Use of strobilurin type compounds for combating phytopathogenic fungi containing amino acid substitution f129l in mitochondrial cytochrome b protein conferring resistance to qo inhibitors iii

Abstract

To provide a method for combating phytopathogenic fungi containing an amino acid substitution F129L conferring resistance to Qo inhibitors.SOLUTION: The present invention employs compounds of formula I, their stereoisomers, their N-oxides, and agriculturally acceptable salts thereof. [R1 is O and / or NH; R2 is CH or N; R3 is halogen or the like; R4 is C1-C6 alkyl or the like; Ra is halogen, CN or the like; n is an integer of 0-5].SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] "Qo inhibitors," as used herein, include any substance capable of reducing and / or inhibiting respiration by binding to the ubihydroquinone oxidation center of the cytochrome bc1 complex in mitochondria. The oxidation center is typically located on the outside of the inner mitochondrial membrane. Many of these compounds are also known as strobilurin-type or strobilurin analog compounds.

[0003] The mutation F129L in the mitochondrial cytochrome b (CYTB) gene is intended to mean a substitution of the nucleotide in codon 129 encoding "F" (phenylalanine; e.g., TTT or TTC) resulting in a codon encoding "L" (leucine; e.g., TTA, TTG, TTG, CTT, CTC, CTA, or CTG), e.g., a substitution of the first nucleotide "T" in codon 129 in the CYTB (cytochrome b) gene for "C" (TTT to CTT), resulting in a single amino acid substitution from F to L at position 129 in the cytochrome b protein. Such an F129L mutation is known to confer resistance to Qo inhibitors.

[0004] QoI fungicides, often referred to as strobilurin-type fungicides (Sauter 2007: Chapter 13.2. Strobilurins and other complex III inhibitors. Kraemer, W.; Schirmer, U. (Ed.) - Modern Crop Protection Compounds. Volume 2. Wiley-VCH Verlag 457-495), have traditionally been used to control several fungal pathogens of crops. Qo inhibitors typically work by inhibiting respiration by binding to the ubihydroquinone oxidation center of the cytochrome bc1 complex (electron transport complex III) in mitochondria. The oxidation center is located on the outer side of the inner mitochondrial membrane. Prime examples of the use of QoIs include the use of strobilurins to control Septoria tritici (also known as Mycosphaerella graminicola), the cause of wheat leaf blight in wheat. Unfortunately, the widespread use of such QoIs has led to the selection of mutant pathogens resistant to them (Gisi et al., Pest Manag Sci 56, 833-841, (2000)). Resistance to QoIs has been detected in several plant pathogenic fungi, such as Blumeria graminis, Mycosphaerella fijiensis, Pseudoperonspora cubensis, and Venturia inaequalis. Most resistance to agriculturally used QoIs is due to pathogens containing a single amino acid residue substitution, G143A, in the cytochrome b gene for the cytochrome bc1 complex (the target protein of QoIs found to be controlled by specific QoIs) (WO 2013 / 092224).Although several commercial QoI fungicides are also widely used to control soybean rust, the single amino acid residue substitution G143A in cytochrome b protein that confers resistance to QoI fungicides has not been observed.

[0005] Instead, soybean rust has also acquired a different genetic mutation in the cytochrome b gene, resulting in a single amino acid substitution, F129L, that confers resistance to QoI fungicides. The efficacy of the QoI fungicides traditionally used against soybean rust, namely pyraclostrobin, azoxystrobin, picoxystrobin, orysastrobin, dimoxystrobin, and metominostrobin, has declined to levels that make them practical problems for agricultural practice (e.g., Klosowski et al. (2016) Pest Manag Sci 72, 1211-1215).

[0006] Although trifloxystrobin appears to be less affected by the F129L amino acid substitution than other QoI fungicides, such as azoxystrobin and pyraclostrobin, trifloxystrobin was less effective against fungal populations carrying the F129L QoI resistance mutation than against susceptible populations (Crop Protection 27, (2008) 427-435).

[0007] WO 2017 / 157923 discloses the use of the tetrazole compound 1-[2-[[1-(4-chlorophenyl)-pyrazol-3-yl]oxymethyl]-3-methylphenyl]-4-methyltetrazol-5-one for the control of plant pathogenic fungi containing the F129L amino acid substitution. Summary of the Invention

[0008] Thus, new methods for controlling pathogen-induced diseases in crops, including plants exposed to pathogens containing the F129L amino acid substitution in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors, are desirable. Furthermore, in many cases, the fungicidal activity of known fungicidal strobilurin compounds is insufficient, especially at low application rates, especially when a high proportion of fungal pathogens contain mutations in the mitochondrial cytochrome b gene that confer resistance to Qo inhibitors. Additionally, there is a continuing need for new fungicidal compounds that are more effective, less toxic, and / or environmentally safer. Based on this, it was also an object of the present invention to provide compounds with improved activity against plant pathogenic fungi and / or a broader spectrum of activity, and / or with significantly lower toxicity to non-target organisms, such as vertebrates and invertebrates.

[0009] The strobilurin analogue compounds used to combat plant pathogenic fungi according to the present invention, which contain the F129L amino acid substitution in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors, are particularly referred to herein as R 3 It differs from trifloxystrobin by containing a specific group attached to the central phenyl ring in the ortho position relative to the side chain defined as:

[0010] Thus, the present invention provides compounds of formula I

[0011] [ka] [In the formula, R 1 is selected from O and NH; R 2 is selected from CH and N; R 3 is selected from halogen, C1-C4-alkyl, C2-C4-alkenyl, C1-C2-monohaloalkyl, C1-C2-dihaloalkyl, monohalo-ethenyl, dihalo-ethenyl, C3-C6-cycloalkyl and —O—C1-C4-alkyl, R4 is selected from C-C-alkyl, C-C-alkenyl, C-C-alkynyl, C-C-haloalkyl, C-C-haloalkenyl, C-C-haloalkynyl, -C(=O)-C-C-alkyl, -(C-C-alkyl)-O-(C-C-alkyl), -(C-C-alkyl)-O-(C-C-haloalkyl) and -C-C-alkyl-C-C-cycloalkyl, R a is halogen, CN, -NR 5 R 6 , 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-C6-cycloalkyl, C3-C6-cycloalkenyl, -C1-C2-alkyl-C3-C6-cycloalkyl, -O-C3-C6-cycloalkyl, phenyl, 3- to 6-membered heterocycloalkyl, 3- to 6-membered heterocycloalkenyl and 5- or 6-membered heteroaryl, The heterocycloalkyl, heterocycloalkenyl, and heteroaryl groups contain, in addition to carbon atoms, 1, 2, or 3 heteroatoms selected from N, O, and S; the phenyl, heterocycloalkyl, heterocycloalkenyl and heteroaryl are bonded directly or via an oxygen atom or a C1-C2-alkylene linker; R a The aliphatic and cyclic portions of the formula are unsubstituted or may be substituted with 1, 2, 3, 4 or up to a maximum number of the same or different R b having a group, R b is selected from halogen, CN, NH, NO, C-C-alkyl, C-C-haloalkyl, —O—C-C-alkyl and O—C-C-haloalkyl, R 5 , R 6are independently selected from the group consisting of H, C-C-alkyl, C-C-haloalkyl and C-C-alkynyl, n is an integer selected from 0, 1, 2, 3, 4 and 5. and their stereoisomers and tautomers, and their N-oxides and agriculturally acceptable salts, for the control of plant pathogenic fungi that contain the amino acid substitution F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors.

[0012] The mutation F129L in the cytochrome b (cytb, also called cob) gene is intended to mean a substitution of the nucleotide in codon 129 encoding "F" (phenylalanine; e.g., TTT or TTC) resulting in a codon encoding "L" (leucine; e.g., TTA, TTG, TTG, CTT, CTC, CTA, or CTG), e.g., a substitution of "T" for "C" in the first nucleotide of codon 129 in the cytochrome b gene (TTT to CTT), resulting in a substitution of a single amino acid at position 129 in the cytochrome b protein (Cytb) from F (phenylalanine) to L (leucine) (F129L). In the present invention, the mutation F129L in the cytochrome b gene is understood to be a single amino acid substitution (F129L) from F (phenylalanine) to L (leucine) at position 129 in the cytochrome b protein.

[0013] Many other plant pathogenic fungi, for example rusts, especially soybean rusts (Phakopsora pachyrhizi and Phakopsora meibromiae), as well as fungi from the genera Alternaria, Pyrenophora, and Rhizoctonia, have acquired the F129L mutation in the cytochrome b gene that confers resistance to Qo inhibitors.

[0014] Preferred fungal species are Alternaria solani, Phakopsora pachyrhizi, Phakopsora meybromiae, Pyrenophora teres, Pyrenophora tritici-repentis and Rhizoctonia solani; in particular Phakopsora pachyrhizi.

[0015] In one aspect, the present invention relates to a method for protecting plants susceptible to infection and / or attack by phytopathogenic fungi that contain the amino acid substitution F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors, comprising applying to said plant, treating plant propagation material of said plant with at least one compound of formula I or a composition comprising at least one compound of formula I, and / or applying to said phytopathogenic fungi.

[0016] According to another embodiment, a method for combating plant pathogenic fungi comprises the steps of: a) identifying plant pathogenic fungi comprising the amino acid substitution F129L in a mitochondrial cytochrome b protein that confers resistance to Qo inhibitors, or material, plants, soil or seeds at risk of disease from plant pathogenic fungi as defined herein, and b) treating the fungi or material, plants, soil or plant propagation material with an effective amount of at least one compound of formula I or a composition comprising same.

[0017] The term "amino acid substitution F129L in the mitochondrial cytochrome b protein of a plant pathogenic fungus, which confers resistance to Qo inhibitors", is to be understood as meaning that at least 10%, preferably at least 30%, more preferably at least 50%, even more preferably at least 75%, and most preferably between 90-100%; in particular 95-100% of the isolates to be controlled contain such an F129L substitution in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors. DETAILED DESCRIPTION OF THE INVENTION

[0018] While the present invention has been described with reference to specific embodiments, this description is not intended to be construed in a limiting sense.

[0019] Before describing exemplary embodiments of the present invention in detail, definitions important for understanding the present invention are provided. As used in this specification and the appended claims, the singular forms "a" and "an" also include the respective plurals unless the context clearly dictates otherwise. In the context of the present invention, the terms "about" and "approximately" represent an interval of accuracy that a person skilled in the art would understand to still ensure the technical effect of the function in question. This term typically represents a deviation from the indicated numerical value of ±20%, preferably ±15%, more preferably ±10%, and even more preferably ±5%. It should be understood that the term "comprises" is not limiting. For the purposes of the present invention, the term "consisting of" is considered a preferred embodiment of the term "consisting of."

[0020] Unless otherwise stated, the following definitions are set forth to illustrate and define the meaning and scope of various terms used to describe the invention and the appended claims herein. These definitions are not intended to be general definitions and are valid only for the purposes of this application and should not be construed in a literal sense.

[0021] The term "compound I" refers to a compound of formula I. Likewise, this term applies to all subformulas, for example, "compound I.2" refers to a compound of formula I.2, or "compound V" refers to a compound of formula V.

[0022] The term "independently," when used in the context of selecting substituents as variables, means that when more than one substituent is selected from a number of possible substituents, those substituents can be the same or different.

[0023] The organic moieties or groups mentioned in the above definitions of the variables are collective terms as individual lists of individual members. v -Cw " indicates the number of carbon atoms possible in each case.

[0024] The term "halogen" refers to fluorine, chlorine, bromine and iodine.

[0025] The term "C1-C4-alkyl" refers to a linear or branched saturated hydrocarbon group having 1 to 4 carbon atoms, such as methyl (CH3), ethyl (C2H5), propyl, 1-methylethyl (isopropyl), butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl.

[0026] The term "C2-C4-alkenyl" refers to a straight-chain or branched unsaturated hydrocarbon group having 2 to 4 carbon atoms and a double bond in any position, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl.

[0027] The term "C2-C4-alkynyl" refers to a straight-chain or branched unsaturated hydrocarbon group having 2 to 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, 1-methyl-prop-2-ynyl.

[0028] The term "C1-C4-haloalkyl" refers to a straight-chain or branched alkyl group having 1 to 4 carbon atoms, some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as described above, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-di-fluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro- This refers to 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.

[0029] The term "monohaloethenyl" refers to ethenyl in which one hydrogen atom has been replaced with a halogen atom, such as 1-chloroethenyl, 1-bromoethenyl, 1-fluoroethenyl, or 2-fluoroethenyl. Similarly, "dihaloethenyl" refers to ethenyl in which two hydrogen atoms have been replaced with halogen atoms.

[0030] The term "-O-C1-C4-alkyl" refers to a straight-chain or branched alkyl group having 1 to 4 carbon atoms attached via an 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.

[0031] The term "C3-C6-cycloalkyl" refers to a monocyclic saturated hydrocarbon group having 3 to 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 to 6 carbon ring members and one or more double bonds.

[0032] The term "3- to 6-membered heterocycloalkyl" refers to a 3- to 6-membered monocyclic saturated ring system having, in addition to carbon atoms, one or more heteroatoms as ring members, such as O, N, and S. The term "C3-C6-membered heterocycloalkenyl" refers to a 3- to 6-membered monocyclic ring system having, in addition to carbon atoms, one or more heteroatoms as ring members, such as O, N, and S, and one or more double bonds.

[0033] The term "-C1-C4-alkyl-C3-C6-cycloalkyl" refers to an alkyl having 1 to 4 carbon atoms (as defined above) in which one hydrogen atom of the alkyl group is replaced by a cycloalkyl group having 3 to 6 carbon atoms.

[0034] The term "phenyl" refers to C6H5.

[0035] The term "5- or 6-membered heteroaryl" containing 1, 2, 3 or 4 heteroatoms from the group consisting of O, N and S should be understood as meaning an aromatic heterocycle having 5 or 6 ring atoms. Examples include: 5-membered heteroaryls which, in addition to carbon atoms, contain, for example, 1, 2 or 3 N atoms and / or 1 sulfur and / or 1 oxygen atom: such as 2-thienyl, 3-thienyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl and 1,3,4-triazol-2-yl; - 6-membered heteroaryl which in addition to carbon atoms contain, for example, 1, 2, 3 or 4 N atoms as ring members, such as 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl.

[0036] The term "C1-C2-alkylene linker" means a divalent alkyl group, for example, -CH2- or -CH2-CH2-, attached at one end to a core structure of Formula I and at the other end to a specified substituent.

[0037] As used herein, "compound," and in particular "compound I," includes all stereoisomers and tautomers and mixtures thereof in all ratios, their prodrugs, isotopes, agriculturally acceptable salts, N-oxides and S-oxides thereof.

[0038] The term "stereoisomer" is a general term used for all isomers of individual compounds that differ only in the arrangement of their atoms in space. The term stereoisomer includes mirror image isomers (enantiomers), mixtures of mirror image isomers (racemates, racemic mixtures), geometric (cis / trans or E / Z) isomers, and isomers of compounds containing more than one asymmetric center that are not mirror images of one another (diastereoisomers). The term "tautomer" refers to the coexistence of two (or more) compounds that differ from each other only in the position of one (or more) mobile atoms and electron distribution, e.g., keto-enol tautomers. As used herein, the term "agriculturally acceptable salt" includes salts of active compounds prepared with an acid or base depending on the specific substituents found on the compounds described herein. "N-oxide" refers to the oxide of a nitrogen atom of a nitrogen-containing heteroaryl or heterocycle. N-oxides can be formed in the presence of an oxidizing agent, such as a peroxide, e.g., m-chloroperbenzoic acid, hydrogen peroxide. N-oxides refer to amine oxides, also known as amine-N-oxides, which are chemicals containing an N→O bond.

[0039] In terms of the variables, the intermediate embodiments correspond to the compound I embodiments.

[0040] Substituents and variables (e.g., n, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R a and R b Preference is given to compounds I, and, where applicable, also to compounds of any sub-formulae provided herein, such as formulae I.1 and I.2, as well as intermediates such as compounds II, III, IV and V, in which the radicals I, II, III, IV and V, independently of one another or, more preferably, in combination (any possible combination of two or more substituents as defined herein), have the following meanings:

[0041] Preferred are uses, methods, mixtures and compositions in which the definitions (e.g. phytopathogenic fungi, treatment, crop, compound II, further active ingredient, solvent, solid carrier) have the following meanings, independently of one another or more preferably in combination, and even more preferably in combination with the preferred meanings of compound I herein (any possible combination of two or more definitions provided herein):

[0042] One embodiment of the present invention is a compound I, wherein R 1 is selected from O and NH; R 2 is selected from CH and N, with the proviso that R 1 If is NH, then R 2 is N]. More preferably, R 1 is NH. In particular, R 1 is NH and R 2 is N. Another embodiment is compound I, wherein R 1 is O and R 2 is CH].

[0043] According to another embodiment, R 3is selected from halogen, C1-C4-alkyl, C2-C4-alkenyl, C1-C2-monohaloalkyl, C1-C2-dihaloalkyl, monohaloethenyl, dihaloethenyl, C3-C5-cycloalkyl and -O-C1-C4-alkyl; preferably from halogen, C1-C2-alkyl, C1-C2-monohaloalkyl, C1-C2-dihaloalkyl, C3-C4-cycloalkyl and -O-C1-C2-alkyl; more preferably from C1-C2-alkyl, C1-C2-monohaloalkyl It is particularly preferably selected from alkyl, C1-C2-dihaloalkyl, C3-C4-cycloalkyl and -O-C1-C2-alkyl; even more preferably from halogen, C1-C2-alkyl, C2-C3-alkenyl, CHF2, CFH2, O-C1-C2-alkyl and cyclopropyl; even more preferably from C1-C2-alkyl, ethenyl, CHF2, CFH2, OCH3 and cyclopropyl; particularly preferably from methyl, ethenyl, CHF2 and CFH2; in particular methyl.

[0044] According to one embodiment, R 4 is selected from C-C-alkyl, C-C-alkenyl, -C(=O)-C-C-alkyl, C-C-haloalkyl, C-C-haloalkenyl, -(C-C-alkyl)-O-(C-C-alkyl) and -CH-cyclopropyl; more preferably from C-C-alkyl, C-C-alkenyl, -C(=O)-C-C-alkyl, C-C-haloalkyl, C-C-haloalkenyl, -(C-C-alkyl)-O-(C-C-alkyl) and -CH-cyclopropyl; even more preferably from C-C-alkyl and C-C-haloalkyl, particularly preferably methyl and C-haloalkyl; in particular methyl.

[0045] According to a further embodiment, n is 1, 2, 3, 4 or 5; more preferably n is 1, 2 or 3, even more preferably n is 1 or 2; in particular n is 1.

[0046] According to a further embodiment, n is 0, 1, 2 or 3, more preferably 0, 1 or 2, in particular 0.

[0047] According to a further embodiment, n is 2 and there are two substituents R a are preferably at the 2-position, 3-position (meaning that one of the substituents is at the 2-position and the other at the 3-position); 2-position, 4-position; 2-position, 5-position; 3-position, 4-position or 3-position, 5-position; even more preferably at the 2-position, 3-position or 2-position, 4-position.

[0048] According to a further embodiment, n is 3 and there are three substituents R a is preferably at the 2-, 3- and 4-positions.

[0049] According to a further embodiment, R a is CN, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, -O-C1-C4-alkyl, -C(=O)-C1-C4-alkyl, -C(=NO-C1-C4-alkyl)-C1-C4-alkyl, -O-CH2-(=NO-C1-C4-alkyl)-C1-C4-alkyl, C(=NO-C1-C4-alkyl)-C(=O-NH-C1-C4-alkyl), C3-C6-cycloalkyl, C3-C6-cycloalkenyl, -C1-C2-alkyl-C3-C6-cycloalkyl, -O-C3-C6-cycloalkyl, phenyl, 3- to 5-membered heterocycloalkyl, 3- to 5-membered heterocycloalkenyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl, heterocycloalkenyl and heteroaryl contain, in addition to carbon atoms, 1, 2 or 3 heteroatoms selected from N, O and S, and said phenyl, heterocycloalkyl, heterocycloalkenyl and heteroaryl are bonded directly or via an oxygen atom or a C1-C2-alkylene linker; R a The aliphatic and cyclic moieties are unsubstituted or contain one, two or three identical or different R b It has a group.

[0050] More preferably, R a is CN, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, -O-C1-C4-alkyl, -C(=O)-C1-C2-alkyl, -C(=NO-C1-C2-alkyl)-C1-C2-alkyl, -O-CH2-C(=NO-C1-C2-alkyl)-C1-C2-alkyl, -C(=NO-C1-C2-alkyl)-C(=O-NH-C1-C2-alkyl), C3-C4-cycloalkyl, C3-C4-cycloalkenyl, -C1-C2- alkyl-C3-C4-cycloalkyl, -O-C3-C4-cycloalkyl, phenyl, 3- to 5-membered heterocycloalkyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl and heterocycloalkyl and heteroaryl contain, in addition to carbon atoms, 1 or 2 heteroatoms selected from N, O and S, and said phenyl, heterocycloalkyl and heteroaryl are bonded directly or via an oxygen atom or a methylene linker; R a The aliphatic or cyclic moiety is unsubstituted or has one, two or three identical or different R b It has a group.

[0051] Even more preferably, R a is selected from C1-C3-alkyl, C2-C3-alkenyl, C2-C3-alkynyl, -O-C1-C3-alkyl, -C(=O)-C1-C2-alkyl, -C(=NO-C1-C2-alkyl)-C1-C2-alkyl, C3-C4-cycloalkyl, -C1-C2-alkyl-C3-C4-cycloalkyl, -O-C3-C4-cycloalkyl, phenyl, 3- to 5-membered heterocycloalkyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl and heteroaryl contain in addition to carbon atoms one or two heteroatoms selected from N, O and S, and said phenyl and heteroaryl are linked directly or via an oxygen atom or a methylene linker, R aThe aliphatic and cyclic moieties of are unsubstituted or are each independently selected from halogen, CN, methyl and C1-haloalkyl, and each independently selected from 1, 2 or 3 identical or different R b It has a group.

[0052] Particularly preferred R a is selected from halogen, C1-C4-alkyl, C2-C3-alkenyl, C2-C3-alkynyl, —O—C1-C4-alkyl, —C(═NO—C1-C2-alkyl)-C1-C2-alkyl and phenyl, where R a The aliphatic or cyclic moiety of is unsubstituted or has one, two or three identical or different R b It has a group.

[0053] According to a further embodiment, R 5 , R 6 are preferably selected independently from one another from the group consisting of H, C1-C4-alkyl, C1-C4-haloalkyl and C2-C4-alkynyl, more preferably from H and C1-C4-alkyl.

[0054] According to a further preferred embodiment, the present invention provides a compound of formula I: [In the formula, R 1 is selected from O and NH; R 2 is selected from CH and N, with the proviso that R 1 If is NH, then R 2 is N, R 3 is selected from halogen, C1-C4-alkyl, C2-C4-alkenyl, C1-C2-monohaloalkyl, C1-C2-dihaloalkyl, C3-C4-cycloalkyl and —O—C1-C4-alkyl, R 4 is selected from C-C-alkyl, C-C-haloalkyl, —C(═O)—C-C-alkyl, —(C-C-alkyl)-O—(C-C-alkyl) and —CH-cyclopropyl, Ra is halogen, CN, -NR 5 R 6 , 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-C6-cycloalkyl, C3-C6-cycloalkenyl, -C1-C2-alkyl-C3-C6-cycloalkyl, -O-C3-C6-cycloalkyl, phenyl, 3- to 6-membered heterocycloalkyl, 3- to 6-membered heterocycloalkenyl and 5- or 6-membered heteroaryl, The heterocycloalkyl, heterocycloalkenyl, and heteroaryl groups contain, in addition to carbon atoms, 1, 2, or 3 heteroatoms selected from N, O, and S; the phenyl, heterocycloalkyl, heterocycloalkenyl and heteroaryl are bonded directly or via an oxygen atom or a C1-C2-alkylene linker; R a The aliphatic and cyclic portions of the formula are unsubstituted or may be substituted with 1, 2, 3, 4 or up to a maximum number of the same or different R b having a group, R b is selected from halogen, CN, NH, NO, C-C-alkyl, C-C-haloalkyl, —O—C-C-alkyl and —O—C-C-haloalkyl, R 5 , R 6 are independently selected from the group consisting of H, C1-C6-alkyl and C2-C4-alkynyl, n is an integer selected from 0, 1, 2 and 3. and their stereoisomers and tautomers, as well as their N-oxides and agriculturally acceptable salts, for combating plant pathogenic fungi that contain the amino acid substitution F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors.

[0055] Certain strobilurin-type compounds of formula I are described in EP 370629 and WO 1998 / 23156. However, these compounds are not said to inhibit fungal pathogens that contain the F129L substitution in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors.

[0056] The compounds according to the present invention are 3 is an aliphatic or cyclic substituent, and a specific substituent R a2 This differs from that described in the above publication in that

[0057] Thus, according to a second aspect, the present invention provides a compound of formula I

[0058] [ka] [In the formula,

[0059] R 1 is selected from O and NH; R 2 is selected from CH and N; R 3 is selected from halogen, C-C-alkyl, C-C-alkenyl, C-C-monohaloalkyl, C-C-dihaloalkyl, monohalo-ethenyl, dihalo-ethenyl, C-C-cycloalkyl and —O—C-C-alkyl, R 4 is selected from C-C-alkyl, C-C-alkenyl, C-C-alkynyl, C-C-haloalkyl, C-C-haloalkenyl, C-C-haloalkynyl, -C(=O)-C-C-alkyl, -(C-C-alkyl)-O-(C-C-alkyl), -(C-C-alkyl)-O-(C-C-haloalkyl) and -C-C-alkyl-C-C-cycloalkyl, R a , R a2 are independently halogen, CN, -NR 5 R 6, 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-C6-cycloalkyl, C3-C6-cycloalkenyl, -C1-C2-alkyl-C3-C6-cycloalkyl, -O-C3-C6-cycloalkyl, phenyl, 3- to 6-membered heterocycloalkyl, 3- to 6-membered heterocycloalkenyl and 5- or 6-membered heteroaryl, The heterocycloalkyl, heterocycloalkenyl, and heteroaryl groups contain, in addition to carbon atoms, 1, 2, or 3 heteroatoms selected from N, O, and S; the phenyl, heterocycloalkyl, heterocycloalkenyl and heteroaryl are bonded directly or via an oxygen atom or a C1-C2-alkylene linker; R a and R a2 The aliphatic and cyclic moieties of are independently unsubstituted or may be substituted with 1, 2, 3, 4 or up to a maximum of the same or different R b having a group, R b is selected from halogen, CN, NH, NO, C-C-alkyl, C-C-haloalkyl, —O—C-C-alkyl and —O—C-C-haloalkyl, n is an integer selected from 0, 1, 2, 3 and 4. and their stereoisomers and tautomers, and N-oxides and agriculturally acceptable salts thereof.

[0060] One embodiment of the present invention is R 1 is selected from O and NH; R 2 is selected from CH and N, with the proviso that R 1 If is NH, then R 2 is N. More preferably, R 1 is NH. In particular, R 1is NH and R 2 is N. Another embodiment of the present invention is 1 is selected from O and NH; R 2 is selected from CH and N, with the proviso that R 1 If is O, then R 2 is CH. More preferably, R 2 is N and R 1 is NH or R 2 is CH and R 1 is O. Another embodiment is 1 is O and R 2 relates to compounds I in which

[0061] According to another embodiment, R 3 is selected from halogen, C1-C4-alkyl, C2-C3-alkenyl, C1-C2-monohaloalkyl, C1-C2-dihaloalkyl, monohalo-ethenyl, dihalo-ethenyl, C3-C6-cycloalkyl and -O-C1-C4-alkyl; preferably from halogen, C1-C2-alkyl, C1-C2-monohaloalkyl, C1-C2-dihaloalkyl, C3-C4-cycloalkyl and -O-C1-C2-alkyl; preferably selected from C1-C4-alkyl, C2-C3-alkenyl, monohalo-methyl, dihalo-methyl, C3-C4-cycloalkyl and -O-C1-C4-alkyl; even more preferably from C1-C2-alkyl, CHF2, CFH2, cyclopropyl and OCH3; particularly preferably selected from methyl, CHF2 and CFH2; in particular R 3 is methyl.

[0062] According to a further embodiment, R 4is selected from C-C-alkyl, C-C-alkenyl, -C(=O)-C-C-alkyl, C-C-haloalkyl, C-C-haloalkenyl, -(C-C-alkyl)-O-(C-C-alkyl) and -CH-cyclopropyl; more preferably from C-C-alkyl and C-C-haloalkyl, even more preferably methyl and C-haloalkyl; in particular methyl.

[0063] According to a further embodiment, n is 1, 2, 3 or 4; more preferably, n is 1, 2 or 3, even more preferably, n is 1 or 2; in particular, n is 1. According to a further embodiment, n is 1 and the substituent R a is at the 3-, 4- or 5-position; more preferably at the 3- or 4-position. According to a further embodiment, n is 2 and two substituents R a are in third and fourth place.

[0064] According to a further embodiment, n is 0, 1, 2 or 3, more preferably 0, 1 or 2, in particular 0.

[0065] According to a further embodiment, R a and R a2are independently of each other halogen, CN, NH-C1-C4-alkyl, N(C1-C4-alkyl)2, 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-C is selected from 3-C4-cycloalkyl, phenyl, 3- to 5-membered heterocycloalkyl, 3- to 5-membered heterocycloalkenyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl, heterocycloalkenyl and heteroaryl contain, in addition to carbon atoms, 1 or 2 heteroatoms selected from N, O and S, and said phenyl, heterocycloalkyl, heterocycloalkenyl and heteroaryl are bonded directly or via an oxygen atom or a C1-C2-alkylene linker.

[0066] Preferably, R a and R a2 are independently selected from halogen, CN, NH-C1-C2-alkyl, N(C1-C2-alkyl)2, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, -O-C1-C4-alkyl, -C(=NO-C1-C4-alkyl)-C1-C4-alkyl, -C(=O)-C1-C2-alkyl, C3-C4-cycloalkyl, -O-C3-C4-cycloalkyl, phenyl, 3- to 5-membered heterocycloalkyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl and heteroaryl contain, in addition to carbon atoms, one or two heteroatoms selected from N, O and S, and wherein said phenyl, heterocycloalkyl and heteroaryl are linked directly or via an oxygen atom or a methylene linker.

[0067] More preferably, R a and R a2are selected independently from one another from halogen, CN, C1-C3-alkyl, -O-C1-C3-alkyl, -C(=NO-CH3)-CH3, C3-C4-cycloalkyl, -O-C3-C4-cycloalkyl, phenyl, 3- to 5-membered heterocycloalkyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl and heteroaryl contain, in addition to carbon atoms, one or two heteroatoms selected from N, O and S, and said phenyl, heterocycloalkyl and heteroaryl are linked directly or via an oxygen atom or a methylene linker.

[0068] In particular, R a and R a2 are selected independently from one another from halogen, CN, C1-C2-alkyl, —O—C1-C2-alkyl, ethenyl, ethynyl and —C(═NO—CH3)—CH3.

[0069] R a and R a2 According to the above-mentioned embodiment, said heterocycloalkyl is more preferably a 4-membered heterocycloalkyl, wherein said heterocycloalkyl contains in addition to carbon atoms one heteroatom selected from N, O and S, preferably N.

[0070] R a and R a2 According to the above-mentioned embodiment, the above-mentioned heteroaryl is more preferably a 5-membered heteroaryl, wherein said heteroaryl contains, in addition to carbon atoms, 1 or 2 heteroatoms selected from N, O and S, preferably N and O.

[0071] R a and R a2 According to the above-described embodiment of R a and R a2The aliphatic and cyclic moieties are, independently of one another, unsubstituted or are substituted with 1, 2, 3, 4 or up to a maximum of the same or different R selected from halogen, CN, NH, NO, C-C-alkyl, C-C-haloalkyl, -O-C-C-alkyl and -O-C-C-haloalkyl. b group; more preferably, R a and R a2 and wherein only the cyclic moieties are, independently of one another, unsubstituted or selected from halogen, CN, NH, NO, C-C-alkyl, C-C-haloalkyl, -O-C-C-alkyl and -O-C-C-haloalkyl, 1, 2, 3, 4 or up to a maximum of the same or different R b group; even more preferably, R a and R a2 and wherein only the phenyl moieties are, independently of one another, unsubstituted or have 1, 2, 3, 4 or 5 identical or different R selected from halogen, CN, C-C-alkyl, C-C-haloalkyl, —O—C-C-alkyl and —O—C-C-haloalkyl b groups; in particular R a and R a2 the phenyl moieties, independently of one another, are unsubstituted or have one, two, three identical or different R selected from halogen, CN, C-C-alkyl, C-C-haloalkyl, —O—C-C-alkyl and —O—C-C-haloalkyl b It has a group.

[0072] According to a further embodiment, R a2is selected from halogen, CN, C-C-alkyl, C-C-haloalkyl, -O-C-C-alkyl, -O-C-C-haloalkyl, -C(=NO-C-C-alkyl)-C-C-alkyl, -C(=O)-C-C-alkyl, C-C-cycloalkyl, -C-C-alkyl-C-C-cycloalkyl, -O-C-C-cycloalkyl and 3- to 5-membered heterocycloalkyl, wherein said heterocycloalkyl contains in addition to carbon atoms 1 or 2 heteroatoms selected from N, O and S, and R a2 The above-mentioned cyclic moieties are unsubstituted or are substituted with one, two or three identical or different R selected from halogen, CN, C-C-alkyl, C-C-haloalkyl, —O—C-C-alkyl and —O—C-C-haloalkyl. b It has a group.

[0073] According to a further preferred embodiment, the present invention provides a compound of formula I [In the formula, R 1 is selected from O and NH; R 2 is selected from CH and N, with the proviso that R 1 If is NH, then R 2 is N, R 3 is selected from halogen, C-C-alkyl, C-C-alkenyl, C-C-monohaloalkyl, C-C-dihaloalkyl, monohalo-ethenyl, dihalo-ethenyl, C-C-cycloalkyl and —O—C-C-alkyl, R 4 is selected from C-C-alkyl, C-C-haloalkyl, —C(═O)—C-C-alkyl, —(C-C-alkyl)-O—(C-C-alkyl) and —CH-cyclopropyl, R a , R a2are independently selected from halogen, CN, C-C-haloalkyl, C-C-alkyl, -O-C-C-alkyl, -O-C-C-haloalkyl, -C(=NO-C-C-alkyl)-C-C-alkyl, -C(=O)-C-C-alkyl, C-C-cycloalkyl, -C-C-alkyl-C-C-cycloalkyl, -O-C-C-cycloalkyl and 3- to 5-membered heterocycloalkyl, wherein said heterocycloalkyl contains, in addition to carbon atoms, 1 or 2 heteroatoms selected from N, O and S, and R a and R a2 are independently of one another unsubstituted or substituted with 1, 2 or 3 identical or different R selected from halogen, CN, C-C-alkyl, C-C-haloalkyl, —O—C-C-alkyl and —O—C-C-haloalkyl. b having a group, n is an integer selected from 0, 1, 2 and 3. and their stereoisomers and tautomers, as well as N-oxides and agriculturally acceptable salts thereof.

[0074] According to a further embodiment, R 1 is O and R 2 is N and the compound is of formula I.1:

[0075] [ka]

[0076] According to a further embodiment, R 1 is O and R 2 is CH and the compound is of formula I.2:

[0077] [ka]

[0078] According to a further embodiment, R 1is NH and R 2 is N and the compound is of formula I.3:

[0079] [ka]

[0080] Preferably, R of compound I 3 is one of the following groups 3-1 to 3-6:

[0081] [Table 1]

[0082] Even more preferably, R 3 is CH3, OCH3, CHF2 or C3H5, in particular CH3.

[0083] A particularly preferred embodiment of the present invention is 4 is one of the following groups 4-1 to 4-8:

[0084] [Table 2]

[0085] A particularly preferred embodiment of the present invention is a is one of the following groups a-1 to a-18:

[0086] [Table 3] A particularly preferred embodiment of the present invention is a2 is one of the following groups a2-1 to a2-19:

[0087] [Table 4] TIFF2025160166000010.tif13166

[0088] According to a further embodiment, n is 0 and the compound has formula IA:

[0089] [ka] It is of

[0090] wherein even more preferably R 1 is O and R 2 is CH or R 1 is NH and R 2 is N.

[0091] According to a further embodiment, n is 1. According to a further embodiment, R a is meta position (3-R a ), which compound has formula IB:

[0092] [ka] It is of

[0093] wherein even more preferably R 1 is NH and R 2 is N. According to a further embodiment, n is 1 and R a Para place (4-R a ), the compound has the formula IC:

[0094] [ka] It is of

[0095] wherein even more preferably R 1 is NH and R 2 is N. According to a further embodiment, n is 1 and R a is ortho-position (6-R a ), which compound has formula ID:

[0096] [ka] It is of

[0097] wherein even more preferably R 1 is NH and R 2 is N.

[0098] In an embodiment, compound I is of formula I.3, wherein n, R a , R 3 and R 4 is one of the rows in Table A below, and the compounds are named I.3-A-1 to I.3-A-6270.

[0099] In another embodiment, compound I is of formula I.2, where n, R a , R 3 and R 4 is one of the rows in Table A below, and the compounds are named I.2-A-1 to I.2-A-6270.

[0100] In an embodiment, compound I is of formula I.1, wherein n, R a , R 3 and R 4 is one of the rows in Table A below, and the compounds are named I.1-A-1 to I.1-A-6270.

[0101] Table A: [Table 5] TIFF2025160166000016.tif252133TIFF2025160166000017.tif252135TIFF2025160166000018.tif252135TIFF2025160166000019.tif251141TIFF2025160166000020.tif252137TIFF2025160166000021.tif254135TIFF2025160166000022.tif253133TIFF2025160166000023.tif252135TIFF2025160166000024.tif253137TIFF2025160166000025.tif252135TIFF2025160166000026.tif251136TIFF2025160166000027.tif253133TIFF2025160166000028.tif252134TIFF2025160166000029.tif253135TIFF2025160166000030.tif251142TIFF2025160166000031.tif252135TIFF2025160166000032.tif251135TIFF2025160166000033.tif252138TIFF2025160166000034.tif252136TIFF2025160166000035.tif253133TIFF2025160166000036.tif253134TIFF2025160166000037.tif251133TIFF2025160166000038.tif252135TIFF2025160166000039.tif253134TIFF2025160166000040.tif253133TIFF2025160166000041.tif252134TIFF2025160166000042.tif252137TIFF2025160166000043.tif252136TIFF2025160166000044.tif253131TIFF2025160166000045.tif252131TIFF2025160166000046.tif252131TIFF2025160166000047.tif253132TIFF2025160166000048.tif253133TIFF2025160166000049.tif253133TIFF2025160166000050.tif251133TIFF2025160166000051.tif252132TIFF2025160166000052.tif252133TIFF2025160166000053.tif252134TIFF2025160166000054.tif251134TIFF2025160166000055.tif253136TIFF2025160166000056.tif252135TIFF2025160166000057.tif252133TIFF2025160166000058.tif253132TIFF2025160166000059.tif253132TIFF2025160166000060.tif252134TIFF2025160166000061.tif252134TIFF2025160166000062.tif253136TIFF2025160166000063.tif252133TIFF2025160166000064.tif252134TIFF2025160166000065.tif252133TIFF2025160166000066.tif252136TIFF2025160166000067.tif253133TIFF2025160166000068.tif251136TIFF2025160166000069.tif252133TIFF2025160166000070.tif251134TIFF2025160166000071.tif252136TIFF2025160166000072.tif253136TIFF2025160166000073.tif252136TIFF2025160166000074.tif253133TIFF2025160166000075.tif253133TIFF2025160166000076.tif253135TIFF2025160166000077.tif253135TIFF2025160166000078.tif252135TIFF2025160166000079.tif251139TIFF2025160166000080.tif252135TIFF2025160166000081.tif252136TIFF2025160166000082.tif253135TIFF2025160166000083.tif252137TIFF2025160166000084.tif254138TIFF2025160166000085.tif251135TIFF2025160166000086.tif253134TIFF2025160166000087.tif254136TIFF2025160166000088.tif252135TIFF2025160166000089.tif252133TIFF2025160166000090.tif253135TIFF2025160166000091.tif252137TIFF2025160166000092.tif252135TIFF2025160166000093.tif253134TIFF2025160166000094.tif251135TIFF2025160166000095.tif252133TIFF2025160166000096.tif253136TIFF2025160166000097.tif252133TIFF2025160166000098.tif253139TIFF2025160166000099.tif253135TIFF2025160166000100.tif253134TIFF2025160166000101.tif253135TIFF2025160166000102.tif252135TIFF2025160166000103.tif252134TIFF2025160166000104.tif252137TIFF2025160166000105.tif253137TIFF2025160166000106.tif252136TIFF2025160166000107.tif253134TIFF2025160166000108.tif255135TIFF2025160166000109.tif253132TIFF2025160166000110.tif252135TIFF2025160166000111.tif252135TIFF2025160166000112.tif252135TIFF2025160166000113.tif252135TIFF2025160166000114.tif253133TIFF2025160166000115.tif254137TIFF2025160166000116.tif252134TIFF2025160166000117.tif252134TIFF2025160166000118.tif251135TIFF2025160166000119.tif253134TIFF2025160166000120.tif251138TIFF2025160166000121.tif251134TIFF2025160166000122.tif252133TIFF2025160166000123.tif253133TIFF2025160166000124.tif252133TIFF2025160166000125.tif252135TIFF2025160166000126.tif252135TIFF2025160166000127.tif253138TIFF2025160166000128.tif252137TIFF2025160166000129.tif253135TIFF2025160166000130.tif251136TIFF2025160166000131.tif253132TIFF2025160166000132.tif252133TIFF2025160166000133.tif251134TIFF2025160166000134.tif253137TIFF2025160166000135.tif253136TIFF2025160166000136.tif252136TIFF2025160166000137.tif252135TIFF2025160166000138.tif253135TIFF2025160166000139.tif253135TIFF2025160166000140.tif252134TIFF2025160166000141.tif253135TIFF2025160166000142.tif252133TIFF2025160166000143.tif252132TIFF2025160166000144.tif252132TIFF2025160166000145.tif253134TIFF2025160166000146.tif253135TIFF2025160166000147.tif251136TIFF2025160166000148.tif252132TIFF2025160166000149.tif252133TIFF2025 160166000150.tif253133TIFF2025160166000151.tif252134TIFF2025160166000152.tif25 3135TIFF2025160166000153.tif253134TIFF2025160166000154.tif251133TIFF202516016 6000155.tif251134TIFF2025160166000156.tif252133TIFF2025160166000157.tif139134.

[0102] synthesis The compounds can be obtained by various routes analogous to known prior art methods (e.g., EP 463488), advantageously by the synthesis shown in Schemes 1 to 4 below and in the experimental part of the present application.

[0103] A suitable method for preparing Compound I is illustrated in Scheme 1. Scheme 1:

[0104] [ka]

[0105] It begins with the conversion of the ketone to the corresponding oxime using hydroxylamine hydrochloride and a base such as pyridine, sodium hydroxide, or sodium acetate in a polar solvent such as methanol, a methanol-water mixture, or ethanol at a reaction temperature of 60-100°C, preferably about 65°C. In cases where an E / Z mixture is obtained, the isomers can be separated by purification techniques known in the art (e.g., column chromatography, crystallization, distillation, etc.). Coupling with intermediate IV (wherein X is a leaving group such as halogen, toluene, and methanesulfonate, preferably Cl or Br) is then carried out under basic conditions using, for example, sodium hydride, cesium carbonate, or potassium carbonate as a base and an organic solvent such as dimethylformamide (DMF) or acetonitrile, preferably using cesium carbonate as the base and acetonitrile as the solvent, at room temperature (RT) of about 24°C. 1 is O can be prepared by reacting the ester compound I of formula I, 1 is NH] can be converted to the amide by reaction with methylamine (preferably a 40% aqueous solution).

[0106] Another general method for preparing compound I is depicted in Scheme 2. Scheme 2:

[0107] [ka]

[0108] Intermediate IV is reacted with N-hydroxysuccinimide VI in DMF using a base such as triethylamine. The reaction temperature is typically 50-70°C, preferably about 70°C. Conversion to the corresponding O-benzylhydroxylamine, intermediate VIII, is achieved by removal of the phthalimide group using hydrazine hydrate in methanol as the solvent, preferably at 25°C. Alternatively, removal of the phthalimide group using methylamine in methanol as the solvent at 25°C can give intermediate IX. Intermediates VIII and IX can each be condensed with a ketone using acetic acid or pyridine in methanol as the solvent at 50-65°C. Alternatively, the condensation can also be carried out with titanium(IV) ethoxide (Ti(OEt)4) in THF as the solvent at about 70°C. The desired product is usually accompanied by an undesired isomer, which can be removed, for example, by column chromatography or crystallization.

[0109] A general method for the preparation of intermediate IV is shown in Scheme 3. Scheme 3:

[0110] [ka]

[0111] Compound XI can be obtained from X by lithium-halogen exchange or by further reaction with dimethyl oxalate or chloromethyl oxalate in the presence of a solvent to generate a Grignard reagent. Preferred solvents are THF and 2-methyl-THF, and the temperature can be between -70 and -78°C. Conversion of intermediate XI to intermediate XII 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 usually obtained, and the isomers can be separated by purification techniques known in the art (e.g., column chromatography, crystallization). Bromination of intermediate XII affords R 1 is O and R2 This gives the desired intermediate compound IV, where =N. This reaction of intermediate XII with N-bromosuccinimide using a radical initiator such as 1,1'-azobis(cyclohexanecarbonitrile) or azobisisobutyronitrile in a solvent such as carbon tetrachloride, chlorobenzene, or acetonitrile is carried out at a temperature of 70-100°C. The preferred radical initiator is 1,1'-azobis(cyclohexanecarbonitrile), the preferred solvent is chlorobenzene, and the preferred temperature is 80°C.

[0112] Different substituents R 3 The synthesis of compounds containing R 3 Following a similar sequence to Scheme 3, where R is bromine. 3 Coupling of intermediate III with intermediate IV, where R is bromine, provides compound I, as described above. Using standard chemistry, e.g., Suzuki or Stille reactions, the bromine group can be converted to, for example, another R 3 Substituents such as cycloalkyl, alkoxy, and alkenyl can be converted. For example, further conversion of ethenyl can result in other R 3 Compound I is obtained with substituents such as ethyl, CN, and haloalkyl.

[0113] Most ketones of general formula II were commercially available, but for those that were not, their preparation was carried out in-house using methods known in the prior art. Scheme 4 depicts various methods known in the literature for the synthesis of these ketones. Scheme 4:

[0114] [ka]

[0115] Ketone II can be obtained from precursor XIV bearing the corresponding halogen, where X is preferably bromine or iodine. Lithium-halogen exchange in compound XIII using n-butyllithium (J Org Chem, 1998, 63 (21), 7399-7407) or synthesis of the corresponding Grignard reagent using THF as solvent (Nature Comm, 2017, 8(1), 1-7) and subsequent reaction with N-methoxy-N-methylacetamide at about -70 to -78 °C can provide ketone II. Alternatively, the coupling reaction of compound XIV with tributyl(1-ethoxyvinyl)stannane in the presence of a transition metal catalyst, preferably palladium, containing a suitable ligand in a solvent such as dioxane at a reaction temperature of about 100°C, followed by treatment with 1N HCl, can provide ketone II (Org Lett, 2016, 18(7), 1630-1633, WO 2018 / 115380). The reaction of XIV with 1,4-butanediol vinyl ether in the presence of a transition metal catalyst, preferably palladium, containing a suitable ligand, and a solvent such as 1,2-propanediol and a base such as sodium carbonate at a reaction temperature of about 120°C, followed by treatment with 1N HCl, can provide ketone II (Chem A Eur J, 2008, 14(18), 5555-5566). Another method uses acid compound XV, which can be converted to the corresponding Weinreb amide or carboxylic acid ester XVII, and subsequent reaction with methylmagnesium bromide (MeMgBr) in a solvent such as THF at a temperature of -78 to 0°C, preferably 0°C, gives ketone II. Another method uses the reaction of nitrile XVI with MeMgBr, which is carried out in a solvent such as THF or toluene, preferably THF, at a reaction temperature of 25 to 60°C, preferably 60°C, followed by treatment with 1N HCl (Eur J Med Chem, 2015, 102, 582-593).

[0116] Compound I and its compositions are each suitable as fungicides effective against a wide range of plant pathogenic fungi, including soil-borne fungi, in particular from the classes Plasmodiophoromycetes, Peronosporomycetes (synonymous with Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes (synonymous with Fungi imperfecti). They can be used in crop protection as foliar fungicides, fungicides for seed dressing, and soil fungicides.

[0117] The compounds I and compositions thereof are preferably useful for controlling phytopathogenic fungi in various cultivated plants, such as cereals, e.g. wheat, rye, barley, triticale, oatmeal, rice; beets, fruits, legumes, e.g. soybeans, oil plants, cucurbits, fiber plants, citrus fruits, vegetables, laurels, energy and raw material plants, corn; tobacco; nuts; coffee; tea; bananas; grapes (table grapes and grape juice, grapevines); rubber trees; or ornamental and forestry plants, in plant propagation material, e.g. seeds; and in crop material of these plants.

[0118] According to the present invention, all of the above-mentioned cultivated plants are understood to include any species, subspecies, modifications, varieties and / or hybrids belonging to the respective cultivated plants, including but not limited to winter and spring varieties, in particular cereals such as wheat and barley, and oilseed rape, such as autumn wheat, spring wheat, autumn barley, etc.

[0119] Corn is also known as Indian corn or maize (Zea mays), which includes all types of corn, e.g., field corn and sweet corn. According to the present invention, all soybean cultivars or varieties are included, particularly indeterminate and determined cultivars or varieties.

[0120] The term "cultivated plants" should be understood to include plants that have been modified by mutagenesis or genetic engineering to give the plant new traits or to modify traits that are already present.

[0121] Compound I and its compositions, respectively, are particularly suitable for controlling the following causes of plant diseases: rust in soybeans and cereals (e.g., Phakopsora pachyrhizi and P. meibomiae in soybeans; Puccinia tritici and P. striiformis in wheat); mildew in specialty crops, soybeans, rapeseed and sunflowers (e.g., Botrytis cinerea in strawberries and grapevines); Sclerotinia sclerotiorum, S. minor and S. rolfsii in rapeseed, sunflower and soybean); Fusarium wilt in cereals (e.g., Fusarium culmorum and F. graminearum in wheat). graminearum); downy mildew in specialty crops (e.g., Plasmopara viticola on grapevine, Phytophthora infestans on potato); powdery mildew in specialty crops and cereals (e.g., Uncinula necator on grapevine, Erysiphe spp. on various specialty crops, Blumeria graminis on cereals); and leaf spots in cereals, soybeans, and corn (e.g., Septoria tritici and S. nodorum on cereals, S. glycines on soybeans, Cercospora spp. on corn and soybeans).

[0122] The compounds I and their compositions, respectively, are also suitable for controlling harmful microorganisms in the protection of stored products or harvests and in the protection of materials.

[0123] Compound I is used by itself or in the form of a composition by treating the fungi, plants, plant propagation materials, such as seeds; soil, surface, material or room to be protected from fungal attack with a fungicidal amount of the active substance.Application can be carried out both before and after the fungal infection of plants, plant propagation materials, such as seeds; soil, surface, material or room.

[0124] The pesticide composition comprises a fungicidally effective amount of Compound I. The term "fungicidally effective amount" refers to an amount of the composition or Compound I that is sufficient to control harmful fungi in cultivated plants or to protect stored produce or harvested material, or materials, without causing substantial damage to the treated plants, treated stored produce or harvested material, or treated materials. Such amounts can vary widely and depend on various factors, such as the fungal species to be controlled, the cultivated plants, stored produce, harvested material, or materials to be treated, climatic conditions, and the particular Compound I used.

[0125] Plant propagation material may be treated prophylactically with Compound I itself or with a composition comprising at least one Compound I either at the time of planting or transplanting or before.

[0126] The user typically applies the pesticide composition from a predosage device, backpack sprayer, spray tank, pesticide spraying aircraft, or irrigation system. The pesticide composition is typically formulated to the desired application concentration with water, buffers, and / or further auxiliaries, thus providing a ready-to-use spray liquid or pesticide composition according to the invention. Typically, 20 to 2000 liters, preferably 50 to 400 liters, of ready-to-use spray liquid are applied per hectare of agriculturally useful area.

[0127] Compound I, its N-oxides and salts can be converted into the customary types of pesticide compositions, such as solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules and mixtures thereof. The composition types (see "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6 th Examples of suitable formulations (as used in the present invention) are suspensions (e.g., SC, OD, FS), emulsifiable concentrates (e.g., EC), emulsions (e.g., EW, EO, ES, ME), capsules (e.g., CS, ZC), pastes, tablets, wettable powders or dusts (e.g., WP, SP, WS, DP, DS), pressed compacts (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), insecticides (e.g., LN), and gel formulations (e.g., GF) for the treatment of plant propagation material, such as seeds. The compositions are prepared in a known manner, as described, for example, by Mollet and Grubemann, "Formulation technology," Wiley VCH, Weinheim, 2001; or by Knowles, "New developments in product formulations for crop protection," Agrow Reports DS243, T&F Informa, London, 2005. The present invention also relates to an agrochemical composition comprising an adjuvant and at least one compound I. Suitable adjuvants are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, humectants, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners, humectants, water repellents, attractants, feeding stimulants, compatibilizers, bactericides, antifreeze agents, antifoaming agents, pigments, tackifiers and binders.

[0128] The agrochemical composition generally comprises between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, more preferably between 1 and 70% by weight, and in particular between 10 and 60% by weight of active substance (e.g., at least one compound I). Furthermore, the agrochemical composition generally comprises between 5 and 99.9% by weight, preferably between 10 and 99.9% by weight, more preferably between 30 and 99% by weight, and in particular between 40 and 90% by weight of at least one adjuvant.

[0129] When used in plant protection, the amounts of active substance applied are, depending on the type of effect desired, between 0.001 and 2 kg per hectare, preferably between 0.005 and 2 kg per hectare, more preferably between 0.05 and 0.9 kg per hectare, in particular between 0.1 and 0.75 kg per hectare.

[0130] For the treatment of plant propagation material, such as seeds, for example by dusting, coating or drenching, amounts of active substance required are generally from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g, most preferably from 5 to 100 g per 100 kg of plant propagation material (preferably seeds).

[0131] Various types of oils, wetting agents, adjuvants, fertilizers or micronutrients, and further pesticides (e.g., fungicides, growth regulators, herbicides, insecticides, safeners) can be added to the compounds I or their compositions as premixes or used without addition until just before use (tank mix). These agents can be mixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

[0132] The mixture of compounds I or compositions containing them in their fungicidal use form with other fungicides often results in an extension of the fungicidal spectrum of activity or in the prevention of the development of fungicide resistance, and in many cases also in synergistic effects (synergistic mixtures).

[0133] The following list of pesticides II with which compounds I can be used in combination is intended to illustrate, but not limit, the possible combinations: A) Respiratory inhibitors - Q oInhibitors of complex III at the site: azoxystrobin (A.1.1), coumethoxystrobin (A.1.2), coumoxystrobin (A.1.3), dimoxystrobin (A.1.4), enestroburin (A.1.5), fenaminstrobin (A.1.6), fenoxystrobin / flufenoxystrobin obin (A.1.7), fluoxastrobin (A.1.8), kresoxim-methyl (A.1.9), mandestrobin (A.1.10), metominostrobin (A.1.11), orysastrobin (A.1.12), picoxystrobin (A.1.13), pyraclostrobin (A.1.14), pyrametostrobin (A.1.15), strobin (A.1.15), pyraoxystrobin (A.1.16), trifloxystrobin (A.1.17), 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2 methoxyimino-N-methyl-acetamide (A.1.18), pyribencarb (A.1.19), triclopyricarb / chlorodincarb (A .1.20), famoxadone (A.1.21), fenamidon (A.1.21), methyl-N-[2-[(1,4-dimethyl-5-phenyl-pyrazol-3-yl)oxylmethyl]phenyl]-N-methoxy-carbamate (A.1.22), methyltetraprole (A.1.25), (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]-oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (A.1.34), (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (A.1.35), pyriminostrobin (A.1.36), bifujunzhi (A.1.37), 2-(ortho-((2,5-dimethylphenyl-oxymethylene)phenyl)-3-methoxy-acrylic acid methyl ester (A.1.38);. - Q i Inhibitors of complex III at the site: cyazofamid (A.2.1), amisulbrom (A.2.2), [(6S,7R,8R)-8-benzyl-3-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-di-oxo-1,5-dioxonan-7-yl]2-methylpropanoate (A.2.3), fenpicoxamid (A.2.4), florylpicoxamid (A.2.5), metarylpicoxamid (A.2.6); - 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), Furametpyr (A.3.10), isofetamide (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), pyraziflumi d) (A.3.18), sedaxane (A.3.19), 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-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-5-fluoro-1-methyl-pyrimidinone razole-4-carboxamide (A.3.29), methyl (E)-2-[2-[(5-cyano-2-methyl-phenoxy)methyl]phenyl]-3-methoxy-prop-2-enoate (A.3.30), isoflucipram (A.3.31), 2-(difluoromethyl)-N-(1,1,3-trimethyl-indan-4-yl)-pyridine-3-carboxamide (A.3.32), 2-(difluoromethyl)-N-[(3R)-1,1,3-trimethylindan-4-yl]-pyridine-3-carboxamide (A.3.33), 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)-pyridine-3-carboxamide (A.3.34), 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (A.3.35), 2-(difluoromethyl)-N-(1,1-dimethyl-3-propyl-indan-4-yl)pyridine-3-carboxamide (A.3.36), 2-(difluoromethyl)-N-[(3R)- 1,1-dimethyl-3-propyl-indan-4-yl]pyridine-3-carboxamide (A.3.37), 2-(difluoromethyl)-N-(3-isobutyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide (A.3.38), (2-(difluoromethyl)-N-[(3R)-3-isobutyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (A.3.39), cyclobutrifluram (A.3.24); - other respiratory inhibitors: 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: fentin salts, for example fentin acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.11); silthiofam (A.4.12); B) Sterol biosynthesis inhibitors (SBI fungicides) - 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), epoxic onazole (B.1.8), fenbuconazole (B.1.9), fluquinconazole (B.1.10), flusilazole (B.1.11), flutriafol (B.1.12), hexaconazole (B.1.13), imibenconazole (B.1.14), ipconazole (B.1.15), metconazole le (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), paclobutrazole (B.1.20), penconazole (B.1.21), propiconazole (B.1.22), 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-difluorophenyl)-1,1-difluoro-3-(tetrazol-1-yl)-1-[5-[4-(2,2,2-trifluoroethoxy)phenyl]-2pyridyl]propan-2-ol (B.1.31), 2-(2,4-difluorophenyl)-1,1-difluoro-3-(tetrazol-1-yl)-1[5-[4-(trifluoromethoxy)phenyl]-2-pyridyl]propan-2-ol (B.1.32), fluooxytioconazole (B.1.33), ipfentrifluconazole (B.1.37), mefentrifluconazole (B.1.38), (2R)-2-[4-(4-chlorophenoxy) -2-(trifluoromethyl)phenyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, (2S)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1,2,4-triazol-1-yl)propan-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-fluoro-phenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(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]benzonitrile (B.1.53), 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (B.1.54), 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (B.1.55);. - Delta-14 reductase inhibitors: aldimorph (B.2.1), dodemorph (B.2.2), dodemorph acetate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spiroxamine (B.2.8); - Inhibitors of 3-ketone reductase: fenhexamid (B.3.1); - Other sterol biosynthesis inhibitors: chlorphenomizole (B.4.1); C) Nucleic acid synthesis inhibitors - phenylamide or acylamino acid fungicides: benalaxyl (C.1.1), benalaxyl-M (C.1.2), chiralaxyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (C.1.5), ofurace (C.1.6), oxadixyl (C.1.7); - other inhibitors of nucleic acid synthesis: 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)pyrimidin-4-amine (C.2.6), 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine (C.2.7), 5-fluoro-2-(4-chlorophenylmethoxy)pyrimidin-4-amine (C.2.8); D) inhibitors of cell division and the cytoskeleton - Tubulin inhibitors: benomyl (D.1.1), carbendazim (D.1.2), fuberidazole (D.1.3), thiabendazole (D.1.4), thiophanate-methyl (D.1.5), pyridaclomethyl (D.1.6), D.1.6), N-ethyl-2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]butanamide (D.1.8), N-ethyl-2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methylsulfanyl-acetamide (D.1.9), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-(2-fluoroethyl)butanamide (D.1.10), 2-[(3-ethynyl-8 -methyl-6-quinolyl)oxy]-N-(2-fluoroethyl)-2-methoxy-acetamide (D.1.11), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-propyl-butanamide (D.1.12), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methoxy-N-propyl-acetamide (D.1.13), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-propyl-2-methoxy-acetamide (D.1.14), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methylsulfanyl-N-propyl-acetamide (D.1.14), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-(2-fluoroethyl)-2-methylsulfanyl-acetamide (D.1.15), 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine (D.1.16); - other cytostatics: diethofencarb (D.2.1), ethaboxam (D.2.2), pencycuron (D.2.3) and fluopicolide (D.2.4), zoxamide (D.2.5), metrafenone (D.2.6), pyriophenone (D.2.7), phenamacril (D.2.8); E) Inhibitors of amino acid and protein synthesis - methionine synthesis inhibitors: cyprodinil (E.1.1), mepanipyrim (E.1.2), pyrimethanil (E.1.3); - Protein synthesis inhibitors: blasticidin-S (E.2.1), kasugamycin (E.2.2), kasugamycin hydrochloride hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracycline (E.2.6); F) Signal transduction inhibitors - MAP / histidine kinase inhibitors: fluoroimide (F.1.1), iprodione (F.1.2), procymidone (F.1.3), vinclozolin (F.1.4), fludioxonil (F.1.5); - G protein inhibitors: quinoxyfen (F.2.1); G) Lipid and membrane synthesis inhibitors - phospholipid biosynthesis inhibitors: edifenphos (G.1.1), iprobenfos (G.1.2), pyrazophos (G.1.3), isoprothiolane (G.1.4); - 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); - 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); - Compounds affecting cell membrane permeability and fatty acids: propamocarb (G.4.1); - Inhibitors of oxysterol-binding proteins: oxathiapiprolin (G.5.1), fluoxapiprolin (G.5.3), 4-[1-[2-[3-(difluoromethyl)-5-methyl-pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.4), 4-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.5), 4-[1-[2-[3-(difluoromethyl)-5-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.5), 4-[1-[2-[3-(difluoromethyl)-5-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.6), 4-[1-[2-[5-cyclopropyl-3-(difluoromethyl)pyrazol-1-yl]acetyl]-4 -piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.7), 4-[1-[2-[5-methyl-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.8), 4-[1-[2-[5-(difluoromethyl)-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl -pyridine-2-carboxamide (G.5.9), 4-[1-[2-[3,5-bis(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.10), (4-[1-[2-[5-cyclopropyl-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.11); H) Multi-site inhibitors - 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); - Thiocarbamates 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); - Organic chlorine 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), pentachlorophenol (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.11); - Guanidines and others: Guanidine (H.4.1), Dodine (H.4.2), Dodine 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]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetraone (H.4.10); I) Cell wall synthesis inhibitors - Inhibitors of glucan synthesis: validamycin (I.1.1), polyoxin B (I.1.2); - Melanin synthesis inhibitors: pyroquilon (I.2.1), tricyclazole (I.2.2), carpropamid (I.2.3), dicyclomet (I.2.4), fenoxanil (I.2.5); J) Plant defense inducers - acibenzolar-S-methyl (J.1.1), probenazole (J.1.2), isotianil (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 phosphite (J.1.11), potassium phosphite (J.1.12), potassium or sodium bicarbonate (J.1.9), 4-cyclopropyl-N-(2,4-dimethoxyphenyl)thiadiazole-5-carboxamide (J.1.10); K) unknown mode of action - Bronopol (K.1.1), quinomethionate (K.1.2), cyflufenamid (K.1.3), cymoxanil (K.1.4), dazomet (K.1.5), debacarb (K.1.6), diclocymet (K.1.7), diclomedine (K.1.8), difenzoquat (K.1.9), difenzoquat-methylsulfate (K.1.10), diphenylamine (K.1.11), fenitropan (K.1.12), fenpyrazamin e) (K.1.13), flumetover (K.1.14), flumethylsulforim (K.1.60), flusulfamide (K.1.15), flutianil (K.1.16), harpin (K.1.17), methasulphocarb (K.1.18), nitrapyrin (K.1.19), nitrothal-isopropyl (K.1.20), tolprocarb rocarb (K.1.21), copper oxine (K.1.22), proquinazid (K.1.23), seboctylamine (K.1.61), tebufloquin (K.1.24), tecloftalam (K.1.25), triazoxide (K.1.26), N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methylformamidine (K.1.27) , N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methylformamidine (K.1.28), N'-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine (K.1.29), N'-(5-bromo-6-indan-2-yloxy-2-methyl-3-pyridyl)-N-ethyl-N-methyl-formamidine (K.1.30), N'-[5-bromo-6-[1-(3,5-difluorophenyl)-ethoxy]-2-methyl-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.31), N'-[5-bromo-6-(4-isopropylcyclohexoxy)-2-methyl-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.32), N'-[5-bromo-2-methyl-6-(1-phenylethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.33), N'-(2-methyl-5-trifluorophenyl)-2-methyl-3-pyridyl-N-ethyl-N-methyl-formamidine N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methylformamidine (K.1.34), N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methylformamidine (K.1.35), 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide (K.1.36), 3-[5-(4-chloro-phenyl)-2,3- Dimethyl-isoxazolidin-3-yl]-pyridine (pyrisoxazole) (K.1.37), 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (K.1.38), 5-chloro-1-(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1H-benzimidazole (K.1.39), ethyl (Z)-3-amino-2-cyano-3-phenyl-prop-2-enoate (K.1.40), picarbutrazox (K.1.41), pentyl N-[6-[[(Z)-[ (1-Methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate (K.1.42), but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxy-methyl]-2-pyridyl]carbamate (K.1.43), ipflufenoquine (K.1.44), quinofumelin (K.1.47), benzothiazolinone (K.1.48), bromothalonil (K.1.49), 2-(6-benzyl-2-pyridyl)quinazoline (K.1.50), 2-[6-(3-fluoro-4-methoxy-phenyl)-5-methyl-2-pyridyl]quinazoline (K.1.51), dichlobentiazox (K.1.52), N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine (K.1.53), aminopyrifen (K.1.54), fluopimomide (K.1.55), N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.56), N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethylphenyl]-N-ethyl-N-methyl-formamidine (K.1.57), flufenoxadiazam (K.1.58), N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide (K.1.59), N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide (WO 2018 / 177894, WO 2020 / 212513).

[0134] In binary mixtures, the weight ratio of component 1) to component 2) generally depends on the nature of the components used; it is usually in the range of 1:10,000 to 10,000:1, often 1:100 to 100:1, always 1:50 to 50:1, preferably 1:20 to 20:1, more preferably 1:10 to 10:1, even more preferably 1:4 to 4:1, and in particular 1:2 to 2:1. According to a further embodiment, the weight ratio of component 1) to component 2) is usually in the range of 1000:1 to 1:1, often 100:1 to 1:1, always 50:1 to 1:1, preferably 20:1 to 1:1, more preferably 10:1 to 1:1, even more preferably 4:1 to 1:1, and in particular 2:1 to 1:1. According to a further embodiment, the weight ratio of component 1) to component 2) is usually in the range of 20,000:1 to 1:10, often 10,000:1 to 1:1, always 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, and in particular 1,000:1 to 100:1. According to a further embodiment, the weight ratio of component 1) to component 2) is usually in the range of 1:1 to 1:1000, often 1:1 to 1:100, always 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, and in particular 1:1 to 1:2. According to a further embodiment, the weight ratio of component 1) to component 2) is usually in the range of from 10:1 to 1:20,000, often from 1:1 to 1:10,000, always from 1:5 to 1:5,000, preferably from 1:10 to 1:5,000, more preferably from 1:30 to 1:2,000, even more preferably from 1:100 to 1:2,000, and in particular from 1:100 to 1:1,000.

[0135] In ternary mixtures, i.e., compositions comprising component 1) and component 2), and compound III (component 3), the weight ratio of component 1) to component 2) depends on the nature of the active substances used and is usually in the range of 1:100 to 100:1, always 1:50 to 50:1, preferably 1:20 to 20:1, more preferably 1:10 to 10:1, and in particular 1:4 to 4:1, while the weight ratio of component 1) to component 3) is usually in the range of 1:100 to 100:1, always 1:50 to 50:1, preferably 1:20 to 20:1, more preferably 1:10 to 10:1, and in particular 1:4 to 4:1. If desired, any further active ingredients are added to component 1 in a ratio of 20:1 to 1:20. These ratios are also suitable for mixtures applied for seed treatment.

[0136] Q in group A) o In particular, mixtures comprising as component 2) at least one active substance selected from (A.1.1), (A.1.4), (A.1.8), (A.1.9), (A.1.13), (A.1.14), (A.1.17), (A.1.21), (A.1.25), (A.1.34) and (A.1.35) are preferred.

[0137] Also, Q in group A) i are selected from inhibitors of complex III at the site, more preferably selected from compounds (A.2.1), (A.2.3), (A.2.4) and (A.2.6); in particular mixtures comprising as component 2) at least one active substance selected from (A.2.3), (A.2.4) and (A.2.6) are preferred.

[0138] Also, more preferably the 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), (A.3. (A.3.37), (A.3.38) and (A.3.39); in particular mixtures comprising as component 2) at least one active substance 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).

[0139] Preference is also given to mixtures which comprise as component 2) at least one active substance selected from other respiratory inhibitors in group A), more preferably selected from the compounds (A.4.5) and (A.4.11); in particular (A.4.11).

[0140] Also, more preferably the 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) are selected from the C14 demethylase inhibitors in group B). , (B.1.43), (B.1.46), (B.1.53), (B.1.54) and (B.1.55); in particular mixtures comprising as component 2) at least one active substance 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).

[0141] Also preferred are mixtures comprising as component 2) at least one active substance selected from the delta-14 reductase inhibitors of group B), more preferably selected from the compounds (B.2.4), (B.2.5), (B.2.6) and (B.2.8), in particular (B.2.4).

[0142] Also preferred are mixtures comprising as component 2) at least one active substance selected from the phenylamide and acylamino acid fungicides of group C), more preferably selected from the compounds (C.1.1), (C.1.2), (C.1.4) and (C.1.5); in particular selected from (C.1.1) and (C.1.4).

[0143] Preference is also given to mixtures which comprise as component 2) at least one active substance selected from other nucleic acid synthesis inhibitors in group C), more preferably selected from the compounds (C.2.6), (C.2.7) and (C.2.8).

[0144] Also preferred are mixtures comprising as component 2) at least one active substance selected from group D), more preferably selected from the compounds (D.1.1), (D.1.2), (D.1.5), (D.2.4) and (D.2.6); in particular selected from (D.1.2), (D.1.5) and (D.2.6).

[0145] Also preferred are mixtures comprising as component 2) at least one active substance selected from group E), more preferably selected from the compounds (E.1.1), (E.1.3), (E.2.2) and (E.2.3), in particular (E.1.3).

[0146] Preference is also given to mixtures which comprise as component 2) at least one active substance selected from group F), more preferably selected from the compounds (F.1.2), (F.1.4) and (F.1.5).

[0147] Also preferred are mixtures comprising as component 2) at least one active substance selected from group G), more preferably from the 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 mixtures comprising at least one active substance selected from (G.3.1), (G.5.1) and (G.5.3).

[0148] Also preferred are mixtures comprising as component 2) at least one active substance selected from group H), more preferably selected from the compounds (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); in particular selected from (H.2.2), (H.2.5), (H.3.2), (H.4.9) and (H.4.10).

[0149] Preference is also given to mixtures which comprise as component 2) at least one active substance selected from group I), more preferably selected from the compounds (I.2.2) and (I.2.5).

[0150] Also preferred are mixtures comprising as component 2) at least one active substance selected from group J), more preferably selected from the compounds (J.1.2), (J.1.5), (J.1.8), (J.1.11) and (J.1.12); in particular (J.1.5).

[0151] Preference is also given to mixtures comprising as component 2) at least one active substance selected from group K), more preferably selected from the compounds (K.1.41), (K.1.42), (K.1.44), (K.1.47), (K.1.57), (K.1.58) and (K.1.59); in particular selected from (K.1.41), (K.1.44), (K.1.47), (K.1.57), (K.1.58) and (K.1.59).

[0152] Compositions containing the mixture of active ingredients can be prepared by conventional means, for example by means of obtaining compositions of Compound I. [Example]

[0153] [Example] Synthesis Process [Example 1] (2E)-2-[2-[[(E)-3-(2-fluorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyiminoacetate methyl ester

[0154] [ka]

[0155] Step 1: 1-(2-fluorophenyl)ethanone oxime 1-(2-Fluorophenyl)ethenone (10 g, 1.0 equiv.) was placed in methanol (300 ml) and hydroxylamine hydrochloride (7.54 g, 1.8 equiv.) was added. Pyridine (33.45 g, 2 equiv.) was added dropwise at 25 °C. The reaction mixture was stirred at 50 °C for 2 hours. LCMS and TLC were used to monitor the reaction. Methanol was evaporated under vacuum. The crude product was diluted with water (200 ml) and extracted with ethyl acetate (3 × 100 ml). The combined organic layers were washed again with water and brine. The organic layer was dried over sodium sulfate and concentrated under vacuum. The crude compound was purified by flash column chromatography. The pure compound was eluted with 0% to 20% ethyl acetate (EtOAc) in heptane. Evaporation of the solvent afforded 8 g of the title compound as a white solid (72% yield). 1 H NMR 300 MHz, DMSO-d6: δ 11.4 (s ,1 H), 7.46-7.41 (m, 2 H), 7.27-7.23 (m, 2H), 2.14 (s, 3H).

[0156] Step 2: (2E)-2-[2-[[(E)-1-(2-fluorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyiminoethyl acetate (Ex. 2) 1-(2-Fluorophenyl)ethanone oxime (0.3 g, 3 equiv.) was placed in dimethylformamide (DMF, 5 mL) and CsCO (3.27 g, 2.0 equiv.) was added. The reaction mixture was stirred at room temperature (RT; approximately 25 °C) for 30 min, and then methyl (2E)-2-[2-(bromomethyl)-3-methyl-phenyl]-2-methoxyiminoacetate (0.6 g, 3.02 equiv.) was added. The reaction mixture was stirred at RT for 32 h and monitored by TLC and LCMS. The reaction was quenched with water (45 mL), and the product was extracted with ethyl acetate (3 × 35 mL). The combined organic layers were washed with brine (50 mL), dried over sodium sulfate, and concentrated in vacuo. The crude product was purified by flash chromatography. The pure compound was eluted using 35–20% EtOAc in heptane. Evaporation of the solvent gave the title compound (0.328 g, 45% yield) as an off-white solid. 1 H NMR (300 MHz, DMSO-d6): δ 7.56 - 7.36 (m, 2H), 7.33 - 7.32 (m, 4H), 7.03 (dd, J = 6.2, 2.8 Hz, 3H), 5.00 (s, 2H), 3.93 (s, 3H), 3.64 (s, 3H), 2.42 (s, 3H), 2.08 (d, J = 2.5 Hz, 3H).

[0157] [Example 2] (2E)-2-[2-[[(E)-1-(2-fluorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-N-methyl-acetamide

[0158] [ka]

[0159] Methyl (2E)-2-[2-[[(E)-1-(2-fluorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyiminoacetate (e.g., 1; 8 g, 1 equivalent) was placed in THF (80 mL) and methylamine (40%, aqueous) solution (16 mL, 2 vol) was added. The reaction mixture was stirred at 25°C for 5 hours and monitored by TLC and LCMS. The reaction was quenched with water (200 mL), and the product was extracted with ethyl acetate (3 x 150 mL). The combined organic layers were washed with brine (150 mL), dried over sodium sulfate, and concentrated in vacuo. The crude product was purified by flash chromatography. The pure compound was eluted using 30-40% EtOAc in heptane. Evaporation of the solvent afforded the title compound (7 g, 87.7% yield) as a white solid. 1 H NMR (500 MHz, DMSO-d6): δ 8.20 (q, J = 4.7 Hz, 1H), 7.44 (ddt, J = 7.8, 5.6, 2.0 Hz, 2H), 7.37 - 7.14 (m, 4H), 6.95 (dd, J = 7.1, 2.0 Hz, 1H), 5.01 (s, 2H), 3.86 (s, 3H), 2.65 (d, J = 4.8 Hz, 3H), 2.42 (s, 3H), 2.09 (d, J = 2.6 Hz, 3H).

[0160] [Example 3] Methyl (2E)-2-[2-[[(E)-1-(3,5-dichlorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyiminoacetate

[0161] [ka]

[0162] Step 1: 1-(3,5-dichlorophenyl)ethanone oxime 3-(3,5-Dichlorophenyl)ethanone (3.0 g, 3 equiv.) was placed in methanol (30 mL) and NHOH (0.735 g, 2 equiv.) was added, followed by pyridine (3.04 g, 2.5 equiv.). The reaction mixture was heated to 70 °C and stirred for 3 h. LCMS and TLC were used to monitor the reaction. The solvent was evaporated, and the residue was diluted with water (50 mL). The product was extracted with ethyl acetate (3 × 30 mL). The combined organic layers were washed with brine (50 mL), dried over sodium sulfate, and concentrated in vacuo. The crude product was purified by flash chromatography. The pure compound was eluted using 15-20% EtOAc in heptane. Evaporation of the solvent afforded the white solid compound 1-(3,5-dichlorophenyl)ethanone oxime (1 g, 92.6% yield).

[0163] Step 2: (2E)-2-[2-[[(E)-1-(3,5-dichlorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyiminoacetate methyl ester 3-(3,5-Dichlorophenyl)ethanone oxime (0.4 g, 1 equiv.) was placed in acetonitrile (10 ml) and CsCO (1.8 g, 2.5 equiv.) was added. The reaction mixture was stirred at RT for 30 min, and then methyl (2E)-2-[2-(bromomethyl)-3-methyl-phenyl]-2-methoxyiminoacetate (0.65 g, 1.05 equiv.) was added. The reaction mixture was stirred at RT for 3 h and monitored by TLC and LCMS. The reaction was quenched with water (50 ml), and the product was extracted with ethyl acetate (3 × 30 ml). The combined organic layers were washed with brine (50 ml), dried over sodium sulfate, and concentrated in vacuo. The crude product was purified by flash chromatography. The pure compound was eluted using 20–25% EtOAc in heptane. Evaporation of the solvent afforded the title compound (0.6 g, 68% yield) as an off-white solid. 1H NMR (500 MHz, DMSO-d6): δ 7.66 (t, J = 1.9 Hz, 1H), 7.61 (d, J = 1.9 Hz, 2H), 7.36 - 7.23 (m, 2H), 7.05 - 6.98 (m, 1H), 5.04 (s, 2H), 3.91 (s, 3H), 3.70 (s, 3H), 2.43 (s, 3H), 2.30 (s, 3H).

[0164] [Example 4] (2E)-2-[2-[[(E)-1-(3,5-dichlorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-N-methyl-acetamide

[0165] [ka]

[0166] Methyl (2E)-2-[2-[[(E)-3-(3,5-dichlorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyiminoacetate (e.g., 3; 0.6 g, 1 eq.) was placed in THF (6 ml) and methylamine (40%, aqueous) solution (1.2 ml, 2 vol) was added. The reaction mixture was stirred at RT for 3 h and monitored by TLC and LCMS. The reaction was quenched with water (25 ml), and the product was extracted with ethyl acetate (3 x 20 ml). The combined organic layers were washed with brine (25 ml), dried over sodium sulfate, and concentrated in vacuo. The crude product was purified by flash chromatography. The pure compound was eluted using 40-45% EtOAc in heptane. Evaporation of the solvent afforded the title compound (Example 2, 0.53 g, 85% yield) as a white solid. 1H NMR (500 MHz, DMSO-d6): δ 8.24 (d, J = 4.8 Hz, 1H), 7.69 - 7.58 (m, 3H), 7.37 - 7.15 (m, 2H), 6.95 (dd, J = 7.1, 1.9 Hz, 1H), 5.05 (s, 2H), 3.86 (s, 3H), 2.68 (d, J = 4.7 Hz, 3H), 2.42 (s, 3H), 2.11 (s, 3H).

[0167] [Example 5] Methyl (2E)-2-methoxyimino-2-[3-methyl-2-[[(E)-1-(p-tolyl)ethylideneamino]oxymethyl]phenyl]acetate

[0168] [ka]

[0169] Step 1: 1-(p-Tolyl)ethanone oxime To a solution of 1-(p-tolyl)ethanone (1.0 g, 4.45 mmol, 3 equiv.) in methanol (10 mL) was added hydroxylamine hydrochloride (0.77 g, 11.17 mmol, 1.5 equiv.), followed by sodium acetate (1.82 g, 15 mmol, 2 equiv.) at RT under a nitrogen atmosphere. The reaction mixture was refluxed for 2 h. The reaction was monitored by TLC. The reaction mixture was concentrated on a rotavapor. Water (20 mL) was added to the crude residue and stirred for 0.5 h. The solid material was filtered and dried to give the pure title compound (1.1 g, 98% yield) as a white solid. MS: [M + H] + 150.

[0170] Step 2: (2E)-2-Methoxyimino-2-[3-methyl-1-[[(E)-3-(p-tolyl)ethylideneamino]oxymethyl]phenyl]acetate methyl To a stirred solution of 1-(p-tolyl)ethanone oxime (0.15 g, 1.0 mmol, 1 equiv.) in acetonitrile (2 mL) was added CsCO (0.66 g, 2.0 mmol, 2 equiv.). The reaction mixture was stirred at 25 °C for 30 min. Then, methyl (2E)-2-[2-(bromomethyl)-3-methyl-phenyl]-2-methoxyiminoacetate (0.33 g, 1.1 mmol, 1.1 equiv.) was added. The mixture was stirred at 25 °C for 6 h. The reaction was monitored by TLC and LCMS. Water (30 mL) was added to the reaction mixture and extracted with EtOAc (3 × 30 mL). The combined organic layers were washed with HO (2 × 25 mL), followed by brine washes (2 × 20 mL). The organic layer was dried over Na2SO4 and concentrated to give the crude compound, which was further purified by flash column chromatography using 0-20% EtOAc in heptane as the eluent to give the pure title compound as a white solid (0.37 g, 96% yield). 1 H NMR (500 MHz, chloroform-d): δ 7.42 (d, J = 8.2 Hz, 2H), 7.26 - 7.19 (m, 3H), 7.07 (d, J = 8.0 Hz, 2H), 6.94 (dd, J = 7.2, 1.8 Hz, 2H), 5.03 (s, MS: [M + H] + 369.

[0171] [Example 6] (2E)-2-Methoxyimino-N-methyl-2-[3-methyl-2-[[(E)-1-(p-tolyl)ethylidene-amino]oxymethyl]phenyl]acetamide

[0172] [ka]

[0173] To a stirred solution of methyl (2E)-2-methoxyimino-2-[3-methyl-1-[[(E)-3-(p-tolyl)-ethylideneamino]oxymethyl]phenyl]acetate in THF (5 mL) at RT was added a solution of methylamine in water (5.0 mL, 40%). The reaction was continued for 1 h. The reaction was monitored by TLC. The reaction mixture was rotary evaporated, and the residue was diluted with EtOAc (20 mL) and washed with 1 N HCl (3 × 20 mL), followed by brine washes (2 × 20 mL). The organic layer was dried over Na2SO4 and concentrated to give the crude compound, which was further purified by flash column chromatography using 0-50% EtOAc in heptane as the eluent to give the pure title compound as a white solid (0.200 g, 88% yield). 1 H NMR (500 MHz, DMSO-d6): δ 8.20 (d, J = 5.0 Hz, 1H), 7.54 - 7.48 (m, 2H), 7.31 - 7.22 (m, 2H), 7.19 (d, J = 8.0 Hz, 2H), 6.95 (dd, J = 6.9, MS: [M + H] + 368.

[0174] [Example 7] (2E)-2-Methoxyimino-N-methyl-2-[3-methyl-2-[[(E)-[3,3,3-trifluoro-1-[3-(trifluoromethyl)phenyl]propylidene]amino]oxymethyl]phenyl]acetamide

[0175] [ka]

[0176] 3,3,3-Trifluoro-1-[3-(trifluoromethyl)phenyl]propan-1-one (0.5 g, 1 equiv.), prepared similarly to a prior art process (Chem Commun, 2016, 52, 13668-13670), was placed in THF (10 mL) and (2E)-2-[2-(aminooxymethyl)-3-methyl-phenyl]-2-methoxyimino-N-methyl-acetamide (0.98 g, 2 equiv.) was added, followed by Ti(OEt) (1.33 g, 3 equiv.). The mixture was heated to 70 °C and stirred for 12 h. The reaction was monitored by TLC and LCMS. The reaction was quenched with water (25 mL) followed by EtOAc (25 mL). The emulsion that formed was filtered through Celite and washed with EtOAc (50 mL). The layers were separated, and the aqueous layer was extracted with EtOAc (2 × 25 mL). The combined organic layers were washed with brine (25 ml), dried over sodium sulfate, and concentrated in vacuo. The crude material was purified by flash chromatography. The pure compound was eluted using 40-45% EtOAc in heptane. Evaporation of the solvent followed by crystallization in heptane gave an off-white solid (0.34 g, 35% yield). 1 H NMR (500 MHz, DMSO-d6): δ 8.27 (q, J = 4.7 Hz, 1H), 8.07 - 8.00 (m, 2H), 7.85 - 7.79 (m, 1H), 7.68 (t, J = 7.8 Hz, 1H), 7.35 - 7.24 (m, 2H), 6.97 (dd, J = 7.3, 1.7 Hz, 1H), 5.12 (s, 2H), 4.03-3.96 (q, J = 10 Hz, 2H), 3.86 (s, 3H), 2.67 (d, J = 4.7 Hz, 3H), 2.43 (s, 3H).

[0177] The following examples in Table S were synthesized according to general Scheme 1 above (except for Examples 7 and 212, which were synthesized according to Scheme 2) and characterized by LCMS as described in Table L.

[0178] Table L: LCMS method

Table 6

[0179] Table S:

Table 7

[0180] biological research Greenhouse and detached leaf tests Compounds were dissolved in a 99:1 solvent-to-emulsifier (by volume) mixture of acetone and / or dimethyl sulfoxide and the wetting / emulsifier Wettol (an ethoxylated alkylphenol) to a total volume of 5 ml. Water was then added to a total volume of 100 ml. This stock solution was then diluted with the indicated solvent-emulsifier-water mixture to the final concentrations shown in the table below.

[0181] [Usage example 1] Curative control of soybean rust in soybean caused by Phakopsora pachyrhizi (PHAKPA K4) Potted soybean seedling leaves were inoculated with Phakopsora pachyrhizi spores. The strain used contains the amino acid substitution F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors. To ensure successful artificial inoculation, plants were transferred to a humid chamber at 20-24°C and approximately 95% relative humidity for 24 hours. The following day, the plants were grown in a greenhouse chamber at 23-27°C and 60-80% relative humidity for 3 days. The plants were then sprayed to runoff with the spray solution described above, containing the active ingredient or mixtures thereof at the concentrations listed below. The plants were then air-dried. Test plants were then grown in a greenhouse chamber at 23-27°C and 60-80% relative humidity for a maximum of 14 days. The extent of fungal attack on the leaves was assessed visually as the percentage of diseased leaf area; disease levels in untreated controls were typically greater than 85%.

[0182] [Usage example 2] Protective control of soybean rust in soybean caused by Phakopsora pachyrhizi (PHAKPA P2) The leaves of potted soybean seedlings were sprayed to runoff point using the spray solutions described above, containing the active ingredient or mixtures thereof at the concentrations listed below. The plants were allowed to air dry. The test plants were grown for two days in a greenhouse chamber at 23-27°C and 60-80% relative humidity. They were then inoculated with spores of Phakopsora pachyrhizi. The strain used contains the amino acid substitution F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors. To ensure successful inoculation, the plants were transferred to a humid chamber at 20-24°C and approximately 95% relative humidity for 24 hours. The test plants were grown in a greenhouse chamber at 23-27°C and 60-80% relative humidity for a maximum of 14 days. The extent of fungal attack on the leaves was assessed visually as the percentage of diseased leaf area; disease levels in untreated controls were typically greater than 85%.

[0183] [Usage example 3] Protective control of soybean rust in soybean caused by Phakopsora pachyrhizi (PHAKPA P6) The leaves of potted soybean seedlings were sprayed to runoff point using the spray solution described above, containing the active ingredient at the concentrations listed below. The plants were allowed to air dry. The test plants were grown for 6 days in a greenhouse chamber at 23-27°C and 60-80% relative humidity. They were then inoculated with spores of Phakopsora pachyrhizi. The strain used contains the amino acid substitution F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors. To ensure successful inoculation, the plants were transferred to a humid chamber at 23-27°C and approximately 95% relative humidity for 24 hours. The test plants were grown in a greenhouse chamber at 23-27°C and 60-80% relative humidity for a maximum of 14 days. The extent of fungal attack on the leaves was assessed visually as the percentage of diseased leaf area; disease levels in untreated controls were typically greater than 85%.

[0184] [Usage example 4] Protective control of soybean rust on detached soybean leaves caused by Phakopsora pachyrhizi (PHAKPA P1 DL) The leaves of potted soybean seedlings were sprayed to runoff point using the spray solution described above, containing the active ingredient at the concentrations indicated below. The plants were left overnight in a greenhouse chamber at 20°C with 14 hours of light to dry. The following day, the leaves were harvested and placed on water agar plates. They were then inoculated with spores of Phakopsora pachyrhizi. Two different isolates were used: one susceptible to Qo inhibitors (wt); the other containing the amino acid substitution F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors (F129L). The inoculated leaves were incubated in a dark, dust-free chamber at room temperature for 16–24 hours, followed by incubation in an incubator at 20°C with 12 hours of light per day for 2–3 weeks. The extent of fungal attack on the leaves was assessed visually as the percentage of infected leaf area.

[0185] Microtiter Plate Test The active compounds were formulated separately as stock solutions with a concentration of 10,000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a microtiter plate (MTP), and diluted with water to the specified concentration.

[0186] After the addition of each spore suspension, as indicated in the different application examples below, the plates were placed in a steam-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTP was measured at 405 nm 7 days after inoculation. To determine the relative growth (%) of the pathogen in each active compound, the measured parameters were compared with the growth of a control variant without active compound (100%) and a blank value without fungi.

[0187] [Usage example 5] Activity against Pyricularia oryzae (PYRIOR), which causes rice blast Spore suspensions of Pyricularia oryzae in aqueous biomalt or yeast-bactopeptone-glycerol, or DOB solutions were used.

[0188] [Usage example 6] Activity against Septoria tritici (SEPTTR) causing leaf blight in wheat A spore suspension of Septoria tritici in aqueous biomalt or yeast-bactopeptone-glycerol or DOB solution was used.

[0189] [Usage example 7] Activity against Colletotrichum orbiculare (COLLLA), which causes anthracnose A spore suspension of Colletotrichum orbiculare in an aqueous 2% malt solution was used.

[0190] [Usage example 8] Activity against Leptosphaeria nodorum (LEPTNO), which causes wheat leaf spot Spore suspensions of Leptosphaeria nodorum in aqueous biomalt or yeast-bactopeptone-glycerol or DOB solutions were used.

[0191] [Usage example 9] Activity against Alternaria solani (ALTESO, wt and F129L) causing summer blight Two different spore suspensions of Alternaria solani in aqueous biomalt or yeast-bactopeptone-glycerol or DOB solution were used: a susceptible wild-type isolate (wt) and a Qo inhibitor-resistant isolate (F129L) containing the amino acid substitution F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors.

[0192] [Usage example 10] Activity against Pyrenophora teres (PYRNTE, wt and F129L) causing net blotch in barley Two different spore suspensions of Pyrenophora teres in aqueous biomalt or yeast-bactopeptone-glycerol or DOB solution were used: a susceptible wild-type isolate (wt) and a Qo inhibitor-resistant isolate (F129L) containing the amino acid substitution F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors.

[0193] [Usage example 11] Activity against Cercospora sojina (CERCSO), which causes frogeye leaf spot of soybean A spore suspension of Cercospora sojina in aqueous biomalt or yeast-bactopeptone-glycerol or DOB solution was then added.

[0194] [Usage example 12] Activity against Microdochium nivale (MONGNI), which causes snow mold Spore suspensions of Microdochium nivale in aqueous biomalt or yeast-bactopeptone-glycerol or DOB solutions were used.

[0195] The table below shows the results of the above use case.

[0196] Test results for the control of plant pathogenic fungi containing the amino acid substitution F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors, are shown in Table 1 and C1 to C4 below.

[0197] Table 1: [Table 8] TIFF2025160166000224.tif255150TIFF2025160166000225.tif255151TIFF2025160166000226.tif251151TIFF2025160166000227.tif250154TIFF2025160166000228.tif253147TIFF2025160166000229.tif250147TIFF2025160166000230.tif251149TIFF2025160166000231.tif249148TIFF2025160166000232.tif252150TIFF2025160166000233.tif244149TIFF2025160166000234.tif250148TIFF2025160166000235.tif253149TIFF2025160166000236.tif255148TIFF2025160166000237.tif255145TIFF2025160166000238.tif244149TIFF2025160166000239.tif242147TIFF2025160166000240.tif241145TIFF2025160166000241.tif243143TIFF2025160166000242.tif246145TIFF2025160166000243.tif244146TIFF2025160166000244.tif252147TIFF2025160166000245.tif243149TIFF2025160166000246.tif245146TIFF2025160166000247.tif248144TIFF2025160166000248.tif248147TIFF2025160166000249.tif254145TIFF2025160166000250.tif247151TIFF2025160166000251.tif242147TIFF2025160166000252.tif255147TIFF2025160166000253.tif237145TIFF2025160166000254.tif255149TIFF2025160166000255.tif247145TIFF2025160166000256.tif106146

[0198] Comparative Test

[0199] Table C1: [Table 9]

[0200] Table C2: [Table 10] TIFF2025160166000259.tif255146TIFF2025160166000260.tif137146

[0201] Table C3: [Table 11] TIFF2025160166000262.tif245145TIFF2025160166000263.tif84145

[0202] Table C4: [Table 12] TIFF2025160166000265.tif247148TIFF2025160166000266.tif251147TIFF2025160166000267.tif198150

[0203] The results in Tables C1 to C4 are 3 Compared to compounds where the R 3 We show that specific substitutions at positions 129L and 132L improve fungicidal activity against plant pathogenic fungi that contain the amino acid substitution F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors.

[0204] Table C5: [Table 13]

[0205] Table C6a: [Table 14]

[0206] Table C6b: [Table 15]

[0207] The results in Tables C5-C6b show that, compared to the use of compounds disclosed in WO 2017 / 157923, the compounds of the present invention have significantly improved fungicidal activity against plant pathogenic fungi that contain the amino acid substitution F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors.

[0208] Table C7a: [Table 16]

[0209] Table C7b: [Table 17]

[0210] Table C8a: [Table 18]

[0211] Table C8b: [Table 19]

[0212] The results in Tables C7a-C8b show that the specific substituent R a improves fungicidal activity against plant pathogenic fungi.

[0213] Table C9: Table 20

[0214] Table C10: Table 21

[0215] Table C11a: Table 22

[0216] Table C11b: Table 23

[0217] Table C12: Table 24

[0218] Table C13: Table 25

[0219] Table C14: Table 26

[0220] Table C15a: Table 27

[0221] Table C15b: Table 28

[0222] Table C16a: [Table 29]

[0223] Table C16b: [Table 30]

[0224] Table C17: [Table 31] TIFF2025160166000287.tif89135

[0225] Table C18: [Table 32]

[0226] The results in Tables C9 to C18 show that the specific substituent R 4 improves fungicidal activity against plant pathogenic fungi.

Claims

1. Formula I 【Chemical 1】 [In the formula, R 1 is selected from O and NH; R 2 is selected from CH and N; R 3 is a halogen, C 1 -C 4 -Alkyl, C 2 -C 4 -Alkenyl, C 1 -C 2 -monohaloalkyl, C 1 -C 2 -dihaloalkyl, monohalo-ethenyl, dihalo-ethenyl, C 3 -C 6 -cycloalkyl and -OC 1 -C 4 -alkyl, R 4 is C 1 -C 6 -Alkyl, C 2 -C 4 -Alkenyl, C 2 -C 4 -alkynyl, C 1 -C 6 -haloalkyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -haloalkynyl, -C(=O)-C 1 -C 4 -alkyl, -(C 1 -C 2 -alkyl)-O-(C 1 -C 2 -alkyl), -(C 1 -C 2 -alkyl)-O-(C 1 -C 2 -haloalkyl) and -C 1 -C 4 -Alkyl-C 3 -C 6 -cycloalkyl, R a is halogen, CN, -NR 5 R 6 , C 1 -C 4 -Alkyl, C 2 -C 4 -Alkenyl, C 2 -C 4 -alkynyl, -OC 1 -C 4 -Alkyl, -C(=NOC 1 -C 4 -alkyl)-C 1 -C 4 -Alkyl, -C(=O)-C 1 -C 4 -Alkyl, -O-CH 2 -C(=NOC 1 -C 4 -alkyl)-C 1 -C 4 -Alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkenyl, -C 1 -C 2 -Alkyl-C 3 -C 6 -cycloalkyl, -OC 3 -C 6 - selected from cycloalkyl, phenyl, 3- to 6-membered heterocycloalkyl, 3- to 6-membered heterocycloalkenyl, and 5- or 6-membered heteroaryl; the heterocycloalkyl, heterocycloalkenyl, and heteroaryl contain, in addition to carbon atoms, one, two, or three heteroatoms selected from N, O, and S; The phenyl, heterocycloalkyl, heterocycloalkenyl and heteroaryl may be directly or by an oxygen atom or C 1 -C 2 - is attached via an alkylene linker, R a The aliphatic and cyclic portions of may be unsubstituted or may be substituted with 1, 2, 3, 4 or up to a maximum number of the same or different R b having a group, R b are halogens, CN, NH 2 , NO 2 , C 1 -C 4 -Alkyl, C 1 -C 4 -haloalkyl, -OC 1 -C 4 -Alkyl and -OC 1 -C 4 -haloalkyl; R 5 , R 6 are independent of each other, H, C 1 -C 6 -Alkyl, C 1 -C 6 -haloalkyl and C 2 -C 4 -alkynyl, n is an integer selected from 0, 1, 2, 3, 4 and 5. and their stereoisomers and tautomers, and N-oxides and agriculturally acceptable salts thereof, for combating plant pathogenic fungi that contain the amino acid substitution F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors.

2. In Formula I, R 1 is selected from O and NH; R 2 is selected from CH and N, with the proviso that R 1 If is NH, then R 2 The use according to claim 1, wherein is N.

3. In Formula I, R 3 But C 1 -C 2 -Alkyl, C 1 -C 2 -monohaloalkyl, C 1 -C 2 -dihaloalkyl, C 3 -C 4 -cycloalkyl and -OC 1 -C 2 3. The use according to claim 1 or 2, wherein the alkyl is selected from the group consisting of -alkyl.

4. In Formula I, R 4 But C 1 -C 4 -Alkyl, C 2 -C 4 -alkenyl, -C(=O)-C 1 -C 2 -Alkyl, C 1 -C 4 -haloalkyl, C 2 -C 4 -haloalkenyl and -(C 1 -C 2 -alkyl)-O-(C 1 -C 2 4. The use according to claim 1, wherein the alkyl group is selected from the group consisting of -alkyl.

5. In Formula I, R a But C 1 -C 3 -Alkyl, C 2 -C 3 -Alkenyl, C 2 -C 3 -alkynyl, -OC 1 -C 3 -Alkyl, -C(=NOC 1 -C 2 -alkyl)-C 1 -C 2 -Alkyl, -O-CH 2 -C(=NOC 1 -C 2 -alkyl)-C 1 -C 2 -Alkyl, C 3 -C 4 -cycloalkyl, -C 1 -C 2 -Alkyl-C 3 -C 4 -cycloalkyl, -OC 3 -C 4 - selected from cycloalkyl, phenyl, 3- to 5-membered heterocycloalkyl and 5- or 6-membered heteroaryl, wherein the heterocycloalkyl and heteroaryl contain, in addition to carbon atoms, 1 or 2 heteroatoms selected from N, O and S, and the phenyl and heteroaryl are bonded directly or via an oxygen atom or a methylene linker; R a The aliphatic and cyclic moieties are unsubstituted or independently of each other are halogen, CN, methyl and C 1 - 1, 2 or 3 identical or different R selected from haloalkyl b 5. The use according to any one of claims 1 to 4, wherein the compound has a group.

6. 6. Use according to any one of claims 1 to 5, wherein the phytopathogenic fungus is soybean rust (Phakopsora pachyrhizi and / or P. meibomiae).

7. 1. A method for combating plant pathogenic fungi that contain the amino acid substitution F129L in a mitochondrial cytochrome b protein that confers resistance to Qo inhibitors, comprising: curatively and / or preventively treating plants or plant propagation materials of said plants at risk of becoming diseased by said phytopathogenic fungi with an effective amount of at least one compound of formula I as defined in any one of claims 1 to 5, or a composition comprising same; and / or applying to said phytopathogenic fungi an effective amount of at least one compound of formula I as defined in any one of claims 1 to 5, or a composition comprising same. A method comprising:

8. Formula I 【Chemistry 2】 [In the formula, R 1 is selected from O and NH; R 2 is selected from CH and N; R 3 is C 1 -C 4 -Alkyl, C 2 -C 4 -Alkenyl, C 1 -C 2 -monohaloalkyl, C 1 -C 2 -dihaloalkyl, monohalo-ethenyl, dihalo-ethenyl, C 3 -C 6 -cycloalkyl and -OC 1 -C 4 -alkyl, R 4 is C 1 -C 6 -Alkyl, C 2 -C 4 -Alkenyl, C 2 -C 4 -alkynyl, C 1 -C 6 -haloalkyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -haloalkynyl, -C(=O)-C 1 -C 4 -alkyl, -(C 1 -C 2 -alkyl)-O-(C 1 -C 2 -alkyl), -(C 1 -C 2 -alkyl)-O-(C 1 -C 2 -haloalkyl) and -C 1 -C 4 -Alkyl-C 3 -C 6 -cycloalkyl, R a , R a2 are independently halogen, CN, -NR 5 R 6 , C 1 -C 4 -Alkyl, C 2 -C 4 -Alkenyl, C 2 -C 4 -alkynyl, -OC 1 -C 4 -Alkyl, -C(=NOC 1 -C 4 -alkyl)-C 1 -C 4 -Alkyl, -C(=O)-C 1 -C 4 -Alkyl, -O-CH 2 -C(=NOC 1 -C 4 -alkyl)-C 1 -C 4 -Alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkenyl, -C 1 -C 2 -Alkyl-C 3 -C 6 -cycloalkyl, -OC 3 -C 6 - selected from cycloalkyl, phenyl, 3- to 6-membered heterocycloalkyl, 3- to 6-membered heterocycloalkenyl, and 5- or 6-membered heteroaryl; The heterocycloalkyl, heterocycloalkenyl, and heteroaryl groups contain, in addition to carbon atoms, 1, 2, or 3 heteroatoms selected from N, O, and S; The phenyl, heterocycloalkyl, heterocycloalkenyl and heteroaryl may be directly or by an oxygen atom or C 1 -C 2 - is attached via an alkylene linker, R a and R a2 The aliphatic and cyclic moieties of each may be unsubstituted or may be substituted with 1, 2, 3, 4 or up to a maximum of the same or different R b having a group, R b are halogens, CN, NH 2 , NO 2 , C 1 -C 4 -Alkyl, C 1 -C 4 -haloalkyl, -OC 1 -C 4 -Alkyl and -OC 1 -C 4 -haloalkyl; n is an integer selected from 0, 1, 2, 3 and 4. and their stereoisomers and tautomers, and their N-oxides and agriculturally acceptable salts.

9. R 1 is selected from O and NH; R 2 is selected from CH and N, with the proviso that R 1 If is NH, then R 2 9. The compound of claim 8, wherein is N.

10. R 3 But C 1 -C 2 -Alkyl, C 1 -C 2 -monohaloalkyl, C 1 -C 2 -dihaloalkyl, C 3 -C 4 -cycloalkyl and -OC 1 -C 2 10. The compound according to claim 8 or 9, wherein the alkyl is selected from the group consisting of -alkyl.

11. R 4 But C 1 -C 6 -Alkyl, C 2 -C 4 -Alkenyl, C 1 -C 6 -haloalkyl, C 2 -C 4 -haloalkenyl, -(C 1 -C 2 -alkyl)-O-(C 1 -C 2 -alkyl) and -(C 1 -C 2 -alkyl)-O-(C 1 -C 2 -haloalkyl).

12. 12. The compound of any one of claims 8 to 11, wherein n is 1, 2 or 3.

13. R a and R a2 are independently halogen, CN, C 1 -C 4 -haloalkyl, C 1 -C 4 -Alkyl, -OC 1 -C 4 -Alkyl, -OC 1 -C 4 -haloalkyl, -C(=NOC 1 -C 4 -alkyl)-C 1 -C 4 -Alkyl, -C(=O)-C 1 -C 4 -Alkyl, C 3 -C 4 -cycloalkyl, -C 1 -C 2 -Alkyl-C 3 -C 4 -cycloalkyl, -OC 3 -C 4 -cycloalkyl and 3- to 5-membered heterocycloalkyl, wherein said heterocycloalkyl contains, in addition to carbon atoms, 1 or 2 heteroatoms selected from N, O and S; R a and R a2 The above-mentioned cyclic moieties are, independently of each other, unsubstituted or substituted with halogen, CN, C 1 -C 2 -Alkyl, C 1 -C 2 -haloalkyl, -OC 1 -C 2 -Alkyl and -OC 1 -C 2 -haloalkyl; b 13. The compound according to any one of claims 8 to 12, having a group.

14. 14. An agrochemical composition comprising an adjuvant and at least one compound of formula I as defined in any one of claims 8 to 13, or a stereoisomer or agriculturally acceptable salt or tautomer or N-oxide thereof.

15. 1. A method for combating plant pathogenic fungi, comprising: curative and / or preventive treatment of plants or plant propagation material of said plants at risk of becoming diseased by said phytopathogenic fungi with at least one compound of formula I as defined in any one of claims 8 to 13 or with an agrochemical composition as defined in claim 14, and / or applying to said phytopathogenic fungi at least one compound of formula I as defined in any one of claims 8 to 13 or the pesticidal composition of claim 14. A method comprising:

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