Use of strobilurin type compounds to control plant pathogenic fungi containing in the mitochondrial cytochrome b protein the amino acid substitution F129L conferring tolerance to Qo inhibitor V

Abstract

The present invention relates to the use of cytoplasmic compounds of the cytoplasmic type of formula I and N-oxides and salts thereof for combating plant pathogenic fungi which contain the amino acid substitution F129L in the cytochrome b protein of the mitochondria (also referred to as F129L mutation in the cytochrome b gene of the mitochondria) which confers resistance to Qo inhibitors and to methods for combating such fungi. The invention also relates to novel compounds, to processes for preparing these compounds, to compositions comprising at least one of the compounds and to seeds coated with at least one of the compounds.

Description

[0001] The present invention relates to the use of strobilurin type compounds of formula I and N-oxides and salts thereof to control plant pathogenic fungi containing the amino acid substitution F129L in the mitochondrial cytochrome b protein which confers tolerance to Qo inhibitors (QoIs) (also referred to as F129L mutation in the mitochondrial cytochrome b gene) and to methods of controlling such fungi. The present invention also relates to novel compounds, to processes for preparing these compounds, to compositions comprising at least one of these compounds, to plant health applications and to seeds coated with at least one of these compounds. The present invention also relates to a method of controlling the soybean rust fungus (Phakopsora pachyrhizi) having the amino acid substitution F129L in the mitochondrial cytochrome b protein.

[0002] As used herein, "Qo inhibitor" includes any substance capable of impairing and / or inhibiting respiration by binding to the ubiquinol oxidation center of the cytochrome bc1 complex in the mitochondria. This oxidation center is usually located on the outside of the inner mitochondrial membrane. Many of these compounds are also known as strobilurin type or strobilurin-like compounds.

[0003] The mutation F129L in the mitochondrial cytochrome b (CYTB) gene shall mean any nucleotide substitution of the codon 129 coding for "F" (phenylalanine; e.g. TTT or TTC) which results in a codon coding for "L" (leucine; e.g. TTA, TTG, TTG, CTT, CTC, CTA or CTG), e.g. the first nucleotide of codon 129 in the CYTB (cytochrome b) gene is replaced from 'T' to 'C' (TTT to CTT), which results in a single amino acid substitution from F to L at position 129 in the cytochrome b protein. This F129L mutation is known to confer tolerance to Qo inhibitors.

[0004] QoI fungicides, commonly known as phalloidin-type fungicides, are frequently used in crops to control many fungal pathogens. QoI inhibitors typically work by binding to the ubiquinone oxidative center of the cytochrome bc1 complex (electron transport complex III) in the mitochondria to inhibit respiration. This oxidative center is located on the outer side of the inner mitochondrial membrane. Major examples of QoI use include, for instance, phalloidin-type fungicides used on wheat to control *Septoria tritici* (also known as *Mycosphaerella graminicola*), the cause of wheat leaf blight. Unfortunately, the widespread use of this class of QoIs has led to the selection of mutant pathogens resistant to them. Resistance to QoIs has been detected in several plant pathogenic fungi such as *Blumeria graminis*, *Mycosphaerella fijiensis*, *Pseudoperonspora cubensis*, and *Venturia inaequalis*. In agricultural applications, tolerance to QoIs is primarily attributed to pathogens containing a single amino acid residue substitution for G143A in the cytochrome b gene of its cytochrome bc1 complex—a QoI target protein that has been found to be controlled by specific QoIs (WO 2013 / 092224). Although several commercial QoI fungicides have been widely used for the control of soybean rust, no single amino acid residue substitution for G143A conferring tolerance to QoI fungicides has been observed in the cytochrome b protein.

[0005] Conversely, soybean rust develops different gene mutations in the cytochrome b gene, resulting in the single amino acid substitution F129L, which also confers resistance to QoI fungicides. The efficacy of commonly used QoI fungicides, namely pyraclostrobin, azoxystrobin, picoxystrobin, orysastrobin, dimoxystrobin, and metominostrobin, against soybean rust has diminished to a level that poses practical problems in agricultural practice.

[0006] Although trifloxystrobin appears to be less affected by F129L amino acid substitutions to achieve the same level of efficacy as other QoI fungicides such as azoxystrobin and pyraclostrobin, it is by no means as effective against fungal populations with F129L QoI tolerance mutations as it is against susceptible populations (Crop Protection 27, (2008) 427-435).

[0007] Therefore, new methods are needed for controlling pathogen-induced diseases in crops, including plants affected by pathogens containing the F129L mutation in the mitochondrial cytochrome b gene, which confers resistance to Qo inhibitors. Furthermore, in many cases, especially at low application rates, the fungicidal activity of known fungicidal agaric compounds is unsatisfactory, particularly when a high proportion of fungal pathogens contain mutations in the mitochondrial cytochrome b gene that confer resistance to Qo inhibitors. Moreover, there is a continued need for novel fungicidal compounds that are more effective, less toxic, and / or more environmentally safe. Based on this, the object of the present invention is to provide compounds with improved activity and / or a broader activity spectrum against plant pathogenic fungi and / or even further reduced toxicity to non-target organisms such as vertebrates and invertebrates.

[0008] Certain cytophoretic compounds have been described in WO 1997 / 05103 and EP 463488. However, no mention is made of the inhibition of fungal pathogens containing F129L substitutes in mitochondrial cytochrome b proteins, which confer resistance to Qo inhibitors.

[0009] The compounds of this invention differ from those described in the above-disclosed publications in that the methyl oxime side chain contains an alkyne linker as defined herein.

[0010] Therefore, the present invention provides novel compounds of Formula I, their stereoisomers and tautomers, as well as their N-oxides and agriculturally usable salts:

[0011]

[0012] in

[0013] R 1 Selected from O and NH;

[0014] R 2 Selected from CH and N;

[0015] R 3 Selected from hydrogen, halogen, CN, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, -O-C1-C4 alkyl, -O-C1-C4 haloalkyl, -O-C3-C6 cycloalkyl, -C1-C2 alkyl-C3-C6 cycloalkyl, phenyl, 3-6 membered heterocyclic alkyl and 5 or 6 membered heteroaryl.

[0016] The heterocyclic alkyl and heteroaryl groups contain one, two, or three heteroatoms selected from N, O, and S in addition to carbon atoms, provided that the heterocycle cannot contain two consecutive atoms selected from O and S.

[0017] The phenyl, heterocyclic alkyl, and heteroaryl groups are bonded directly or via an oxygen atom or via a C1-C2 alkylene linker, and the phenyl and heteroaryl groups are not substituted or are substituted by 1, 2, or 3 identical or different substituents selected from halogens, CN, NH2, NO2, C1-C4 alkyl, C1-C4 haloalkyl, -O-C1-C4 alkyl, and -OC1-C4 haloalkyl.

[0018] R 4 Selected from hydrogen, C1-C6 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C6 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, -(C1-C2 alkyl)-O(C1-C2 alkyl), -(C1-C2 alkyl)-O(C1-C2 haloalkyl) and -C1-C4 alkyl-C3-C6 cycloalkyl;

[0019] X and Y are either direct bonds or divalent groups -CL. 1 L 2 -;

[0020] L 1 L 2 Independently selected from hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 haloalkenyl, C2-C3 haloalkynyl, -(C1-C2 alkyl)-O(C1-C2 alkyl), -(C1-C2 alkyl)-O-(C1-C2 haloalkyl), cyclopropyl, and -C1-C2 alkyl-cyclopropyl; or

[0021] L 1 and L 2 Together with the middle carbon atom, it forms a cyclopropyl group;

[0022] Where L 1 and L 2 The cyclic structures are independently unsubstituted or contain one or two identical or different groups R. L :

[0023] R L Selected from halogens, CN, NO2, C1-C4 alkyl, C1-C4 haloalkyl, -O-C1-C4 alkyl and -O-C1-C4 haloalkyl;

[0024] Z is selected from C3-C6 cycloalkyl, phenyl, 3-6 membered heterocyclic alkyl, 3-6 membered heterocyclic alkenyl and 5 or 6 membered heteroaryl.

[0025] The heterocyclic alkyl, heterocyclic alkenyl, and heteroaryl groups contain one, two, or three heteroatoms selected from N, O, and S in addition to carbon atoms, provided that the heterocycle cannot contain two consecutive atoms selected from O and S.

[0026] Where Z is unsubstituted or contains 1, 2, 3, or at most a maximum number of identical or different groups R a :

[0027] R a Selected from halogen, CN, NR A R B C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, -O-C1-C4 alkyl, -C(=NO-C1-C4 alkyl)-C1-C4 alkyl, -C(=O)-C1-C4 alkyl, -C(=O)-O-C1-C4 alkyl, -C(=O)-NH-C1-C4 alkyl, -O-CH2-C(=NO-C1-C4 alkyl)-C1-C4 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, -C1-C2 alkyl-C3-C6 cycloalkyl, -O-C3-C6 cycloalkyl, phenyl, 3-6 membered heterocyclic alkyl, 3-6 membered heterocyclic alkenyl and 5 or 6 membered heteroaryl,

[0028] The heterocyclic alkyl, heterocyclic alkenyl, and heteroaryl groups contain one, two, or three heteroatoms selected from N, O, and S in addition to carbon atoms, provided that the heterocycle cannot contain two consecutive atoms selected from O and S.

[0029] The phenyl, heterocyclic alkyl, heterocyclic alkenyl, and heteroaryl groups are bonded directly or via oxygen atoms or via C1-C2 alkylene linkages.

[0030] and / or

[0031] Two R atoms bonded to adjacent carbon ring atoms a The substituents, together with the two intermediate carbon ring atoms, form partially unsaturated or aromatic 5-6 membered fused carbon rings or heterocycles.

[0032] In addition to carbon atoms, the heterocycle also includes one or two independent heteroatoms selected from N, O and S as ring member atoms, provided that the heterocycle cannot contain two consecutive atoms selected from O and S.

[0033] And R a The aliphatic and cyclic structural portions are not substituted or contain 1, 2, 3, 4, or at most a maximum number of identical or different groups R. b :

[0034] R b Selected from halogens, CN, NO2, C1-C4 alkyl, C1-C4 haloalkyl, -O-C1-C4 alkyl and -O-C1-C4 haloalkyl;

[0035] R A R B They are independently selected from hydrogen, C1-C4 alkyl and C1-C4 haloalkyl.

[0036] Although the invention has been described with respect to specific embodiments, this description should not be interpreted in a limiting sense.

[0037] Before describing exemplary embodiments of the invention in detail, definitions important for understanding the invention are given. As used in this specification and the appended claims, the singular forms “a” and “an” also include the corresponding plurals, unless the context clearly specifies otherwise. In the context of this invention, the terms “about” and “approximately” represent a range of accuracy that, when understood by those skilled in the art, still ensures the technical effect of the stated features. This term typically indicates a deviation from the indicated value of ±20%, preferably ±15%, more preferably ±10%, and even more preferably ±5%. It should be understood that the term “comprising” is not restrictive. For the purposes of this invention, the term “consisting of” is considered a preferred embodiment of the term “comprising.”

[0038] Unless otherwise stated, the following definitions are set forth to illustrate and define the meaning and scope of various terms used in describing the invention and the appended claims herein. These definitions should not be interpreted literally, as they are not intended to be general definitions and are only relevant to this application.

[0039] The term "compound I" refers to compound I. Similarly, this specialized term is used for all subforms, such as "compound I.2" referring to compound I.2 or "compound V" referring to compound V, and so on.

[0040] The term “independently” when used in the context of substituent selection for a variable means that when more than one substituent is selected from many possible substituents, those substituents may be the same or different.

[0041] The organic structural parts or groups mentioned in the definitions of the variables above are collective terms that individually enumerate the members of each group. The term "C" v -C w "This shows the possible number of carbon atoms in each case."

[0042] The term "halogen" encompasses fluorine, chlorine, bromine, and iodine.

[0043] The term “C1-C4 alkyl” refers to straight-chain or branched saturated hydrocarbon groups having 1-4 carbon atoms, such as methyl (CH3), ethyl (C2H5), propyl, 1-methylethyl (isopropyl), butyl, 1-methylpropyl, 2-methylpropyl, and 1,1-dimethylethyl.

[0044] The term "C2-C4 alkenyl" refers to straight-chain or branched unsaturated hydrocarbon groups having 2-4 carbon atoms and double bonds in any position, such as vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, and 2-methyl-2-propenyl.

[0045] The term “C2-C4 ynyl” refers to a straight-chain or branched unsaturated hydrocarbon group having 2-4 carbon atoms and containing at least one triple bond, such as ethynyl, prop-1-ynyl, prop-2-ynyl, but-1-ynyl, but-2-ynyl, but-3-ynyl, and 1-methylprop-2-ynyl.

[0046] The term "C1-C4 haloalkyl" refers to straight-chain or branched alkyl groups having 1-4 carbon atoms, wherein some or all of the hydrogen atoms in these groups can be replaced by halogen atoms as described above, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichloromonofluoromethyl, monochlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2 -Fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, CH2-C2F5, CF2-C2F5, CF(CF3)2, 1-fluoromethyl-2-fluoroethyl, 1-chloromethyl-2-chloroethyl, 1-bromomethyl-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl.

[0047] The term "-O-C1-C4 alkyl" refers to a straight-chain or branched alkyl group having 1 to 4 carbon atoms bonded via oxygen at any position in the alkyl group, such as OCH3, OCH2CH3, O(CH2)2CH3, 1-methylethoxy, O(CH2)3CH3, 1-methylpropoxy, 2-methylpropoxy, or 1,1-dimethylethoxy.

[0048] The term "C3-C6 cycloalkyl" refers to a monocyclic saturated hydrocarbon group having 3-6 carbon ring members, such as cyclopropyl (C3H5), cyclobutyl, cyclopentyl, or cyclohexyl. The term "C3-C6 cycloalkenyl" refers to a monocyclic saturated hydrocarbon group having 3-6 carbon ring members and one or more double bonds.

[0049] The term "3-6 member heterocyclic alkyl" refers to a 3-6 member monocyclic saturated ring system having one or more heteroatoms such as O, N, and S as ring members in addition to a carbon atom. The term "C3-C6 heterocyclic alkenyl" refers to a 3-6 member monocyclic system having one or more heteroatoms such as O, N, and S as ring members in addition to a carbon atom and having one or more double bonds.

[0050] The term “-C1-C4 alkyl-C3-C6 cycloalkyl” refers to an alkyl group having 1-4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl group is replaced by a cycloalkyl group having 3-6 carbon atoms.

[0051] The term "phenyl" refers to C6H5.

[0052] The term "5 or 6-membered heteroaryl" containing 1, 2, 3, or 4 heteroatoms selected from O, N, and S should be understood to refer to an aromatic heterocycle having 5 or 6 ring atoms. Examples include:

[0053] - Five-membered heteroaryl groups containing, for example, 1, 2, or 3 nitrogen atoms and / or one sulfur and / or one oxygen atom in addition to carbon atoms: e.g., 2-thienyl, 3-thienyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2- azole group, 4- azole, 5- Azolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl and 1,3,4-triazol-2-yl;

[0054] - Six-membered heteroaryl groups, such as 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, and 2-pyrazinyl, which contain 1, 2, 3, or 4 N atoms as ring members in addition to carbon atoms.

[0055] The term "C1-C2 alkylene linker" refers to a divalent alkyl group, such as -CH2- or -CH2-CH2-, that is bonded at one end to the core structure of Formula I and at the other end to that specific substituent.

[0056] The term "compound" as used herein, especially "compound I," includes all stereoisomers and tautomers, as well as mixtures thereof in all proportions, prodrugs, isotopic forms, agricultural salts, N-oxides, and S-oxides.

[0057] The term "stereoisomer" is a general term used for all isomers of a single compound that differ only in the spatial orientation of their atoms. Stereoisomers include mirror-image isomers (enantiomers), mixtures of mirror-image isomers (racemic mixtures), geometric (cis / trans or E / Z) isomers, and isomers of compounds having more than one chiral center—that are not mirror images of each other (diastereomers). The term "tautomer" refers to the coexistence of two (or more) compounds that differ from each other only in the position and electronic distribution of one (or more) mobile atoms, such as keto-enol tautomers. The term "agricultural salt" as used herein includes salts of active compounds prepared with acids or bases depending on the specific substituents found on the compounds described herein. "N-oxide" refers to oxides containing nitrogen atoms of a nitrogen-containing heteroaryl group or heterocycle. N-oxides can be formed in the presence of oxidizing agents, such as peroxides like m-chloroperbenzoic acid or hydrogen peroxide. N-oxides involve amine oxides, which are also known as amine-N-oxides, and are compounds containing N→O bonds.

[0058] In terms of each variable, the implementation scheme of the intermediate corresponds to the implementation scheme of compound I.

[0059] Preferred compounds I and, where applicable, all sub-formula compounds provided herein, such as compounds I.1 and I.2, and intermediates such as compounds II, III, IV, and V, wherein each substituent and variable (e.g., n, X, Y, Z, R) is preferred. 1 R 2 R 3 R 4 R a and R b The following meanings are given: (1) mutually independent or more preferably combined (any possible combination of two or more substituents as defined herein)

[0060] Furthermore, it is preferred to use, methods, mixtures, and compositions in which the definitions (e.g., plant pathogenic fungi, treatment, crop, compound II, other active ingredients, solvent, solid carrier) independently or more preferably in combination have the following meanings, even more preferably in combination with the preferred meanings of compound I herein (any possible combination of two or more definitions provided herein):

[0061] One embodiment of the present invention relates to R 1 Selected from O and NH; and R 2 Selected from CH and N, provided that R 1 In the case of NH, R 2 It is a preferred compound I of N. Another embodiment involves R. 2 It is a compound of N. Another embodiment involves R. 2 It is compound I of CH.

[0062] According to another implementation scheme, R 3 The heterocyclic alkyl group is selected from hydrogen, halogen, CN, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C3-C6 cycloalkyl, -O-C1-C4 alkyl, -OC1-C4 haloalkyl, -C1-C2 alkyl-C3-C6 cycloalkyl, and 3-6 membered heterocyclic alkyl; more preferably selected from hydrogen, halogen, CN, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 ynyl, C1-C4 haloalkyl, C3-C4 cycloalkyl, -O-C1-C4 alkyl, -O-C1-C4 haloalkyl, and 3-4 membered heterocyclic alkyl, wherein the heterocyclic alkyl group contains one or two heteroatoms selected from N, O, and S in addition to the carbon atom, provided that the heterocycle does not contain Two consecutive atoms selected from O and S, wherein the heterocyclic alkyl group is bonded directly or via an oxygen atom or via a C1-C2 alkylene linker; even more preferably selected from hydrogen, C1-C2 alkyl, C2-alkenyl, C1-C2 haloalkyl, -O-C1-C2 alkyl, O-C1-C2 haloalkyl, C3-C4 cycloalkyl, -C1-C2 alkyl-C3-C4 cycloalkyl and 3-4 membered heterocyclic alkyl; even more preferably selected from hydrogen, C1-C2 alkyl, C1-C2 haloalkyl, C3-C4 cycloalkyl, -O-C1-C2 alkyl and -O-C1-C2 haloalkyl; particularly preferably selected from hydrogen, halogen, C1-C2 alkyl and C1-C2 haloalkyl, especially hydrogen or methyl.

[0063] Preferably, R 3 These compounds have formula IA at the ortho position of the methyl oxime side chain of the molecule:

[0064]

[0065] According to another implementation scheme, R 4 It is selected from hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, -(C1-C2alkyl)-O-(C1-C2alkyl) and -CH2-cyclopropyl; more preferably selected from hydrogen, C1-C4 alkyl and C1-C4 haloalkyl, even more preferably selected from methyl and C1 haloalkyl; especially methyl.

[0066] According to another implementation, X is a direct key.

[0067] According to another embodiment, Y is a direct bond. More preferably, X and Y are direct bonds.

[0068] According to another embodiment, at least one of X and Y is a divalent group -CL. 1 L 2 -

[0069] According to another implementation scheme, L 1 and L 2 Independently selected from hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, cyclopropyl, and -CH2-cyclopropyl; or, L 1 and L 2 Together with the middle carbon atom, it forms a cyclopropyl group; more preferably, L 1 and L 2 Independently selected from hydrogen and C1-C3 alkyl groups; or, L 1 and L 2 Together with the middle carbon atom, it forms a cyclopropyl group; in particular, L 1 and L 2 They're all hydrogen.

[0070] According to another embodiment, Z is selected from C3-C6 cycloalkyl, phenyl, and 5- or 6-membered heteroaryl groups, wherein the heteroaryl group contains, in addition to a carbon atom, one, two, or three heteroatoms selected from N, O, and S, provided that the heteroaryl group does not contain two consecutive atoms selected from O and S, and wherein Z is not substituted or has one, two, or three identical or different groups R as defined herein. a More preferably, Z is unsubstituted or contains one or two identical or different groups R as defined herein. a In particular, Z is either unsubstituted or contains a group R as defined herein. a .

[0071] According to another embodiment, Z is selected from C3-C6 cycloalkyl, phenyl, and 5- or 6-membered heteroaryl groups, wherein the heteroaryl group contains, in addition to a carbon atom, one, two, or three heteroatoms selected from N, O, and S, provided that the heteroaryl group does not contain two consecutive atoms selected from O and S, and wherein Z carries one, two, or three identical or different groups R as defined herein. a More preferably, Z has one or two identical or different groups R as defined herein. a In particular, Z carries a group R as defined in this paper. a .

[0072] According to another embodiment, Z is selected from cyclopropyl and phenyl, and wherein Z is not substituted or has 1, 2 or 3 identical or different groups R as defined herein. a More preferably, Z is unsubstituted or contains one or two identical or different groups R as defined herein. a In particular, Z is either unsubstituted or contains a group R as defined herein. a .

[0073] According to another embodiment, Z is phenyl and wherein Z is not substituted or contains one, two, or three identical or different groups R as defined herein.a and / or two R atoms bonded to adjacent carbon ring atoms a The substituent, together with the two intermediate carbocyclic atoms, forms a partially unsaturated or aromatic 5-6 membered fused carbocyclic or heterocyclic ring, wherein the heterocyclic ring, in addition to the carbon atom, includes one or two independent heteroatoms selected from N, O, and S as ring member atoms, provided that the heterocyclic ring cannot contain two consecutive atoms selected from O and S; and wherein R a Unsubstituted or containing 1, 2, 3, 4 or at most a maximum number of identical or different groups R b R b Selected from halogens, CN, NO2, C1-C4 alkyl, C1-C4 haloalkyl, -O-C1-C4 alkyl and -O-C1-C4 haloalkyl. The fused carbide ring may be a cyclopentene ring (to form an indane bicyclic system with a fused phenyl ring), a cyclopentadiene ring (to form a 1H-indane bicyclic system with a fused phenyl ring), a cyclohexene ring (to form a tetrahydronaphthalene bicyclic system with a fused phenyl ring), a cyclohexadiene ring (to form a dihydronaphthalene bicyclic system with a fused phenyl ring), or a cycloheptene ring (to form a 6,7,8,9-tetrahydro-5H-benzo[7]annulene bicyclic system with a fused phenyl ring). The fused heterocycle can be a 2,3-dihydrofuran ring (forming a 2,3-dihydrobenzofuran bicyclic system with a fused phenyl ring), a 3,4-dihydro-2H-pyran ring (forming a benzodihydropyran bicyclic system with a fused phenyl ring), a furan ring (forming a benzofuran bicyclic system with a fused phenyl ring), or a 1,3-m-dioxacyclopentene ring (forming a benzo-1,3-m-dioxacyclopentene bicyclic system with a fused phenyl ring). 2,3-Dihydro-1H-pyrrole ring (forming a dihydroindole bicyclic system together with a fused phenyl ring), 1,3-dihydro-pyrrole-2-one ring (forming a dihydroindole-2-one bicyclic system together with a fused phenyl ring), more preferably the fused heterocycle can be a 1,3-m-dioxacyclopentene ring (forming a benzo-1,3-m-dioxacyclopentene bicyclic system together with a fused phenyl ring), which is bonded to the side chain at the 5-position, resulting in Z being bonded to both R. a The substituents together form 1,3-benzodioxane-5-yl.

[0074] According to the above implementation plan, R aPreferably selected from halogens, CN, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, -O-C1-C4 alkyl, -C(=NO-C1-C4 alkyl)-C1-C4 alkyl, -C(=O)-C1-C4 alkyl, -O-CH2-C(=NO-C1-C4 alkyl)-C1-C4 alkyl, C3-C4 cycloalkyl, -C1-C2 alkyl-C3-C4 cycloalkyl, -O-C3 -C4 cycloalkyl, phenyl, 3-5-membered heterocycloalkyl, 3-5-membered heterocycloalkenyl and 5 or 6-membered heteroaryl, wherein the heterocycloalkyl, heterocycloalkenyl and heteroaryl contain 1, 2 or 3 heteroatoms selected from N, O and S in addition to carbon atoms, provided that the heterocycle does not contain 2 consecutive atoms selected from O and S, wherein the phenyl, heterocycloalkyl, heterocycloalkenyl and heteroaryl are bonded directly or via oxygen atoms or via C1-C2 alkylene linkages.

[0075] Preferably, R a The compounds are selected from halogens, CN, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, -O-C1-C4 alkyl, -C(=O)-C1-C2 alkyl, -C(=NO-C1-C4 alkyl)-C1-C4 alkyl, C3-C4 cycloalkyl, -O-C3-C4 cycloalkyl, phenyl, 3-5-membered heterocyclic alkyl and 5 or 6-membered heteroaryl, wherein the heterocyclic alkyl and heteroaryl contain one or two heteroatoms selected from N, O and S in addition to carbon atoms, provided that the heterocycle does not contain two consecutive atoms selected from O and S, wherein the phenyl, heterocyclic alkyl and heteroaryl are bonded directly or via oxygen atoms or via methylene linkers.

[0076] More preferably, R a The compounds are selected from halogens, CN, C1-C3 alkyl, -O-C1-C3 alkyl, -C(=NO-CH3)-CH3, C3-C4 cycloalkyl, -O-C3-C4 cycloalkyl, phenyl, 3-5-membered heterocyclic alkyl and 5 or 6-membered heteroaryl, wherein the heterocyclic alkyl and heteroaryl contain one or two heteroatoms selected from N, O and S in addition to carbon atoms, provided that the heterocycle does not contain two consecutive atoms selected from O and S, wherein the phenyl, heterocyclic alkyl and heteroaryl are bonded directly or via oxygen atoms or via methylene linkers.

[0077] In particular, R a Selected from halogens, CN, C1-C2 alkyl, -O-C1-C2 alkyl, alkenyl, ethynyl and -C(=NO-CH3)-CH3.

[0078] According to another implementation scheme, R a Selected from halogens, C1-C2 alkyl groups, and -O-C1-C2 alkyl groups, wherein the aliphatic portion is not substituted or contains 1, 2, or 3 identical or different halogen-selected groups R.b .

[0079] According to R a In the above-described embodiments, the heterocyclic alkyl group is more preferably a 4-membered heterocyclic alkyl group, wherein the heterocyclic alkyl group contains, in addition to a carbon atom, one heteroatom selected from N, O and S, preferably N.

[0080] According to R a In the above-described embodiments, the heteroaryl group is more preferably a 5-membered heteroaryl group, wherein the heteroaryl group contains one or two heteroatoms selected from N, O and S in addition to carbon atoms, provided that the heteroaryl group does not contain two consecutive atoms selected from O and S, and preferably the heteroatoms are selected from N and O.

[0081] According to R a The above implementation scheme, R a The aliphatic and cyclic structural portions are not substituted or contain 1, 2, 3, 4, or at most a maximum number of identical or different groups selected from halogens, CN, NO2, C1-C4 alkyl, C1-C4 haloalkyl, -O-C1-C4 alkyl, and -O-C1-C4 haloalkyl; more preferably, R groups selected from halogens. b Even better, only R a The cyclic structure portion is not substituted or contains 1, 2, 3, 4, or at most a maximum number of identical or different groups R selected from halogens, CN, NO2, C1-C4 alkyl, C1-C4 haloalkyl, -O-C1-C4 alkyl, and -O-C1-C4 haloalkyl. b Even better, only R a The phenyl structural moiety is not substituted or contains 1, 2, 3, 4 or 5 identical or different groups R selected from halogens, CN, C1-C4 alkyl, C1-C4 haloalkyl, -O-C1-C4 alkyl and -O-C1-C4 haloalkyl. b Specifically, the phenyl group is not substituted or contains one, two, or three identical or different R groups selected from halogens, CN, C1-C2 alkyl, C1-C2 haloalkyl, -O-C1-C2 alkyl, and -O-C1-C2 haloalkyl. b .

[0082] According to another embodiment, X and Y are both direct bonds, and Z is an unsubstituted bond or a bond with 1, 2, or 3 identical or different substituents R. a phenyl, wherein R a Selected from halogens, C1-C2 alkyl groups, and -O-C1-C2 alkyl groups, wherein R a The aliphatic structural portion is not substituted or contains 1, 2, or 3 identical or different R groups selected from halogens. b .

[0083] According to another preferred embodiment, the present invention relates to compounds of formula I and their stereoisomers and tautomers, as well as their N-oxides and agronomical salts, wherein:

[0084] R 1 Selected from O and NH;

[0085] R 2 For CH or N;

[0086] R 3 It is hydrogen, halogen, or C1-C4 alkyl, wherein R 3 In the position adjacent to the side chain of methyl oxime;

[0087] R 4 Selected from C1-C6 alkyl groups;

[0088] X and Y are both direct bonds;

[0089] Z is selected from cyclopropyl, phenyl, and 5-membered heteroaryl groups.

[0090] The heteroaryl group contains one, two, or three heteroatoms selected from N, O, and S in addition to a carbon atom, provided that the heteroaryl group cannot contain two consecutive atoms selected from O and S.

[0091] Where Z is unsubstituted or contains 1, 2, 3, or at most a maximum number of identical or different groups R a :

[0092] R a The compounds are selected from halogens, CN, C1-C4 haloalkyl, C1-C4 alkyl, -O-C1-C4 alkyl, -O-C1-C4 haloalkyl, -C(=NO-C1-C4 alkyl)-C1-C4 alkyl, -C(=O)-C1-C4 alkyl, C3-C4 cycloalkyl, -C1-C2 alkyl-C3-C4 cycloalkyl, -O-C3-C4 cycloalkyl, phenyl, 3-5-membered heterocyclic alkyl, and 5 or 6-membered heteroaryl, wherein the heterocyclic alkyl and heteroaryl contain one or two heteroatoms selected from N, O, and S in addition to a carbon atom, provided that the heterocycle does not contain two consecutive atoms selected from O and S, wherein the phenyl, heterocyclic alkyl, and heteroaryl are bonded directly or via an oxygen atom or via a methylene linker, wherein R a The aforementioned cyclic structure portion is either unsubstituted or contains 1, 2, or 3 identical or different groups R selected from halogens, CN, C1-C2 alkyl, C1-C2 haloalkyl, -O-C1-C2 alkyl, and -O-C1-C2 haloalkyl. b ;

[0093] and / or

[0094] Two R atoms bonded to adjacent carbon ring atoms aThe substituents, together with the two intermediate carbon ring atoms, form partially unsaturated or aromatic 5-6 membered fused carbon rings or heterocycles.

[0095] In addition to carbon atoms, the heterocycle also includes one or two independent heteroatoms selected from N, O and S as ring member atoms, provided that the heterocycle cannot contain two consecutive atoms selected from O and S.

[0096] According to another implementation scheme, R 3 At the position adjacent to the methyl oxime side chain, R 1 It is NH and R 2 It is N, and these compounds have formula I.A1:

[0097]

[0098] According to another implementation scheme, R 3 At the position adjacent to the methyl oxime side chain, R 1 It is O and R 2 It is N, and these compounds have formula I.A2:

[0099]

[0100] According to another implementation scheme, R 3 At the position adjacent to the methyl oxime side chain, R 1 It is O and R 2 These compounds are CH, and have formula I.A3:

[0101]

[0102] According to another implementation scheme, R 1 It is NH, R 2 It is N and R 3 H is present, and these compounds have formula I.B1:

[0103]

[0104] According to another implementation scheme, R 1 It is O, R 2 It is N and R 3 H is present, and these compounds have formula I.B2:

[0105]

[0106] According to another implementation scheme, R 1 It is O, R 2 It is CH and R 3 H is present, and these compounds have formula I.B3:

[0107]

[0108] Preferably, the R of compound I 3 It is one of the following groups 3-1 to 3-8:

[0109]

[0110] Even better R 3 It is H, CH3, OCH3, CF3, CHF2 or C3H5, especially H or CH3.

[0111] A particularly preferred embodiment of the present invention relates to compound I, wherein R 4 It is one of the following groups 4-1 to 4-10:

[0112]

[0113] A particularly preferred embodiment of the present invention relates to compound I, wherein X and Y are direct bonds and Z is a phenyl group. Even more preferably, X and Y are direct bonds, Z is a phenyl group, and R... 3 At the position adjacent to the methyl oxime side chain, R 1 For NH and R 2 For N, where the phenyl Z is unsubstituted or surrounded by 1, 2 or 3 groups R as defined herein. a By substitution, these compounds have the formula I.A1.1:

[0114]

[0115] According to another embodiment, X and Y are direct bonds, Z is a phenyl group, and R... 3 At the position adjacent to the methyl oxime side chain, R 1 It is O and R 2 It is N, wherein the phenyl Z is unsubstituted or is substituted by 1, 2 or 3 R as defined herein. a With group substitution, these compounds have formula I.A2.1:

[0116]

[0117] According to another embodiment, X and Y are direct bonds, Z is a phenyl group, and R... 3 At the position adjacent to the methyl oxime side chain, R 1 It is O and R 2 It is CH, where the phenyl Z is unsubstituted or replaced by 1, 2 or 3 R as defined herein. a With group substitution, these compounds have formula I.A3.1:

[0118]

[0119] According to another embodiment, X and Y are direct bonds, Z is a phenyl group, and R... 1 It is NH, R2 It is N and R 3 It is H, wherein the phenyl Z is unsubstituted or surrounded by 1, 2 or 3 groups R as defined herein. a By substitution, these compounds have the formula I.B1.1:

[0120]

[0121] According to another embodiment, X and Y are direct bonds, Z is a phenyl group, and R... 1 It is O, R 2 It is N and R 3 It is H, wherein the phenyl Z is unsubstituted or surrounded by 1, 2 or 3 groups R as defined herein. a By substitution, these compounds have the formula I.B2.1:

[0122]

[0123] According to another embodiment, X and Y are direct bonds, Z is a phenyl group, and R... 1 It is O, R 2 It is CH and R 3 It is H, wherein the phenyl Z is unsubstituted or surrounded by 1, 2 or 3 groups R as defined herein. a By substitution, these compounds have the formula I.B3.1:

[0124]

[0125] A particularly preferred embodiment of the present invention relates to compound I, wherein R a Selected from one of the following groups a-1 to a-17:

[0126]

[0127]

[0128] In one embodiment, compound I has the formula I.A1.1, wherein R 3 It is CH3 and R a and R 4 As shown in any row of Table A below, these compounds are named I.A1.1-A-1 to I.A1.1-A-552.

[0129] In another embodiment, compound I has the formula I.A2.1, wherein R 3 It is CH3, R a and R 4 As shown in any row of Table A below, these compounds are named I.A2.1-A-1 to I.A2.1-A-552.

[0130] In another embodiment, compound I has the formula I.A3.1, wherein R 3 It is CH3, R a and R 4 As shown in any row of Table A below, these compounds are named I.A3.1-A-1 to I.A3.1-A-552.

[0131] In another embodiment, compound I has the formula I.B1.1, R a and R 4 As shown in any row of Table A below, these compounds are named I.B1.1-A-1 to I.B1.1-A-552.

[0132] In another embodiment, compound I has the formula I.B2.1, R a and R 4 As shown in any row of Table A below, these compounds are named I.B2.1-A-1 to I.B2.1-A-552.

[0133] In another embodiment, compound I has the formula I.B3.1, R a and R 4 As shown in any row of Table A below, these compounds are named I.B3.1-A-1 to I.B3.1-A-552.

[0134] Table A:

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149] *Refers to trifluorine at positions 3, 4, and 5.

[0150] These compounds can be obtained by various routes similar to those known in the prior art (e.g., EP463488), and advantageously by the synthesis shown in schemes 1-4 below and the experimental section of this application.

[0151] A suitable method for preparing compound I is shown in Scheme 1.

[0152] Option 1:

[0153]

[0154] The reaction begins with the formation of ketone II from the corresponding acetylene compound VIII. First, in a solvent such as tetrahydrofuran (THF) or 2-methyl-THF, at a reaction temperature of -78°C, a base such as n-butyllithium is used to abstract a proton from the acetylene compound, followed by quenching at -78°C with an electrophilic agent such as ethyl acetate in the presence of BF3-diethyl ether. The conversion of ketone II to the corresponding oxime is carried out using hydroxylamine hydrochloride and a base such as pyridine or sodium acetate in a polar solvent such as a methanol-water mixture at a reaction temperature of about 10-25°C for 2-4 hours, preferably at about 15°C. This reaction yields a mixture of E-oxime III and Z-oxime IIIa. The E / Z oxime mixture (III and IIIa) is reacted under alkaline conditions with an intermediate IV, wherein X is a leaving group such as halogen, toluene-methane sulfonate, preferably Cl or Br, at room temperature (RT) of about 24°C for 12 hours using a base such as sodium hydride, cesium carbonate, or potassium carbonate and an organic solvent such as dimethylformamide (DMF) or acetonitrile, preferably cesium carbonate as the base and acetonitrile (AcN) as the solvent. The resulting intermediate IV contains R... 1 Ester compound I.2, where O is an ester, can be converted to R by reacting it with methylamine (preferably a 40% aqueous solution) at RT using THF as a solvent. 1 It is an amide of formula I.1 of NH.

[0155] A general method for preparing intermediate IV is shown in Scheme 2.

[0156] Option 2:

[0157]

[0158] Compound VI can be obtained from compound V via lithium-halogen exchange or by generating a Grignard reagent and further reacting it with dimethyl oxalate or chloromethyl oxalate in the presence of a solvent. Preferred solvents are THF or 2-methyl-THF, and the temperature can be -70°C to -78°C. The conversion of intermediate VI to intermediate VII can be achieved using N-methylhydroxylamine hydrochloride and a base such as pyridine or sodium acetate in a polar solvent such as methanol. The reaction temperature is preferably about 65°C. An E / Z mixture is typically obtained. These isomers can be separated using purification techniques known in the art (e.g., column chromatography, crystallization). Bromination of intermediate VII provides the desired intermediate compound IV, wherein R... 1 It is O, R 2 =N and X is Br. The reaction of intermediate VII with N-bromosuccinimide in solvents such as carbon tetrachloride, chlorobenzene, or acetonitrile, using a free radical initiator such as 1,1′-azobis(cyclohexanecarboxynitrile) or azobisisobutyronitrile, is carried out at a temperature of about 70-100°C. A preferred free radical initiator is 1,1′-azobis(cyclohexanecarboxynitrile), a preferred solvent is chlorobenzene, and a preferred temperature is 80°C.

[0159] Contains different substituents R 3 The synthesis of the compound is carried out in accordance with R. 3 The sequence is similar to that of scheme 2 for bromine. Intermediate III and R therein 3 The coupling of bromine intermediate IV provides compound I as described above. Using standard chemical reactions, such as the Suzuki or Stille reactions, the bromine group can be converted to, for example, other R groups. 3 Substituents such as cycloalkyl, alkoxy, and alkenyl groups. For example, additional conversion of vinyl groups provides groups with other R groups. 3 Compound I includes compounds with substituents such as ethyl, CN, and haloalkyl groups.

[0160] Ketone II can also be prepared using other known methods (Scheme 3).

[0161] Option 3:

[0162]

[0163] The cross-coupling of terminal alkyne compound VIII with acyl chloride is typically catalyzed by palladium and / or copper (J. Org. Chem. 2004, 69, 1615). Another possibility is the aluminization of terminal alkyne VIII catalyzed by a base, followed by its reaction with an acyl chloride (J. Org. Chem. 2005, 70, 6126-6128). Alternatively, it can be obtained from acetylene VIII by abstracting an alkyne proton, quenching it with an aldehyde, and then oxidizing it with an alcohol (Org. Biomol. Chem. 2018, 16, 6659). Ketone II can also be obtained from precursor IX, where X is a halogen, preferably iodine b, palladium and copper catalyzed by the cross-coupling of aryl halide IX with a terminal alkyne ketone (Chem. Cat. Chem. 2015, 7, 3266) or alkyne alcohol, followed by oxidation of the alcohol (Adv. Synth. Cat. 2017, 22, 4062).

[0164] Compound VIII is generally commercially available, or can be obtained using methods known in the art (Org. Lett. 2019, 21, 3990).

[0165] Another general method for preparing compound I is shown in scheme 4.

[0166] Option 4:

[0167]

[0168] Intermediate IV is reacted with N-hydroxysuccinimide X in DMF using a base such as triethylamine. The reaction temperature is typically 50-70°C, preferably about 70°C. The conversion to the corresponding O-benzylhydroxylamine XII is achieved by removing the phthalimide group, preferably using hydrazine hydrate in methanol as a solvent at about 25°C. Alternatively, removing the phthalimide group using methylamine in methanol as a solvent at about 25°C can provide intermediate XIII. Intermediates XII and XIII can be condensed with ketones using acetic acid or pyridine in methanol as a solvent at a temperature of about 50-65°C. Alternatively, this condensation can also be carried out with titanium ethoxide (IV) (Ti(OEt)4) using THF as a solvent at about 70°C. The desired product is usually accompanied by undesirable isomers, which can be removed, for example, by column chromatography or crystallization.

[0169] Schemes 1-4 above describe R in which 3 The synthesis of compound I located ortho to the side chain of methyl oxime is also applicable to R. 3 Corresponding compounds located at different positions on the benzene ring.

[0170] Compound I and its compositions are suitable as fungicides effective against a wide range of plant pathogenic fungi, including soil-borne fungi, particularly those belonging to the classes Plasmodiophoromycetes, Peronosporomycetes (synonyms for Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes (synonyms for Fungi imperfecti). They can be used as foliar fungicides, seed dressing fungicides, and soil fungicides for crop protection.

[0171] Compound I and its compositions are preferably used to control plant pathogenic fungi on various cultivated plants such as cereals, such as wheat, rye, barley, triticale, oats or rice; sugar beets, fruits, legumes such as soybeans, oilseed plants, cucurbitaceae plants, fiber plants, citrus fruits, vegetables, laurel plants, energy and raw material plants, corn; tobacco; nuts; coffee; tea; bananas; grapevines (table grapes and wine grapes); natural rubber plants or ornamental and forest plants; plant propagation materials such as seeds and crop materials of these plants.

[0172] According to the present invention, all the above-mentioned cultivated plants should be understood to include all genera, species, subspecies, varieties, cultivars and / or hybrids belonging to the corresponding cultivated plants, including but not limited to winter and spring varieties, especially cereals such as wheat and barley, and oilseed rape, such as winter wheat, spring wheat, winter barley and so on.

[0173] Maize is also known as Indian maize or sweet maize (Zea mays), which includes all types of maize such as feed maize and sweet maize. According to the invention, all maize cultivars or varieties are included, especially indeterminate and definite cultivars or varieties.

[0174] The term “cultivated plant” should be understood to include plants that have been modified through mutagenesis or genetic engineering to provide new traits or modify existing traits.

[0175] Compound I and its combinations are particularly suitable for controlling the following pathogenic agents of plant diseases: rust diseases on soybeans and cereals (e.g., *P. meibomiae* and *P. striiformis* on soybeans; *Puccinia tritici* and *P. striiformis* on wheat); mildew diseases on specialty crops, soybeans, rapeseed, and sunflowers (e.g., *Botrytis cinerea* on strawberries and grapevines; *Sclerotinia sclerotiorum*, *S. minor*, and *S. rolfsii* on rapeseed, sunflower, and soybeans); Fusarium diseases on cereals (e.g., *Fusarium culmorum* and *F. graminearum* on wheat); downy mildew on specialty crops (e.g., *Plasmopara* on grapevines). Powdery mildew (e.g., *Uncinula necator* on grapevines, *Erysiphe* on various specialty crops, *Wheat powdery mildew* on cereals); and leaf spot diseases on cereals, soybeans, and maize (e.g., *S. noodorum* on cereals, *S. glycines* on soybeans, *Cercospora* on maize and soybeans).

[0176] Compound I and its compositions are particularly suitable for controlling plant pathogenic fungi containing amino acid substitutes for F129L in mitochondrial cytochrome b protein that confer tolerance to the Qo inhibitor V.

[0177] The mutation F129L in the cytochrome b (cytb, also known as cob) gene should refer to any nucleotide substitution at codon 129 (phenylalanine; e.g., TTT or TTC) encoding "F", which results in a codon encoding "L" (leucine; e.g., TTA, TTG, TTG, CTT, CTC, CTA, or CTG). For example, in the cytochrome b gene, the first nucleotide of codon 129 is replaced by 'C' (TTT replaced by CTT), which produces a single amino acid substitution (F129L) at position 129 in the cytochrome b protein (Cytb) from F (phenylalanine) to L (leucine). In this invention, the mutation F129L in the cytochrome b gene should be understood as a single amino acid substitution (F129L) at position 129 in the cytochrome b protein from F (phenylalanine) to L (leucine).

[0178] Many other plant pathogenic fungi, such as rust, especially soybean rust (Phakopsora meibromiae) and fungi from the genera Alternaria, Pyrenophora, and Rhizoctonia, have acquired the F129L mutation in the cytochrome b gene that confers resistance to Qo inhibitors.

[0179] Preferred fungal species include Alternaria solani, sap rust, barley rust, Pyrenophora teres, Pyrenophora tritici-repentis, and Rhizoctonia solani, especially sap rust.

[0180] One aspect of the present invention relates to a method for protecting plants susceptible to and / or affected by plant pathogenic fungi that contain amino acid substitutes for F129L in mitochondrial cytochrome b protein, which confer tolerance to Qo inhibitors. The method comprises applying the plant to at least one compound of formula I or a composition containing at least one compound of formula I, treating the plant's propagation material with at least one compound of formula I or a composition containing at least one compound of formula I, and / or applying the plant pathogenic fungus to the plant pathogenic fungus to at least one compound of formula I or a composition containing at least one compound of formula I.

[0181] According to another embodiment, the method for controlling plant pathogenic fungi includes: a) identifying plant pathogenic fungi containing an amino acid substitute F129L in the mitochondrial cytochrome b protein that confers tolerance to Qo inhibitors, or materials, plants, soil, or seeds at risk of disease caused by plant pathogenic fungi as defined herein, and b) treating the fungi or materials, plants, soil, or plant propagation materials with an effective amount of at least one compound of formula I or a composition containing it.

[0182] The term "plant pathogenic fungus containing an amino acid substitute F129L in the mitochondrial cytochrome b protein that confers resistance to Qo inhibitors" should be understood to mean at least 10%, preferably at least 30%, more preferably at least 50%, even more preferably at least 75%, most preferably 90-100%, and especially 95-100% of the fungal isolate to be controlled contains the F129L substitute in the mitochondrial cytochrome b protein that confers resistance to Qo inhibitors.

[0183] Compound I and its compositions are also suitable for the protection of stored or harvested products and for the prevention of harmful microorganisms in the protection of materials.

[0184] Compound I is used directly or in combination form by treating fungi with an effective amount of the active substance for fungal infection of plants, plant propagation materials such as seeds, soil, surfaces, materials, or spaces where fungal invasion needs to be prevented. Application can be carried out before or after fungal infection of the plant, plant propagation material such as seeds, soil, surfaces, materials, or spaces.

[0185] Agricultural chemical compositions contain a fungicide-effective amount of compound I. The term "fungicide-effective amount" means an amount of composition or compound I sufficient to control harmful fungi on cultivated plants or in the protection of stored or harvested products or materials without causing significant damage to the treated plants, stored or harvested products, or treated materials. This amount can vary over a wide range and depends on various factors such as the species of fungus to be controlled, the cultivated plant being treated, the stored product, the harvested product or material, climatic conditions, and the specific compound I used.

[0186] Plant propagation material may be preventively treated with compound I itself or a composition containing at least one compound I during or before planting or transplanting.

[0187] When used for plant protection, the amount of active substance applied depends on the type of desired effect and is 0.001-2 kg / ha, preferably 0.005-2 kg / ha, more preferably 0.05-0.9 kg / ha, and especially 0.1-0.75 kg / ha.

[0188] In the treatment of plant propagation materials such as seeds, for example by powdering, coating or soaking, the amount of active substance is generally required to be 0.1-1000g / 100kg, preferably 1-1000g / 100kg, more preferably 1-100g / 100kg, and most preferably 5-100g / 100kg of plant propagation material (preferably seeds).

[0189] Users typically use this agricultural chemical composition in pre-dosing devices, backpack sprayers, spray cans, spray aircraft, or irrigation systems. The agricultural chemical composition is usually formulated with water, buffers, and / or other adjuvants to the desired application concentration to obtain a ready-to-use spray or the agricultural chemical composition of this invention. 20-2000 liters, preferably 50-400 liters, of ready-to-use spray are typically applied per hectare of agricultural land.

[0190] Compound I, its N-oxide, and salt can be converted into types commonly used in agrochemical compositions, such as solutions, emulsions, suspensions, powders, pastes, granules, molded products, capsules, and mixtures thereof. Examples of composition types (see also "Catalogue of pesticide formulation types and international coding system", Technical Monograph, Vol. 2, May 2008, 6th edition, CropLife International) are suspensions (SC, OD, FS), emulsifiable concentrates (EC), emulsions (EW, EO, ES, ME), capsules (e.g., CS, ZC), pastes, tablets, wettable powders or granules (WP, SP, WS, DP, DS), molded products (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), insecticides (e.g., LN), and gel formulations for treating plant propagation materials such as seeds (e.g., GF). Compositions prepared in a known manner, as described in Mollet and Grubemann, *Formulation Technology*, Wiley VCH, Weinheim, 2001; or Knowles, *New Developments in Crop Protection Product Formulation*, Agrow Reports DS243, T&F Informa, London, 2005. The invention also relates to agricultural chemical compositions comprising an adjuvant and at least one compound I. Suitable adjuvants are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, auxiliary agents, solvents, penetration enhancers, protective colloids, adhesives, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, fungicides, antifreeze agents, defoamers, colorants, tackifiers, and binders.

[0191] Mixing compound I or compositions containing them in fungicide form with other fungicides in many cases broadens the fungicidal activity spectrum or prevents the development of fungicide resistance. Furthermore, synergistic effects (synergistic mixtures) are often achieved.

[0192] The following pesticides II, which can be used with compound I, are used to illustrate possible combinations, but are not limited thereto:

[0193] A) Respiratory depressants

[0194] -Q oSite-specific complex III inhibitors: azoxystrobin (A.1.1), coumethoxystrobin (A.1.2), coumoxystrobin (A.1.3), fenoxystrobin (A.1.4), enestroburin (A.1.5), fenaminstrobin (A.1.6), fenoxystrobin / flufenoxystrobin (A.1.7), fluoxastrobin (A.1.8), kresoxim-methyl (A.1.9), mandestrob In (A.1.10), pyraclostrobin (A.1.11), pyraclostrobin (A.1.12), azoxystrobin (A.1.13), pyraclostrobin (A.1.14), pyraclostrobin (A.1.15), pyraoxystrobin (A.1.16), pyraclostrobin (A.1.17), 2-(2-(3-(2,6-dichlorophenyl)-1-methylallylaminooxymethyl)phenyl)-2-methoxyimino-N-methylacetamide (A.1.18), pyribencarb (A.1.19), triclopyricarb / chlorodincarb (A.1.20), Famoxadone (A.1.21), fenamidone (A.1.21), N-[2-[(1,4-dimethyl-5-phenylpyrazol-3-yl)oxymethyl]phenyl]-N-methoxycarbamate (A.1.22), metyltetraprole (A.1.25), (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl 3-pyriminosyl-N,3-dimethylpentan-3-enamide (A.1.34), (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethylpentan-3-enamide (A.1.35), pyriminostrobin (A.1.36), bifujunzhi (A.1.37), methyl 2-(o-((2,5-dimethylphenyloxymethylene)phenyl)-3-methoxyacrylate (A.1.38);

[0195] -Q iSite-specific complex III inhibitors: cyazofamid (A.2.1), amisulbrom (A.2.2), 2-methylpropionic acid [(6S,7R,8R)-8-benzyl-3-[(3-hydroxy-4-methoxypyridin-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] ester (A.2.3), fenpicoxamid (A.2.4), florylpicoxamid (A.2.5), metarylpicoxamid (A.2.6);

[0196] - Complex II inhibitors: benodanil (A.3.1), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furamepyr (A.3.9) A.3.10), isofetamid (A.3.11), isopyrazam (A.3.12), mepronil (A.3.13), oxycarboxin (A.3.14), penflufen (A.3.15), penthiopyrad (A.3.16), pydiflumetofen (A.3.17), piraziflumid (A.3.18), sedaxane (A.3.19), leaf Tecloftalam (A.3.20), thifluzamide (A.3.21), inpyrfluxam (A.3.22), pyrapropoyne (A.3.23), fluindapyr (A.3.28), N-[2-[2-chloro-4-trifluoromethylphenoxy]phenyl]-3-difluoromethyl-5-fluoro-1-methylpyrazole-4-carboxamide (A.3.29), (E)-2-[2-[(5-cyano-2-methylphenoxy)methyl]phenyl]-3-methoxyprop-2-enoic acid methyl ester (A.3.30), isoflucypram (A.3.29) 3.31), 2-difluoromethyl-N-(1,1,3-trimethyl-indane-4-yl)pyridine-3-carboxamide (A.3.32), 2-difluoromethyl-N-[(3R)-1,1,3-trimethyl-indane-4-yl]pyridine-3-carboxamide (A.3.33), 2-difluoromethyl-N-(3-ethyl-1,1-dimethyl-indane-4-yl)pyridine-3-carboxamide (A.3.34), 2-difluoromethyl-N-[(3R)-3-ethyl-1,1-dimethyl-indane-4-yl]pyridine-3-carboxamide (A.3.35), 2-difluoromethyl-N-(1,1-dimethyl-3-propyl-indane-4-yl)pyridine-3-carboxamide (A.3.3).36) 2-Difluoromethyl-N-[(3R)-1,1-dimethyl-3-propyl-indane-4-yl]pyridine-3-carboxamide (A.3.37), 2-difluoromethyl-N-(3-isobutyl-1,1-dimethyl-indane-4-yl)pyridine-3-carboxamide (A.3.38), 2-difluoromethyl-N-[(3R)-3-isobutyl-1,1-dimethyl-indane-4-yl]pyridine-3-carboxamide (A.3.39), cyclobutrifluram (A.3.24);

[0197] - Other respiratory depressants: diflumetorim (A.4.1); nitrophenyl derivatives: binapacryl (A.4.2), dinobuton (A.4.3), dinocap (A.4.4), fluazinam (A.4.5), meptyldinocap (A.4.6), ferimzone (A.4.7); organometallic compounds: triphenyltin salts, such as fentin-acetate (A.4.8), fentin chloride (A.4.9), or fentin hydroxide (A.4.10); ametoctradin (A.4.11); silthiofam (A.4.12);

[0198] B) Sterol biosynthesis inhibitors (SBI fungicides)

[0199] -C14 demethylase inhibitors: Triazoles: azaconazole (B.1.1), bitertanol (B.1.2), bromuconazole (B.1.3), cyproconazole (B.1.4) Difenoconazole (B.1.5), diniconazole (B.1.6), diniconazole-M (B.1.7), epoxiconazole (B.1.8), fenbuconazole (B.1.9), fluquinconazole (B.1.10), flusilazole (B.1.11), flutriafol (B.1.12), hexaconazole azole)(B.1.13), imibenconazole)(B.1.14), ipconazole)(B.1.15), metconazole)(B.1.17), myclobutanil)(B.1.18), oxpoconazole(B.1.19), paclobutrazole)(B.1.20), penconazole)(B.1.21), propiconazole)(B.1.22), and propiconazole. Prothioconazole (B.1.23), simeconazole (B.1.24), tebuconazole (B.1.25), tetraconazole (B.1.26), triadimefon (B.1.27), triadimenol (B.1.28), triticonazole (B.1.29), uniconazole (B.1.30), 2-(2,4-difluorobenzyl) 2-(2,4-difluorophenyl)-1,1-difluoro-3-(tetrazol-1-yl)-1-[5-[4-(2,2,2-trifluoroethoxy)phenyl]-2-pyridyl]prop-2-ol (B.1.31), 2-(2,4-difluorophenyl)-1,1-difluoro-3-(tetrazol-1-yl)-1-[5-[4-(trifluoromethoxy)phenyl]-2-pyridyl]prop-2-ol (B.1.32), fluooxytioconazole (B.1.33), ipfentrifluconazole (B.1.37), mefentrifluconazole (B.1.38).38) (2R)-2-[4-(4-chlorophenoxy)-2-trifluoromethylphenyl]-1-(1,2,4-triazol-1-yl)prop-2-ol, (2S)-2-[4-(4-chlorophenoxy)-2-trifluoromethylphenyl]-1-(1,2,4-triazol-1-yl)prop-2-ol, 2-chloromethyl-2-methyl-5-(p-tolylmethyl)-1-(1,2,4-triazol-1-ylmethyl)cyclopentanol (B.1.43); imidazoles: imazalil (B.1.44) Pefurazoate (B.1.45), prochloraz (B.1.46), triflumizol (B.1.47); pyrimidines, pyridines, piperazines: fenarimol (B.1.49), pyrifenox (B.1.50), triforine (B.1.51), [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)isocyanate. [4-pyridyl]-(3-pyridyl)methanol (B.1.52), 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzylnitrile (B.1.53), 2-[6-(4-bromophenoxy)-2-trifluoromethyl-3-pyridyl]-1-(1,2,4-triazol-1-yl)prop-2-ol (B.1.54), 2-[6-(4-chlorophenoxy)-2-trifluoromethyl-3-pyridyl]-1-(1,2,4-triazol-1-yl)prop-2-ol (B.1.55);

[0200] -Δ14-Reductase Inhibitors: 4-Dodecyl-2,6-Dimethylmorpholine (aldimorph) (B.2.1), Dodemorph (B.2.2), Dodemorph-acetate (B.2.3), Fenpropimorph (B.2.4), Tridmorph (B.2.5), Fenpropidin (B.2.6), Piperalin (B.2.7), Spirodiclofen Spiroxamine (B.2.8);

[0201] -3-Ketoreductase inhibitor: fenhexamid (B.3.1);

[0202] - Other sterol biosynthesis inhibitors: chlorphenomizole (B.4.1);

[0203] C) Nucleic acid synthesis inhibitors

[0204] - Phenylamide or acyl amino acid fungicides: benalaxyl (C.1.1), benalaxyl-M (C.1.2), kiralaxyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (C.1.5), and ofofurace (C.1.6). Oxadixyl (C.1.7);

[0205] Other nucleic acid synthesis inhibitors: hymexazole (C.2.1), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidine-4-amine (C.2.6), 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidine-4-amine (C.2.7), 5-fluoro-2-(4-chlorophenylmethoxy)pyrimidine-4-amine (C.2.8);

[0206] D) Inhibitors of cell division and cytoskeleton

[0207] - Microtubule inhibitors: benomyl (D1.1), carbendazim (D1.2), fuberidazole (D1.3), thiabendazole (D1.4), thiophanate-methyl (D1.5), pyridachlometyl (D1.6), N-ethyl-2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]butyramide (D1.8), N-ethyl-2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]-2-methylthioacetamide (D1.9), 2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]-N-(2-fluoroethyl)butyramide (D1.10), 2 -[(3-ethynyl-8-methyl-6-quinolinyl)oxy]-N-(2-fluoroethyl)-2-methoxyacetamide (D.1.11), 2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]-N-propylbutyramide (D.1.12), 2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]-2-methoxy-N-propylacetamide (D.1.13), 2-[(3-... [3-ethynyl-8-methyl-6-quinolinyl)oxy]-2-methylthio-N-propylacetamide (D.1.14), 2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]-N-(2-fluoroethyl)-2-methylthioacetamide (D.1.15), 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-2,5-dimethylpyrazol-3-amine (D.1.16);

[0208] Other cell division inhibitors: diethofencarb (D.2.1), ethaboxam (D.2.2), pencycuron (D.2.3), fluopicolide (D.2.4), zoxamide (D.2.5), metrafenone (D.2.6), pyriofenone (D.2.7), phenamacril (D.2.8);

[0209] E) Inhibitors of amino acid and protein synthesis

[0210] - Methionine synthesis inhibitors: cyprodinil (E.1.1), mepanipyrim (E.1.2), pyrimethanil (E.1.3);

[0211] - Protein synthesis inhibitors: blasticidin-S (E.2.1), kasugamycin (E.2.2), kasugamycin hydrochloride-

[0212] (E.2.3) hydrate, (E.2.4) mildiomycin, (E.2.4) streptomycin

[0213] (E.2.5), oxytetracycline (E.2.6);

[0214] F) Signal transduction inhibitors

[0215] -MAP / histidine kinase inhibitors: fluoroimid (F.1.1), iprodione (F.1.2), procymidone (F.1.3), vinclozolin (F.1.4), fluoroimid... Fludioxonil (F. 1.5);

[0216] -G protein inhibitor: quinoxyfen (F.2.1);

[0217] G) Inhibitors of lipid and membrane synthesis

[0218] - Phospholipid biosynthesis inhibitors: edifenphos (G.1.1), iprobenfos (G.1.2), pyrazophos (G.1.3), isoprothiolane (G.1.4);

[0219] - Lipid peroxidation: dicloran (G.2.1), quintozene (G.2.2), tecnazene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7), zinc thiazole (G.2.8);

[0220] - Phospholipid biosynthesis and cell wall deposition: dimethomorph (G.3.1), flumorph (G.3.2), mandipropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7);

[0221] - Compounds and fatty acids that affect cell membrane permeability: propamocarb (G.4.1);

[0222] -Oxidized sterol-binding protein inhibitors: oxathiapiprolin (G.5.1), fluoxapiprolin (G.5.3), 4-[1-[2-[3-difluoromethyl-5-methylpyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphthyl-1-ylpyridin-2-carboxamide (G.5.4), 4-[1-[2-[3,5-di(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphthyl-1-ylpyridin-2-carboxamide (G.5.5), 4-[1-[2-[3-difluoromethyl]acet ... [5-Trifluoromethylpyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphth-1-ylpyridin-2-carboxamide (G.5.6), 4-[1-[2-[5-cyclopropyl-3-difluoromethylpyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphth-1-ylpyridin-2-carboxamide (G.5.7), 4-[1-[2-[5-methyl-3-trifluoromethylpyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphth-1-ylpyridin-2-carboxamide (G.5.8), 4-[1-[2-[5-difluoromethyl-3-trifluoromethylpyrazol-1-yl]

[0223] [Acetyl]-4-piperidinyl]-N-tetrahydronaphth-1-ylpyridin-2-carboxamide (G.5.9), 4-[1-[2-[3,5-bis(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphth-1-ylpyridin-2-carboxamide (G.5.10), (4-[1-[2-[5-cyclopropyl-3-trifluoromethylpyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphth-1-ylpyridin-2-carboxamide (G.5.11);

[0224] H) Inhibitors with multi-site action

[0225] -Inorganic active substances: Bordeaux mixture (H.1.1), copper (H.1.2), copper acetate (H.1.3), copper hydroxide (H.1.4), copper oxychloride (H.1.5), basic copper sulfate (H.1.6), sulfur (H.1.7);

[0226] -Thio- and dithiocarbamates: ferbam (H.2.1), mancozeb (H.2.2), maneb (H.2.3), metam (H.2.4), metiram (H.2.5), propineb (H.2.6), thiram (H.2.7), zineb (H.2.8), ziram (H.2.9);

[0227] - Organochlorine compounds: anilazine (H.3.1), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorophenole (H.3.9) and its salts, tetrachlorophthalide (H.3.10), and tolylfluanid (H.3.11);

[0228] -Guaridines and others: guanidine (H.4.1), dextrin (H.4.2), dextrin free base (H.4.3), guazatine (H.4.4), guazatine-acetate (H.4.5), iminoctadine (H.4.6), iminoctadine-triacetate (H.4.7), iminoctadine-tris(albesilate) (H.4.8), dithianon (H.4.9), 2,6-dimethyl-1H,5H-[1,4]dithiadieno[2,3-c:5,6-c′]bipyrrole-1,3,5,7(2H,6H)-tetraone (H.4.10);

[0229] I) Cell wall synthesis inhibitors

[0230] - Dextran synthesis inhibitors: validamycin (I.1.1), polyoxin B (I.1.2);

[0231] -Melanin synthesis inhibitors: pyroquilon (I.2.1), tricyclazole (I.2.2), carpropamid (I.2.3), dicyclomet (I.2.4), fenoxanil (I.2.5);

[0232] J) Plant defense inducers

[0233] - Thiadiazol (acibenzolar-S-methyl) (J.1.1), probenazole (J.1.2), isothiazol (J.1.3), tiadinil (J.1.4), prohexadione-calcium (J.1.5); Phosphonates: fosetyl (J.1.6), fosetyl-aluminum (J.1.7), phosphorous acid and its salts (J.1.8), calcium phosphonate (J.1.11), potassium phosphonate (J.1.12), potassium or sodium bicarbonate (J.1.9), 4-cyclopropyl-N-(2,4-dimethoxyphenyl)thiadiazole-5-carboxamide (J.1.10);

[0234] K) Unknown mode of action

[0235] - Bronopol (K.1.1), Chinomethionat (K.1.2), Cyflufenamid (K.1.3), Cymoxanil (K.1.4), Dazomet (K.1.5), Debacarb (K.1.6), Diclomymet (K.1.7), Diclomezine (K.1.8), Difenzoquat (K.1.9), Difenzoquat-methylsulfate lfate (K.1.10), diphenylamine (K.1.11), fenitropan (K.1.12), fenpyrazamine (K.1.13), flumetover (K.1.14), flumetylsulforim (K.1.60), flusulfamide (K.1.15), flutianil (K.1.16), harpin (K.1.17), methasulfocarb (K.1.18), nitrapyrin (K.1.18) .1.19), nitrothal-isopropyl (K.1.20), tolprocarb (K.1.21), oxin-copper (K.1.22), proquinazid (K.1.23), seboctylamine (K.1.61), tebufloquin (K.1.24), chlorothalonil (K.1.25), triazoxide (K.1.26), N′-(4-(4-chloro-3-trifluoromethylphenoxy)-2,5-dimethylphenyl)-N-ethyl-N-methylformamidin (K.1.19), nitrothal-isopropyl (K.1.20), tolprocarb (K.1.21), oxin-copper (K.1.22), proquinazid (K.1.23), seboctylamine (K.1.61), tebufloquin (K.1.24), tebufloquin (K.1.25), triazoxide (K.1.26), N′-(4-(4-chloro-3-trifluoromethylphenoxy)-2,5-dimethylphenyl)-N-ethyl-N-methylformamidin (K.1.26) .1.27), N′-(4-(4-fluoro-3-trifluoromethylphenoxy)-2,5-dimethylphenyl)-N-ethyl-N-methylformamidin (K.1.28), N′-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethylphenyl]-N-ethyl-N-methylformamidin (K.1.29), N′-(5-bromo-6-(indan-2-yl)oxy-2-methyl-3-pyridyl)-N-ethyl-N-methylformamidin (K.1.30), N′-[5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methyl-3-pyridyl]-N-ethyl-N-methylformamidin (K.1.27), N′-(4-(4-fluoro-3-trifluoromethylphenoxy)-2,5-dimethylphenyl)-N-ethyl-N-methylformamidin (K.1.28), N′-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethylphenyl]-N-ethyl-N-methylformamidin (K.1.29), N′-(5-bromo-6-(indan-2-yl)oxy-2-methyl-3-pyridyl]-N-ethyl-N-methylformamidin (K.1.28), N′-[5-bromo-6-[1-(3,5-difluorophenyl)ethoxy] ...31) N′-[5-bromo-6-(4-isopropylcyclohexyloxy)-2-methyl-3-pyridyl]-N-ethyl-N-methylformamidin (K.1.32), N′-[5-bromo-2-methyl-6-(1-phenylethoxy)-3-pyridyl]-N-ethyl-N-methylformamidin (K.1.33), N′-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilylpropoxy)phenyl)-N-ethyl-N-methylformamidin (K.1.34), N′-(5-difluoromethyl-2-methyl-4-(3-trimethylsilylpropoxy)phenyl)-N-ethyl-N-methylformamidin (K.1.35), 2-(4-chlorophenyl)-N-[4-(3,4-dimethoxyphenyl)iso... [Azol-5-yl]-2-prop-2-alkynoxyacetamide (K.1.36), 3-[5-(4-chlorophenyl)-2,3-dimethylisocyanate] [3-yl]pyrisoxazole (K. 1.37), 3-[5-(4-methylphenyl)-2,3-dimethylisopyridine] [Zyzolidin-3-yl]pyridine (K. 1.38), 5-chloro-1-(4,6-dimethoxypyrimidin-2-yl)-2-methyl-1H-benzimidazole (K. 1.39), (Z)-3-amino-2-cyano-3-phenylprop-2-enoic acid ethyl ester (K. 1.40), picarbutrazox (K. 1.41), N-[6-[[(Z)-[(1-methyltetrazole-5-yl)phenylmethylene]amino]oxymethyl]-2-pyridyl]amino Amyl carbamate (K.1.42), N-[6-[[(Z)-[(1-methyltetrazol-5-yl)phenylmethylene]amino]oxymethyl]-2-pyridyl]carbamate butyl-3-ynyl ester (K.1.43), ipflufenoquin (K.1.44), quinofumelin (K.1.47), benzothiazolinone (K.1.48), bromothalonil (K.1.49) 1.49), 2-(6-benzyl-2-pyridyl)quinazoline (K.1.50), 2-[6-(3-fluoro-4-methoxyphenyl)-5-methyl-2-pyridyl]quinazoline (K.1.51), dichlobentiazox (K.1.52), N′-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylformamidin (K.1.53), aminopyrifen (K.1.54), fluopyram (K. ...55) momide)(K.1.55), N′-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-ethyl-N-methylformamidin (K.1.56), N′-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethylphenyl]-N-ethyl-N-methylformamidin (K.1.57), flufenoxadiazam (K.1.58), N-methyl-4-[5-trifluoromethyl-1,2,4- [Diazol-3-yl]benzenethiocarboxamide (K. 1.59), N-methoxy-N-[[4-[5-trifluoromethyl-1,2,4-] [Diazol-3-yl]phenyl]methyl]cyclopropane formamide (WO2018 / 177894, WO 2020 / 212513);

[0236] In binary mixtures, the weight ratio of component 1) to component 2) typically depends on the properties of the components used, and is generally in the range of 1:10,000-10,000:1, often 1:100-100:1, frequently 1:50-50:1, preferably 1:20-20:1, more preferably 1:10-10:1, even more preferably 1:4-4:1, especially 1:2-2:1. According to other embodiments, the weight ratio of component 1) to component 2) is generally in the range of 1000:1-1:1, often 100:1-1:1, frequently 50:1-1:1, preferably 20:1-1:1, more preferably 10:1-1:1, even more preferably 4:1-1:1, especially 2:1-1:1. According to other embodiments, the weight ratio of component 1) to component 2) is generally in the range of 20,000:1 to 1:10, often 10,000:1 to 1:1, frequently 5,000:1 to 5:1, preferably 5,000:1 to 10:1, more preferably 2,000:1 to 30:1, even more preferably 2,000:1 to 100:1, especially 1,000:1 to 100:1. According to other embodiments, the weight ratio of component 1) to component 2) is generally in the range of 1:1 to 1:1000, often 1:1 to 1:100, frequently 1:1 to 1:50, preferably 1:1 to 1:20, more preferably 1:1 to 1:10, even more preferably 1:1 to 1:4, especially 1:1 to 1:2. According to other embodiments, the weight ratio of component 1) and component 2) is generally in the range of 10:1 to 1:20,000, often 1:1 to 1:10,000, frequently 1:5 to 1:5,000, preferably 1:10 to 1:5,000, more preferably 1:30 to 1:2,000, even more preferably 1:100 to 1:2,000, especially 1:100 to 1:1,000.

[0237] In a ternary mixture, i.e., a composition comprising component 1) and component 2) and compound III (component 3), the weight ratio of component 1) to component 2) depends on the properties of the active substance used, and is generally in the range of 1:100-100:1, often 1:50-50:1, preferably 1:20-20:1, more preferably 1:10-10:1, and especially 1:4-4:1. The weight ratio of component 1) to component 3) is generally in the range of 1:100-100:1, often 1:50-50:1, preferably 1:20-20:1, more preferably 1:10-10:1, and especially 1:4-4:1. If desired, any other active component may be added to component 1) in a ratio of 20:1 to 1:20. These ratios are also suitable for mixtures applied via seed treatment.

[0238] Preferably, it contains at least one Q selected from group A). oThe site-specific complex III inhibitor, more preferably selected from compounds (A.1.1), (A.1.4), (A.1.8), (A.1.9), (A.1.10), (A.1.12), (A.1.13), (A.1.14), (A.1.17), (A.1.21), (A.1.25), (A.1.34), and (A.1.35); particularly active substances selected from (A.1.1), (A.1.4), (A.1.8), (A.1.9), (A.1.13), (A.1.14), (A.1.17), (A.1.25), (A.1.34), and (A.1.35) as component 2), is a mixture.

[0239] It also preferably contains at least one Q selected from group A). i The site-specific complex III inhibitor is more preferably selected from compounds (A.2.1), (A.2.3), (A.2.4) and (A.2.6); particularly, the active substances selected from (A.2.3), (A.2.4) and (A.2.6) are used as component 2) in a mixture.

[0240] It also preferably contains at least one inhibitor of complex II selected from group A), more preferably selected from compounds (A.3.2), (A.3.3), (A.3.4), (A.3.7), (A.3.9), (A.3.11), (A.3.12), (A.3.15), (A.3.16), (A.3.17), (A.3.18), (A.3.19), (A.3.20), (A.3.21), (A.3.22), (A.3.23), (A.3.24), (A.3.28), (A.3.31), (A.3.32), (A.3.33), (A.3.34), (A.3.35), (A.3.36). 3.36), (A.3.37), (A.3.38) and (A.3.39); particularly a mixture of active substances selected from (A.3.2), (A.3.3), (A.3.4), (A.3.7), (A.3.9), (A.3.12), (A.3.15), (A.3.17), (A.3.19), (A.3.22), (A.3.23), (A.3.24), (A.3.31), (A.3.32), (A.3.33), (A.3.34), (A.3.35), (A.3.36), (A.3.37), (A.3.38) and (A.3.39) as component 2).

[0241] It is also preferred to include at least one other respiratory inhibitor selected from group A), more preferably selected from compounds (A.4.5) and (A.4.11); especially the active substance of (A.4.11) as a component 2) of the mixture.

[0242] It also preferably contains at least one C14 demethylase inhibitor selected from group B), more preferably selected from compounds (B.1.4), (B.1.5), (B.1.8), (B.1.10), (B.1.11), (B.1.12), (B.1.13), (B.1.17), (B.1.18), (B.1.21), (B.1.22), (B.1.23), (B.1.25), (B.1.26), (B.1.29), (B.1.33), (B.1.34), (B.1.37). (B.1.38), (B.1.43), (B.1.46), (B.1.53), (B.1.54) and (B.1.55); particularly active substances selected from (B.1.5), (B.1.8), (B.1.10), (B.1.17), (B.1.22), (B.1.23), (B.1.25), (B.1.33), (B.1.34), (B.1.37), (B.1.38), (B.1.43) and (B.1.46) as component 2) of a mixture.

[0243] It is also preferred to include at least one Δ14-reductase inhibitor selected from group B), more preferably selected from compounds (B.2.4), (B.2.5), (B.2.6) and (B.2.8); especially the active substance of (B.2.4) as a mixture of components 2).

[0244] It is also preferred to include at least one fungicide selected from phenylamides and acyl amino acids in group C), more preferably selected from compounds (C.1.1), (C.1.2), (C.1.4) and (C.1.5); in particular, active substances selected from (C.1.1) and (C.1.4) are used as components 2) in the mixture.

[0245] It is also preferred that the mixture contains at least one other nucleic acid synthesis inhibitor selected from group C), and more preferably an active substance selected from compounds (C.2.6), (C.2.7) and (C.2.8) as component 2).

[0246] It is also preferred to include at least one active substance selected from group D), more preferably selected from compounds (D.1.1), (D.1.2), (D.1.5), (D.2.4) and (D.2.6); in particular, active substances selected from (D.1.2), (D.1.5) and (D.2.6) as component 2) of the mixture.

[0247] It is also preferred to include at least one selected from group E), more preferably selected from compounds (E.1.1), (E.1.3), (E.2.2) and (E.2.3); especially the active substance of (E.1.3) as component 2) in the mixture.

[0248] It is also preferred to include at least one active substance selected from group F), more preferably selected from compounds (F.1.2), (F.1.4) and (F.1.5) as component 2) of the mixture.

[0249] It is also preferred to include at least one selected from group G), more preferably selected from compounds (G.3.1), (G.3.3), (G.3.6), (G.5.1), (G.5.3), (G.5.4), (G.5.5), (G.5.6), (G.5.7), (G.5.8), (G.5.9), (G.5.10) and (G.5.11); in particular, active substances selected from (G.3.1), (G.5.1) and (G.5.3) as component 2) of the mixture.

[0250] It is also preferred to include at least one compound selected from group H), more preferably compounds selected from (H.2.2), (H.2.3), (H.2.5), (H.2.7), (H.2.8), (H.3.2), (H.3.4), (H.3.5), (H.4.9) and (H.4.10); particularly active substances selected from (H.2.2), (H.2.5), (H.3.2), (H.4.9) and (H.4.10) as component 2) of the mixture.

[0251] It is also preferred that the mixture contains at least one active substance selected from group I), more preferably selected from compounds (I.2.2) and (I.2.5) as component 2).

[0252] It is also preferred to include at least one of the compounds selected from group J), more preferably selected from compounds (J.1.2), (J.1.5), (J.1.8), (J.1.11) and (J.1.12); especially the active substance of (J.1.5) as a mixture of components 2).

[0253] It is also preferred to include at least one active substance selected from group K), more preferably selected from compounds (K.1.41), (K.1.42), (K.1.44), (K.1.47), (K.1.57), (K.1.58) and (K.1.59); particularly an active substance selected from (K.1.41), (K.1.44), (K.1.47), (K.1.57), (K.1.58) and (K.1.59) as component 2) of the mixture.

[0254] Compositions containing mixtures of active ingredients can be prepared by conventional means, such as by the means given for compositions of compound I. Example:

[0255] Synthesis method

[0256] Example 1: Methyl (2E)-2-methoxyimino-2-[2-[[(E)-(1-methyl-3-phenyl-prop-2-ynyl imino)amino]oxymethyl]phenyl]acetate (Examples are based on S numbers in the table below)

[0257]

[0258] Step 1: 4-Phenylacet-3-yn-2-one

[0259] At -78°C, 10 g (1 eq.) of phenylacetylene in 150 mL of THF was added dropwise with n-butyllithium (73 mL, 1.6 M hexane solution, 1.2 eq.) and stirred simultaneously for 30 min at the same temperature. Then, at -78°C, 12 mL (1.2 eq.) of ethyl acetate in 15 mL of THF was added dropwise, followed by the addition of a boron trifluoride diethyl ether complex (33 mL, 50% solution, 1.2 eq.) at the same temperature, and the reaction mixture was stirred for 30 min. After TLC indicated the reaction was complete, the reaction mixture was quenched with 200 mL of saturated ammonium chloride solution, followed by the addition of 100 mL of water. The mixture was extracted with ethyl acetate (3 x 200 mL), and the combined organic phases were washed with brine and dried over sodium sulfate. The solvent was removed to obtain the crude product, which was then purified by Combi rapid column chromatography using 15-20% ethyl acetate in heptane as the mobile phase to give 4-phenylbut-3-yn-2-one (10 g, 71% yield). 1 H NMR (500MHz, DMSO-d6): δ7.67-7.65(m,2H),7.59–7.56(m,1H),7.37–7.15(m,2H),2.45(s,3H).

[0260] Step 2: 4-Phenylacet-3-yne-2-one oxime

[0261] Hydroxylamine hydrochloride (190 mg, 2 eq.) and sodium acetate (394 mg, 2 eq.) were added to a stirred solution of 200 mg, 1 eq. of 4-phenylbut-3-yn-2-one in methanol (10 mL) and water (2.0 mL) at 25 °C. The mixture was stirred at about 20 °C for 4 hours. After the reaction was indicated by TLC, the mixture was evaporated to dryness, and water (30 mL) was added. The mixture was extracted with ethyl acetate (3 x 30 mL), and the combined organic phases were washed with brine and dried over sodium sulfate. The solvent was removed to give 220 mg of crude 4-phenylbut-3-yn-2-one oxime, a mixture of cis and trans (50:50) isomers, which were used directly in the next step without purification.

[0262] Step 3: Methyl (2E)-2-methoxyimino-2-[2-[[(E)-(1-methyl-3-phenyl-prop-2-ynyl imino)amino]oxy-methyl]phenyl]acetate

[0263] In a stirred solution of 4-phenylbut-3-yn-2-one oxime (15 g as a mixture of cis:trans isomers) in AcN (200 ml), methyl (2E)-2-[2-(addition of chloromethyl)-phenyl]-2-methoxyimino-acetic acid (82 ml, 33% DMF solution) was added, followed by the addition of cesium carbonate (61.4 g, 2 eq.). The reaction mixture was then stirred at 25 °C for 16 h. After TLC indicated the reaction was complete, water (200 ml) was added and the mixture was extracted with ethyl acetate (3 x 200 ml). The combined organic phases were washed with brine and dried over sodium sulfate. The solvent was removed to give the crude product, which was purified by column chromatography to give 7.5 g (21% yield) of the pure title compound. 1 H NMR (500MHz, DMSO-d6): δ7.54-7.52(m,2H),7.46-7.41(m,6H),7.24-7.22(m,1H),5.01(s,2H),3.96(s,3H),3.76(s,3H),1.99(s,3H).

[0264] Alternatively, the title compound can be obtained as follows.

[0265] Step 2a: (2E)-2-[2-(aminooxymethyl)phenyl]-2-methoxyimino-acetic acid methyl ester

[0266] Hydrazine hydrate (54 mg, 1 eq.) was added to a stirred solution of (2E)-2-[2-[(1,3-dioxoisoindoline-2-yl)oxymethyl]phenyl]-2-methoxyimino-acetic acid methyl ester (400 mg, 1 eq.) in methanol (10 mL) at 25 °C, and the mixture was stirred for 30 min at the same temperature. After the reaction was complete as indicated by TLC, the solvent was evaporated, and the crude reaction mixture was subjected to column chromatography to give the pure product (150 mg). 1 H NMR (300MHz, DMSO-d6): δ7.41-7.33(m,3H),7.18-7.16(m,1H),5.93(s,2H),4.39(s,2H),3.92(s,3H),3.75(s,3H).

[0267] Step 3a: (2E)-2-methoxyimino-2-[2-[[(E)-(1-methyl-3-phenyl-prop-2-ynyl imino)amino]oxymethyl]phenyl]methyl acetate

[0268] Acetic acid (0.2 ml) was added to a stirred solution of 4-phenylbut-3-yn-2-one (240 mg, 1.2 eq.) and (2E)-2-[2-(aminooxymethyl)phenyl]-2-methoxyimino-acetic acid methyl ester (330 mg, 1 eq.) in methanol (5 ml), and the mixture was heated at 65 °C and stirred at that temperature for 2 hours. After TLC indicated the reaction was complete, the mixture was evaporated to dryness, and water (50 ml) was added. Extraction was performed with ethyl acetate (3 x 30 ml). The combined organic phases were washed with brine and dried over sodium sulfate. The crude product was purified by column chromatography using 20% ​​ethyl acetate in heptane as the mobile phase to give 160 mg (32% yield) of the title compound. Example 2: (2E)-2-methoxyimino-N-methyl-2-[2-[[(E)-(1-methyl-3-phenyl-prop-2-ynylene)amino]oxymethyl]phenyl]acetamide

[0269]

[0270] Methylamine (0.4 mL, 40% aqueous solution) was added to a stirred solution of (2E)-2-methoxyimino-2-[2-[[(E)-(1-methyl-3-phenyl-prop-2-ynyl)amino]oxymethyl]phenyl]acetate (Example 1) (120 mg, 1 eq.) in THF (5 mL) at 25 °C and stirred for 4 hours. After the reaction was indicated by TLC to be complete, the reaction mixture was evaporated and washed with pentane (5 mL x 3 times) and purified by Combi rapid column chromatography to give 11 mg (9% yield) of the title compound.

[0271] Example 15: Methyl (2E)-2-methoxyimino-2-[3-methyl-2-[[(E)-(1-methyl-3-phenyl-prop-2-ynyl imide)amino]oxymethyl]phenyl]acetate

[0272]

[0273] Cesium carbonate (4.08 g, 2 eq.) and (2E)-2-[2-(bromo-methyl)-3-methyl-phenyl]-2-methoxyimino-acetic acid methyl ester (1.7 g, 1 eq.) (dissolved in acetonitrile (5 ml)) were added to a stirred solution of 4-phenylbut-3-yn-2-one oxime (1 g, as a mixture of cis:trans isomers) in acetonitrile (15 ml) at 25 °C and stirred at this temperature for 4 h. After the reaction was indicated by TLC to be complete, the mixture was filtered through diatomaceous earth and washed with ethyl acetate (3 x 30 ml). The filtrate was then evaporated and purified by column chromatography using 15% ethyl acetate in heptane as the mobile phase to give 1.1 g (51% yield) of the title compound.

[0274] 1 H NMR (500MHz, DMSO-d6): δ7.54-7.52(m,2H),7.47-7.42(m,3H),7.34-7.29(m,2H),7 .04-7.02(m,1H),5.01(bs,2H),3.93(s,3H),3.74(s,3H)2.40(s,3H),1.96(s,3H).

[0275] Example 16: (2E)-2-methoxyimino-N-methyl-2-[3-methyl-2-[[(E)-(1-methyl-3-phenyl-prop-2-ynyl imide)amino]oxymethyl]phenyl]acetamide

[0276]

[0277] Methylamine (0.6 ml, 40% aqueous solution) was added to a stirred solution of (2E)-2-methoxyimino-2-[2-[[(E)-(1-methyl-3-phenyl-prop-2-ynyl imide)amino]oxymethyl]phenyl]acetate (Example 15) (750 mg, 1 eq.) in THF (10 ml) at 25 °C and stirred for 5 hours. After the reaction was complete as shown by TLC, water (50 ml) was added to the reaction mixture and extracted with ethyl acetate (3 × 30 ml). The combined organic phases were washed with brine and dried over sodium sulfate. The solvent was removed to give the crude product, which was purified by column chromatography using 35% ethyl acetate in heptane as the mobile phase to give 450 mg (60% yield) of the pure title compound. 1 H NMR (500MHz, DMSO-d6): δ8.21(s,1H)7.54-7.52(m,2H),7.46-7.42(m,3H),7.31-7.26(m, 2H),6.96-6.94(m,1H),5.00(bs,2H),3.88(s,3H),2.70(s,3H)2.39(s,3H),1.96(s,3H).

[0278] Example 12: Methyl (2E)-2-methoxyimino-2-[2-[[(E)-[1-methyl-3-[4-(trifluoromethoxy)phenyl]prop-2-ynylylene]amino]oxymethyl]phenyl]acetate

[0279]

[0280] Cesium carbonate (820 mg, 2 eq.) and (2E)-2-[2-(bromomethyl)phenyl]but-3-yn-2-one oxime (300 mg, as a mixture of cis:trans isomers, 1 eq.) were added to a stirred solution of 4-[4-(trifluoromethoxy)phenyl]-2-methoxyimino-acetic acid methyl ester (350 mg, 1 eq.) in acetonitrile (8 mL) at 25 °C and stirred at this temperature for 2 h. After the reaction was indicated by TLC to be complete, the mixture was filtered through diatomaceous earth and washed with ethyl acetate (25 mL). The filtrate was then evaporated and purified by column chromatography using 15–20% ethyl acetate in heptane as the mobile phase to give the title compound (500 mg, 90%). 1 H NMR (500MHz, DMSO-d6): δ7.69-7.67(m,2H),7.46-7.24(m,5H),7.24-7.22(m,1H),5.01(s,2H),3.95(s,3H),3.76(s,3H),1.99(s,3H).

[0281] Example 11: (2E)-2-methoxyimino-N-methyl-2-[2-[[(E)-[1-methyl-3-[4-(trifluoromethoxy)phenyl]-prop-2-ynylylene]amino]oxymethyl]phenyl]acetamide

[0282]

[0283] Methylamine (0.6 ml, 40% aqueous solution) was added to a stirred solution of (2E)-2-methoxyimino-2-[2-[[(E)-[1-methyl-3-[4-(trifluoromethoxy)phenyl]prop-2-ynylene]amino]oxymethyl]phenyl]acetate (Example 12 above) in THF (6 ml) at room temperature and stirred for 2 hours. After the reaction was complete as shown by TLC, water (15 ml) was added to the reaction mixture and extracted with ethyl acetate (3 x 15 ml). The combined organic phases were washed with brine and dried over sodium sulfate. The solvent was removed to give the crude product, which was purified by column chromatography using 30-35% ethyl acetate in heptane as the mobile phase to give the title compound (220 mg, 73% yield). 1 H NMR (500MHz, DMSO-d6): δ8.26 (s, 1H), 8.25–8.25 (d, J = 5Hz, 2H), 7.69-7.67 (m, 5H ),7.36-7.15(m,1H),5.02(s,2H),3.90(s,3H),2.71(d,J=5Hz,3H),2.02(s,3H).

[0284] Example 22: Methyl (2E)-2-methoxyimino-2-[3-methyl-2-[[(E)-[1-methyl-3-[4-(trifluoromethoxy)-phenyl]prop-2-ynylylene]amino]oxymethyl]phenyl]acetate

[0285]

[0286] Step 1: Trimethyl-[2-[4-(trifluoromethoxy)phenyl]ethynyl]silane

[0287] Triethylamine (3.5 ml, 3 eq.), trimethylsilylacetylene (0.731 ml, 3 eq.), CuI (33 mg, 0.1 eq.), and PdCl2(PPh3)2 (122 mg, 0.1 eq.) were added to a stirred solution of 1-iodo-4-(trifluoromethoxy)benzene (500 mg, 1 eq.) in THF (5 ml) under nitrogen atmosphere and stirred at 60 °C for 2 h. After the reaction was indicated by TLC to be complete, the mixture was filtered through diatomaceous earth and water (10 ml) was added. The organic phase was extracted with ethyl acetate (3 × 15 ml), and the combined organic phases were washed with brine and dried over sodium sulfate. The solvent was removed to give the crude product, which was purified by column chromatography to trimethyl-[2-[4-(trifluoromethoxy)phenyl]ethynyl]silane (400 mg, 89% yield). 1 H NMR (500MHz, CDCl3): δ7.29 (d, J = 8.00Hz, 2H), 6.95 (d, J = 8.00Hz, 2H), 0.06 (s, 9H).

[0288] Step 2: 1-Ethynyl-4-(trifluoromethoxy)benzene

[0289] Tetrabutylammonium fluoride (TBAF) (1.7 ml, 1 M THF solution) was added dropwise to a stirred solution of trimethyl-[2-[4-(trifluoromethoxy)phenyl]ethynyl]silane (4.4 g, 1 eq.) in THF (44 ml) at 0 °C. The resulting solution was stirred at 0–5 °C for 5 min. After the reaction was complete as shown by TLC, the reaction mixture was quenched at 0 °C by adding water (50 ml). The organic phase was extracted with ethyl acetate (3 × 25 ml), and the combined organic phases were washed with brine and dried over sodium sulfate. The solvent was removed to give the crude product, which was purified by column chromatography using 2–5% ethyl acetate in heptane as the mobile phase to give 1-ethynyl-4-(trifluoromethoxy)benzene (1 g, 41% yield). 1 H NMR (500MHz, CDCl3): δ7.43 (d, J = 8.00 Hz, 2H), 7.08 (d, J = 8.00 Hz, 2H), 3.01 (s, 1H).

[0290] Step 3: 4-[4-(trifluoromethoxy)phenyl]but-3-yn-2-one

[0291] To a stirred solution of 1-ethynyl-4-(trifluoromethoxy)benzene (1 g, 1 eq.) in 10 mL of THF at -78 °C, 2.5 M n-butyllithium solution (2.58 mL, 2.5 M hexane solution, 1.2 eq.) was added dropwise, and the mixture was stirred for 20 min at the same temperature. Then, ethyl acetate (0.63 mL, 1.2 eq.) in 2 mL of THF was added dropwise at -78 °C, followed by the addition of a boron trifluoride diethyl ether complex (0.72 mL, 1.2 eq.) at the same temperature, and the reaction mixture was stirred for 1 h. After TLC indicated the reaction was complete, the reaction mixture was quenched with saturated ammonium chloride solution and extracted with ethyl acetate (3 × 15 mL). The combined organic phases were washed with brine and dried over sodium sulfate. After removing the solvent, the crude product was purified by column chromatography using 15-20% ethyl acetate in heptane as the mobile phase to give 4-[4-(trifluoromethoxy)phenyl]but-3-yn-2-one (0.5 g, 41% yield). 1 H NMR (500MHz, CDCl3): δ7.64 (d, J = 8.00 Hz, 2H), 7.26 (d, J = 8.00 Hz, 2H), 3.1 (s, 3H).

[0292] Step 4: 4-[4-(trifluoromethoxy)phenyl]but-3-yn-2-one oxime

[0293] Hydroxylamine hydrochloride (302 mg, 2 eq.) and sodium acetate (359 mg, 2 eq.) were added to a methanol:water (4:1) mixture at 10 °C. The mixture was stirred at 10–15 °C for 2 h. After the reaction was indicated by TLC to be complete, the mixture was evaporated to dryness and water (15 mL) was added and extracted with ethyl acetate (3 x 15 mL). The combined organic phases were washed with brine and dried over sodium sulfate to remove the solvent to give 4-[4-(trifluoromethoxy)phenyl]but-3-yn-2-one oxime (500 mg, 93% yield), a mixture of E and Z isomers (50:50), which could be used directly for the next step without any purification.

[0294] Step 5: (2E)-2-methoxyimino-2-[3-methyl-2-[[(E)-[1-methyl-3-[4-(trifluoromethoxy)phenyl]prop-2-ynylylene]amino]oxymethyl]phenyl]methyl acetate

[0295] Cesium carbonate (670 mg, 2 eq.) and (2E)-2-[2-(bromomethyl)-3-methyl-phenyl]-2-methoxyimino-acetic acid methyl ester (308 mg, 1 eq.) were added to a stirred solution of 4-[4-(trifluoromethoxy)phenyl]but-3-yn-2-one oxime (250 mg, as a mixture of cis:trans isomers, 1 eq.) in acetonitrile (8 mL) at 25 °C and stirred at this temperature for 2 h. After the reaction was indicated by TLC to be complete, the mixture was filtered through diatomaceous earth and washed with ethyl acetate (25 mL). The filtrate was then evaporated and purified by column chromatography using 15–20% ethyl acetate in heptane as the mobile phase to give the title compound (400 mg, 84% yield). 1 H NMR (500MHz, DMSO-d6): δ7.77(d,J=8Hz,2H),7.49(d,J=8Hz,2H),7.34–7.29(m,2H),7.01–7 .00(m,1H),5.50(bs,1H),5.00(bs,1H),3.86(s,3H),3.65(s,3H),2.46(s,3H),2.05(s,3H).

[0296] Example 21: (2E)-2-methoxyimino-N-methyl-2-[3-methyl-2-[[(E)-[1-methyl-3-[4-(trifluoromethoxy)-phenyl]prop-2-ynylylene]amino]oxymethyl]phenyl]acetamide

[0297]

[0298] Methylamine (0.6 ml, 40% aqueous solution) was added to a stirred solution of (2E)-2-methoxyimino-2-[3-methyl-2-[[(E)-[1-methyl-3-[4-(trifluoromethoxy)phenyl]prop-2-ynylene]amino]oxymethyl]phenyl]acetate (Example 22 above) (300 mg, 1 eq.) in THF (6 ml) and stirred for 2 h. After the reaction was complete as shown by TLC, water (15 ml) was added to the reaction mixture and extracted with ethyl acetate (3 x 15 ml). The combined organic phases were washed with brine and dried over sodium sulfate. After solvent removal, the crude product was purified by column chromatography using 30-35% ethyl acetate in heptane as the mobile phase to give the title compound (220 mg, 71% yield). 1H NMR (500MHz, DMSO-d6): δ8.2(bs,1H),7.67(d,J=5Hz,2H),7.44(d,J=10Hz,2H),7.30–7.27 (m,2H),6.9–7.00(m,1H),5.00(bs,2H),3.3(s,3H),2.68(d,3H),2.39(s,3H),1.97(s,3H).

[0299] The following implementations in Table S are synthesized as described above and characterized by LCMS as described in Table L.

[0300] Table L: LCMS Method

[0301]

[0302]

[0303]

[0304] Table S:

[0305]

[0306]

[0307]

[0308]

[0309]

[0310]

[0311]

[0312]

[0313]

[0314]

[0315]

[0316] Biological research

[0317] greenhouse

[0318] The compound was dissolved in a mixture of acetone and / or dimethyl sulfoxide and Wettol, a wetting / emulsifier based on ethoxylated alkylphenol, at a solvent / emulsifier ratio of 99:1 (by volume), to obtain a total volume of 5 ml. Water was then added to a total volume of 100 ml. The stock solution was then diluted with the solvent-emulsifier-water mixture to the final concentration given in the table below.

[0319] Application Example 1. Protective control of soybean rust caused by *Phyllostachys spp.* on soybeans (PHAKPAP2)

[0320] Spray the leaves of potted soybean seedlings with the aforementioned spray solution containing the active ingredients or mixtures described below at concentrations as follows until dripping. Allow the plants to air dry. Cultivate the test plants in a greenhouse at 23-27°C and 60-80% relative humidity for 2 days. Then inoculate the plants with spores of *Pseudomonas beanus* rust fungus. The strain used contains the amino acid substitute F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors. To ensure successful artificial inoculation, the plants were transferred to a humid chamber at approximately 95% relative humidity and 20-24°C for 24 hours. The test plants were then cultivated in a greenhouse at 23-27°C and 60-80% relative humidity for up to 14 days. The degree of fungal invasion on the leaves was assessed visually as a percentage of diseased leaf area; the disease level in the untreated control was typically higher than 85%.

[0321] Application Example 2. Protective control of soybean rust caused by *Phyllostachys spp.* (PHAKPAP6) on soybeans.

[0322] Spray the leaves of potted soybean seedlings with the aforementioned spray solution containing the active ingredients described below at concentrations until dripping. Allow the plants to air dry. Cultivate the test plants in a greenhouse at 23-27°C and 60-80% relative humidity for 6 days. Then inoculate the plants with spores of *Pseudomonas beanus* rust. The strain used contains the amino acid substitute F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors. To ensure successful artificial inoculation, the plants were transferred to a humid chamber at approximately 95% relative humidity and 23-27°C for 24 hours. The test plants were then cultivated in a greenhouse at 23-27°C and 60-80% relative humidity for up to 14 days. The degree of fungal invasion on the leaves was assessed visually as a percentage of diseased leaf area; the disease level in the untreated control was typically higher than 85%.

[0323] The results of the above application examples are given in the table below. All the following test results are given for the control of plant pathogenic fungi containing an amino acid substitute F129L in the mitochondrial cytochrome b protein that confers resistance to Qo inhibitors.

[0324] Table 1:

[0325]

[0326]

[0327]

[0328]

[0329]

Claims

1. Compounds of Formula I and their tautomer forms: in R 1 It is O; and R 2 For CH; or R 1 It is NH; and R 2 Let N be the number of people in the group. R 3 The side chain of the methyl oxime is adjacent to and selected from hydrogen and C1-C4 alkyl groups; R 4 Selected from hydrogen, methyl, and -(C1-C2 alkyl)-O(C1-C2 alkyl); X and Y are both direct bonds; Z stands for phenyl. and Z carries one R group. a : R a Selected from halogens and C1-C4 alkyl groups, And R a The aliphatic structural portion is either unsubstituted or contains 1, 2, or 3 identical or different groups R. b : R b Selected from halogens.

2. The compound according to claim 1, wherein R 1 It is NH; and R 2 It is N.

3. The compound according to claim 1, wherein R 3 Selected from hydrogen and C1-C2 alkyl groups.

4. The compound according to claim 2, wherein R 3 Selected from hydrogen and C1-C2 alkyl groups.

5. The compound according to claim 1, wherein R 3 Selected from C1-C2 alkyl groups.

6. The compound according to claim 2, wherein R 3 Selected from C1-C2 alkyl groups.

7. The compound according to claim 1, wherein R 3 It can be hydrogen or methyl.

8. The compound according to claim 2, wherein R 3 It can be hydrogen or methyl.

9. The compound according to any one of claims 1-8, wherein R 4 It is a methyl group.

10. The compound according to any one of claims 1-8, wherein R a Selected from halogens and C1-C2 alkyl groups.

11. The compound according to claim 9, wherein R a Selected from halogens and C1-C2 alkyl groups.

12. The compound according to any one of claims 1-8, wherein R a Selected from F, Cl, methyl, CHF2 and CF3.

13. The compound according to claim 9, wherein R a Selected from F, Cl, methyl, CHF2 and CF3.

14. An agricultural chemical composition comprising an adjuvant and at least one compound of formula I as defined in any one of claims 1-13.

15. Use of the compound as defined in any one of claims 1-13 or the composition as defined in claim 14 in the control of plant pathogenic fungi.

16. The use according to claim 15, wherein the plant pathogenic fungus contains an amino acid substitute F129L in the mitochondrial cytochrome b protein that confers resistance to Qo inhibitors.

17. A method for controlling plant pathogenic fungi, comprising treating and / or preventingly treating a plant or plant propagation material of a plant at risk of disease caused by the plant pathogenic fungi with at least one compound of Formula I as defined in any one of claims 1-13 or an agricultural chemical composition as defined in claim 14, and / or applying at least one compound of Formula I as defined in any one of claims 1-13 or an agricultural chemical composition as defined in claim 14 to the plant pathogenic fungi.

18. The method of claim 17, wherein the plant pathogenic fungus contains an amino acid substitute F129L in the mitochondrial cytochrome b protein that confers resistance to Qo inhibitors.

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