tributyl(1-ethoxyvinyl)stannane [97674-02-7] (1.244 g, 3.44 mmol), and bis(triphenylphosphine)palladium(II) dichloride [13965-03-2] (194 mg, 0.27 mmol) in DMF (9.7 mL) was heated at 120 °C for 20 min under microwave irradiation. After cooling to room temperature, the mixture was poured into saturated aqueous sodium chloride solution and extracted with ethyl acetate. The combined organic layers were dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (gradient heptane / ethyl acetate) to give, after evaporation of the solvent, 1.024 g (87% purity, 59% yield) of (5RS)-3-[3-(3-cyclopropyl-2-fluorophenoxy)-6-(1-ethoxyvinyl)pyridazin-4-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine as a yellow solid.

[0261] Preparation of Example 6: Preparation of (1RS)-1-[6-(3-cyclopropyl-2-fluorophenoxy)-5-[(5RS)-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazin-3-yl]pyridazin-3-yl]ethanol (Compound I-023) Step 1: Preparation of 1-[6-(3-cyclopropyl-2-fluorophenoxy)-5-[(5RS)-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazin-3-yl]pyridazin-3-yl]ethanone To a solution of (5RS)-3-[3-(3-cyclopropyl-2-fluorophenoxy)-6-(1-ethoxyvinyl)pyridazin-4-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine [2446126-79-8] (960 mg, 1.76 mmol) in THF (5 mL) was added 2N aqueous hydrochloric acid (5 mL) and the reaction mixture was stirred at room temperature for 30 minutes. The reaction mixture was diluted with water and extracted with ethyl acetate. The combined organic layers were dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel, followed by silica gel chromatography (heptane / ethyl acetate 100 / 0 to 60 / 40) to give 780 mg (purity 99%, yield 85%) of 1-[6-(3-cyclopropyl-2-fluorophenoxy)-5-[(5RS)-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazin-3-yl]pyridazin-3-yl]ethenone.

[0262] Step 2: Preparation of (1RS)-1-[6-(3-cyclopropyl-2-fluorophenoxy)-5-[(5RS)-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazin-3-yl]pyridazin-3-yl]ethanol To a solution of 1-[6-(3-cyclopropyl-2-fluorophenoxy)-5-[(5RS)-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazin-3-yl]pyridazin-3-yl]ethenon (680 mg, 1.31 mmol) in dry methanol (10 mL) was added dropwise a solution of sodium borohydride (29 mg, 0.79 mmol) in dry methanol (0.5 mL) at 0 °C. The reaction mixture was stirred at 0 °C for 10 minutes and then quenched with saturated aqueous ammonium chloride solution. The aqueous phase was extracted with ethyl acetate. The combined organic layers were dried on a hydrophobic filter and concentrated. The crude product was purified by silica gel flash chromatography to give 510 mg (99% purity, 74% yield) of (1RS)-1-[6-(3-cyclopropyl-2-fluorophenoxy)-5-[(5RS)-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazin-3-yl]pyridazin-3-yl]ethanol.

[0263] Preparation of Example 7: Preparation of (5RS)-3-[3-(3-cyclopropyl-2-fluorophenoxy)-6-[(1RS)-1-fluoroethyl]pyridazin-4-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-1H,2,4-oxadiazine (Compound I-018) To a solution of (1RS)-1-[6-(3-cyclopropyl-2-fluorophenoxy)-5-[(5RS)-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazin-3-yl]pyridazin-3-yl)ethanol (compound I-023) (410 mg, 0.79 mmol) in dichloromethane (2 mL) was added diethylaminosulfur trifluoride [38078-09-0] (0.209 mL, 0.58 mmol) dropwise at 0° C. The reaction was stirred at 0° C. for 2 hours and then quenched with saturated aqueous sodium bicarbonate solution. The aqueous phase was extracted with ethyl acetate. The combined organic layers were dried on a hydrophobic filter and concentrated. The crude product was purified by silica gel flash chromatography to give 240 mg (99% purity, 58% yield) of (5RS)-3-[3-(3-cyclopropyl-2-fluorophenoxy)-6-[(1RS)-1-fluoroethyl]pyridazin-4-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine.

[0264] Example 8: Preparation of (5RS)-3-[6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)pyridazin-4-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-1,2,4-oxadiazine-4-carbaldehyde (Compound I-025) A solution of 6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)-N-[(1RS)-1-(aminooxymethyl)-2-(2,4-dichlorophenyl)ethyl]pyridazine-4-carboxamide (4.78 g, 9.09 mmol) (compound 4-02) in acetonitrile (40 mL) was heated at 85 °C, then phosphorus oxychloride (2.54 mL, 27.2 mmol) was added, and the reaction mixture was stirred for 18 hours. The reaction mixture was cooled to room temperature and then poured into a saturated aqueous solution of NaHCO3, followed by extraction with ethyl acetate. The collected organic phase was dried on a hydrophobic filter and concentrated under reduced pressure.

[0265] The crude product was purified by flash chromatography and then by HPLC chromatography to give 1.02 g (99% purity, 21% yield) of (5RS)-3-[6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)pyridazin-4-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-1,2,4-oxadiazine-4-carbaldehyde.

[0266] The compounds of formula (I-1) shown in Table 1 were prepared by the procedure described above. [Table 1] JPEG0007735329000020.jpg38170

[0267] [Table 2] JPEG0007735329000022.jpg219170 JPEG0007735329000023.jpg187170 JPEG0007735329000024.jpg217170

[0268] [Table 3]

[0269] [Table 4]

[0270] [Table 5]

[0271] [Table 6]

[0272]

Table 7

[0273]

Table 8

[0274]

Table 9

[0275]

Table 10

[0276]

Table 11

[0277]

Table 12

[0278]

Table 13

[0279]

Table 14

[0280]

Table 15

[0281] Table 16 JPEG0007735329000039.jpg145165

[0282] [Table 17]

[0283] [Table 18] JPEG0007735329000042.jpg131166

[0284] B. Biological example B-1. In vivo prevention trials of Botrytis cinerea (gray mold) Solvent: dimethyl sulfoxide 5% by volume Acetone 10% by volume Emulsifier: 1 μl Tween® 80 per 1 mg of active ingredient

[0285] The active ingredient was solubilized in a mixture of dimethyl sulfoxide / acetone / Tween® 80, homogenized, and then diluted with water to the desired concentration.

[0286] Cucumber or cabbage seedlings were treated by spraying with the active ingredient prepared as described above, while control plants were treated with the aqueous solution of acetone / dimethyl sulfoxide / Tween® 80 alone.

[0287] After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Botrytis cinerea spores. The contaminated cucumber plants were incubated at 17°C and 90% relative humidity for 4-5 days. The contaminated cabbage plants were incubated at 20°C and 100% relative humidity for 4-5 days.

[0288] The test was evaluated 4-5 days after inoculation. 0% means efficacy equivalent to that of the control plants, and 100% efficacy means that no disease was observed.

[0289] In this test, the following compounds of the present invention showed an efficacy of 90-100% at a concentration of 500 ppm of active ingredient: I-001; I-002; I-003; I-004; I-005; I-006; I-007; I-008; I-010; I-011; I-012; I-013; I-014; I-015; I-016; I-018; I-019; I-020; I-022; I-023; I-025.

[0290] B-2. In vivo prevention test against Pyrenophora teres (barley net blotch) Solvent: dimethyl sulfoxide 5% by volume Acetone 10% by volume Emulsifier: 1 μl Tween® 80 per 1 mg of active ingredient

[0291] The active ingredient was solubilized in a mixture of dimethyl sulfoxide / acetone / Tween® 80, homogenized, and then diluted with water to the desired concentration.

[0292] Barley seedlings were treated by spraying with the active ingredient prepared as described above, control plants were treated with the aqueous solution of acetone / dimethyl sulfoxide / Tween® 80 only.

[0293] After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Pyrenophora teres spores. The contaminated barley plants were incubated at 20°C and 100% relative humidity for 48 hours, then at 20°C and 70-80% relative humidity for 8 days.

[0294] The test was evaluated 10 days after inoculation, 0% meaning an efficacy corresponding to that of the control plants, 100% meaning that no disease was observed.

[0295] In this test, the following compounds of the present invention showed 80-89% efficacy at a concentration of 500 ppm of active ingredient: I-013; I-016.

[0296] In this test, the following compounds of the invention showed an efficacy of between 90 and 100% at a concentration of 500 ppm of active ingredient: I-001; I-002; I-003; I-004; I-005; I-006; I-007; I-008; I-010; I-011; I-012; I-014; I-015; I-018; I-019; I-020; I-022; I-023; I-025.

[0297] B-3. In vivo prevention test of Sphaerotheca fuliginea (Cucurbit powdery mildew) Solvent: dimethyl sulfoxide 5% by volume Acetone 10% by volume Emulsifier: 1 μl Tween® 80 per 1 mg of active ingredient

[0298] The active ingredient was solubilized in a mixture of dimethyl sulfoxide / acetone / Tween® 80, homogenized, and then diluted with water to the desired concentration.

[0299] Small cucumber seedlings were treated by spraying with the active ingredient prepared as described above, control plants were treated with the aqueous solution of acetone / dimethyl sulfoxide / Tween® 80 only.

[0300] After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Sphaerotheca fuliginea spores. The contaminated small cucumber plants were incubated at 20°C and 70-80% relative humidity for 8 days.

[0301] The test was evaluated 8 days after inoculation, 0% means an efficacy corresponding to that of the control plants, 100% means that no disease was observed.

[0302] In this test, the following compounds of the present invention showed an efficacy of 90-100% at a concentration of 500 ppm of active ingredient: I-001; I-002; I-003; I-004; I-005; I-006; I-007; I-008; I-010; I-011; I-012; I-013; I-014; I-015; I-016; I-018; I-019; I-020; I-022; I-023; I-025.

[0303] B-5. In vivo prevention trials of Colletotrichum lindemuthianum (pea leaf spot) Solvent: dimethyl sulfoxide 5% by volume Acetone 10% by volume Emulsifier: 1 μl Tween® 80 per 1 mg of active ingredient

[0304] The active ingredient was solubilized in a mixture of dimethyl sulfoxide / acetone / Tween® 80, homogenized, and then diluted with water to the desired concentration.

[0305] Bean seedlings were treated by spraying with the active ingredient prepared as described above, control plants were treated with the aqueous solution of acetone / dimethyl sulfoxide / Tween® 80 only.

[0306] After 24 hours, the plants were contaminated by spraying the leaves with an aqueous suspension of Colletrichum lindemutianum spores. The contaminated bean plants were incubated at 20°C and 100% relative humidity for 24 hours, then at 20°C and 90% relative humidity for 6 days.

[0307] The test was evaluated 7 days after inoculation, 0% means an efficacy corresponding to that of the control plants, 100% means that no disease was observed.

[0308] In this test, the following compounds of the present invention showed an efficacy of 90-100% at a concentration of 500 ppm of active ingredient: I-001; I-002; I-003; I-004; I-005; I-006; I-007; I-008; I-010; I-011; I-012; I-013; I-014; I-015; I-016; I-018; I-019; I-020; I-022; I-023; I-025.

[0309] B-6. In vitro cell assay of Alternaria alternata Solvent: DMSO Medium: 14.6 g anhydrous D-glucose (VWR), 7.1 g mycological peptone (Oxoid), 1.4 g granulated yeast extract (Merck), 1 L QSP Inoculum: spore suspension

[0310] The fungicides were solubilized in DMSO and used to prepare the required range of concentrations. The final concentration of DMSO used in the assay was ≦1%.

[0311] A suspension of A. alternata spores was prepared and diluted to the desired spore concentration.

[0312] Fungicides were evaluated for their ability to inhibit spore germination and mycelium growth in liquid culture assays. Compounds were added to the spore-containing medium at the desired concentration. After 5 days of incubation, the fungal toxicity of the compounds was determined by spectrophotometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values ​​of the fungicide-containing wells with those of the control wells that did not contain the fungicide.

[0313] In this test, the following compounds of the present invention showed 90-100% efficacy at a concentration of 20 ppm of active ingredient: I-001; I-002; I-003; I-004; I-005; I-006; I-007; I-008; I-009; I-010; I-011; I-012; I-013; I-014; I-015; I-016; I-018; I-019; I-020; I-022; I-023; I-025.

[0314] B-7. In vitro cell assay for Fusarium culmorum Solvent: DMSO Medium: 14.6 g anhydrous D-glucose (VWR), 7.1 g mycological peptone (Oxoid), 1.4 g granulated yeast extract (Merck), 1 L QSP Inoculum: spore suspension

[0315] The fungicides were solubilized in DMSO and used to prepare the required range of concentrations. The final concentration of DMSO used in the assay was ≦1%.

[0316] A suspension of F. culmorum spores was prepared and diluted to the desired spore concentration.

[0317] Fungicides were evaluated for their ability to inhibit spore germination and mycelium growth in liquid culture assays. Compounds were added to the spore-containing medium at the desired concentration. After 4 days of incubation, the fungal toxicity of the compounds was determined by spectrophotometric measurement of mycelium growth. The inhibition of fungal growth was determined by comparing the absorbance values ​​of the wells containing the fungicide with the absorbance of the control wells without the fungicide.

[0318] In this test, the following compounds of the present invention showed an efficacy of 70-79% at a concentration of 20 ppm of active ingredient: I-011; I-019.

[0319] In this test, the following compounds of the present invention showed 80-89% efficacy at a concentration of 20 ppm of active ingredient: I-015.

[0320] In this test, the following compounds of the present invention showed 90-100% efficacy at a concentration of 20 ppm of active ingredient: I-001; I-002; I-003; I-004; I-005; I-006; I-007; I-009; I-010; I-012; I-014; I-018; I-023; I-025.

[0321] B-8. In vitro cell assay of Pyricularia oryzae Solvent: DMSO Medium: 14.6 g anhydrous D-glucose (VWR), 7.1 g mycological peptone (Oxoid), 1.4 g granulated yeast extract (Merck), 1 L QSP Inoculum: spore suspension

[0322] The fungicides were solubilized in DMSO and used to prepare the required range of concentrations. The final concentration of DMSO used in the assay was ≦1%.

[0323] A suspension of P. oryzae spores was prepared and diluted to the desired spore concentration.

[0324] Fungicides were evaluated for their ability to inhibit spore germination and mycelium growth in liquid culture assays. Compounds were added to the spore-containing medium at the desired concentration. After 5 days of incubation, the fungal toxicity of the compounds was determined by spectrophotometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values ​​of the fungicide-containing wells with those of the control wells that did not contain the fungicide.

[0325] In this test, the following compounds of the present invention showed an efficacy of 70-79% at a concentration of 20 ppm of active ingredient: I-022.

[0326] In this test, the following compounds of the present invention showed 80-89% efficacy at a concentration of 20 ppm of active ingredient: I-013.

[0327] In this test, the following compounds of the present invention showed 90-100% efficacy at a concentration of 20 ppm of active ingredient: I-001; I-002; I-003; I-004; I-005; I-006; I-007; I-008; I-009; I-010; I-011; I-012; I-014; I-015; I-016; I-018; I-019; I-020; I-023; I-025.

[0328] B-9. In vitro cell assay of Colletotrichum lindemuthianum Solvent: DMSO Medium: 14.6 g anhydrous D-glucose (VWR), 7.1 g mycological peptone (Oxoid), 1.4 g granulated yeast extract (Merck), 1 L QSP Inoculum: spore suspension

[0329] The fungicides were solubilized in DMSO and used to prepare the required range of concentrations. The final concentration of DMSO used in the assay was ≦1%.

[0330] A suspension of C. lindemutianum spores was prepared and diluted to the desired spore concentration.

[0331] Fungicides were evaluated for their ability to inhibit spore germination and mycelium growth in liquid culture assays. Compounds were added to the spore-containing medium at the desired concentration. After 6 days of incubation, the fungal toxicity of the compounds was determined by spectrophotometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values ​​of the fungicide-containing wells with the absorbance of the control wells without fungicide.

[0332] In this test, the following compounds of the present invention showed 90-100% efficacy at a concentration of 20 ppm of active ingredient: I-001; I-002; I-003; I-004; I-005; I-006; I-007; I-008; I-009; I-010; I-011; I-012; I-013; I-014; I-015; I-016; I-018; I-019; I-020; I-023; I-025.

[0333] B-10. In vitro cell assay for Septoria tritici Solvent: DMSO Culture medium: 1g KH2PO4 (VWR), 1g K2HPO4 (VWR), 0.5g urea (VWR), 3g KNO3 (Prolabo), 10g sucrose (VWR), 0.5g MgSO4·7H2O (Sigma), 0.07g CaCl2·2H2O (Prolabo), 0.2mg MnSO4·H2O (Sigma), 0.6mg CuSO4·5H2O (Sigma), 7.9mg ZnSO4·7H2O (Sigma), 0.1mg H3BO3 (Merck), 0.14mg NaMoO4·2H2O (Sigma), 2mg thiamine (Sigma), 0.1mg biotin (VWR), 4mg FeSO4·7H2O (Sigma), 1L QSP Inoculum: spore suspension

[0334] The fungicides were solubilized in DMSO and used to prepare the required range of concentrations. The final concentration of DMSO used in the assay was ≦1%.

[0335] A suspension of S. tritici spores was prepared and diluted to the desired spore concentration.

[0336] Fungicides were evaluated for their ability to inhibit spore germination and mycelium growth in liquid culture assays. Compounds were added to the spore-containing medium at the desired concentration. After 7 days of incubation, the fungal toxicity of the compounds was determined by spectrophotometric measurement of mycelium growth. Inhibition of fungal growth was determined by comparing the absorbance values ​​of the fungicide-containing wells with the absorbance of the control wells without fungicide.

[0337] In this test, the following compounds of the present invention showed 90-100% efficacy at a concentration of 20 ppm of active ingredient: I-001; I-002; I-003; I-004; I-005; I-006; I-007; I-008; I-009; I-010; I-011; I-012; I-013; I-014; I-016; I-018; I-020; I-025.

[0338] B-10. In vivo prevention test of Alternaria brassicae (causing spot blotch of radish and cabbage) Solvent: dimethyl sulfoxide 5% by volume Acetone 10% by volume Emulsifier: 1 μl Tween® 80 per 1 mg of active ingredient

[0339] The active ingredient was solubilized in a mixture of dimethyl sulfoxide / acetone / Tween® 80, homogenized, and then diluted with water to the desired concentration.

[0340] Radish or cabbage seedlings were treated by spraying with the active ingredient prepared as described above, control plants were treated with the aqueous solution of acetone / dimethyl sulfoxide / Tween® 80 only.

[0341] After 24 hours, the plants were contaminated by spraying them with an aqueous suspension of Alternaria brassicae spores. The contaminated radish or cabbage plants were incubated at 20°C and 100% relative humidity for 3–4 days.

[0342] The test was evaluated 6 days after inoculation, 0% means an efficacy corresponding to that of the control plants, 100% means that no disease was observed.

[0343] In this test, the following compounds of the present invention showed an efficacy of 90-100% at a concentration of 500 ppm of active ingredient: I-001; I-002; I-003; I-004; I-005; I-006; I-007; I-008; I-010; I-011; I-012; I-013; I-014; I-015; I-016; I-018; I-019; I-020; I-022; I-023; I-025.

Claims

1. Compound of formula (I-1): 【Chemical 1】 [In the formula, R ３ and R ４ is hydrogen, R ５ is hydrogen, L is methylene; R ６ is phenyl, the phenyl is substituted with two substituents independently selected from chloro, bromo, and methyl; R ７ is chloro, methyl, ethyl or ethenyl; said methyl, ethyl and ethenyl are optionally substituted with one or two substituents independently selected from the group consisting of fluoro, chloro, hydroxy, methoxy and ethoxy; R ８ is hydrogen, R ９ is hydrogen or formyl, Q is phenyl; the phenyl is substituted with one or two substituents independently selected from fluoro, chloro, methyl, ethyl, and cyclopropyl; The cyclopropyl is optionally substituted with one or two substituents independently selected from the group consisting of fluoro and chloro. And, (I-001) (5RS)-5-(2-bromo-4-methylbenzyl)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I-002) (5RS)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5-(2,4-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-003) (5RS)-5-(2-chloro-4-methylbenzyl)-3-[3-(2-fluoro-3-methylphenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I-004) (5RS)-5-(2-chloro-4-methylbenzyl)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I-005) (5RS)-3-[6-chloro-3-(2-fluoro-3-methylphenoxy)pyridazin-4-yl]-5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-006) (5RS)-5-(2-bromo-4-methylbenzyl)-3-[3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I-007) (5RS)-5-(2,4-dichlorobenzyl)-3-[3-(2-fluoro-3-methylphenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I-008) (5RS)-5-(3,5-dimethylbenzyl)-3-[3-(2-fluoro-3-methylphenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I-009) (5RS)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5-(3,5-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-010) (5RS)-3-[3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5-(3,5-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-011) (5RS)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5-(2,5-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-012) (5RS)-3-[3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5-(2,5-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-013) (5RS)-5-(2,5-dimethylbenzyl)-3-[3-(2-fluoro-3-methylphenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I-014) (5RS)-5-(2,4-dimethylbenzyl)-3-[3-(3-ethyl-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I-015) (5RS)-5-(2,4-dimethylbenzyl)-3-{3-[3-(1-fluorocyclopropyl)phenoxy]-6-methylpyridazin-4-yl}-5,6-dihydro-4H-1,2,4-oxadiazine, (I-016) 1-{6-(3-cyclopropylphenoxy)-5-[5-(2,4-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazin-3-yl]pyridazin-3-yl}ethanol, (I-017) (5RS)-3-[6-chloro-3-(3-chlorophenoxy)pyridazin-4-yl]-5-(2-chloro-4-methylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-018) (5RS)-3-{3-(3-cyclopropyl-2-fluorophenoxy)-6-[(1RS)-1-fluoroethyl]pyridazin-4-yl}-5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-019) (5RS)-3-[3-(3-cyclopropylphenoxy)-6-(1-ethoxyvinyl)pyridazin-4-yl]-5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-020) (5RS)-3-[3-(3-cyclopropyl-2-fluorophenoxy)-6-(1-ethoxyvinyl)pyridazin-4-yl]-5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-021) (5S)-3-[3-(3-cyclopropyl-2-fluorophenoxy)-6-(dichloromethyl)pyridazin-4-yl]-5-(2,4-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-022) (5RS)-3-{3-[3-(1-chlorocyclopropyl)phenoxy]-6-methylpyridazin-4-yl}-5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-023) 1-{6-(3-cyclopropyl-2-fluorophenoxy)-5-[5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazin-3-yl]pyridazin-3-yl}ethanol, (I-024) (5RS)-3-{6-chloro-3-[3-(1-chlorocyclopropyl)phenoxy]pyridazin-4-yl}-5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-025) (5RS)-3-[6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)pyridazin-4-yl]-5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine-4-carbaldehyde The compound of formula (I-1) is selected from the group consisting of:

2. The compound of formula (I-1) (I.001) (5RS)-5-(2-bromo-4-methylbenzyl)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I.002) (5RS)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5-(2,4-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I-003) (5RS)-5-(2-chloro-4-methylbenzyl)-3-[3-(2-fluoro-3-methylphenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I.004) (5RS)-5-(2-chloro-4-methylbenzyl)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I.005) (5RS)-3-[6-chloro-3-(2-fluoro-3-methylphenoxy)pyridazin-4-yl]-5-(2,4-dichlorobenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I.006) (5RS)-5-(2-bromo-4-methylbenzyl)-3-[3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I.007) (5RS)-5-(2,4-dichlorobenzyl)-3-[3-(2-fluoro-3-methylphenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I.008) (5RS)-5-(3,5-dimethylbenzyl)-3-[3-(2-fluoro-3-methylphenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I.009) (5RS)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5-(3,5-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I.010) (5RS)-3-[3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5-(3,5-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I.011) (5RS)-3-[3-(3-chlorophenoxy)-6-methylpyridazin-4-yl]-5-(2,5-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I.012) (5RS)-3-[3-(3-chloro-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5-(2,5-dimethylbenzyl)-5,6-dihydro-4H-1,2,4-oxadiazine, (I.013) (5RS)-5-(2,5-dimethylbenzyl)-3-[3-(2-fluoro-3-methylphenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I.014) (5RS)-5-(2,4-dimethylbenzyl)-3-[3-(3-ethyl-2-fluorophenoxy)-6-methylpyridazin-4-yl]-5,6-dihydro-4H-1,2,4-oxadiazine, (I.015) (5RS)-5-(2,4-dimethylbenzyl)-3-{3-[3-(1-fluorocyclopropyl)phenoxy]-6-methylpyridazin-4-yl}-5,6-dihydro-4H-1,2,4-oxadiazine The compound of formula (I-1) according to claim 1, selected from the group consisting of:

3. A composition for controlling phytopathogenic harmful fungi, comprising at least one compound of formula (I-1) according to claim 1 or 2 and at least one carrier and / or surfactant.

4. A method for controlling harmful microorganisms in crop protection and material protection, in which at least one compound of formula (I-1) according to claim 1 or 2 and / or a composition according to claim 3 is applied to the harmful microorganisms and / or their habitat.

5. Use of one or more compounds of formula (I-1) according to claim 1 or 2 and / or one or more compositions according to claim 3 for controlling harmful microorganisms in crop protection and material protection.

6. A method for producing a compound of formula (Ia), comprising the steps of: Compound of formula (1) 【Chemistry 2】 [In the formula, R ７ , R ８ and Q is as defined in claim 1; U １ is hydroxy, halogen or C １ -C ６ is an alkoxy group. with an amine of formula (2) 【Chemistry 3】 [In the formula, R ３ , R ４ , R ５ , R ６ and L is as defined in claim 1; W is hydrogen, tert-butoxycarbonyl, benzyl, allyl, or (4-methoxyphenyl)methyl. or a salt thereof to form a compound of formula (3) 【Chemistry 4】 [In the formula, R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , L, W and Q are defined as above. and removing the phthalimide group from the compound of formula (3) to obtain a compound of formula (4) 【Chemistry 5】 [In the formula, R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , L, W and Q are defined as above, When W is hydrogen, the compound of formula (4) is then treated with a dehydrating agent, optionally in the presence of a base, to give a compound of formula (Ia): 【Chemistry 6】 [In the formula, R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , L and Q are defined as above. directly or or Next, when W is an amino-protecting group selected from the group consisting of tert-butoxycarbonyl, benzyl, allyl, and (4-methoxyphenyl)methyl, the compound of formula (4) is treated with a dehydrating agent, optionally in the presence of a base, followed by a deprotection step to obtain a compound of formula (I-a).

7. A method for producing a compound of formula (Ia), comprising the steps of: Compound of formula (5) 【Chemistry 7】 [In the formula, R ７ and R ８ is as defined in claim 1, X is a halogen; U １ is hydroxy, halogen or C １ -C ６ is an alkoxy group. with an amine of formula (2) 【Chemistry 8】 [In the formula, R ３ , R ４ , R ５ , R ６ and L is as defined in claim 1; W is hydrogen, tert-butoxycarbonyl, benzyl, allyl, or (4-methoxyphenyl)methyl. or a salt thereof to form a compound of formula (6a) 【Chemistry 9】 [In the formula, R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , L, X and W are defined as above. R, G is phthalimide. and removing the phthalimide group from the compound of formula (6a) to obtain a compound of formula (6b) 【Chemistry 10】 [In the formula, R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , L, X and W are defined as above. Obtained, When W is hydrogen, the compound of formula (6b) is then treated with a dehydrating agent, optionally in the presence of a base, to give a compound of formula (7) directly, or or If W is an amino protecting group, the compound of formula (6b) is then treated with a dehydrating agent, optionally in the presence of a base, followed by a deprotection step to give a compound of formula (7) 【Chemistry 11】 [In the formula, R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , L and X are defined as above. Obtained, Finally, the compound of formula (7) is reacted with a compound of formula (8) in which Q is defined in claim 1 in the presence of an organic or inorganic base, and optionally in the presence of a suitable copper salt or complex, to give a compound of formula (I-a) 【Chemistry 12】 [In the formula, R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , L and Q are defined as above. The manufacturing method of the present invention.

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