Use of strobilurin-type compounds to combat plant pathogenic fungi containing the amino acid substitution F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitor XV

Abstract

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

Description

[Technical Field]

[0001] The present invention relates to the use of strobilurin-type compounds of formula I and their N-oxides and salts to combat plant pathogenic fungi containing the amino acid substitution F129L in the mitochondrial cytochrome b protein (also referred to as an F129L mutation in the mitochondrial cytochrome b gene), which confers resistance to Qo inhibitors (QoIs), and to methods for combating such fungi. The present invention also relates to novel compounds, processes for preparing these compounds, compositions comprising 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 the soybean rust fungus (Phakopsora pachyrhizi) having 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] An F129L mutation in the mitochondrial cytochrome b (CYTB) gene is intended to mean any 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), for example, a substitution of the first nucleotide "T" in codon 129 of the CYTB (cytochrome b) gene for "C" (TTT to CTT), resulting in a single amino acid substitution from F to L at position 129 of the cytochrome b protein. Such F129L mutations are 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. In: Kramer, W.; Schirmer, U. (Ed.) - Modern Crop Protection Compounds. Volume 2. Wiley-VCH Verlag 457-495), have traditionally been used to control numerous fungal pathogens in crops. Qo inhibitors typically act 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. A prime example of the use of QoIs is the use of strobilurins in wheat to control Septoria tritici (also known as Mycosphaerella graminicola), the cause of wheat leaf blight. Unfortunately, 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 QoIs in agricultural applications has been attributed to pathogens containing a single amino acid residue substitution, G143A, in the cytochrome b gene of the cytochrome bc1 complex, a QoI target protein found to be regulated by certain QoIs (WO 2013 / 092224).Although several commercially available QoI fungicides are also widely used to control soybean rust, the single amino acid residue substitution G143A in the cytochrome b protein that confers resistance to QoI fungicides was not observed.

[0005] Instead, soybean rust has acquired a different genetic mutation in the cytochrome b gene, resulting in a single amino acid substitution, F129L, which also 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 decreased to levels that pose practical problems in agricultural practice (e.g., Klosowski et al. (2016) Pest Manag Sci 72, 1211-1215).

[0006] Although trifloxystrobin appears to be unaffected by the F129L amino acid substitution to the same extent as other QoI fungicides such as azoxystrobin and pyraclostrobin, trifloxystrobin was less effective against fungal populations harboring 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 to combat plant pathogenic fungi containing the F129L amino acid substitution.

[0008] Therefore, 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 strobilin 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 to mammals, less toxic to non-target organisms such as birds, aquatic vertebrates and invertebrates, pollinators, and arthropods, and / or otherwise environmentally safer. Based on this, it was also an object of the present invention to provide compounds with improved activity and / or a broader activity spectrum against plant pathogenic fungi and / or reduced toxicity to non-target organisms such as vertebrates and invertebrates. Certain per- and polyfluoroalkyl substances (PFAs) are of increasing regulatory concern in many countries due to their toxicological potential and environmental persistence.PFAS have recently been redefined (OECD 2021, Reconciling Terminology of the Universe of Per- and Polyfluoroalkyl Substances: Recommendations and Practical Guidance, OECD Series on Risk Management, No. 61, OECD Publishing, Paris: https: / / www.oecd.org / chemicalsafety / portal-perfluorinated-chemicals / terminology-per-and-polyfluoroalkyl-substances.pdf; Environ. Sci. Technol. 2021 55(23), 15575–15578: https: / / pubs.acs.org / doi / 10.1021 / acs.est.1c06896) to contain at least one fully fluorinated methyl or methylene carbon atom (with no H / Cl / Br / I atoms attached to it), i.e., with some exceptions, they have at least one perfluoromethyl group (-CF3) or perfluoromethylene group (-CF2-). It is therefore also an object of the present invention to provide compounds with improved activity and / or a broader spectrum of activity against plant pathogenic fungi that have low or no PFAS restrictions and / or reduced environmental persistence.

[0009] Certain strobilurin-type compounds of formula I are described in EP 370629 and WO 1998 / 23156, but there is no mention that these compounds inhibit fungal pathogens that contain the F129L substitution in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors.

[0010] Its use to combat plant pathogenic fungi containing the F129L amino acid substitution in the mitochondrial cytochrome b protein, which confers resistance to further strobilurin compounds and Qo inhibitors, is disclosed in WO 2021 / 153754, WO 2021 / 219386, WO 2021 / 219387, WO 2021 / 219388, WO 2021 / 219390 and WO 2021 / 249928. Summary of the Invention [Means for solving the problem]

[0011] The strobilurin analogue compounds according to the invention are, inter alia, those referred to herein as R 3 This compound differs from the above-mentioned references in that it contains a specific combination of a halogen group attached to the central phenyl ring in the ortho position to the side chain, and an alkyl ether group attached to the oxime group in the side chain, which is defined as:

[0012] Thus, the present invention provides compounds of formula I [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 Cl, F and Br, R is selected from C1-C3 alkyl, C1-C3 haloalkyl, C3-C6 cycloalkyl, and C1-C3 alkyl-C3-C6 cycloalkyl; m is an integer selected from 0 and 1; Z is selected from phenyl and 5- or 6-membered heteroaryl; The heteroaryl contains, in addition to carbon atoms, 1, 2 or 3 heteroatoms selected from N, O and S, Z is unsubstituted or contains 1, 2, 3 or up to a maximum of the same or different groups R a and R a is halogen, CN, hydroxy, NR A R B , C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, -O-C1-C4 alkyl, -C(=NO-C1-C4 alkyl)-C1-C4 alkyl, -C(=O)-C1-C4 alkyl, -C(=O)-O-C1-C4 alkyl, -C(=O)-NH-C1-C4 alkyl, -O-CH2-C(=NO-C1-C4 alkyl)-C1-C4 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl, -C1-C2 alkyl-C3-C6 cycloalkyl, -O-C3-C6 cycloalkyl, phenyl and 5- or 6-membered heteroaryl; The heteroaryl contains, in addition to carbon atoms, 1, 2 or 3 heteroatoms selected from N, O and S, the phenyl and heteroaryl are bonded directly, through an oxygen atom, or through a C1-C2 alkylene linker; R a is unsubstituted or contains 1, 2, 3 or up to a maximum of the same or different groups R b and R b is selected from halogen, CN, hydroxy, NO2, C1-C4 alkyl, C1-C4 haloalkyl; R A , R B are each independently selected from hydrogen, C1-C4 alkyl, and C1-C4 haloalkyl and in the form of its stereoisomers and tautomers and its N-oxides and agriculturally acceptable salts. DETAILED DESCRIPTION OF THE INVENTION

[0013] While the present invention has been described with reference to specific embodiments, this description is not intended to be construed in a limiting sense.

[0014] 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 plural forms unless the context clearly dictates otherwise. In the context of the present invention, the terms "about" and "approximately" indicate an interval of accuracy that a person skilled in the art would understand to still ensure the technical effect of the feature in question. This term typically denotes a deviation of ±20%, preferably ±15%, more preferably ±10%, and even more preferably ±5% from the indicated numerical value. The term "comprising" should be understood to be open-ended. The term "consisting of" for the purposes of the present invention is considered to be a preferred embodiment of the term "comprising."

[0015] Unless otherwise indicated, the following definitions are set forth to illustrate and define the meaning and scope of various terms used to interpret this specification and the appended claims. These definitions are not intended to be general definitions and should not be taken in a literal sense as they relate only to this application.

[0016] 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, etc.

[0017] The term "independently," when used with respect to a variable in connection with the selection of substituents, means that when multiple substituents are selected from a number of possible substituents, the substituents can be the same or different.

[0018] The organic moieties or groups referred to in the definitions of the variables above are generic to the individual enumerated lists of the individual members of that group. v -C w The term " indicates in each case the possible number of carbon atoms.

[0019] The term "halogen" refers to fluorine, chlorine, bromine and iodine.

[0020] The term "C1-C4 alkyl" refers to a branched or unbranched 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. Similarly, the term "C1-C3 alkyl" refers to a branched or unbranched saturated hydrocarbon group having 1 to 3 carbon atoms selected from methyl (CH3), ethyl (C2H5), propyl, 1-methylethyl (isopropyl).

[0021] 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 at 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.

[0022] 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.

[0023] The term "C1-C4 haloalkyl" refers to a straight-chain or branched alkyl group having 1 to 4 carbon atoms, in which some or all of the hydrogen atoms may be replaced by the above-mentioned halogen atoms, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2- ... Fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, CH2-C2F5, CF2-C2F5, CF(CF3)2, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl.

[0024] The term "-O-C1-C4 alkyl" refers to a straight or branched alkyl group having 1 to 4 carbon atoms attached through an oxygen at any position of the alkyl group, such as OCH3, OCH2CH3, O(CH2)2CH3, 1-methylethoxy, O(CH2)3CH3, 1-methylpropoxy, 2-methylpropoxy, or 1,1-dimethylethoxy.

[0025] 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.

[0026] The term "-C1-C3 alkyl-C3-C6 cycloalkyl" refers to an alkyl having 1 to 3 carbon atoms (as defined above) in which one hydrogen atom of the alkyl group is replaced with a cycloalkyl group having 3 to 6 carbon atoms.

[0027] The term "phenyl" refers to C6H5.

[0028] The term "5- or 6-membered heteroaryl" containing 1, 2, 3 or 4 heteroatoms from the group consisting of O, N and S is understood to mean 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: for example, 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 heteroaryls which, in addition to carbon atoms, contain, for example, 1, 2, 3 or 4 nitrogen 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.

[0029] The term "C1-C2 alkylene linker" refers to a divalent alkyl group, such as -CH2- or -CH2-CH2-, that is attached at one end to the core structure of Formula I and at the other end to a specified substituent.

[0030] As used herein, "compound," and in particular "compound I," includes all stereoisomers and tautomers and mixtures thereof in all ratios, prodrugs, isotopic forms, agriculturally acceptable salts thereof, N-oxides and S-oxides thereof.

[0031] The term "stereoisomer" is a general term used for all isomers of individual compounds that differ only in the orientation 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 (e.g., Formulae Ia, Ib, and Ic and their subformulas), and isomers of compounds with multiple chiral centers that are not mirror images of one another (diastereoisomers). The term "tautomer" refers to the coexistence of two or more compounds that differ from one another only in the position and electron distribution of one or more mobile atoms, such as 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 an oxide of a nitrogen atom of a nitrogen-containing heteroaryl or heterocycle. N-oxides can be formed in the presence of an oxidizing agent, for example, a peroxide such as m-chloroperbenzoic acid or hydrogen peroxide. N-oxides refer to amine oxides, also known as amine-N-oxides, which are compounds containing an N→O bond.

[0032] With respect to the variables, the intermediate embodiments correspond to the compound I embodiments.

[0033] Preferred compounds are those compounds I and, where applicable, all sub-formulae described herein, such as compounds of formula I.1 and I.2, stereoisomers of formula I shown as formula Ia, Ib and Ic and their respective sub-formulae, such as formula Ib.1, and intermediates such as compounds II, III, IV and V, inclusive of substituents and variables (m, R 1 , R 2 , R 3 , R, R A , R B , R a and R b etc.) have the following meanings, independently of one another or more preferably in combination (in any possible combination of two or more substituents defined herein):

[0034] Also preferred are uses, methods, mixtures and compositions in which the definitions (phytopathogenic fungus, treatment, crop, compound II, further active ingredient, solvent, solid carrier, etc.) have the following meanings independently of one another or, more preferably, in combination, and even more preferably, in combination (any possible combination of two or more definitions described herein) have the preferred meanings of compound I herein.

[0035] One embodiment of the present invention is R 1 is selected from O and NH, and R 2 is selected from CH and N, with the proviso that R 1 If is NH, R 2 is N. More preferably, R 1 is NH. In particular, R 1 is NH and R 2 is N. Another embodiment is 1 is O and R 2 is CH.

[0036] According to another embodiment, R 3 is selected from Cl and F, in particular Cl. According to a further embodiment, R 3 is F. According to a further embodiment, R 3 is Br.

[0037] According to one embodiment, R is selected from methyl, ethyl, isopropyl, C1-C2 haloalkyl, cyclopropyl, CH2-cyclopropyl and (CH2)2 cyclopropyl, more preferably selected from methyl, ethyl, isopropyl, CHF2, CF3, CH2CHF2, CH2CF3, cyclopropyl and CH2 cyclopropyl, even more preferably selected from methyl and ethyl, in particular methyl.

[0038] According to a further embodiment, m is 0 and the compound is of formula I.1. [ka]

[0039] According to a further embodiment, m is 1 and the compound is of formula IB. [ka]

[0040] According to a further embodiment, Z is selected from phenyl and 5- or 6-membered heteroaryl, said heteroaryl containing, in addition to carbon atoms, 1, 2 or 3 heteroatoms selected from N, O and S, and Z is unsubstituted or contains 1, 2 or 3 identical or different groups R as defined herein. a and more preferably Z is unsubstituted or has one or two identical or different groups R as defined herein. a and in particular Z is unsubstituted or contains one group R as defined herein. a It has.

[0041] According to a further embodiment, Z is phenyl and Z is selected from the group consisting of 1, 2 or 3 identical or different groups R as defined herein. a and more preferably Z has one or two identical or different groups R as defined herein. a and in particular Z has one group R as defined herein a According to a further embodiment, Z is phenyl, and Z is unsubstituted or has 1, 2 or 3 identical or different groups R as defined herein. a and more preferably Z is unsubstituted or has 1, 2 or 3 identical or different groups R selected from halogen. a It has.

[0042] According to a further embodiment, Z is selected from pyridyl and thiazolyl, and Z is unsubstituted or contains 1, 2 or 3 identical or different groups R as defined herein. a and more preferably Z is unsubstituted or has one or two identical or different groups R as defined herein. aand in particular Z is unsubstituted or contains one group R as defined herein. a It has.

[0043] According to the above embodiment, R a is preferably selected from halogen, CN, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, -O-C1-C4 alkyl, -C(=NO-C1-C4 alkyl)-C1-C4 alkyl, -C(=O)-C1-C4 alkyl, -O-CH2-C(=NO-C1-C4 alkyl)-C1-C4 alkyl, C3-C4 cycloalkyl, -C1-C2 alkyl-C3-C4 cycloalkyl, -O-C3-C4 cycloalkyl, phenyl, and 5- or 6-membered heteroaryl, wherein the heteroaryl contains, in addition to carbon atoms, 1, 2, or 3 heteroatoms selected from N, O, and S, and the phenyl and heteroaryl are bonded directly or via an oxygen atom or via a C1-C2 alkylene linker.

[0044] Preferably, R a is selected from halogen, CN, C1-C4 alkyl, —O—C1-C4 alkyl, —C(═O)—C1-C2 alkyl, —C(═NO—C1-C4 alkyl)-C1-C4 alkyl, C3-C4 cycloalkyl, —O—C3-C4 cycloalkyl, phenyl, and 5- or 6-membered heteroaryl, wherein the heterocycloalkyl and heteroaryl contain, in addition to carbon atoms, one or two heteroatoms selected from N, O, and S, and the phenyl, heterocycloalkyl, and heteroaryl are bonded directly or via an oxygen atom or via a methylene linker.

[0045] More preferably, R ais selected from halogen, CN, C1-C3 alkyl, —O—C1-C3 alkyl, —C(═NO-CH3)—CH3, C3-C4 cycloalkyl, —O—C3-C4 cycloalkyl, phenyl, and 5- or 6-membered heteroaryl, wherein the heteroaryl contains, in addition to carbon atoms, one or two heteroatoms selected from N, O, and S, and the phenyl and heteroaryl are linked directly or via an oxygen atom or via a methylene linker.

[0046] In particular, R a is selected from halogen, CN, C1-C2 alkyl, —O—C1-C2 alkyl, ethenyl, ethynyl, and —C(═NO—CH3)—CH3.

[0047] According to a further embodiment, R a is selected from halogen, C1-C2 alkyl, —O—C1-C2 alkyl, and the aliphatic portion is unsubstituted or contains one, two or three identical or different groups R b It has.

[0048] R a According to the above-mentioned embodiment, the heteroaryl is a 5-membered heteroaryl, and the heteroaryl contains, in addition to carbon atoms, one or two heteroatoms selected from N, O and S, preferably the heteroatoms are selected from N and O.

[0049] R a According to the above-described embodiment of R a The aliphatic and cyclic portions of the formula (I) are unsubstituted or contain up to 1, 2, 3 or a maximum number of the same or different groups R selected from halogen, CN, NO, C1-C4 alkyl, C1-C4 haloalkyl, —O—C1-C4 alkyl and —O—C1-C4 haloalkyl, more preferably halogen. b and even more preferably R aonly the cyclic portion of the b and even more preferably only the phenyl portion of Ra is unsubstituted or has 1, 2, 3, 4 or 5 identical or different groups R selected from halogen, CN, C1-C4 alkyl, C1-C4 haloalkyl, —O—C1-C4 alkyl and —O—C1-C4 haloalkyl. b In particular, said phenyl is unsubstituted or bears one, two or three identical or different groups R selected from halogen, CN, C1-C2 alkyl, C1-C2 haloalkyl, —O—C1-C2 alkyl and —O—C1-C2-haloalkyl b It has.

[0050] According to a further embodiment, m is 0 and Z is unsubstituted or contains 1, 2 or 3 identical or different substituents R a is a phenyl having R a is selected from halogen, C1-C2 alkyl, —O—C1-C2 alkyl, and the aliphatic portion is unsubstituted or contains one, two or three identical or different groups R b It has.

[0051] According to a further embodiment, m is 1 and Z is unsubstituted or contains 1, 2 or 3 identical or different substituents R a is a phenyl having R a is selected from halogen, C1-C2 alkyl, —O—C1-C2 alkyl, and the aliphatic portion is unsubstituted or contains one, two or three identical or different groups R b It has.

[0052] According to a further embodiment, Z is phenyl and is preferably substituted with two substituents R in the 2,3 position (meaning that one substituent is in the 2 position and the other substituent is in the 3 position), the 2,4 position, the 2,5 position, the 3,4 position or the 3,5 position, and even more preferably in the 2,3 position or the 2,4 position. a It has.

[0053] According to a further embodiment, Z is phenyl and preferably contains three substituents R in the 2, 3 and 4 positions. a It has.

[0054] According to a further preferred embodiment, the present invention provides a compound of formula I, wherein R 1 is selected from O and NH; R 2 is selected from CH and N; R 3 is selected from F, Cl and Br, R is selected from C1-C2 alkyl and cyclopropyl; m is an integer selected from 0 and 1; Z is unsubstituted or contains 1, 2 or 3 identical or different substituents R a is a phenyl or pyridyl having the formula R a is selected from halogen, CN, C1-C4 alkyl, and —O—C1-C4 alkyl; R a is unsubstituted or contains 1, 2, 3 or up to a maximum of the same or different groups R b and R b is selected from halogens) and in the form of its stereoisomers and tautomers and its N-oxides and agriculturally acceptable salts.

[0055] According to a further preferred embodiment, the present invention provides a compound of formula I, wherein R 1 is selected from O and NH; R 2is selected from CH and N; R 3 is selected from F, Cl and Br, R is selected from C1-C2 alkyl; m is an integer selected from 0 and 1; Z is unsubstituted or contains 1, 2 or 3 identical or different substituents R a is a phenyl or pyridyl having the formula R a is selected from halogen, CN, methyl and methoxy and in the form of its stereoisomers and tautomers and its N-oxides and agriculturally acceptable salts.

[0056] According to a further preferred embodiment, the present invention provides a compound of formula 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, R 2 is N, R 3 is selected from Cl and Br, R is selected from C1-C3 alkyl; m is an integer selected from 0 and 1; Z is unsubstituted or contains 1, 2 or 3 identical or different substituents R a is a phenyl having the formula R a is halogen, CN, -NR A R B , C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, -O-C1-C4 alkyl, -C(=NO-C1-C4 alkyl)-C1-C4 alkyl, -C(=O)-C1-C4 alkyl, -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 and 5- or 6-membered heteroaryl; The heteroaryl contains, in addition to carbon atoms, 1, 2 or 3 heteroatoms selected from N, O and S, the phenyl and heteroaryl are bonded directly, through an oxygen atom, or through a C1-C2 alkylene linker; R a is unsubstituted or contains 1, 2, 3 or up to a maximum of the same or different groups R b and R b is selected from halogen, CN, NH2, NO2, C1-C4 alkyl, C1-C4 haloalkyl, —O—C1-C4 alkyl and —O—C1-C4 haloalkyl; R A , R B are each independently selected from the group consisting of hydrogen, C1-C3 alkyl, and C1-C3 haloalkyl. and in the form of its stereoisomers and tautomers and its N-oxides and agriculturally acceptable salts.

[0057] According to a further preferred embodiment, the present invention provides a compound of formula 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, R 2 is N, R 3 is selected from Cl and Br, R is selected from C1-C2 alkyl; m is an integer selected from 0 and 1; Z is unsubstituted or contains 1, 2 or 3 identical or different substituents R a is a phenyl having the formula R a is selected from halogen and C1-C4 alkyl, R a is unsubstituted or contains 1, 2, 3 or up to a maximum of the same or different groups R b and R b is selected from halogens) and in the form of its stereoisomers and tautomers and its N-oxides and agriculturally acceptable salts.

[0058] According to a further preferred embodiment, the present invention provides a compound of formula 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, R 2 is N, R 3 is selected from Cl and Br, R is selected from C1-C2 alkyl; m is an integer selected from 0 and 1; Z is unsubstituted or contains 1, 2 or 3 identical or different substituents R a is a phenyl having the formula R is selected from halogen and C1-C4 alkyl. and in the form of its stereoisomers and tautomers and its N-oxides and agriculturally acceptable salts.

[0059] According to a further embodiment, R 1 is NH and R 2 is N, m is 0, and Z is unsubstituted or contains 1, 2 or 3 substituents R as defined herein. a and the compound is of formula I.A1. [ka]

[0060] According to a further embodiment, R 1 is O and R 2 is N, m is 0, and Z is unsubstituted or contains 1, 2 or 3 substituents R as defined herein.a and the compound is of formula I.A2. [ka]

[0061] According to a further embodiment, R 1 is O and R 2 is CH, m is 0, and Z is unsubstituted or contains 1, 2 or 3 substituents R as defined herein. a and the compound is of formula I.A3. [ka]

[0062] According to a further embodiment, R 1 is NH and R 2 is N, m is 1, and Z is unsubstituted or contains 1, 2 or 3 substituents R as defined herein. a and the compound is of formula IB1. [ka]

[0063] According to a further embodiment, R 1 is O and R 2 is N, m is 1, and Z is unsubstituted or contains 1, 2 or 3 substituents R as defined herein. a and the compound is of formula IB2. [ka]

[0064] According to a further embodiment, R 1 is O and R 2is CH, m is 1, and Z is unsubstituted or contains 1, 2 or 3 substituents R as defined herein. a and the compound is of formula IB3. [ka]

[0065] Preferably, R of compound I 3 is one of the following groups 3-1 to 3-6.

[0066] [Table 1]

[0067] A particularly preferred embodiment of the invention relates to compounds I in which R is one of the following groups 4-1 to 4-8:

[0068] [Table 2]

[0069] Preferably, Z of compound I is one of the following groups Z-1 to Z-44:

[0070] [Table 3]

[0071] A particularly preferred embodiment of the present invention is a is selected from one of the following groups a-1 to a-57:

[0072] [Table 4]

[0073] In one embodiment, compound I is a compound of formula IA1, Z is phenyl (Z-1), and R 3is F, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated I.A1.1-Z-1-A-1 to IA1.1-Z-1-A-2389.

[0074] In another embodiment, compound I is a compound of formula IA2, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated IA2.1-Z-1-A-1 to I.A2.1-Z-1-A-2389.

[0075] In another embodiment, compound I is a compound of formula IA3, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated IA3.1-Z-1-A-1 to I.A3.1-Z-1-A-2389.

[0076] In another embodiment, compound I is a compound of formula IB1, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated IB1.1-Z-1-A-1 to I.B1.1-Z-1-A-2389.

[0077] In another embodiment, compound I is a compound of formula IB2, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as in one row of Table A below, and these compounds are named IB2.1-Z-1-A-1 to IB2.1-Z-1-A-2389.

[0078] In another embodiment, compound I is a compound of formula IB3, Z is phenyl (Z-1), and R 3is F, R and 0 to 3 R a The substituents are as shown in one of the rows of Table A below, and these compounds are named IB3.1-Z-1-A-1 to IB3.1-Z-1-A-2389.

[0079] In another embodiment, compound I is a compound of formula IA1, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as in one row of Table A below, and these compounds are designated I.A1.2-Z-1-A-1 through IA1.2-Z-1-A-2389.

[0080] In another embodiment, compound I is a compound of formula IA2, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as in any row of Table A below, and these compounds are designated IA2.2-Z-1-A-1 to I.A2.2-Z-1-A-2389.

[0081] In another embodiment, compound I is a compound of formula IA3, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated IA3.2-Z-1-A-1 to I.A3.2-Z-1-A-2389.

[0082] In another embodiment, compound I is a compound of formula IB1, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as in one row of Table A below, and these compounds are named IB1.2-Z-1-A-1 to IB1.2-Z-1-A-2389.

[0083] In another embodiment, compound I is a compound of formula IB2, Z is phenyl (Z-1), and R3 is Cl, R and 0 to 3 R a The substituents are as in any row of Table A below, and these compounds are named IB2.2-Z-1-A-1 to IB2.2-Z-1-A-2389.

[0084] In another embodiment, compound I is a compound of formula IB3, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as in one row of Table A below, and these compounds are named IB3.2-Z-1-A-1 to IB3.2-Z-1-A-2389.

[0085] In another embodiment, compound I is a compound of formula IA1, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R a The substituents are as in one row of Table A below, and these compounds are designated I.A1.3-Z-1-A-1 to IA1.3-Z-1-A-2389.

[0086] In another embodiment, compound I is a compound of formula IA2, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R a The substituents are as in any row of Table A below, and these compounds are designated IA2.3-Z-1-A-1 to I.A2.3-Z-1-A-2389.

[0087] In another embodiment, compound I is a compound of formula IA3, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R a The substituents are as shown in one of the rows of Table A below, and these compounds are designated IA3.3-Z-1-A-1 to I.A3.3-Z-1-A-2389.

[0088] In another embodiment, compound I is a compound of formula IB1, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R a The substituents are as in one row of Table A below, and these compounds are named IB1.3-Z-1-A-1 to IB1.3-Z-1-A-2389.

[0089] In another embodiment, compound I is a compound of formula IB2, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R a The substituents are as shown in one of the rows of Table A below, and these compounds are named IB2.3-Z-1-A-1 to IB2.3-Z-1-A-2389.

[0090] In another embodiment, compound I is a compound of formula IB3, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R a The substituents are as shown in one of the rows of Table A below, and these compounds are named IB3.3-Z-1-A-1 to IB3.3-Z-1-A-2389.

[0091] [Table 5]

[0092] [Table 6]

[0093] [Table 7]

[0094] [Table 8]

[0095]

Table 9

[0096]

Table 10

[0097]

Table 11

[0098]

Table 12

[0099]

Table 13

[0100]

Table 14

[0101]

Table 15

[0102] Table 16

[0103] Table 17

[0104] Table 18

[0105] Table 19

[0106] Table 20

[0107] Table 21

[0108] Table 22

[0109] Table 23

[0110] Table 24

[0111] Table 25

[0112] Table 26

[0113] Table 27

[0114] Table 28

[0115] Table 29

[0116] [Table 30]

[0117] [Table 31]

[0118] [Table 32]

[0119] In one embodiment, compound I is a compound of formula IA1, Z is pyridin-4-yl (Z-4), and R 3 is F, R and 0 or 1 R a The substituents are as in any row of Table O below, and these compounds are designated IA1.1-Z-4-O-1 to I.A1.1-Z-4-O-150.

[0120] In another embodiment, compound I is a compound of formula IA2, Z is pyridin-4-yl (Z-4), and R 3 is F, R and 0 or 1 R a The substituents are as in any row of Table O below, and these compounds are designated IA2.1-Z-4-O-1 to I.A2.1-Z-4-O-150.

[0121] In another embodiment, compound I is a compound of formula IA3, Z is pyridin-4-yl (Z-4), and R 3 is F, R and 0 or 1 R a The substituents are as in any row of Table O below, and these compounds are designated IA3.1-Z-4-O-1 to I.A3.1-Z-4-O-150.

[0122] In another embodiment, compound I is a compound of formula IB1, Z is pyridin-4-yl (Z-4), and R 3 is F, R and 0 or 1 R aThe substituents are as in any row of Table O below, and these compounds are designated IB1.1-Z-4-O-1 to I.B1.1-Z-4-O-150.

[0123] In another embodiment, compound I is a compound of formula IB2, Z is pyridin-4-yl (Z-4), and R 3 is F, R and 0 or 1 R a The substituents are as shown in one of the rows of Table O below, and these compounds are named IB2.1-Z-4-O-1 to IB2.1-Z-4-O-150.

[0124] In another embodiment, compound I is a compound of formula IB3, Z is pyridin-4-yl (Z-4), and R 3 is F, R and 0 or 1 R a The substituents are as in any row of Table O below, and these compounds are named IB3.1-Z-4-O-1 to IB3.1-Z-4-O-150.

[0125] In another embodiment, compound I is a compound of formula IA1, Z is pyridin-4-yl (Z-4), and R 3 is Cl, R and 0 or 1 R a The substituents are as in any row of Table O below, and these compounds are designated I.A1.2-Z-4-O-1 to IA1.2-Z-4-O-150.

[0126] In another embodiment, compound I is a compound of formula IA2, Z is pyridin-4-yl (Z-4), and R 3 is Cl, R and 0 or 1 R a The substituents are as in any row of Table O below, and these compounds are designated IA2.2-Z-4-O-1 to I.A2.2-Z-4-O-150.

[0127] In another embodiment, compound I is a compound of formula IA3, Z is pyridin-4-yl (Z-4), and R 3is Cl, R and 0 or 1 R a The substituents are as in any row of Table O below, and these compounds are designated IA3.2-Z-4-O-1 to I.A3.2-Z-4-O-150.

[0128] In another embodiment, compound I is a compound of formula IB1, Z is pyridin-4-yl (Z-4), and R 3 is Cl, R and 0 or 1 R a The substituents are as in any row of Table O below, and these compounds are named IB1.2-Z-4-O-1 to IB1.2-Z-4-O-150.

[0129] In another embodiment, compound I is a compound of formula IB2, Z is pyridin-4-yl (Z-4), and R 3 is Cl, R and 0 or 1 R a The substituents are as in any row of Table O below, and these compounds are named IB2.2-Z-4-O-1 to IB2.2-Z-4-O-150.

[0130] In another embodiment, compound I is a compound of formula IB3, Z is pyridin-4-yl (Z-4), and R 3 is Cl, R and 0 or 1 R a The substituents are as in any row of Table O below, and these compounds are named IB3.2-Z-4-O-1 to IB3.2-Z-4-O-150.

[0131] In another embodiment, compound I is a compound of formula IA1, Z is pyridin-4-yl (Z-4), and R 3 is Br, R and 0 or 1 R a The substituents are as in any row of Table O below, and these compounds are designated I.A1.3-Z-4-O-1 to IA1.3-Z-4-O-150.

[0132] In another embodiment, compound I is a compound of formula IA2, Z is pyridin-4-yl (Z-4), and R 3 is Br, R and 0 or 1 R a The substituents are as in any row of Table O below, and these compounds are designated IA2.3-Z-4-O-1 to I.A2.3-Z-4-O-150.

[0133] In another embodiment, compound I is a compound of formula IA3, Z is pyridin-4-yl (Z-4), and R 3 is Br, R and 0 or 1 R a The substituents are as in any row of Table O below, and these compounds are designated IA3.3-Z-4-O-1 to I.A3.3-Z-4-O-150.

[0134] In another embodiment, compound I is a compound of formula IB1, Z is pyridin-4-yl (Z-4), and R 3 is Br, R and 0 or 1 R a The substituents are as in any row of Table O below, and these compounds are named IB1.3-Z-4-O-1 to IB1.3-Z-4-O-150.

[0135] In another embodiment, compound I is a compound of formula IB2, Z is pyridin-4-yl (Z-4), and R 3 is Br, R and 0 or 1 R a The substituents are as shown in one of the rows of Table O below, and these compounds are named IB2.3-Z-4-O-1 to IB2.3-Z-4-O-150.

[0136] In another embodiment, compound I is a compound of formula IB3, Z is pyridin-4-yl (Z-4), and R 3 is Br, R and 0 or 1 R a The substituents are as shown in one of the rows of Table O below, and these compounds are named IB3.3-Z-4-O-1 to IB3.3-Z-4-O-150.

[0137] [Table 33]

[0138] [Table 34]

[0139] In one embodiment, compound I is a compound of formula IA1, Z is pyridin-3-yl (Z-3), and R 3 is F, R and 0 or 1 R a The substituents are as in one of the rows of Table P below, and these compounds are designated IA1.1-Z-3-P-1 to I.A1.1-Z-3-P-150.

[0140] In another embodiment, compound I is a compound of formula IA2, Z is pyridin-3-yl (Z-3), and R 3 is F, R and 0 or 1 R a The substituents are as in any row of Table P below, and these compounds are designated IA2.1-Z-3-P-1 to I.A2.1-Z-3-P-150.

[0141] In another embodiment, compound I is a compound of formula IA3, Z is pyridin-3-yl (Z-3), and R 3 is F, R and 0 or 1 R a The substituents are as in one of the rows of Table P below, and these compounds are designated IA3.1-Z-3-P-1 to I.A3.1-Z-3-P-150.

[0142] In another embodiment, compound I is a compound of formula IB1, Z is pyridin-3-yl (Z-3), and R 3 is F, R and 0 or 1 R aThe substituents are as in one of the rows of Table P below, and these compounds are designated IB1.1-Z-3-P-1 through I.B1.1-Z-3-P-150.

[0143] In another embodiment, compound I is a compound of formula IB2, Z is pyridin-3-yl (Z-3), and R 3 is F, R and 0 or 1 R a The substituents are as in any row of Table P below, and these compounds are designated IB2.1-Z-3-P-1 to IB2.1-Z-3-P-150.

[0144] In another embodiment, compound I is a compound of formula IB3, Z is pyridin-3-yl (Z-3), and R 3 is F, R and 0 or 1 R a The substituents are as in one of the rows of Table P below, and these compounds are designated IB3.1-Z-3-P-1 to IB3.1-Z-3-P-150.

[0145] In another embodiment, compound I is a compound of formula IA1, Z is pyridin-3-yl (Z-3), and R 3 is Cl, R and 0 or 1 R a The substituents are as in one of the rows of Table P below, and these compounds are designated I.A1.2-Z-3-P-1 through IA1.2-Z-3-P-150.

[0146] In another embodiment, compound I is a compound of formula IA2, Z is pyridin-3-yl (Z-3), and R 3 is Cl, R and 0 or 1 R a The substituents are as in any row of Table P below, and these compounds are designated IA2.2-Z-3-P-1 to I.A2.2-Z-3-P-150.

[0147] In another embodiment, compound I is a compound of formula IA3, Z is pyridin-3-yl (Z-3), and R 3is Cl, R and 0 or 1 R a The substituents are as in one of the rows of Table P below, and these compounds are designated IA3.2-Z-3-P-1 to I.A3.2-Z-3-P-150.

[0148] In another embodiment, compound I is a compound of formula IB1, Z is pyridin-3-yl (Z-3), and R 3 is Cl, R and 0 or 1 R a The substituents are as in one of the rows of Table P below, and these compounds are named IB1.2-Z-3-P-1 to IB1.2-Z-3-P-150.

[0149] In another embodiment, compound I is a compound of formula IB2, Z is pyridin-3-yl (Z-3), and R 3 is Cl, R and 0 or 1 R a The substituents are as in one of the rows of Table P below, and these compounds are designated IB2.2-Z-3-P-1 to IB2.2-Z-3-P-150.

[0150] In another embodiment, compound I is a compound of formula IB3, Z is pyridin-3-yl (Z-3), and R 3 is Cl, R and 0 or 1 R a The substituents are as in one of the rows of Table P below, and these compounds are named IB3.2-Z-3-P-1 to IB3.2-Z-3-P-150.

[0151] In another embodiment, compound I is a compound of formula IA1, Z is pyridin-3-yl (Z-3), and R 3 is Br, R and 0 or 1 R a The substituents are as in one of the rows of Table P below, and these compounds are designated I.A1.3-Z-3-P-1 through IA1.3-Z-3-P-150.

[0152] In another embodiment, compound I is a compound of formula IA2, Z is pyridin-3-yl (Z-3), and R 3 is Br, R and 0 or 1 R a The substituents are as in any row of Table P below, and these compounds are designated IA2.3-Z-3-P-1 to I.A2.3-Z-3-P-150.

[0153] In another embodiment, compound I is a compound of formula IA3, Z is pyridin-3-yl (Z-3), and R 3 is Br, R and 0 or 1 R a The substituents are as in one of the rows of Table P below, and these compounds are designated IA3.3-Z-3-P-1 to I.A3.3-Z-3-P-150.

[0154] In another embodiment, compound I is a compound of formula IB1, Z is pyridin-3-yl (Z-3), and R 3 is Br, R and 0 or 1 R a The substituents are as in one of the rows of Table P below, and these compounds are designated IB1.3-Z-3-P-1 to IB1.3-Z-3-P-150.

[0155] In another embodiment, compound I is a compound of formula IB2, Z is pyridin-3-yl (Z-3), and R 3 is Br, R and 0 or 1 R a The substituents are as in any row of Table P below, and these compounds are designated IB2.3-Z-3-P-1 to IB2.3-Z-3-P-150.

[0156] In another embodiment, compound I is a compound of formula IB3, Z is pyridin-3-yl (Z-3), and R 3 is Br, R and 0 or 1 R a The substituents are as in one of the rows of Table P below, and these compounds are named IB3.3-Z-3-P-1 to IB3.3-Z-3-P-150.

[0157] [Table 35]

[0158] [Table 36]

[0159] In one embodiment, compound I is a compound of formula IA1, Z is pyridin-2-yl (Z-2), and R 3 is F, R and 0 or 1 R a The substituents are as in any row of Table Q below, and these compounds are designated IA1.1-Z-2-Q-1 to I.A1.1-Z-2-Q-150.

[0160] In another embodiment, compound I is a compound of formula IA2, Z is pyridin-2-yl (Z-2), and R 3 is F, R and 0 or 1 R a The substituents are as shown in one of the rows of Table Q below, and these compounds are designated IA2.1-Z-2-Q-1 to I.A2.1-Z-2-Q-150.

[0161] In another embodiment, compound I is a compound of formula IA3, Z is pyridin-2-yl (Z-2), and R 3 is F, R and 0 or 1 R a The substituents are as shown in one of the rows of Table Q below, and these compounds are designated IA3.1-Z-2-Q-1 to I.A3.1-Z-2-Q-150.

[0162] In another embodiment, compound I is a compound of formula IB1, Z is pyridin-2-yl (Z-2), and R 3 is F, R and 0 or 1 R aThe substituents are as in one of the rows of Table Q below, and these compounds are designated IB1.1-Z-2-Q-1 to I.B1.1-Z-2-Q-150.

[0163] In another embodiment, compound I is a compound of formula IB2, Z is pyridin-2-yl (Z-2), and R 3 is F, R and 0 or 1 R a The substituents are as shown in one of the rows of Table Q below, and these compounds are named IB2.1-Z-2-Q-1 to IB2.1-Z-2-Q-150.

[0164] In another embodiment, compound I is a compound of formula IB3, Z is pyridin-2-yl (Z-2), and R 3 is F, R and 0 or 1 R a The substituents are as shown in one of the rows of Table Q below, and these compounds are named IB3.1-Z-2-Q-1 to IB3.1-Z-2-Q-150.

[0165] In another embodiment, compound I is a compound of formula IA1, Z is pyridin-2-yl (Z-2), and R 3 is Cl, R and 0 or 1 R a The substituents are as in one of the rows of Table Q below, and these compounds are designated I.A1.2-Z-2-Q-1 to IA1.2-Z-2-Q-150.

[0166] In another embodiment, compound I is a compound of formula IA2, Z is pyridin-2-yl (Z-2), and R 3 is Cl, R and 0 or 1 R a The substituents are as shown in one of the rows of Table Q below, and these compounds are designated IA2.2-Z-2-Q-1 to I.A2.2-Z-2-Q-150.

[0167] In another embodiment, compound I is a compound of formula IA3, Z is pyridin-2-yl (Z-2), and R 3is Cl, R and 0 or 1 R a The substituents are as shown in one of the rows of Table Q below, and these compounds are designated IA3.2-Z-2-Q-1 to I.A3.2-Z-2-Q-150.

[0168] In another embodiment, compound I is a compound of formula IB1, Z is pyridin-2-yl (Z-2), and R 3 is Cl, R and 0 or 1 R a The substituents are as shown in one of the rows of Table Q below, and these compounds are named IB1.2-Z-2-Q-1 to IB1.2-Z-2-Q-150.

[0169] In another embodiment, compound I is a compound of formula IB2, Z is pyridin-2-yl (Z-2), and R 3 is Cl, R and 0 or 1 R a The substituents are as in any row of Table Q below, and these compounds are named IB2.2-Z-2-Q-1 to IB2.2-Z-2-Q-150.

[0170] In another embodiment, compound I is a compound of formula IB3, Z is pyridin-2-yl (Z-2), and R 3 is Cl, R and 0 or 1 R a The substituents are as in one of the rows of Table Q below, and these compounds are named IB3.2-Z-2-Q-1 to IB3.2-Z-2-Q-150.

[0171] In another embodiment, compound I is a compound of formula IA1, Z is pyridin-2-yl (Z-2), and R 3 is Br, R and 0 or 1 R a The substituents are as in one of the rows of Table Q below, and these compounds are designated I.A1.3-Z-2-Q-1 to IA1.3-Z-2-Q-150.

[0172] In another embodiment, compound I is a compound of formula IA2, Z is pyridin-2-yl (Z-2), and R 3 is Br, R and 0 or 1 R a The substituents are as shown in one of the rows of Table Q below, and these compounds are designated IA2.3-Z-2-Q-1 to I.A2.3-Z-2-Q-150.

[0173] In another embodiment, compound I is a compound of formula IA3, Z is pyridin-2-yl (Z-2), and R 3 is Br, R and 0 or 1 R a The substituents are as shown in one of the rows of Table Q below, and these compounds are designated IA3.3-Z-2-Q-1 to I.A3.3-Z-2-Q-150.

[0174] In another embodiment, compound I is a compound of formula IB1, Z is pyridin-2-yl (Z-2), and R 3 is Br, R and 0 or 1 R a The substituents are as shown in one of the rows of Table Q below, and these compounds are named IB1.3-Z-2-Q-1 to IB1.3-Z-2-Q-150.

[0175] In another embodiment, compound I is a compound of formula IB2, Z is pyridin-2-yl (Z-2), and R 3 is Br, R and 0 or 1 R a The substituents are as shown in one of the rows of Table Q below, and these compounds are named IB2.3-Z-2-Q-1 to IB2.3-Z-2-Q-150.

[0176] In another embodiment, compound I is a compound of formula IB3, Z is pyridin-2-yl (Z-2), and R 3 is Br, R and 0 or 1 R a The substituents are as shown in one of the rows of Table Q below, and these compounds are named IB3.3-Z-2-Q-1 to IB3.3-Z-2-Q-150.

[0177] [Table 37]

[0178] [Table 38]

[0179] [Table 39]

[0180] These compounds I include substituted (2E)-2-[3-halo-2-[[(Z)-[2-(alkoxy)-1-aryl-ethylidene]amino]oxymethyl]phenyl]-2-methoxyimino-N-methyl-acetamides (formula IA1), (2E)-2-[3-halo-2-[[(Z)-[1-(alkoxymethyl)-3-aryl-prop-2-ynylidene]amino]oxymethyl]phenyl]-2-methoxyimino-N-methyl-acetamides (formula IB1), methyl (2E)-2-[3-halo-2-[[(Z)-[2-(alkoxy)-1-(3-aryl)ethylidene]amino]oxymethyl]phenyl]-2-methoxyimino-acetates (formula IA2), methyl (2E)-2-[3-halo-2-[ [(Z)-[1-(alkoxymethyl)-3-(3-aryl)prop-2-ynylidene]amino]oxymethyl]phenyl]-2-methoxyimino-acetate (Formula IB2), methyl (E)-2-[3-halo-2-[[(Z)-[2-(alkoxy)-1-(3-aryl)ethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (Formula IA3), methyl (E)-2-[3-halo-2-[[(Z)-[1-(alkoxymethyl)-3-(3-aryl)prop-2-ynylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (Formula IB3) and stereoisomers thereof (see, for example, Formulas Ia, Ib and IC below).

[0181] Thus, the present invention also relates to the stereoisomers shown below: E / E isomer of formula Ia: [ka] Z / E isomers of formula Ib: [ka] and Z / Z isomers of formula Ic: [ka]

[0182] Therefore, the present invention provides 1 is NH and R 2 is N (these compounds are compounds of formula Ia.1 or Ia.2), 1 is O and R 2 is N (these compounds are compounds of formula Ia.3 or Ia.4) and R 1 is O and R 2 is CH (these compounds are compounds of formula Ia.5 or Ia.6). [ka]

[0183] The present invention is 1 is NH and R 2 is N (these compounds are compounds of formula Ib.1 or Ib.2), 1 is O and R 2 is N (these compounds are compounds of formula Ib.3 or Ib.4) and R 1 is O and R 2 is CH (these compounds are compounds of formula Ib.5 or Ib.6). [ka]

[0184] The present invention is 1 is NH and R 2 is N (these compounds are compounds of formula Ic.1), 1 is O and R 2 is N (these compounds are compounds of formula Ic.2) and R 1 is O and R 2 is CH (these compounds are compounds of formula Ic.3). [ka]

[0185] In 2389 embodiments, compound I is a compound of formula Ia.1, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as in any row of Table A above, and these compounds are designated Ia.1.1-Z-1-A-1 through Ia.1.1-Z-1-A-2389.

[0186] In a further 2389 embodiment, compound I is a compound of formula Ia.2, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ia.2.1-Z-1-A-1 to Ia.2.1-Z-1-A-2389.

[0187] In a further 2389 embodiment, compound I is a compound of formula Ia.3, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ia.3.1-Z-1-A-1 to Ia.3.1-Z-1-A-2389.

[0188] In a further 2389 embodiment, compound I is a compound of formula Ia.4, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ia.4.1-Z-1-A-1 to Ia.4.1-Z-1-A-2389.

[0189] In a further 2389 embodiment, compound I is a compound of formula Ia.5, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ia.5.1-Z-1-A-1 to Ia.5.1-Z-1-A-2389.

[0190] In a further 2389 embodiment, compound I is a compound of formula Ia.6, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ia.6.1-Z-1-A-1 to Ia.6.1-Z-1-A-2389.

[0191] In a further 2389 embodiment, compound I is a compound of formula Ia.1, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as in any row of Table A above, and these compounds are designated Ia.1.2-Z-1-A-1 through Ia.1.2-Z-1-A-2389.

[0192] In a further 2389 embodiment, compound I is a compound of formula Ia.2, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ia.2.2-Z-1-A-1 to Ia.2.2-Z-1-A-2389.

[0193] In a further 2389 embodiment, compound I is a compound of formula Ia.3, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ia.3.2-Z-1-A-1 to Ia.3.2-Z-1-A-2389.

[0194] In a further 2389 embodiment, compound I is a compound of formula Ia.4, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ia.4.2-Z-1-A-1 to Ia.4.2-Z-1-A-2389.

[0195] In a further 2389 embodiment, compound I is a compound of formula Ia.5, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ia.5.2-Z-1-A-1 to Ia.5.2-Z-1-A-2389.

[0196] In a further 2389 embodiment, compound I is a compound of formula Ia.6, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ia.6.2-Z-1-A-1 to Ia.6.2-Z-1-A-2389.

[0197] In a further 2389 embodiment, compound I is a compound of formula Ia.1, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R aThe substituents are as in any row of Table A above, and these compounds are designated Ia.1.3-Z-1-A-1 through Ia.1.3-Z-1-A-2389.

[0198] In a further 2389 embodiment, compound I is a compound of formula Ia.2, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ia.2.3-Z-1-A-1 to Ia.2.3-Z-1-A-2389.

[0199] In a further 2389 embodiment, compound I is a compound of formula Ia.3, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ia.3.3-Z-1-A-1 to Ia.3.3-Z-1-A-2389.

[0200] In a further 2389 embodiment, compound I is a compound of formula Ia.4, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ia.4.3-Z-1-A-1 to Ia.4.3-Z-1-A-2389.

[0201] In a further 2389 embodiment, compound I is a compound of formula Ia.5, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ia.5.3-Z-1-A-1 to Ia.5.3-Z-1-A-2389.

[0202] In a further 2389 embodiment, compound I is a compound of formula Ia.6, Z is phenyl (Z-1), and R3 is Br, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ia.6.3-Z-1-A-1 to Ia.6.3-Z-1-A-2389.

[0203] In a further 2389 embodiment, compound I is a compound of formula Ib.1, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as in any row of Table A above, and these compounds are designated Ib.1.1-Z-1-A-1 through Ib.1.1-Z-1-A-2389.

[0204] In a further 2389 embodiment, compound I is a compound of formula Ib.2, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ib.2.1-Z-1-A-1 to Ib.2.1-Z-1-A-2389.

[0205] In a further 2389 embodiment, compound I is a compound of formula Ib.3, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ib.3.1-Z-1-A-1 to Ib.3.1-Z-1-A-2389.

[0206] In a further 2389 embodiment, compound I is a compound of formula Ib.4, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ib.4.1-Z-1-A-1 to Ib.4.1-Z-1-A-2389.

[0207] In a further 2389 embodiment, compound I is a compound of formula Ib.5, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ib.5.1-Z-1-A-1 to Ib.5.1-Z-1-A-2389.

[0208] In a further 2389 embodiment, compound I is a compound of formula Ib.6, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ib.6.1-Z-1-A-1 to Ib.6.1-Z-1-A-2389.

[0209] In a further 2389 embodiment, compound I is a compound of formula Ib.1, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as in any row of Table A above, and these compounds are designated Ib.1.2-Z-1-A-1 through Ib.1.2-Z-1-A-2389.

[0210] In a further 2389 embodiment, compound I is a compound of formula Ib.2, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as in one row of Table A below, and these compounds are designated Ib.2.2-Z-1-A-1 to Ib.2.2-Z-1-A-2389.

[0211] In a further 2389 embodiment, compound I is a compound of formula Ib.3, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ib.3.2-Z-1-A-1 to Ib.3.2-Z-1-A-2389.

[0212] In a further 2389 embodiment, compound I is a compound of formula Ib.4, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as in one row of Table A below, and these compounds are designated Ib.4.2-Z-1-A-1 to Ib.4.2-Z-1-A-2389.

[0213] In a further 2389 embodiment, compound I is a compound of formula Ib.5, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ib.5.2-Z-1-A-1 to Ib.5.2-Z-1-A-2389.

[0214] In a further 2389 embodiment, compound I is a compound of formula Ib.6, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ib.6.2-Z-1-A-1 to Ib.6.2-Z-1-A-2389.

[0215] In a further 2389 embodiment, compound I is a compound of formula Ib.1, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R a The substituents are as in any row of Table A above, and these compounds are designated Ib.1.3-Z-1-A-1 through Ib.1.3-Z-1-A-2389.

[0216] In a further 2389 embodiment, compound I is a compound of formula Ib.2, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R aThe substituents are as in one of the rows of Table A below, and these compounds are designated Ib.2.3-Z-1-A-1 to Ib.2.3-Z-1-A-2389.

[0217] In a further 2389 embodiment, compound I is a compound of formula Ib.3, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ib.3.3-Z-1-A-1 to Ib.3.3-Z-1-A-2389.

[0218] In a further 2389 embodiment, compound I is a compound of formula Ib.4, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ib.4.3-Z-1-A-1 to Ib.4.3-Z-1-A-2389.

[0219] In a further 2389 embodiment, compound I is a compound of formula Ib.5, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R a The substituents are as in one row of Table A below, and these compounds are designated Ib.5.3-Z-1-A-1 to Ib.5.3-Z-1-A-2389.

[0220] In a further 2389 embodiment, compound I is a compound of formula Ib.6, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R a The substituents are as in one of the rows of Table A below, and these compounds are designated Ib.6.3-Z-1-A-1 to Ib.6.3-Z-1-A-2389.

[0221] In a further 2389 embodiment, compound I is a compound of formula Ic.1, Z is phenyl (Z-1), and R3 is F, R and 0 to 3 R a The substituents are as in any row of Table A above, and these compounds are designated Ic.1.1-Z-1-A-1 through Ic.1.1-Z-1-A-2389.

[0222] In a further 2389 embodiment, compound I is a compound of formula Ic.2, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as in one row of Table A below, and these compounds are named Ic.2.1-Z-1-A-1 to Ic.2.1-Z-1-A-2389.

[0223] In a further 2389 embodiment, compound I is a compound of formula Ic.3, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as in any row of Table A below, and these compounds are designated Ic.3.1-Z-1-A-1 to Ic.3.1-Z-1-A-2389.

[0224] In a further 2389 embodiment, compound I is a compound of formula Ic.4, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as shown in one of the rows of Table A below, and these compounds are named Ic.4.1-Z-1-A-1 to Ic.4.1-Z-1-A-2389.

[0225] In a further 2389 embodiment, compound I is a compound of formula Ic.5, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as shown in one of the rows of Table A below, and these compounds are named Ic.5.1-Z-1-A-1 to Ic.5.1-Z-1-A-2389.

[0226] In a further 2389 embodiment, compound I is a compound of formula Ic.6, Z is phenyl (Z-1), and R 3 is F, R and 0 to 3 R a The substituents are as shown in one of the rows of Table A below, and these compounds are named Ic.6.1-Z-1-A-1 to Ic.6.1-Z-1-A-2389.

[0227] In a further 2389 embodiment, compound I is a compound of formula Ic.1, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as in any row of Table A above, and these compounds are designated Ic.1.2-Z-1-A-1 through Ic.1.2-Z-1-A-2389.

[0228] In a further 2389 embodiment, compound I is a compound of formula Ic.2, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as in one row of Table A below, and these compounds are named Ic.2.2-Z-1-A-1 to Ic.2.2-Z-1-A-2389.

[0229] In a further 2389 embodiment, compound I is a compound of formula Ic.3, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as in one row of Table A below, and these compounds are named Ic.3.2-Z-1-A-1 to Ic.3.2-Z-1-A-2389.

[0230] In a further 2389 embodiment, compound I is a compound of formula Ic.4, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as shown in one of the rows of Table A below, and these compounds are named Ic.4.2-Z-1-A-1 to Ic.4.2-Z-1-A-2389.

[0231] In a further 2389 embodiment, compound I is a compound of formula Ic.5, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as shown in one of the rows of Table A below, and these compounds are named Ic.5.2-Z-1-A-1 to Ic.5.2-Z-1-A-2389.

[0232] In a further 2389 embodiment, compound I is a compound of formula Ic.6, Z is phenyl (Z-1), and R 3 is Cl, R and 0 to 3 R a The substituents are as shown in one of the rows of Table A below, and these compounds are named Ic.6.2-Z-1-A-1 to Ic.6.2-Z-1-A-2389.

[0233] In a further 2389 embodiment, compound I is a compound of formula Ic.1, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R a The substituents are as in any row of Table A above, and these compounds are designated Ic.1.3-Z-1-A-1 through Ic.1.3-Z-1-A-2389.

[0234] In a further 2389 embodiment, compound I is a compound of formula Ic.2, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R a The substituents are as shown in one of the rows of Table A below, and these compounds are named Ic.2.3-Z-1-A-1 to Ic.2.3-Z-1-A-2389.

[0235] In a further 2389 embodiment, compound I is a compound of formula Ic.3, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R aThe substituents are as in one row of Table A below, and these compounds are named Ic.3.3-Z-1-A-1 to Ic.3.3-Z-1-A-2389.

[0236] In a further 2389 embodiment, compound I is a compound of formula Ic.4, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R a The substituents are as shown in one of the rows of Table A below, and these compounds are named Ic.4.3-Z-1-A-1 to Ic.4.3-Z-1-A-2389.

[0237] In a further 2389 embodiment, compound I is a compound of formula Ic.5, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R a The substituents are as shown in one of the rows of Table A below, and these compounds are named Ic.5.3-Z-1-A-1 to Ic.5.3-Z-1-A-2389.

[0238] In a further 2389 embodiment, compound I is a compound of formula Ic.6, Z is phenyl (Z-1), and R 3 is Br, R and 0 to 3 R a The substituents are as shown in one of the rows of Table A below, and these compounds are named Ic.6.3-Z-1-A-1 to Ic.6.3-Z-1-A-2389.

[0239] The compounds according to the present invention include isomers shown in formulas I, Ia, Ib, and Ic. Preferably, the compounds according to the present invention contain more than 50% of the stereoisomer shown in formula I and less than 50% of the stereoisomer shown in formula Ia, Ib, and Ic. Preferably, the compounds according to the present invention contain more than 80% of the stereoisomer shown in formula I and less than 20% of the stereoisomer shown in formula Ia, Ib, and Ic. Preferably, the compounds according to the present invention contain more than 90% of the stereoisomer shown in formula I and less than 10% of the stereoisomer shown in formula Ia, Ib, and Ic. Preferably, the compounds according to the present invention contain more than 95% of the stereoisomer shown in formula I and less than 5% of the stereoisomer shown in formula Ia, Ib, and Ic. Preferably, the compounds according to the present invention contain more than 98% of the stereoisomer shown in formula I and less than 2% of the stereoisomer shown in formula Ia, Ib, and Ic. Preferably, the compounds according to the invention contain more than 99% of the stereoisomer shown in formula I and less than 1% of the stereoisomer shown in formulas Ia, Ib and Ic. Preferably, the compounds according to the invention contain more than 99.5% of the stereoisomer shown in formula I and less than 0.5% of the stereoisomer shown in formulas Ia, Ib and Ic.

[0240] According to another embodiment, the compound according to the present invention comprises the stereoisomers of formula I and formula Ia. Preferably, the compound according to the present invention comprises more than 50% of the stereoisomer of formula I and less than 50% of the stereoisomer of formula Ia. Preferably, the compound according to the present invention comprises more than 80% of the stereoisomer of formula I and less than 20% of the stereoisomer of formula Ia. Preferably, the compound according to the present invention comprises more than 90% of the stereoisomer of formula I and less than 10% of the stereoisomer of formula Ia. Preferably, the compound according to the present invention comprises more than 95% of the stereoisomer of formula I and less than 5% of the stereoisomer of formula Ia. Preferably, the compound according to the present invention comprises more than 99% of the stereoisomer of formula I and less than 1% of the stereoisomer of formula Ia. Preferably, the compound according to the present invention comprises more than 99.5% of the stereoisomer of formula I and less than 0.5% of the stereoisomer of formula Ia. According to a further embodiment, the compounds according to the invention are essentially stereoisomerically pure stereoisomers as shown in formula I.

[0241] synthesis The compounds can be obtained by a variety of routes analogous to known prior art processes (see, for example, EP 463488, WO 2021 / 153754, WO 2021 / 219386, WO 2021 / 219387, WO 2021 / 219388, WO 2021 / 219390 and WO 2021 / 249928), and can be advantageously obtained as shown in Schemes 1-4 and in the Examples section below. One suitable method is illustrated in Scheme 1. [ka]

[0242] This reaction begins with the conversion of the ketone to the corresponding oxime using hydroxylamine hydrochloride and a base such as pyridine, NaOH, or sodium acetate (NaAc) in a polar solvent such as methanol, a methanol-water mixture, or ethanol at 60-100°C, preferably about 65°C. If an E / Z mixture is obtained, the isomers can be separated by known purification techniques (e.g., column chromatography, crystallization, distillation, etc.). Coupling with intermediate IV (where X is a leaving group such as a halogen, toluenesulfonate, or methanesulfonate; preferably, X is Cl or Br) is then carried out using a base such as sodium hydride, cesium carbonate, or potassium carbonate and an organic solvent such as dimethylformamide (DMF) or acetonitrile (AcN), preferably using cesium carbonate as the base and AcN as the solvent, at room temperature (RT) of about 24°C. This general procedure can also be adapted to prepare compounds of formula I (where Z is not phenyl and / or m is 1). R 1 The ester compound I, where R is O, can be obtained by reaction with methylamine (preferably a 40% aqueous solution) at room temperature using tetrahydrofuran (THF) as the solvent to give the compound R 1can be converted to an amide of Formula I, where N is NH. If an E / Z mixture is obtained, the isomers can be separated by known purification techniques (e.g., column chromatography, crystallization, distillation, etc.). Thus, these procedures can be used to separate the E / Z isomer (e.g., (2E)-2-methoxyimino-2-[2-[[(Z)-[2-methoxy-1-(2,4-difluorophenyl)ethylidene]amino]oxymethyl]-3-chlorophenyl]-N-methylacetamide), as well as the E / E, Z / E, and Z / Z isomers of Formulas Ia, Ib, and Ic, respectively (e.g., (2E)-2-methoxyimino-2-[2-[[(E)-[2-methoxy-1-(2,4-difluorophenyl)ethylidene]amino]oxymethyl]- (2Z)-2-methoxyimino-2-[2-[[(E)-[2-methoxy-1-(2,4-difluorophenyl)ethylidene]amino]oxymethyl]-3-bromophenyl]-N-methylacetamide and (2Z)-2-methoxyimino-2-[2-[[(Z)-[2-methoxy-1-(2,4-difluorophenyl)ethylidene]amino]oxymethyl]-3-chlorophenyl]-N-methylacetamide).

[0243] Another general method for preparing Compound I is shown in Scheme 2. [ka]

[0244] 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 preferably achieved by removing the phthalimide group using hydrazine hydrate in methanol at 25°C. Alternatively, removal of the phthalimide group using methylamine in methanol at 25°C yields intermediate IX. Intermediates VIII and IX can be condensed with ketones using acetic acid or pyridine in methanol at 50-65°C, respectively. Alternatively, the condensation can be carried out using 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.

[0245] A general method for preparing intermediate IV is shown in Scheme 3. [ka]

[0246] Compound XI can be obtained from X by lithium-halogen exchange or Grignard reagent formation followed by further reaction with dimethyl oxalate or chloromethyl oxalate in the presence of a solvent. Preferred solvents are THF and 2-methyl THF, and the temperature can range from -70 to -78°C. Conversion of intermediate XI to intermediate XII can be achieved by 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. Typically, an E / Z mixture is obtained, and these 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 R 2=N, providing the desired intermediate compound IV. This reaction of intermediate XII with N-bromosuccinimide (NBS) in a solvent such as carbon tetrachloride, chlorobenzene, or ACN using a radical initiator such as 1,1'-azobis(cyclohexanecarbonitrile) or azobisisobutyronitrile 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.

[0247] Different substituents R 3 The synthesis of compounds containing R 3 is bromo. 3 Coupling of intermediate III, where R is bromo, with intermediate IV provides the above compound I. Standard chemistry such as Suzuki or Stille reactions can be used to convert the bromo group to other R groups such as cycloalkyl, alkoxy, and alkenyl. 3 Further transformation of ethenyl can lead to other R substituents such as ethyl, CN, and haloalkyl. 3 Compound I is provided having a substituent.

[0248] Most of the 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. Various methods known in the literature for the synthesis of these ketones are shown in Scheme 4. [ka]

[0249] Ketone II can be obtained from the corresponding halogen-containing precursor XIV, where X is preferably bromine or iodine. Ketone II can be obtained by lithium-halogen exchange with compound XIV using n-butyllithium (J Org Chem, 1998, 63(21), 7399-7407) or by synthesis of the corresponding Grignard reagent using THF as a solvent (Nature Comm, 2017, 8(1), 1-7) followed by reaction with N-methoxy-N-methylalkoxyacetamide at about -70 to -78 °C.

[0250] Compound I and its compositions are suitable as fungicides that are effective against a wide range of plant pathogenic fungi, including soil-borne fungi, especially those 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, seed dressing fungicides and soil fungicides.

[0251] The compounds I and compositions thereof are preferably used on cereals such as wheat, rye, barley, triticale, oats or rice; beets such as sugar beet or fodder beet; fruits such as pome fruits (e.g. apples, pears), stone fruits (e.g. plums, peaches, almonds, cherries) or soft fruits also called berries (strawberries, raspberries, blackberries, gooseberries, etc.); legumes such as lentils, peas, alfalfa or soybeans; oil plants such as rapeseed, mustard, olives, sunflowers, coconuts, cocoa beans, castor beans, oil palm, groundnuts or soybeans; cucurbits such as pumpkin, cucumber or melon; fiber plants such as cotton, flax, hemp or jute; citrus fruits such as oranges, lemons, The compounds are useful for controlling phytopathogenic fungi in various cultivated plants such as: spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato, cucurbit or pepper; lauraceae plants such as avocado, cinnamon or camphor; energy and raw material plants such as corn, soybean, rapeseed, sugarcane or oil palm; maize; tobacco; nuts; coffee; tea; banana; grapes (table grapes and juice grapes); hops; turf; flaxseed (also called stevia); natural rubber plants; or ornamental and forest plants, for example flowers, shrubs, broadleaf or evergreen trees (conifers, eucalyptus, etc.); plant propagation material such as seeds; and crop material of these plants.

[0252] More preferably, compound I and compositions thereof, respectively, are used to control fungi on agricultural crops such as potato, sugar beet, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybean, rapeseed, legumes, sunflower, coffee or sugarcane; fruits; grapes; ornamental plants; or vegetables such as cucumber, tomato, bean or pumpkin.

[0253] The term "plant propagation material" should be understood to mean all reproductive parts of a plant, such as seeds and vegetative plant material, such as cuttings and tubers (e.g., potatoes), that can be used for plant propagation. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, buds, shoots, and other parts of a plant, including seedlings and young plants that are transplanted after germination or emergence from the soil.

[0254] Preferably, the treatment of plant propagation material with Compound I and compositions thereof, respectively, is used to control fungi on cereals such as wheat, rye, barley and oats; rice, corn, cotton and soybean.

[0255] In accordance with the present invention, all of the above-mentioned cultivated plants are understood to include all species, subspecies, variants, varieties and / or hybrids within each cultivated plant, including but not limited to winter and spring species, particularly cereals such as wheat and barley, and rapeseed, such as winter wheat, spring wheat and winter wheat varieties, as well as dwarf, semi-dwarf and fully dwarf varieties and / or hybrids with low height and thick stems, such as low-profile maize (also known as "smart corn"), semi-dwarf wheat and dwarf rice.

[0256] Corn, also known as Indian corn or maize (Zea mays), includes all varieties such as fodder corn and sweet corn. According to the present invention, all maize or maize subspecies and / or varieties are included, in particular flour corn (Zea mays var. amylacea), popcorn (Zea mays var. everta), dent corn (Zea mays var. indentata), flint corn (Zea mays var. indurata), sweet corn (Zea mays var. saccharata and var. rugosa), waxy corn (Zea mays var. ceratina), amylomaize (high-amylose Zea mays varieties), guanylated or wild maize (Zea mays var. tunicata), and striped corn (Zea mays var. japonica).

[0257] Most soybean varieties are classified into indeterminate and determinate growth habits, although the wild ancestor of soybean, Glycine soja, is indeterminate (PNAS 2010,107(19)8563-8568). Indeterminate growth habits (maturity groups, MG 00 to MG 4.9) are characterized by continued vegetative growth after flowering begins, whereas determinate soybean varieties (MG 5 to MG 8) are characterized by the termination of most of their vegetative growth once flowering begins. All soybean cultivars or varieties are included in accordance with the present invention, particularly indeterminate and determinate cultivars or varieties.

[0258] The term "cultivated plants" is understood to include plants that have been modified by mutagenesis or genetic engineering to confer new traits or alter existing traits. Mutagenesis includes not only random mutagenesis using X-rays or mutagenic chemicals, but also targeted mutagenesis to induce mutations at specific loci in the plant genome. Targeted mutagenesis often uses oligonucleotides or proteins such as CRISPR / Cas, zinc finger nucleases, TALENs, or meganucleases. Genetic engineering typically uses recombinant DNA techniques to introduce modifications into the plant genome that are not readily obtainable by breeding, mutagenesis, or natural recombination under natural circumstances. Typically, one or more genes are integrated into the plant genome to add or improve or alter traits. These integrated genes are also referred to as transgenes, while plants containing such transgenes are referred to as transgenic plants. The plant transformation process typically results in several transformation events, each with different genomic loci at which the transgenes are integrated. A plant containing a particular transgene at a particular genomic locus is usually said to contain a particular "event" and is referred to by the name of the particular event. Traits that have been introduced or modified in plants include herbicide tolerance, insect resistance, high yield, and tolerance to abiotic conditions such as drought.

[0259] Herbicide tolerance is achieved by using mutagenesis and genetic engineering. Plants that have been made tolerant to acetolactate synthase (ALS) inhibitor herbicides through mutagenesis and breeding are available, for example, under the name Clearfield®. Herbicide tolerance to glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbicides such as bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitors, and 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors such as isoxaflutole and mesotrione is achieved through the use of transgenes.

[0260] The use of compound I and its compositions on cultivated plants can result in effects specific to the cultivated plants containing a particular transgene or event. These effects can include changes in growth behavior or altered tolerance to biotic or abiotic stress factors. Such effects can include, inter alia, increased yield, increased resistance or resistance to insect pathogens, nematode pathogens, fungal pathogens, bacterial pathogens, mycoplasma pathogens, viral pathogens, or viroid pathogens, as well as early plant vigor, early or delayed maturation, low or high temperature tolerance, and changes in the spectrum or content of amino acids or fatty acids.

[0261] The compounds I and their compositions are particularly suitable for controlling the etiology of the following plant diseases, respectively: Albugo species (white rust) on ornamental plants, vegetables (e.g., A. candida) and sunflowers (e.g., A. tragopogonis); vegetables (e.g., A. dauci or A. porri), rapeseed (A. brassicicola or A. brassicae) Alternaria species (Alternaria leaf spot) on cereals and vegetables, such as A. brassicae), sugar beet (A. tenuis), fruits (e.g., A. grandis), rice, soybean, potato, and tomato (e.g., A. solani, A. grandis, or A. alternata), tomato (e.g., A. solani, or A. alternata), and wheat (e.g., A. triticina); Aphanomyces species on sugar beet and vegetables; Ascochyta species on cereals and vegetables, such as A. tritici (anthracnose) on wheat and A. hordei on barley; eyespot (Aureobasidium) on maize. zeae (synonymous with Kapatiella zeae); Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), such as brown spot (D. maydis) or northern leaf blight (B. zeicola) on maize, leaf spot (B. sorokiniana) on cereals and B. oryzae (B. zeicola) on rice and turfgrass.oryzae; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e.g., wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: gray mold) on fruits and berries (e.g., strawberries) and vegetables (e.g., lettuce, carrots, celery, and cabbage); B. squamosa or gray rot (B. allii) on onion, rapeseed, ornamentals (e.g., B. eliptica), grapes, forest plants, and wheat; Bremia lactucae on lettuce lactucae (downy mildew); Ceratocystis (syn. Ophiostoma) species (root rot or damping-off) on deciduous and evergreen trees, such as C. ulmi (Dutch elm disease) on elm; Cercospora species on maize (e.g. gray spot: C. zeae-maydis), rice, sugar beet (e.g. C. beticola), sugarcane, vegetables, coffee, soybean (e.g. C. sojina or C. kikuchii) and rice. spp. (Cercospora leaf spot); Cladobotryum (synonymous with Dactylium) species on mushrooms (e.g., C. mycophilum (formerly synonymous with Dactylium dendroide, teleomorphs: Nectria albertinii, Nectria rosella, Hypomyces rosellus); Cladosporium species on tomato (e.g., C. fulvum: leaf mold) and cereals, e.g., C. herbalum on wheat.herbarum (black rot); Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Bipolaris) on corn (C. carbonum), cereals (e.g., C. sativus, anamorph: B. sorokiniana), and rice (e.g., C. miyabeanus, anamorph: H. oryzae). Helminthosporium species (leaf spot) of (Helminthosporium solaris); cotton (e.g., C. gossypii), corn (e.g., C. graminicola: anthracnose root rot), soft fruit, potato (e.g., C. coccodes: black spot), legumes (e.g., C. lindemuthianum) , soybean (e.g., C. truncatum or C. gloeosporioides), vegetables (e.g., C. lagenarium or C. capsici), fruits (e.g., C. acutatum), coffee (e.g., C. coffeanum or C. kahawae Colletotrichum (teleomorph: Glomerella) species (anthracnose) on rice and C. gloeosporioides on various crops; Corticium species, e.g., C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spot) on soybean, cotton and ornamentals; Cycloconium species, e.g., C. oleaginum on olive trees; fruit trees, grapes (e.g., C. liriodendri) on grapes (e.g., C.liriodendri, teleomorph: Neonectria liriodendri (Black Foot disease) on ornamental plants; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybean; Diaporthe spp., e.g., D. phaseolorum (damping-off) on soybean; Drechslera spp. (Helminthosporium spp., teleomorph: Pyrenophora on maize, cereals such as barley (e.g., Drescherella teres, net blotch) and wheat (e.g., Drescherella tritici-repentis: yellow spot), rice and turf; on Formitiporia (F. mediterranea, Phaeomoniella chlamydospora (formerly synonymous with Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and / or Botryosphaeria obtusa). obtusa, Esca disease (canker, apoplexy) on grapes; Elsinoe species on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose) and grapes (E. ampelina: anthracnose); Entyloma oryzae (leaf sooty mildew) on rice; Epicoccum species (black mold) on wheat; sugar beet (E. betae), vegetables (e.g., E. pisi), such as cucurbits (e.g., E. cichoracearum), cabbage, rapeseed (e.g., E. cruciferarum),Erysiphe (powdery mildew) on Erysiphe spp. (powdery mildew) on Eutypa lata (Eutypa canker or blight, anamorph: Cytosporina lata (synonymous with Libertella blepharis) on fruit trees, grapes, and ornamental trees; Exserohilum spp. (synonymous with Helminthosporium spp.) on maize (e.g., E. turcicum); Fusarium spp. spp.) (telomorph: Gibberella) (wilt, root rot or stem rot) on various plants, e.g., Fusarium graminearum or Fusarium culmorum (root rot, scab, head blight) on cereals (e.g., wheat or barley). blight, Fusarium oxysporum on tomatoes, Fusarium solani (f.sp.glycines, now synonymous with F.virguliforme) and Fusarium tucumaniae and Fusarium brasiliense causing acute blight on soybeans, and Fusarium verticillioides on maize; Gaeumannomyces graminis (bottom rot) on cereals (e.g., wheat or barley) and maize; Gibberella spp. spp. on cereals (e.g., Gibberella zeae) and rice (e.g., Gibberella fujikuroi: bakanae disease); Glomerella cingulata on grapevines, pome fruits, and other plants, and Glomerella gossypii on cotton.gossypii; Grainstaining complex on rice; Guignardia bidwellii (black spot) on grapevine; Gymnosporangium spp. on Rosaceae and Juniper plants, e.g., G. sabinae (rust) on pear; Helminthosporium spp. (Drechslera, teleomorph: synonymous with Cochliobolus spp.) on maize, cereals, and rice; Hemileia spp., such as H. vastatrix (coffee rust) on coffee; Isariopsis clavispora (synonymous with Cladosporium vitis) on grapevine; Macrophomina phaseolina (synonymous with phaseoli) on soybeans and cotton (root and stem rot); cereals (e.g. Microdochium (synonymous with Fusarium) nivale (pink snow mold) on wheat or barley; Microsphaera diffusa (powdery mildew) on soybean; Monilinia spp., such as M. laxa, M. fructicola and M. fructigena (synonymous with Monilla spp.), on stone fruits and other Rosaceae plants; flower blight and twig blight, brown rot; Mycosphaerella spp., on cereals, bananas, soft fruits and groundnuts, such as M. graminicola (anamorph: Zymoseptoria spp.), on wheat. tritici, formerly Septoria tritici (Septoria leaf spot) or M. fijiensis (synonymous with Pseudocercospora fijiensis: Black Sigatoka disease) on bananas and M. musicola, M. arachidicola (M. arachidis or Cercospora arachidis) on peanuts. synonymous with P. arachidis), M. berkeleyi, M. pisi on pea and M. brassiciola on Brassicaceae plants; Peronospora spp. (downy mildew) on cabbage (e.g. P. brassicae), rapeseed (e.g. P. parasitica), onion (e.g. P. destructor), tobacco (P. tabacina) and soybean (e.g. P. manshurica); Phakopsora pachyrhizi on soybean pachyrhizi and P. meibomiae (soybean rust); e.g., grape (e.g., P. tracheiphila and P.Phialophora spp. on rapeseed and cabbage (synonymous with Leptosphaeria biglobosa and L. maculans: root and stem rot), P. betae on sugar beet (root rot, leaf spot and damping-off) and P. zeae-maydis on maize (synonymous with Phyllostica zeae); sunflower, grapevine (synonymous with P. viticola: stem and leaf spot) and soybean (synonymous with P. phaseoli: stem rot, teleomorph: Diaporthe phaseolus). phaseolorum); Physoderma maydis (leaf spot) on maize; Phytophthora spp. (chlorosis, root, leaf, fruit, or stem root) on various plants, such as peppers and cucurbits (e.g., P. capsici), soybeans (e.g., P. megasperma (synonymous with P. sojae)), potatoes and tomatoes (e.g., P. infestans: leaf rot) and deciduous trees (e.g., P. ramorum: oak death); Plasmodiophora brassicae on cabbage, rapeseed, radish, and other plants (damage, root, leaf, fruit, and stem rot). brassicae (club root disease); Plasmopara species, such as P. viticola (grape downy mildew) on grapes and P. halstedii on sunflowers; Rosaceae, hops, pome and soft fruits (e.g. P. leucotricha on apples) and Cucurbits (P. xanthii on apples).Podosphaera species (powdery mildew) on cereals such as barley and wheat (P. graminis) and sugar beet (P. betae) and the viral diseases transmitted by them; Pseudocercosporella herpotrichoides on cereals such as wheat or barley (Oculimacula yallundae, synonymous with O. acuformis: eyespot disease, teleomorph: Tapesia yallundae) yallundae); Pseudoperonospora (downy mildew) on various plants, e.g., P. cubensis on cucurbits or P. humili on hops; Pseudopezicula trakeiphila on grapes tracheiphila (red fireworks or "Rottbrenner", anamorph: Phialophora); Puccinia species (rusts) on various plants, for example P. triticina (brown rust or leaf rust), P. striiformis (stripe rust or yellow rust), P. hordei (dwarf rust), P. graminis (stem rust or black rust) or P. recondita (brown rust or leaf rust), P. kuehnii (orange rust) on sugarcane and P. asparagi on asparagus; Pyrenopeziza species, e.g. P. brassicae, on rapeseed; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia species, e.g. P.P. oryzae (teleomorph: Magnaporthe grisea: rice blast) and P. grisea in turfgrass and cereals; Pythium spp. (seedling damping-off) in turfgrass, rice, corn, wheat, cotton, rapeseed, sunflower, soybean, sugar beet, vegetables, and various other plants (e.g., P. ultimum or P. aphanidermatum) and P. oligandrum in mushrooms; Ramularia spp. spp., e.g. R. collo-cygni (Ramuraria leaf spot, physiological leaf spot) in barley, R. areola (teleomorph: Mycosphaerella areola) in cotton and R. beticola in sugar beet; Rhizoctonia spp. in cotton, rice, potato, turfgrass, maize, rapeseed, potato, sugar beet, vegetables and various other plants. spp., such as R. solani (root and stem rot) in soybean, R. solani (sheath blight) in rice or R. cerealis (Rhizoctonia spring blight) in wheat or barley; Rhizopus stolonifer (black mold, soft rot) in strawberries, carrots, cabbage, grapes and tomatoes; Rhynchosporium secalis and R. commune (fire blight) in barley, rye and triticale; Sarocladium oryzae in rice. oryzae and S. attenuatum (pod rot); Sclerotinia spp. (stem rot or white mold) in vegetables (S. minor and S. sclerotiorum) and field crops, e.g., rapeseed, sunflower (e.g., S.S. sclerotiorum and soybean, S. rolfsii (syn. Athelia rolfsii) on soybean, peanut, vegetables, maize, cereals, and ornamentals; Septoria spp. on various plants, e.g., S. glycines (brown spot) on soybean, S. tritici (syn. Zymoseptoria tritici, Septoria leaf spot) on wheat, and S. (syn. Stagonospora) nodorum (Stagonospora leaf spot) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on grapes. tuckeri); Setosphaeria spp. (black leaf blight) on maize (e.g., S. turcicum, synonymous with Helminthosporium turcicum) and on turfgrass; Sphacelotheca spp. (sooty mildew) on maize (e.g., S. reiliana, synonymous with Ustilago reiliana: smut), Sphacelotheca spp. (sooty mildew) on sorghum and sugarcane; Sphaerotheca fuliginea on cucurbits (synonymous with Podosphaera xanthii: powdery mildew); Spongosphaera subbrellanea on potato subterranea (powdery scab) and the viral diseases transmitted by it; Stagonospora spp. in cereals, e.g., S. nodorum in wheat;nodorum (Stagonospora leaf spot, teleomorph: Leptosphaeria [synonym: Phaeosphaeria] nodorum, synonym: Septoria nodorum); Synchytrium endobioticum (potato wart) on potato; Taphrina spp., e.g., T. deformans (leaf curl) on peach and T. pruni (pocket plum) on plum; Thielaviopsis spp. (black root) on tobacco, pome fruit, vegetables, soybeans, and cotton. rot), e.g., T. basicola (syn. Chalara elegans); Tilletia spp. (common or smut) on cereals, e.g., T. tritici (syn., T. caries, net smut) and T. controversa (stunt smut) on wheat; Trichoderma harzianum on mushrooms; Typhula incarnata (gray snow mold) on barley or wheat; Urocystis spp., e.g., U. occulta (striped sooty mold) on rye; Uromyces spp. on vegetables. spp.) (rusts), for example on bean (e.g. U. appendiculatus, synonymous with U. phaseoli), on sugar beet (e.g. U. betae or U. beticola) and legumes (e.g. U. vignae, U. pisi, U. viciae-fabae and U. fabae); Ustilago spp. spp. (naked smut) in cereals (e.g., U. nuda and U. avaenae), in maize (e.g., U. maydis; maize sooty mildew) and in sugarcane; Venturia spp. (black scab) in apples (e.g., V. inaequalis) and in pears; and Verticillium spp. (damage) in various plants, such as fruit and ornamental plants, grapes, soft fruits, vegetables and field crops, for example, V. longisporum in rapeseed, V. dahliae in strawberry, rapeseed and potato.The compounds I and compositions thereof are particularly suitable for controlling the causes of the following plant diseases, respectively: rusts (from the order Puccinales) in various plants, preferably rusts in soybeans and cereals, more preferably Phakopsora pachyrhizi and P. meibomiae causing Asian soybean rust in soybeans, Puccinia graminis causing stem or black rust in cereals, graminis, P. triticina (synonymous with P. recondita), which causes wheat leaf rust or leaf rust, P. striiformis, which causes wheat yellow rust or stripe rust, P. hordei, which causes barley leaf rust, P. sorghi, which causes common corn rust, and P. polysora, which causes southern corn leaf rust.

[0262] The present invention therefore also relates to a method for treating phytopathogenic rust fungi (from the order Puccinales), comprising curatively and / or preventively treating infected plants, plants at risk of lesions caused by said phytopathogenic rust fungi, and / or applying to said phytopathogenic fungi an agrochemical composition comprising at least one compound of formula I at a dosage rate of 50 to 200 g per ha, more preferably in which the plants are selected from soybeans and cereals.

[0263] Furthermore, compound I and its compositions are particularly suitable for controlling other causative agents of plant diseases caused by plant pathogenic fungi, at least a portion of whose populations have acquired the F129L mutation in the cytochrome b gene, which confers resistance to Qo inhibitors. Alternaria solani causes late blight in nightshade plants (Solanaceae), Pyrenophora teres causes barley net blotch, Pyrenophora tritici-repentis causes yellow spot, yellow leaf spot, yellow leaf blight, or helminthosporiosis in cereals, and Rhizoctonia solani causes various plant diseases, such as root rot, damping-off, and stem blight in various plants.

[0264] Furthermore, the compounds I and their compositions are particularly suitable for controlling the causes of the following plant diseases, respectively: fungal diseases on specialty crops, soybeans, rapeseed and sunflowers (e.g. Botrytis cinerea on strawberries and grapes, Sclerotinia sclerotiorum, S. minor and S. rolfsii on rapeseed, sunflower and soybeans); Fusarium diseases on cereals (e.g. Fusarium culmorum and F. graminearum on wheat); downy mildew on specialty crops (e.g. Plasmopara viticola on grapes, Phytophthora infestans on potatoes). infestans); powdery mildews on specialty crops and cereals (e.g., Uncinula necator on grapes, Erysiphe spp. on various specialty crops, Blumeria graminis on cereals); leaf spot diseases on cereals, soybeans and maize (e.g., Septoria tritici and S. nodorum on cereals, S. glycines on soybeans, Cercospora spp. on maize and soybeans).

[0265] It has been observed that populations of plant pathogenic fungi consisting of apparently non-resistant strains can easily develop resistance. The compounds can be applied under such conditions to prevent the development of resistance and the spread of resistant strains altogether. In this regard, it is useful that they also have strong activity against non-resistant plant pathogenic fungi.

[0266] Fungicide-resistant strains of various plant pathogens have been reported, and strains resistant to one or more fungicides of various modes of action have been observed through target-site mutations in the genes of respective proteins (e.g., QoI (C3, according to the FRAC convention; see www.frac.info for details), quinone external stigmatellin-binding subsite inhibitors (QoSI; C8), and quinone internal inhibitors (QiI; C4): CytB target proteins; sterol demethylation (DMI; G1): Cyp51 / Erg11; carboxylic acid amides (CAA; H5): CesA3; SDHI (C2): SdhB, SdhC, and SdhD; dicarboximides (E3): Os-1 (including Bos1, Daf1, etc.); ketoreductase inhibitors (KRI; class III SBI; G3): Erg27; and oxysterol-binding protein inhibitors (OSBPI; F9): ORP1).

[0267] Examples of mutation sites in genes encoding target proteins that result in the exchange, deletion, or insertion of a single amino acid in the target protein sequence that confers resistance to a particular fungicide are shown in Table M (see also Pest Manag Sci 72(8)2016:1449-1459).

[0268] [Table 40]

[0269] [Table 41]

[0270] [Table 42]

[0271] [Table 43]

[0272] [Table 44]

[0273] [Table 45]

[0274] Compound I is therefore particularly useful for controlling such fungicide-resistant strains of plant pathogenic fungi as set forth in Table M. Such strains may have one or more resistances resulting from one or more mutations in one or more genes encoding target proteins of various types of fungicides and / or resistance resulting from overexpression of the respective target proteins, including but not limited to the mutations listed in Table M.

[0275] Furthermore, certain strains may develop so-called multidrug resistance, ultimately resulting in widespread cross-resistance to many structurally and functionally unrelated compounds. "Multidrug resistance" (MDR), also known as "pleiotropic drug resistance" (PDR), describes a resistance phenomenon typically caused by the overexpression of specific membrane transporters, which results in increased activity of efflux pumps that extrude specific substrates, such as fungal toxins, as well as fungicidal compounds. Examples of such membrane transporters include ATP-binding cassette (ABC) transporters and major facilitator superfamily (MFS) transporters. Overexpression of membrane transporters can be confirmed, for example, by measuring the amount of the transporter protein or the corresponding mRNA. The measured amount of mRNA can be, for example, 2-fold, 5-fold, 20-fold, or even 100-fold or more relative to the mRNA amount of the corresponding fungicide-susceptible wild-type fungus.

[0276] Compound I of the present invention can be applied to control plant diseases caused by multidrug-resistant (MDR) fungi. Multidrug-resistant fungi may further have one or more resistances resulting from one or more mutations in one or more genes encoding target proteins of various types of fungicides and / or resistance resulting from overexpression of the target proteins, including, but not limited to, the mutations listed in Table M. Therefore, compound I is also particularly useful for controlling such multidrug-resistant fungi.

[0277] According to another embodiment of the present invention, the present invention also relates to the use of compounds of formula I for combating plant pathogenic fungi containing mutations in the mitochondrial cytochrome b gene that confer resistance to Qo inhibitors. According to a further embodiment of the present invention, the present invention also relates to a method for combating plant pathogenic fungi containing mutations in the mitochondrial cytochrome b gene that confer resistance to Qo inhibitors, comprising treating plant pathogenic fungi containing mutations in the mitochondrial cytochrome b gene that confer resistance to Qo inhibitors or material, plants, soil or seeds at risk of disease caused by plant pathogenic fungi containing mutations in the mitochondrial cytochrome b gene that confer resistance to Qo inhibitors with an effective amount of at least one compound I or a composition comprising same.

[0278] The term "phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene that confers resistance to Qo inhibitors" is understood to mean that at least 10% of the fungal isolates to be controlled contain a mutation in the mitochondrial cytochrome b gene that confers resistance to Qo inhibitors, more preferably at least 30%, even more preferably at least 50%, most preferably at least 75%, and especially 90-100%.

[0279] It has been observed that under field conditions, populations of plant pathogenic fungi consisting of apparently non-resistant strains can easily develop resistance. The compounds can also be applied under such conditions to prevent the development of resistance and the spread of resistant strains altogether. In this regard, it is useful that they also have strong activity against non-resistant plant pathogenic fungi.

[0280] According to another embodiment, a method for combating plant pathogenic fungi comprises: a) identifying material, plants, soil or seeds at risk of lesions caused by plant pathogenic fungi containing a mutation in a mitochondrial cytochrome b gene that confers resistance to a Qo inhibitor, or a plant pathogenic fungus as defined herein; and b) treating the fungus or material, plants, soil or seeds with an effective amount of at least one compound I or a composition comprising same.

[0281] According to another embodiment, the present invention also relates to a method for combating plant pathogenic fungi containing a mutation in the mitochondrial cytochrome b gene that confers resistance to Qo inhibitors, the method comprising treating material, plants, soil or seeds at risk of being affected by plant pathogenic fungi, in which at least 10% of the plant pathogenic fungi contain a mutation in the mitochondrial cytochrome b gene that confers resistance to Qo inhibitors, or plant pathogenic fungi contain a mutation in the mitochondrial cytochrome b gene that confers resistance to Qo inhibitors, with an effective amount of at least one compound I or a composition comprising same, wherein more preferably at least 30%, even more preferably at least 50%, and most preferably at least 75% of the fungi contain a mutation in the mitochondrial cytochrome b gene that confers resistance to Qo inhibitors.

[0282] According to one embodiment of the uses and methods for combating plant pathogenic fungi containing a mutation in the mitochondrial cytochrome b gene that confers resistance to Qo inhibitors, the mutation in the mitochondrial cytochrome b gene of the plant pathogenic fungus is G143A.

[0283] The mutation G143A in the cytochrome b (cytb, also called cob) gene is intended to mean any substitution of the nucleotide in codon 143 encoding "G" (glycine, e.g., GGT, GGC, GGA or GGG) resulting in a codon encoding "A" (alanine, e.g., GCT, GCC, GCA or GCG), for example a substitution of the second nucleotide "G" in codon 143 of the cytochrome b gene for "C" (GGT to GCT), resulting in a single amino acid substitution of G (glycine) to A (alanine) at position 143 of the cytochrome b protein (Cytb) (G143A). In the present invention, the mutation G143A in the cytochrome b gene is understood to be a single amino acid substitution of G (glycine) to A (alanine) at position 143 of the cytochrome b protein (G143A).

[0284] According to further embodiments, plant pathogenic fungi comprising a mutation in the mitochondrial cytochrome b gene that confers resistance to Qo inhibitors, wherein the mutation in the mitochondrial cytochrome b gene of the plant pathogenic fungus is G143A, include Alternaria alternata, Blumeria graminis, Pyricularia oryzae (also known as Magnaporthe grisea), Septoria tritici (also known as Mycosphaerella graminicola), Mycosphaerella fijiensis, Venturia inaequalis, Pyrenophora teres, teres, Pyrenophora tritici-repentis and Plasmopara viticola, in particular Septoria tritici.

[0285] According to another embodiment of the uses and methods for combating plant pathogenic fungi containing a mutation in the mitochondrial cytochrome b gene that confers resistance to Qo inhibitors, the mutation in the mitochondrial cytochrome b gene of the plant pathogenic fungus is F129L.

[0286] The F129L mutation in the cytochrome b (cytb, also called cob) gene is intended to mean any 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), for example a substitution of the first nucleotide "T" in codon 129 of the cytochrome b gene for "C" (TTT to CTT), resulting in a single amino acid substitution of F (phenylalanine) to L (leucine) at position 129 of the cytochrome b protein (Cytb) (F129L). In the present invention, the mutation F129L in the cytochrome b gene is understood to be a single amino acid substitution of F (phenylalanine) to L (leucine) at position 129 of the cytochrome b protein (F129L).

[0287] For example, rust fungi, particularly soybean rust (Phakopsora pachyrhizi and Phakopsora meibomiae), as well as many other plant pathogenic fungi, such as fungi from the genera Alternaria, Pyrenophora, and Rhizoctonia, have acquired the F129L mutation in the cytochrome b gene, which confers resistance to Qo inhibitors. Preferred fungal species are Alternaria solani, Phakopsora pachyrhizi, Phakopsora meibromiae, Pyrenophora teres, Pyrenophora tritici-repentis and Rhizoctonia solani, in particular Phakopsora pachyrhizi.

[0288] In one aspect, the present invention relates to a method for protecting a plant susceptible to and / or under attack by a plant pathogenic fungus containing the amino acid substitution F129L in a mitochondrial cytochrome b protein that confers resistance to a Qo inhibitor, the method comprising applying to said plant at least one compound of formula I or a composition comprising at least one compound of formula I, treating plant propagation material of said plant with the compound, and / or applying to said plant pathogenic fungus.

[0289] According to another embodiment, a method for combating plant pathogenic fungi comprises: a) identifying plant pathogenic fungi or material, plant, soil or seeds at risk of lesions due to plant pathogenic fungi as defined herein, containing the substitution F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors; and b) treating the fungi or material, plant, soil or plant propagation material with an effective amount of at least one compound of formula I or a composition comprising same.

[0290] The term "plant pathogenic fungal amino acid substitution F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors" is understood to mean that at least 10% of the fungal isolates to be controlled contain the F129L substitution in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors, preferably at least 30%, more preferably at least 50%, even more preferably at least 75% of the fungi, most preferably 90-100%, in particular 95-100%.

[0291] The compounds I and their compositions are also suitable for controlling harmful microorganisms in the protection of stored products or harvests and in the protection of materials, respectively.

[0292] The term "stored products or harvested goods" is understood to mean natural substances of plant or animal origin and their processed forms for which long-term protection is desired. Stored products of plant origin, such as stems, leaves, tubers, seeds, fruits, or grains, can be protected in their freshly harvested state or in processed forms such as pre-drying, wetting, crushing, pulverizing, pressing, roasting, etc., processes also known as post-harvest treatment. Also falling within the definition of stored products is wood in the form of rough lumber, such as construction timber, electricity transmission towers, and barriers, or in the form of finished products, such as furniture or objects made of wood. Stored products of animal origin include hides, leather, fur, hair, etc. Preferably, "stored products" is understood to mean natural substances of plant origin and their processed forms, more preferably fruits and their processed forms, such as fruits, stone fruits, soft fruits, and citrus fruits, and their processed forms, and application of compound I and its compositions can also prevent adverse effects such as decay, discoloration, or mold.

[0293] The term "protection of materials" is understood to mean the protection of technical and non-biological materials, such as adhesives, glues, wood, paper, paperboard, textiles, leather, paint dispersions, plastics, cooling lubricants, fibers or fabrics, from infestation and destruction by harmful microorganisms, such as fungi and bacteria.

[0294] When used in the protection of materials or stored products, the application rate of the active substance depends on the type of application area and the desired effect. Customary application rates in the protection of materials are from 0.001 g to 2 kg, preferably from 0.005 g to 1 kg, of active substance per cubic meter of treated material.

[0295] Compound I and its compositions can each be used to improve plant health. The present invention also relates to a method for improving plant health by treating a plant, its propagation material, and / or a locus where the plant is growing or intended to grow with an effective amount of Compound I and its compositions, respectively.

[0296] The term "plant health" is understood to refer to the state of a plant and / or its products, determined by several indicators, alone or in combination with each other, such as yield (e.g., increased biomass and / or increased content of useful substances), plant vigor (e.g., improved plant growth and / or increased leaf greenness ("greening effect")), quality (e.g., improved content or composition of certain substances) and resistance to abiotic and / or biotic stress. The above-identified indicators of plant health may be interdependent and may affect each other's results.

[0297] Compound I is applied as is or in the form of a composition by treating fungi, plants, plant propagation materials such as seeds, soil, surfaces, materials, or rooms to be protected from fungal attack with a fungicidally effective amount of the active substance. Application can be carried out both before and after infection of plants, plant propagation materials such as seeds, soil, surfaces, materials, or rooms with fungi.

[0298] The pesticide composition comprises a fungicidally effective amount of Compound I. The term "fungicidally effective amount" means an amount of the composition or Compound I sufficient to control harmful fungi on cultivated plants or to protect stored products or harvested materials or materials, and which does not cause substantial damage to the treated plants, treated stored products or harvested materials, 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 products, harvested materials, or materials to be treated, climatic conditions, and the particular Compound I used.

[0299] Plant propagation material can be treated either at the time of planting or transplanting or before with Compound I on its own or prophylactically with a composition comprising at least one Compound I.

[0300] When used for plant protection, the amount of active substance applied is, depending on the type of effect desired, 0.001 to 2 kg / ha, preferably 0.005 to 2 kg / ha, more preferably 0.05 to 0.9 kg / ha, in particular 0.1 to 0.75 kg / ha.

[0301] For example, the treatment of plant propagation material such as seeds by dusting, coating or drenching generally requires an amount of active substance of 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).

[0302] The user typically applies the pesticide composition from a pre-dosed device, backpack sprayer, spray tank, spray plane, or irrigation system. The pesticide composition is typically made up to the desired application concentration with water, buffers, and / or further adjuvants, thus providing a ready-to-use spray solution or pesticide composition according to the invention. Typically, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray solution are applied per hectare of agriculturally useful area.

[0303] Compound I and compositions containing them can be applied in combination with or by utilizing smart agriculture technologies, such as precision agriculture, remote and near-field imaging and image recognition, or smart agricultural field management programs. Such technologies typically include models (such as computer programs) that support users by taking into account information from various sources, improving crop quality and yield, reducing pest damage, including predicting pest pressure and intelligently applying crop protection products, ensuring environmental protection, supporting fast and reliable agricultural decision-making, reducing the use of fertilizers and crop protection products, reducing product residues in consumables, improving the spatial and temporal accuracy of agricultural measurements, automating processes, and enabling measurement traceability. Commercially available systems that include agricultural models include, for example, FieldScripts™ (The Climate Corporation), Xarvio™ (BASF), and AGLogic™ (John Deere).

[0304] Compound I, its N-oxides and salts can be converted into pesticide compositions of the customary types, such as solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules and mixtures. Examples of composition types (see "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6) are given. th(Ed. May 2008, CropLife International) 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, lozenges, wettable powders or dusts (e.g., WP, SP, WS, DP, DS), presses (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 seedlings, such as seeds. The compositions are prepared by known methods, for example, as described by Mollet and Grubemann, "Formulation technology," Wiley VCH, Weinheim, 2001, or Knowles, "New developments in crop protection product formulation," Agrow Reports DS243, T&F Informa, London, 2005. The present invention also relates to agrochemical compositions comprising an adjuvant and at least one compound I.

[0305] Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners, moisturizing agents, repellents, attractants, feeding stimulants, compatibilizers, bactericides, antifreeze agents, antifoaming agents, colorants, tackifiers and binders.

[0306] Suitable solvents and liquid carriers are water and organic solvents, such as medium to high boiling mineral oil fractions, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, paraffin, tetrahydronaphthalene and alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactate esters, carbonate esters, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamide and mixtures thereof.

[0307] Suitable solid carriers or fillers are mineral earths such as silicates, silica gel, talc, kaolin, limestone, lime, chalk, clay, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides such as cellulose, starch; fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; products of plant origin such as grain meal, bark meal, wood meal, nut meal and mixtures thereof.

[0308] Suitable surfactants are surface-active compounds such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifiers, dispersants, solubilizers, wetting agents, penetration enhancers, protective colloids, or adjuvants. Examples of surfactants are listed in McCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Edition or North American Edition).

[0309] Suitable anionic surfactants are alkali salts, alkaline earth salts, or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates include alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl and tridecylbenzenes, sulfonates of naphthalene and alkylnaphthalenes, sulfosuccinates, or sulfosuccinamates. Examples of sulfates include sulfates of fatty acids, oils, ethoxylated alkylphenols, alcohols, ethoxylated alcohols, or fatty acid esters. Examples of phosphates include phosphoric acid esters. Examples of carboxylates include alkyl carboxylates and carboxylated alcohol or alkylphenol ethoxylates.

[0310] Suitable nonionic surfactants include alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates include compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids, or fatty acid esters, alkoxylated with 1 to 50 equivalents. Ethylene oxide and / or propylene oxide, preferably ethylene oxide, can be used for the alkoxylation. Examples of N-substituted fatty acid amides include fatty acid glucamides or fatty acid alkanolamides. Examples of esters include fatty acid esters, glycerol esters, or monoglycerides. Examples of sugar-based surfactants include sorbitan, ethoxylated sorbitan, sucrose and glucose esters, or alkyl polyglucosides. Examples of polymeric surfactants include homopolymers or copolymers of vinylpyrrolidone, vinyl alcohol, or vinyl acetate.

[0311] Suitable cationic surfactants are quaternary surfactants, such as quaternary ammonium compounds with one or two hydrophobic groups or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetaines and imidazolines. Suitable block polymers are AB or ABA type block polymers containing polyethylene oxide and polypropylene oxide blocks, or ABC type block polymers containing alkanol, polyethylene oxide, and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are polyacrylic acid or alkali salts of polyacid comb polymers. Examples of polyhydric bases are polyvinylamine or polyethyleneamine.

[0312] Suitable adjuvants are compounds that have negligible or even no pesticidal activity themselves but enhance the biological performance of Compound I on the target. Examples include surfactants, mineral or vegetable oils, and other adjuvants listed in Knowles, Adjuvants and Additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5. Suitable thickeners are polysaccharides (e.g., xanthan gum, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates. Suitable fungicides are bronopol and isothiazolinone derivatives, such as alkylisothiazolinone and benzisothiazolinone. Suitable antifreeze agents are ethylene glycol, propylene glycol, urea, and glycerin. Suitable antifoaming agents are silicones, long-chain alcohols, and salts of fatty acids. Suitable colorants (e.g., red, blue, or green) are low-water-soluble pigments and water-soluble dyes. Examples are inorganic colorants (e.g., iron oxide, titanium oxide, ferricyanide) and organic colorants (e.g., alizarin-, azo- and phthalocyanine colorants). Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylates, biological or synthetic waxes and cellulose ethers.

[0313] The agrochemical composition generally contains 0.01 to 95% by weight, preferably 0.1 to 90% by weight, more preferably 1 to 70% by weight, and in particular 10 to 60% by weight of an active substance (e.g., at least one compound I). The agrochemical composition generally contains 5 to 99.9% by weight, preferably 10 to 99.9% by weight, more preferably 30 to 99% by weight, and in particular 40 to 90% by weight of at least one adjuvant. The active substance (e.g., compound I) is used at a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectroscopy).

[0314] For the treatment of plant propagation materials, particularly seeds, liquid seed treatment formulations (LS), suspoemulsions (SE), flowable seed treatment formulations (FS), dry seed treatment powders (DS), wettable seed treatment slurries (WS), water-soluble seed treatment powders (SS), emulsions (ES), emulsifiable concentrates (EC), and gel formulations (GF) are usually used. The target compositions are diluted 2-10 times to give ready-to-use formulations with active substance concentrations of 0.01-60% by weight, preferably 0.1-40%. Application can be carried out before or during sowing. Methods for applying the compound I and its compositions to plant propagation materials, particularly seeds, include dressing, coating, pelleting, dusting, dipping, and in-seed application. Preferably, the compound of formula I or its compositions is applied to plant propagation materials in a manner that does not induce germination, such as by seed dressing, pelleting, coating, or dusting.

[0315] Various types of oils, wetting agents, adjuvants, fertilizers or micronutrients and additional pesticides (e.g., fungicides, growth regulators, herbicides, insecticides, safeners) may be added to compound I or its compositions as a premix or may not be added until just before use (tank mix). These agents may 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.

[0316] Pesticides are generally chemical or biological agents (such as pesticidal active ingredients, compounds, compositions, viruses, bacteria, antimicrobial agents, or fungicides) that deter, incapacitate, kill, or otherwise eliminate pests through their effects. Target pests include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microorganisms that destroy property, are a nuisance, spread disease, or transmit disease. The term "pesticide" also includes plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to fall from plants, usually to facilitate harvesting; desiccants that promote the drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for protection against specific pests; antidotes that reduce the undesirable herbicidal effects of pesticides on crop plants; and plant growth promoters that affect plant physiology, for example, to increase plant growth, biomass, yield, or any other quality parameter of the harvestable product of a crop plant.

[0317] Biopesticides are defined as forms of pesticides based on microorganisms (bacteria, fungi, viruses, nematodes, etc.) or natural products (compounds such as metabolites, proteins, or extracts from organisms or other natural sources) (US Environmental Protection Agency: http: / / www.epa.gov / pesticides / biopesticides / ). Biopesticides are divided into two main classes: microbial pesticides and biochemical pesticides: (1) Microbial pesticides consist of bacteria, fungi, or viruses (often containing metabolic products produced by bacteria and fungi). Entomopathogenic nematodes, which are multicellular, are also classified as microbial pesticides. (2) Biochemical pesticides are naturally occurring substances that control pests or provide other crop protection uses, as defined below, but which are relatively nontoxic to mammals.

[0318] The mixture of the compounds I in their fungicidal use form or compositions containing them with other fungicides often results in an expansion of the fungicidal spectrum of activity or in the prevention of the development of fungicide resistance. Furthermore, synergistic effects are often obtained (synergistic mixtures).

[0319] The following list of pesticides II that can be used in combination with compounds I is intended to illustrate, but not limit, the possible combinations: A) Respiratory inhibitors Q oInhibitors of complex III at the site (QoI, C3, FRAC convention; www.frac.info): azoxystrobin (A.1.1), coumetoxystrobin (A.1.2), coumoxystrobin (A.1.3), dimoxystrobin (A.1.4), enestrobulin (A.1.5), phenaminestrobin (A.1.6), fenoxystrobin / flufenoxystrobin (A.1.7), fluoxastrobin (A.1.8), kresoxim-methyl (A.1.9), mandestrobin (A.1.10), mexazoline (A.1.11), methionine (A.1.12), methionine (A.1.13), methionine (A.1.14), methionine (A.1.15), methionine (A.1.16), methionine (A.1.17), methionine (A.1.18), methionine (A.1.19), methionine (A.1.20), methionine (A.1.21), methionine (A.1.22), methionine (A.1.23), methionine (A.1.24), methionine (A.1.25), methionine (A.1.26), methionine (A.1.27), methionine (A.1.28), methionine (A.1.29), methionine (A.1.30), methionine (A.1.31), methionine (A.1.32), methionine (A.1.33), methionine (A.1.34), methionine (A.1.35), methionine (A.1.36), methionine (A.1.37), methionine (A.1.38), methionine (A.1.39), methionine Tominostrobin (A.1.11), orysastrobin (A.1.12), picoxystrobin (A.1.13), pyraclostrobin (A.1.14), pyrametostrobin (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), triclopiricarb / chlorozinecarb (A.1.20), famoxadone (A.1.21), fenamidone (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; member of MoA subgroup A), (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]-o 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), bifujunchi (A.1.37), 2-(ortho-((2,5-dimethylphenyl-oxymethylene)phenyl)-3-methoxy-acrylic acid methyl ester (A.1.38); Q iInhibitors of complex III at the site (QiI, C4): cyazofamid (A.2.1), amisulbrom (A.2.2), [(6S,7R,8R)-8-benzyl-3-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate (A.2.3), fenpicoxamide (A.2.4), florylpicoxamide (A.2.5), methallylpicoxamide (A.2.6); Inhibitors of complex II (SDHI, C2): 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), penflufenam (A.3.15), penthiopyrad (A.3.16), pydiflumetofen (A.3.17), pyraziflumide (A.3.18), sedaxane (A.3.19), tecloftalam (A.3.20), thifluzamide (A.3.21), inpirfluxam (A.3.22), pyrapropine (A.3.23), fluindapyr (A.3.28), N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-5-fluoro-1-methylpyrazole-4-carboxamide (A.3. 29), methyl (E)-2-[2-[(5-cyano-2-methylphenoxy)methyl]phenyl]-3-methoxy-2-propanoate (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-Dimethylindan-4-yl)pyridine-3-carboxamide (A.3.34), 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethylindan-4-yl]pyridine-3-carboxamide (A.3.35), 2-(difluoromethyl)-N-(1,1-dimethyl-3-propylindan-4-yl)pyridine-3-carboxamide (A.3.36), 2-(difluoromethyl)-N-[(3R)-1,1-dimethyl-3-propylindan-4-yl]pyridine-3-carboxamide (A.3.37).37) 2-(Difluoromethyl)-N-(3-isobutyl-1,1-dimethylindan-4-yl)pyridine-3-carboxamide (A.3.38), 2-(Difluoromethyl)-N-[(3R)-3-isobutyl-1,1-dimethylindan-4-yl]pyridine-3-carboxamide (A.3.39) cyclobutrifluram (A.3.24);. Other respiratory inhibitors: diflumetrim (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, e.g. fentin acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); silthiofam (A.4.11); ·Quinone external inhibitor stigmatellin binding type (QoSI; C8): ametoctrazine (A.5.1); B) Sterol biosynthesis inhibitors (SBI fungicides) C14 demethylase inhibitors (DMI, G1): Triazoles: Azaconazole (B.1.1), Bitertanol (B.1.2), Bromuconazole (B.1.3), Cyproconazole (B.1.4), Difenoconazole (B.1.5), Diniconazole (B.1.6), Diniconazole-M (B.1.7), Epoxiconazole (B.1.8), Fenbuconazole (B.1.9), Fluquinconazole (B.1.10), Flusilazole (B.1.11), Flutriafol (B.1.12), Hexaconazole (B.1.13), Imibenco nazole (B.1.14), ipconazole (B.1.15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), paclobutrazol (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), Niconazole (B.1.30), 2-(2,4-difluorophenyl)-1,1-difluoro-3-(tetrazol-1-yl)-1-[5-[4-(2,2,2-trifluoroethoxy)phenyl]-2-pyridyl]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), fluoxythioconazole (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-toluylmethyl)-1-(1,2,4-triazol-1-ylmethyl)cyclopentanol (B.1.43); Imidazoles: Imazalil (B.1.44), Pefurazoate (B.1.45), Prochloraz (B.1.46), Triflumizole (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), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propanoate methyl ester (B.1.56), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propanoate methyl ester (B.1.57); Delta-14 reductase inhibitors (G2): 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-ketoreductases: fenhexamid (B.3.1), fenpyrazamine (B.3.2); Other sterol biosynthesis inhibitors: chlorphenomizole (B.4.1); C) Nucleic acid synthesis inhibitors · RNA polymerase I inhibitors (A1): benalaxyl (C.1.1), benalaxyl-M (C.1.2), chiralaxyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (C.1.5), ofrace (C.1.6), oxadixyl (C.1.7); Other nucleic acid synthesis inhibitors (A2-A5): 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); DHODH inhibitors: ipflufenoquine (C.2.9), quinofumelin (C.2.10); D) inhibitors of cell division and the cytoskeleton Tubulin polymerization inhibitors (MBC, B1): 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), 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]-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 (B2-B7): diethofencarb (D.2.1), ethaboxam (D.2.2), pencycuron (D.2.3), fluopicolide (D.2.4), zoxamide (D.2.5), metrafenone (D.2.6), pyriophenone (D.2.7), fenamacryl (D.2.8), fluopimomide (D.2.9); E) Amino acid and protein synthesis inhibitors · Methionine synthesis inhibitors (D1): cyprodinil (E.1.1), mepanipyrim (E.1.2), pyrimethanil (E.1.3); Protein synthesis inhibitors (D2-D5): 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 (E2 and E3): iprodione (F.1.2), procymidone (F.1.3), vinclozolin (F.1.4), fludioxonil (F.1.5); · Unknown mechanism (E1): quinoxyfen (F.2.1), proquinazid (F.2.2); G) Lipid and membrane synthesis inhibitors · Phospholipid biosynthesis inhibitors (F2): edifenphos (G.1.1), iprobenfos (G.1.2), pyrazophos (G.1.3), isoprothiolane (G.1.4); Lipid peroxidation (F3): 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); Compounds affecting cell membrane permeability and fatty acids (F4): propamocarb (G.4.1); Oxysterol-binding protein inhibitors (OSBPI, F9): 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.5.6), 4-[1-[2-[5-cyclopropyl-3-(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.7), Larin-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 (M01, M02): 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 (M03): 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), zinc thiazole (H.2.10); · Organic chlorine compounds (M04, M05, M06, M08): 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 (M07, M09, M10; M11, M12): 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 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), Fluorimide (H.4.11), Metasulfocarb (H.4.12), Chinomethionate (H.4.13); I) Cell wall synthesis inhibitors Inhibitors of glucan synthesis: validamycin (I.1.1); Chitin synthase inhibitors (H4): polyoxin B (I.1.2); Melanin synthesis inhibitors (I1-I3): trihydroxynaphthalene reductase inhibitors (MBI-R; I1), pyroquilon (I.2.1), tricyclazole (I.2.2); dehydratase inhibitors (MBI-D, I2); carpropamid (I.2.3), dicyclomet (I.2.4), fenoxanil (I.2.5); polyketide synthase inhibitors (MBI-P, I3): tolprocarb (I.2.6); Cellulose synthase inhibitors (H5): dimethomorph (I.3.1), flumorph (I.3.2), mandipropamid (I.3.3), pyrimorph (I.3.4), benthiavalicarb (I.3.5), iprovalicarb (I.3.6), valifenalate (I.3.7); J) Plant defense inducers (P1-P8) Acibenzolar-S-methyl (J.1.1), probenazole (J.1.2), isotianil (J.1.3), tiadinil (J.1.4), prohexadione calcium salt (J.1.5); phosphonates: fosetyl (J.1.6), fosetylaluminium (J.1.7), phosphorous acid and its salts (J.1.8), potassium bicarbonate or sodium carbonate (J.1.9), 4-cyclopropyl-N-(2,4-dimethoxyphenyl)thiadiazole-5-carboxamide (J.1.10), calcium phosphonate (J.1.11), potassium phosphonate (J.1.12), diclobentiazox (J.1.13); K) Unknown mechanism of action (U, unknown) Bronopol (K.1.1), cyflufenamid (K.1.3), cymoxanil (K.1.4), dazomet (K.1.5), debacarb (K.1.6), diclomedine (K.1.8), difenzoquat (K.1.9), difenzoquat methylsulfate (K.1.10), diphenylamine (K.1.11), fenitropan (K.1.12), flumetobir (K.1.14), flumethylsulfolim (K.1.60), flusulfamide (K.1.15), flutianil (K.1.16), harpin (K.1.1 7), nitrapyrin (K.1.19), nitrosalisopropyl (K.1.20), copper oxine (K.1.22), seboxylamine (K.1.61), tebufloquine (K.1.24), tecloftalam (K.1.25), triazoxide (K.1.26), N'-(4-(4-chloro-3-trifluoromethylphenoxy)-2,5-dimethylphenyl)-N-ethyl-N-methylformamidine (K.1.27), N'-(4-(4-fluoro-3-trifluoromethylphenoxy)-2,5-dimethylphenyl)-N -Ethyl-N-methylformamidine (K.1.28), N'-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethylphenyl]-N-ethyl-N-methylformamidine (K.1.29), N'-(5-bromo-6-indan-2-yloxy-2-methyl-3-pyridyl)-N-ethyl-N-methylformamidine (K.1.30), N'-[5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methyl-3-pyridyl]-N -ethyl-N-methylformamidine (K.1.31), N'-[5-bromo-6-(4-isopropylcyclohexoxy)-2-methyl-3-pyridyl]-N-ethyl-N-methylformamidine (K.1.32), N'-[5-bromo-2-methyl-6-(1-phenylethoxy)-3-pyridyl]-N-ethyl-N-methylformamidine (K.1.33), N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanylpropoxy)phenyl)-N-ethyl-N-methylformamidine (K.1.34), N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanylpropoxy)phenyl)-N-ethyl-N-methylformamidine (K.1.35), 2-(4-chlorophenyl)-N-[4-(3,4-dimethoxyphenyl)-isoxazol-5-yl]-2-prop-2-ynyloxyacetamide (K.1.36), 3-[5-(4-chlorophenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (pyrisoxazole) (K.1.37), 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidine-3-yl]-pyridine (pyrisoxazole) (K.1.38), [6-[[(Z)-[(1-methyltetrazol-5-yl)-phenylmethylene]amino]oxymethyl]-2-pyridyl]carbamate (K.1.42), but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenylmethylene]amino]oxymethyl]-2-pyridyl]carbamate (K.1.43), 5-chloro-1-(4,6-dimethoxypyrimidin-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)-phenylmethylene]amino]oxymethyl]-2-pyridyl]carbamate (K.1.42), but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenylmethylene]amino]oxymethyl]-2-pyridyl]carbamate (K.1.43). N-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylformamidine (K.1.53), aminopyrifen (K.1.54), N'-[5-(4-methyl-2-pyridyl)-2-methyl-4-methyl-1-methyl-2-pyridyl]-benzothiazolinone (K.1.45), bromothalonil (K.1.46), 2-(6-benzyl-2-pyridyl)quinazoline (K.1.57), 2-[6-(3-fluoro-4-methoxyphenyl)-5-methyl-2-pyridyl]quinazoline (K.1.58), N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylformamidine (K.1.59), N'-[5-(4-methyl-2-pyridyl)-2-methyl-2-pyridyl]-benzothiazolinone (K.1.60), N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylformamidine (K.1.61), N'-(5-(4-methyl-2-pyridyl)-2-methyl-2-pyridyl)-benzothiazolinone (K.1.62), N'-(5-(4-methyl-2-pyridyl)-2-methyl-2-pyridyl)-benzothiazolinone (K.1.63), N'-(5-(4-methyl-2-pyridyl)-2-methyl-2-pyridyl)-benzothiazolinone (K.1.64), N'-(5-(4-methyl-2-pyridyl)-2-methyl-2-pyridyl)-benzothiazolinone (K.1.65), N'-(5-(4-methyl-2-pyridyl)-2-methyl-2-pyridyl)-benzothiazolinone (K.1.66), N'-( -Bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-ethyl-N-methylformamidine (K.1.56), N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethylphenyl]-N-ethyl-N-methylformamidine (K.1.57), flufenoxadiazam (K.1.58) [proposed MoA: class II histone deacetylase inhibitor], N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide (K.1.59).59), N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide (K.1.60; WO 2018 / 177894, WO 2020 / 212513), N-((4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl)methyl)propanamide (K.1.62), 3,3,3-trifluoro-N-[[3-fluoro-4-[5-(trifluoromethyl)-1, 2,4-Oxadiazol-3-yl]phenyl]methyl]propanamide (K.1.63), 3,3,3-trifluoro-N-[[2-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide (K.1.64), N-[2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl]butanamide (K.1.65), N-[[2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl]butanamide (K.1.66),

[0044] 1-Methoxy-1-methyl-3-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (K.1.67), 1,1-diethyl-3-[[4-[5-[trifluoromethyl]-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (K.1.68), N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide (K.1.69), N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide (K.1.70), 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (K.1.71), 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one (K.1.72), 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one (K.1.73), 4-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]morpholin-3-one (K.1.74), 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one (K.1.75), 2-[[4-[5-(trifluoromethyl)-1,2 ,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one (K.1.76), 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one (K.1.77), 3,3-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one (K.1.78), 2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl] phenyl]methyl]oxazinan-3-one (K.1.79), 1-[[3-fluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]azepan-2-one (K.1.80), 4,4-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one (K.1.81), 5-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one (K.1.82), ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate (K.1.83), N-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxamide (K.1.84), N,N-dimethyl-1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl]-1H-1,2,4-triazol-3-amine (K.1.85), N-methoxy-N-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxamide (K.1.86), propyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxamide (K.1.87), N-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole Allyl-4-carboxamide (K.1.88), N-allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide (K.1.89), 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (K.1.90), 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (K.1.10). .91), N-allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]acetamide (K.1.92), N-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl]cyclopropanecarboxamide (K.1.93), 1-methyl-3-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (K.1.94), N'-[2-chloro-4-(2-fluorophenyl)-2-methyl ... N'-[2-chloro-4-[(4-methoxyphenyl)methyl]-5-methylphenyl]-N-ethyl-N-methylformamidine (K.1.95), N'-[2-chloro-4-[(4-cyanophenyl)methyl]-5-methylphenyl]-N-ethyl-N-methylformamidine (K.1.96), N'-[2-chloro-4-[(4-cyanophenyl)methyl]-5-methylphenyl]-N-ethyl-N-methylformamidine (K.1.97), N'-[2,5-dimethyl-4-(o-tolylmethyl)phenyl]-N-ethyl-N-methylformamidine (K.1.98), 6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoroethyl]-5-methylpyridazine-4-carboxamide (K.1.99), 3-(3-bromo-2-fluorophenoxy)-6-chloro-N-[2-(2-chloro-4-methylphenyl)-2,2-difluoroethyl]-5-methylpyridazine-4-carboxamide (K.1.100), 6-chloro-N-[2-(2-chloro-4-methylphenyl)-2,2-difluoroethyl]-3-(3-cyclopropyl-2-fluorophenoxy)-5-methylpyridazine-4-carboxamide (K.1.101), 6-chloro-3. -(3-Cyclopropyl-2-fluorophenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoroethyl]-5-methylpyridazine-4-carboxamide (K.1.102), 6-chloro-3-(3-chloro-2-fluorophenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoroethyl]-5-methylpyridazine-4-carboxamide (K.1.103), N-[2-(2-bromo-4-methylphenyl)-2,2-difluoroethyl]-6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)-5-methylpyridazine-4-carboxamide (K.1.104); L) Biological pesticides L1) Microbial pesticides with fungicidal, bactericidal, virucidal and / or plant defense activator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. amyloliquefaciens subsp. plantarum ssp. plantarum (also known as B. velezensis), B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, B. velezensis, Candida oleophila, C. saitoana, Clavibacter michiganensis michiganensis (bacteriophage), Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonostachys rosea f.catenulate (also named Gliocladium catenulate), Gliocladium roseum, Lysobacter antibioticus, L. enzymogenes, Metschnikowia fructicola, Microdochium dimerum, Microsphaeropsis ochracea, Muscodor albus, Paenibacillus alvei, Paenibacillus epiphyticus, P. polymyxa, Pantoea bagans vagans, Penicillium bilaiae, Phlebiopsis gigantea, Pseudomonas sp., Pseudomonas chloraphis, Pseudozyma flocculosa, Pichia anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces griseoviridis, S. lydicus, S. violaceusniger, Talaromyces flavus flavus), Trichoderma asperelloides, T. asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum, T.T. harzianum, T. polysporum, T. stromaticum, T. virens, T. viride, Typhula phacorrhiza, Ulocladium oudemansii, Verticillium dahlia, Zucchini yellow mosaic virus (non-virulent strain); L2) Biochemical pesticides with fungicidal, bactericidal, virucidal and / or plant defense activator activity: harpin protein, Reynoutria sachalinensis extract; L3) Microbial pesticides with insecticidal, acaricidal, molluscicidal and / or nematicidal activity: Agrobacterium radiobacter, Bacillus cereus, B. firmus, B. thuringiensis, B. thuringiensis ssp. aizawai, Bt ssp. israelensis, Bt ssp. galleriae, Bt ssp. kurstaki, Bt ssp. tenebrionis, Beauveria bassiana bassiana, B. bronniartii, Burkholderia spp., Chromobacterium subtsugae, Cydia pomonella granulovirus (CpGV), Cryptophlebia leucotreta granulovirus (CrleGV), Flavobacterium spp., Helicoverpa armigera nucleopolyhedrovirus (HearNPV), Helicoverpa zea nucleopolyhedrovirus (HearNPV), Helicoverpa zea nucleopolyhedrovirus (HearNPV), Helicoverpa zea nucleopolyhedrovirus (HearNPV), Helicoverpa zea granulovirus (HearNPV), Helicoverpa pomonella granulo ... nucleopolyhedrovirus (HzNPV), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV), Heterorhabditis bacteriophora, Isaria fumosorosea, Lecanicillium longisporum, L. muscarium (L.muscarium, Metarhizium anisopliae, M. anisopliae var. anisopliae, M. anisopliae var. acridum, Nomuraea rileyi, Paecilomyces fumosoroseus, P. lilacinus, Paenibacillus popilliae, Pasteuria spp. spp.), P. nishizawae, P. penetrans, P. ramosa, P. thornea, P. usgae, Pseudomonas fluorescens, Spodoptera littoralis nucleopolyhedrovirus (SpliNPV), Steinernema carpocapsae, S. feltiae, S. kraussei, Streptomyces galbus, and S. microflavus; L4) Biochemical pesticides having insecticidal, acaricidal, molluscicidal, pheromone and / or nematicidal activity; L-carvone, citral, (E,Z)-7,9-dodecadien-1-yl acetate, ethyl formate, (E,Z)-2,4-decadienoic acid ethyl (pear ester), (Z,Z,E)-7,11,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, cis-jasmone, 2-methyl-1-butanol, methyl eugenol, methyl jasmonate, (E,Z)-2,13 -Octadecadien-1-ol, (E,Z)-2,13-octadecadien-1-ol acetate, (E,Z)-3,13-octadecadien-1-ol, (R)-1-octen-3-ol, pentatemanone, (E,Z,Z)-3,8,11-tetradecatrienyl acetate, (Z,E)-9,12-tetradecadien-1-yl acetate, (Z)-7-tetradecen-2-one, (Z)-9-tetradecen-1-yl acetate, (Z)-11-tetradecenal, (Z)-11-tetradecen-1-ol, Chenopodium ambrosiodes extract; neem oil, Quillaya extract; L5) Microbial pesticides with plant stress reduction activity, plant growth regulator activity, plant growth promoting activity and / or yield enhancing activity: Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium spp., B. elkanii, B. japonicum, B. liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices intraradices, Mesorhizobium spp., Rhizobium leguminosarum bv. phaseoli, Rlbv. trifolii, Rlbv. viciae, R. tropici, Sinorhizobium meliloti; O) Insecticides from classes O.1 to O.29 O.1 Acetylcholinesterase (AChE) inhibitors: aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate, acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyphos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos / DDVP, dicrotophos, dimethoate, dimethicone Rubinphos, Disulfoton, EPN, Ethion, Ethoprophos, Famfur, Fenamiphos, Fenitrothion, Fenthion, Fosthiazate, Heptenophos, Imicyaphos, Isofenphos, Isopropyl O-(Methoxyaminothio-phosphoryl)salicylate, Isoxathion, Malathion, Mecarbam, Methamidophos, Methidathion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion, Parathion-methyl, Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimiphos-methyl, Profenofos, Propetamphos, Prothiofos, Pyraclofos, Pyridaphenthion, Quinalphos, Sulfotep, Tebupirimfos, Temephos, Terbufos, Tetrachlorvinphos, Thiometon, Triazophos, Trichlorfon, Vamidothion; O.2 GABA-gated chloride channel antagonists: endosulfan, chlordane, ethiprole, fipronil, flufiprole, pyrafluprole, pyriprole; O.3 Sodium channel modulators: acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, kappa-bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenba Relate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, taufluvalinate, halfenprox, heptafluthrin, imiprothrin, meperfluthrin, metofluthrin, monflufluorothrin, epsilonmonfluorothrin, permethrin, fenothrin, prallethrin, profluthrin, pyrethrins (pyrethrum), resmethrin, silafluofen, tefluthrin, kappa-tefluthrin, tetramethylfluthrin, tetramethrin, tralomethrin, transfluthrin, DDT, methoxychlor; O.4 Nicotinic acetylcholine receptor (nAChR) agonists: acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam; 4,5-dihydro-N-nitro-1-(2-oxiranylmethyl)-1H-imidazol-2-amine, (2E)-1-[(6-chloropyridin-3-yl)methyl]-N'-nitro-2-pentylidenehydrazinecarboximidamide; 1-[(6-chloropyridin-3-yl)methyl]-7-methyl-8-nitro-5-propoxy-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine; nicotine; sulfoxaflor, flupyradifurone, triflumezopyrim, phenmezodithiaz, flupirimine; O.5 Nicotinic acetylcholine receptor allosteric activators: spinosad, spinetoram; O.6 Chloride channel activators: abamectin, emamectin benzoate, ivermectin, lepimectin, milbemectin; O.7 Juvenile hormone mimetics: hydroprene, kinoprene, methoprene; fenoxycarb, pyriproxyfen; O.8 Various nonspecific (multi-site) inhibitors: methyl bromide and other alkyl halides; chloropicrin, sulfuryl fluoride, borax, tartar emetic; O.9 Chordotonal organ TRPV channel modulators: afidopiropene, pymetrozine, pyrifluquinazone; O.10 Mite growth inhibitors: Clofentezine, hexythiazox, diflobidazine; etoxazole; O.11 Microbial-derived insect midgut membrane disruptors: Bacillus thuringiensis, B. sphaericus, and the insecticidal proteins they produce: Bacillus thuringiensis subsp. Israelensis, B. sphaericus, B. thuringiensis subsp. aizawai, B. thuringiensis subsp. Kurstaki, B. thuringiensis subsp. tenebrionis subsp. Tenebrionis), proteins found in Bt crops: Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34 / 35Ab1; O.12 Mitochondrial ATP synthase inhibitors: diafenthiuron; azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon; O.13 Oxidative phosphorylation uncouplers via disruption of the proton gradient: chlorfenapyr, DNOC, sulfluramide; O.14 Nicotinic acetylcholine receptor (nAChR) channel blockers: bensultap, cartap hydrochloride, thiocyclam, thiosultap sodium salt; O.15 Chitin biosynthesis inhibitors, type 0: bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron; O.16 Chitin biosynthesis inhibitors, type 1: buprofezin; O.17 Molting inhibitors: cyromazine; O.18 Ecdysone receptor agonists: methoxyfenozide, tebufenozide, halofenozide, fufenozide, chromafenozide; O.19 Octopamine receptor agonists: Amitraz; O.20 Mitochondrial electron transport chain complex III inhibitors: hydramethylnon, acequinocyl, fluacrylpyrim, bifenazate; O.21 Mitochondrial electron transport chain complex I inhibitors: fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad, rotenone; O.22 Voltage-dependent sodium channel blockers: indoxacarb, metaflumizone, 2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydrazinecarboxamide, N-(3-chloro-2-methylphenyl)-2-[(4-chlorophenyl)-[4-[methyl(methylsulfonyl)amino]phenyl]methylene]-hydrazine hydrazinecarboxamide, N-[4-chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-1H-pyrazole-5-carboxamide, 2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydrazinecarboxamide; O.23 Acetyl-CoA carboxylase inhibitors: spirodiclofen, spiromesifen, spirotetramat, spiropydione, spirobudifen, 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1,4-dioxa-9-azadispiro[4.2.4.2]tetradec-11-en-10-one, spidoxamat; O.24 Mitochondrial electron transport chain complex IV inhibitors: aluminum phosphide, calcium phosphide, phosphine, zinc phosphide, cyanide: O.25 Mitochondrial electron transport chain complex II inhibitors: cyenopyrafen, cyflumetofen, sietopyrafen, piflubumid; O.28 Ryanodine receptor modulators: chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide, fluchlodiniliprole, (R)-3-chloro-N1-{2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}-N2-(1-methyl-2-methylsulfonylethyl)phthalamide, (S)-3-chloro-N1-{2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}-N 2-(1-Methyl-2-methylsulfonylethyl)phthalamide, methyl-2-[3,5-dibromo-2-({[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)benzoyl]-1,2-dimethylhydrazinecarboxylate; N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; N-[4-chloro-2-[(diethyl-lambda-4 N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide;3-chloro-1-(3-chloro-2-pyridinyl)-N-[2,4-dichloro-6-[[(1-cyano-1-methylethyl)amino]carbonyl]phenyl]-1H-pyrazole -5-carboxamide;Tetrachlorantraniliprole;Tetraniliprole;Thiolanthraniliprole;N-[4-chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-1H-pyrazole-5-carboxamide;Cyhalodiamide;N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide; O.29 Chordotonal organ modulators: flonicamide; O.30 GABA-gated chloride ion channel allosteric modulators: broflanilide, fluxametamide, isocycloceram; O.33 Calcium-activated potassium channel modulators: acinonapir; O.34 Inhibitors at the Qi site of mitochondrial electron transport chain complex III: flometoquine; O.UN Insecticidal compounds with unknown or unclear mechanism of action: afoxolaner, azadirachtin, amidoflumet, benzoximate, bromopropylate, chinomethionate, cryolite, cyprofuranilide, dichloromezothiaz, dicofol, dinpropylidaz, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metaldehyde, metoxadiazone, piperonyl butoxide, pyridalyl, thioxazaphen, trifluenfuronate, umifoxolaner, 11-(4-chloro- 3-(4'-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4.5]dec-3-en-2-one, 4-cyano-N-[2-cyano-5-[[[2,6-dibromo-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]amino]carbonyl]phenyl]-2-methyl Benzamide, 4-cyano-3-[(4-cyano-2-methylbenzoyl)amino]-N-[2,6-dichloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]-2-fluorobenzamide, N-[5-[[[2-chloro-6-cyano-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]amino]carbonyl]-2-cyanophenyl]-4-cyano-2-methylbenzamide, N-[5-[[[2-bromo-6-chloro N-[5-[[[2-bromo-6-chloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]amino]carbonyl]-2-cyanophenyl]-4-cyano-2-methylbenzamide, 4-cyano-N-[2-cyano-5-[[[2,6-dichloro-4-[1,2,2,3,3,3-Hexafluoro-1-(trifluoromethyl)propyl]phenyl]amino]carbonyl]phenyl]-2-methylbenzamide, 1-[2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-1H-1,2,4-triazol-5-amine, N-[5-[[[2-bromo-6-chloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]amino]carbonyl]-2-cyanophenyl]-4-cyano-2-methylbenzamide, 4-cyano-N-[2-cyano-5-[[[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]amino]carbonyl]phenyl]-2-methylbenzamide (Bacillus firmus firmus) (Votivo, I-1582) based active substance); fluazaindolizine; 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1H-pyrazole; N-[5-[[2-bromo-6-chloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]carbamoyl]-2-cyanophenyl]-4-cyano-2-methylbenzamide; 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]carbamoyl]-2-cyanophenyl]-4-cyano-2-methylbenzamide 4-Cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]phenyl]-2-methylbenzamide;N-[5-[[2-bromo-6-chloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyanophenyl]-4-cyano-2-methylbenzamide;2-(1,3-Dioxan-2-yl)-6-[2-(3-pyridinyl)-5-thiazolyl]pyridine;2-[6-[2-(5-fluoro-3-pyridinyl)-5-thiazolyl]-2-pyridinyl]pyrimidine;2-[6-[2-(3-pyridinyl)-5-thiazolyl]-2-pyridinyl]pyrimidine;N-Methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide;N-Methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide;1-[(6-chloro-3-pyridinyl) 1-[(6-chloropyridin-3-yl)methyl]-7-methyl-8-nitro-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine;1-[(6-chloropyridin-3-yl)methyl]-7-methyl-8-nitro-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-5-ol;N-(3-chloro-2-methylphenyl)-2-[(4-chlorophenyl)[4-[methyl(methylsulfonyl)amino]phenyl]methylene]hydrazinecarboxamide;1-[(6-chloro-3-pyridinyl)methyl]-1,2,3,5,6, 7-Hexahydro-5-methoxy-7-methyl-8-nitroimidazo[1,2-a]pyridine;2-(3-pyridinyl)-N-(2-pyrimidinylmethyl)-2H-indazole-5-carboxamide;Cyclopyrazofurol;Sarolaner, Lotilaner;N-[4-chloro-3-[[(phenylmethyl)amino]carbonyl]phenyl]-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide;N-[4-chloro-3-[[(phenylmethyl)amino]carbonyl ]phenyl]-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide;2-(3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine;2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine;N-[4-chloro-3-(cyclopropylcarbamoyl)phenyl]-2-methyl-5-(1,1,2,2,2-Pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carboxamide; N-[4-chloro-3-[(1-cyanocyclopropyl)carbamoyl]phenyl]-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carboxamide; Benzpyrimoxane; Tigolaner; Oxazosulfuryl; [(2S,3R,4R,5S,6S)-3,5-dimethoxy-6-methyl-4-propoxytetrahydropyran-2-yl]-N-[4-[1-[4-(trifluoromethoxy)phenyl] [(2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyltetrahydropyran-2-yl]-N-[4-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]carbamate;[(2S,3R,4R,5S,6S)-3,5-dimethoxy-6-methyl-4-propoxytetrahydropyran-2-yl]-N-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1,2,4- [(2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyltetrahydropyran-2-yl]-N-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]carbamate;(2Z)-3-(2-isopropylphenyl)-2-[(E)-[4-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]methylenehydrazono]thiazolidin-4-one, (2 Z)-3-(2-isopropylphenyl)-2-[(E)-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]methylenehydrazono]thiazolidin-4-one, (2Z)-3-(2-isopropylphenyl)-2-[(E)-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]methylenehydrazono]thiazolidin-4-one; 2-(6-chloro-3-ethylsulfonyl-imidazo[1,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-(6-bromo-3-ethylsulfonyl-imidazo[1,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-(3-ethylsulfonyl-6-iodo-imidazo[1,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-(7-chloro-3-ethylsulfonyl-imidazo[1,2-a]pyridin-2-yl )-3-Methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-(7-chloro-3-ethylsulfonyl-imidazo[1,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-(3-ethylsulfonyl-7-iodo-imidazo[1,2-a]pyridin-2-yl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 3-ethylsulfonyl-6-iodo-2-[3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine 2-[3-ethylsulfonyl-8-fluoro-6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-[3-ethylsulfonyl-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethylsulfinyl)imidazo[4,5-b]pyridine, 2-[3-ethylsulfonyl-7-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl]-3-methyl-6-(trifluoromethylsulfinyl)imidazo[4,5-b]pyridine 2-(6-Bromo-3-ethylsulfonylimidazo[1,2-a]pyridin-2-yl)-6-(trifluoromethyl)pyrazolo[4,3-c]pyridine;N-[[2-Fluoro-4-[(2S,3S)-2-hydroxy-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)pyrrolidin-1-yl]phenyl]methyl]cyclopropanecarboxamide;2-[2-Fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfinyl)phenyl]imino-3-(2,2,2-trifluoroethyl)thiazolidin-4-one; Flupentiophenox, N-[3-chloro-1-(3-pyridyl)pyrazol-4-yl]-2-methylsulfonylpropanamide, cyclobutrifluram; N-[4-chloro-3-[(1-cyanocyclopropyl)carbamoyl]phenyl]-2-methyl-4-methylsulfonyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazole-3-carboxamide, ciprofuranilide, nicofluprole; 1,4-dimethyl-2-[2-(pyridin-3-yl)-2H-indazol-5-yl]-1,2,4-triazolidine-3,5-dione, 2-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenyl], Imino-3-(2,2,2-trifluoroethyl)thiazolidin-4-one, Indazapiroxamet, N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-3-methylsulfonylpropanamide, N-cyclopropyl-5-[(5S)-5-(3,5-dichloro-4-fluorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]isoquinoline-8-carboxamide, 5-[(5S)-5-(3,5-dichloro-4-fluorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-(pyrimidin-2-ylmethyl)isoquinoline-8-carboxamide, N-[1-(2,6-difluorophenyl) pyrazol-3-yl]-2-(trifluoromethyl)benzamide, 5-((1R,3R)-3-(3,5-bis(trifluoromethyl)phenyl)-2,2-dichlorocyclopropane-1-carboxamido)-2-chloro-N-(3-(2,2-difluoroacetamido)-2,4-difluorophenyl)benzamide, 1-[6-(2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazol-6-yl)-5-ethylsulfonyl-3-pyridyl]cyclopropanecarbonitrile, 6-(5-cyclopropyl-3-ethylsulfonyl-2-pyridyl)-2,2-difluoro-7-methyl-[1,3]dioxolo[4,5-f]benzimidazole.

[0320] The active substances referred to as component 2, their preparation and their activity against, for example, harmful fungi are known (see https: / / pesticidecompendium.bcpc.org / ); these substances are commercially available. Compounds described according to IUPAC nomenclature, their preparation and pesticidal activity are also known (Can. J. Plant Sci. 48(6), 587-94, 1968; EP-A-141317; EP-A-152031; EP-A-226917; EP-A-243970; EP-A-256503; EP-A-428941; EP-A-532022; EP-A-1028125; EP-A-11028126; EP-A-11028127; EP-A-11028128; EP-A-11028129). 035122; EP-A1201648; EP-A1122244; JP-A-2002316902; DE-A-19650197; DE-A-10021412; DE-A-102005009458; U.S. Pat. No. 3,296,272; U.S. Pat. No. 3,325,503; WO-A-98 / 46608; WO-A-99 / 14187 Brochure; WO 99 / 24413; WO 99 / 27783; WO 00 / 29404; WO 00 / 46148; WO 00 / 65913; WO 01 / 54501; WO 01 / 56358; WO 02 / 22583; WO 02 / 40431; WO 03 / 10149; WO 03 / 11853; WO 03 / 14103; WO 03 / 16286; WO 03 / 53145; WO 03 / 61388; WO 03 / 66609; WO 03 / 74491; WO 04 / 49804; WO 04 / 83193;WO 05 / 120234; WO 05 / 123689; WO 05 / 123690; WO 05 / 63721; WO 05 / 87772; WO 05 / 87773; WO 06 / 15866; WO 06 / 87325; WO 06 / 87343; WO 07 / 82098; WO 07 / 90624; WO 10 / 1392 WO 71; WO 11 / 028657; WO 12 / 168188; WO 07 / 006670; WO 11 / 77514; WO 13 / 047749; WO 10 / 069882; WO 13 / 047441; WO 03 / 16303; WO 09 / 90181; WO 13 / 007767; WO 13 / 010862 WO 13 / 127704; WO 13 / 024009; WO 13 / 24010; WO 13 / 047441; WO 13 / 162072; WO 13 / 092224; WO 11 / 135833; Chinese Patent Application Publication No. 1907024; Chinese Patent Application Publication No. 1456054; Chinese Patent Application Publication No. 103387541; Chinese Patent Application Publication No. 1309897; WO 1 2 / 84812; Chinese Patent Application Publication No. 1907024; International Publication No. 09094442; International Publication No. 14 / 60177; International Publication No. 13 / 116251; International Publication No. 08 / 013622; International Publication No. 15 / 65922; International Publication No. 94 / 01546; European Patent No. 2865265; International Publication No. 07 / 129454; International Publication No. 12 / 165511; International Publication No. 11 / 081174;(See WO 13 / 47441; WO 16 / 156241; WO 16 / 162265). Some compounds are identified by their CAS Registry Number, which consists of three parts, the first of which consists of 2 to 7 digits, the second of which consists of 2 digits, and the third of which consists of 1 digit, separated by hyphens.

[0321] According to the present invention, the solid matter (dry matter) of the biopesticide (excluding oils such as neem oil) is considered to be the active ingredient (e.g., in the case of liquid formulations of microbial pesticides, obtained after drying or evaporation of the extraction or suspension medium). The weight ratios and percentages used for biological extracts, such as Quillay extract, are based on the total weight of the dry content (solid matter) of the respective extract.

[0322] The total weight ratio of the composition comprising at least one microbial pesticide in the form of viable microbial cells, including dormant forms, is 1×10 10 The CFU of each microorganism can be used to calculate the total weight of each active ingredient by the formula: CFU is equal to 1 gram of total weight of each active ingredient. Colony forming units are a measure of viable microbial cells. Furthermore, in the case of nematode biopesticides such as Steinernema feltiae, CFU can be understood as the number of individual (juvenile) nematodes.

[0323] In binary mixtures, the weight ratio of component 1) to component 2) generally depends on the properties of the components used and is usually in the range of 1:10,000 to 10,000:1, often 1:100 to 100:1, usually 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, usually 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 typically in the range of 20,000:1 to 1:10, often 10,000:1 to 1:1, usually 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 typically in the range of 1:1 to 1:1000, often 1:1 to 1:100, usually 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 typically in the range of from 10:1 to 1:20,000, often from 1:1 to 1:10,000, usually 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.

[0324] In ternary mixtures, i.e., compositions comprising component 1), component 2), and compound III (component 3), the weight ratio of component 1) to component 2) depends on the properties of the active substances used and is usually in the range of 1:100 to 100:1, usually 1:50 to 50:1, preferably 1:20 to 20:1, more preferably 1:10 to 10:1, and especially 1:4 to 4:1, and the weight ratio of component 1) to component 3) is usually in the range of 1:100 to 100:1, usually 1:50 to 50:1, preferably 1:20 to 20:1, more preferably 1:10 to 10:1, and especially 1:4 to 4:1. Optional additional active ingredients are added in a ratio of 20:1 to 1:20 relative to component 1), if necessary. These ratios are also suitable for mixtures applied by seed treatment.

[0325] When mixtures containing microbial pesticides are used for crop protection, the application rate is 1 x 10 6 ~5×10 16 (or more) CFU / ha, preferably 1 x 10 8 ~1×10 13 CFU / ha, even more preferably 1 x 10 9 ~5×10 15 CFU / ha, especially 1 × 10 12 ~5×10 14 CFU / ha. For nematodes (e.g., Steinernema feltiae) as microbial pesticides, application rates are usually in the range of 1 x 10 per hectare. 5 ~1×10 12 (or more), preferably 1 × 10 8 ~1×10 11 , more preferably 5 × 10 8 ~1×10 10 A range of individuals (eg, in the form of eggs, juveniles or any other live stage, preferably in the immature juvenile stage).

[0326] When mixtures containing microbial pesticides are used for seed treatment, the application rate is generally 1 x 10 6 ~1×10 12 (or more) CFU / seed, preferably 1 x 10 6 ~1×109 Furthermore, the application rate for seed treatments is generally in the range of 1 x 10 CFU / 100 kg of seed. 7 ~1×10 14 (or more) CFU, preferably 1 x 10 per 100 kg of seeds 9 ~1×10 12 CFU range.

[0327] As component 2), Q of group A o Preference is given to mixtures comprising at least one active substance selected from inhibitors of Complex III at the site, more preferably selected from compounds (A.1.1), (A.1.4), (A.1.8), (A.1.9), (A.1.10), (A.1.12), (A.1.13), (A.1.14), (A.1.17), (A.1.21), (A.1.25), (A.1.34) and (A.1.35), in particular selected from (A.1.1), (A.1.4), (A.1.8), (A.1.9), (A.1.13), (A.1.14), (A.1.17), (A.1.25), (A.1.34) and (A.1.35).

[0328] As component 2), Q of group A i Preference is given to mixtures comprising at least one active substance 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 selected from (A.2.3), (A.2.4) and (A.2.6).

[0329] As component 2), 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) selected from the inhibitors of complex II of group A), Preferred are mixtures comprising at least one active substance selected from (A.3.37), (A.3.38) and (A.3.39), in particular 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).

[0330] Also preferred are mixtures comprising as component 2) at least one active substance selected from other respiratory inhibitors and QoSIs of group A), more preferably selected from the compounds (A.4.5) and (A.5.1), in particular (A.5.1).

[0331] As component 2) there is provided a compound selected from the C14 demethylase inhibitors of group B), 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), (B.1.40), (B.1.41), (B.1.42), (B.1.43), (B.1.44), (B.1.45), (B.1.46), (B.1.47), (B.1.48), (B.1.49), (B.1.50), (B.1.51), (B.1.52), (B.1.53), (B.1.54), (B.1.55), (B.1.56), (B.1.57), (B.1.58), (B.1.59), (B.1.60), (B.1.61), (B.1.62), (B.1.63), (B.1.64), (B.1.65), (B.1.66), (B.1.67), (B.1.68), (B.1.69), (B.1.70), (B.1.71), (B.1.72), (B.1.73), (B.1.74), (B.1.75), (B.1.76), (B.1.77), (B.1.78), (B.1.79), (B.1.80), (B.1. Also preferred are mixtures comprising 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), (B.1.46), (B.1.53), (B.1.54) and (B.1.55), in particular (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).

[0332] 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).

[0333] 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).

[0334] Also preferred are mixtures comprising as component 2) at least one active substance selected from other nucleic acid synthesis inhibitors of group C), more preferably selected from the compounds (C.2.6), (C.2.7), (C.2.8), (C.2.9) and (C.2.10), in particular selected from (C.2.9) and (C.2.10).

[0335] 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).

[0336] Also preferred are mixtures which comprise 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).

[0337] 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).

[0338] Also preferred are mixtures comprising as component 2) at least one active substance selected from group G), more preferably selected from the compounds (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 selected from (G.5.1) and (G.5.3).

[0339] Preference is also given to 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).

[0340] Also preferred are mixtures comprising as component 2) at least one active substance selected from group I), more preferably selected from the compounds (I.2.2), (I.2.5), (I.3.1), (I.3.3) and (I.3.6), in particular (I.3.1).

[0341] Also preferred are mixtures which comprise 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).

[0342] 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.1.57), (K.1.58) and (K.1.59), in particular selected from (K.1.41), (K.1.57), (K.1.58) and (K.1.59).

[0343] Any of the above mixtures preferably comprises as component 1) a compound I as explicitly disclosed herein, e.g. in the tables, more preferably from the list of compounds I.A1.1-Z-1-A-1 to IA1.1-Z-1-A-2389, IA2.1-Z-1-A-1 to IA2.1-Z-1-A-2389, IA3.1-Z-1-A-1 to IA3.1-Z-1-A-2389, I.A1.2- Z-1-A-1~IA1.2-Z-1-A-2389, IA2.2-Z-1-A-1~IA2.2-Z-1-A-2389, IA3.2-Z-1-A-1~IA3.2-Z-1-A-238 9, I.A1.3-Z-1-A-1~IA1.3-Z-1-A-2389, IA2.3-Z-1-A-1~IA2.3-Z-1-A-2389, IA3.3-Z-1-A-1~IA3.3-Z -1-A-2389, I.B1.1-Z-1-A-1~IB1.1-Z-1-A-2389, IB2.1-Z-1-A-1~IB2.1-Z-1-A-2389, IB3.1-Z-1-A- 1~IB3.1-Z-1-A-2389, I.B1.2-Z-1-A-1~IB1.2-Z-1-A-2389, IB2.2-Z-1-A-1~IB2.2-Z-1-A-2389, IB3. The compounds I include compounds I selected from IB2-Z-1-A-1 to IB3.2-Z-1-A-2389, IB1.3-Z-1-A-1 to IB1.3-Z-1-A-2389, IB2.3-Z-1-A-1 to IB2.3-Z-1-A-2389 and IB3.3-Z-1-A-1 to IB3.3-Z-1-A-2389, and compounds I selected from Example Compound Nos. 1 to 128 of Table S are particularly preferred.

[0344] Biopesticides from groups L1) and / or L2) may also have insecticidal, acaricidal, molluscicidal, pheromone, nematicidal, plant stress-relieving, plant growth regulator, plant growth-promoting, and / or yield-increasing activity. Biopesticides from groups L3) and / or L4) may also have fungicidal, bactericidal, virucidal, plant defense active, plant stress-relieving, plant growth regulator, plant growth-promoting, and / or yield-increasing activity. Biopesticides from group L5) may also have fungicidal, bactericidal, virucidal, plant defense active, insecticidal, acaricidal, molluscicidal, pheromone, and / or nematicidal activity.

[0345] Microbial pesticides, especially those from groups L1), L3) and L5), encompass not only isolated, pure cultures of the respective microorganisms as defined herein, but also cell-free extracts thereof, suspensions thereof in whole broth cultures and metabolite-containing culture media or purified metabolites obtained from whole broth cultures of the microorganisms.

[0346] Many of these biopesticides have been deposited under the accession numbers mentioned herein (the prefixes such as ATCC or DSM refer to the acronym of the respective culture collection, for details see, for example, here: http: / / www.wfcc.info / ccinfo / collection / by_acronym / ), are mentioned in the literature, are registered, and / or are commercially available: Aureobasidium pullulans DSM 14940 and DSM 14941 mixture isolated in 1989 in Konstanz, Germany (e.g., blastospores in BlossomProtect® from bio-ferm GmbH, Austria), Azospirillum brasilense Sp245 (BR 11005; e.g., BASF Agricultural Specialties), originally isolated in the wheat belt (Paso Fundo) of South Brazil at least before 1980, Azospirillum brasilense Sp245 (BR 11005; e.g., BASF Agricultural Specialties), and Azospirillum brasilense Sp245 (BR 11005; e.g., BASF Agricultural Specialties). Ltd., Brazil), A. brasilense strains Ab-V5 and Ab-V6 (e.g., in AzoMax from Novozymes BioAg Produtos papra Agricultura Ltda., Quattro Barras, Brazil or Simbiose-Maiz from Simbiose-Agro, Brazil; Plant Soil 331, 413-425, 2010), Bacillus amyloliquefaciens strain AP-188 (NRRL B-50615 and B-50331; U.S. Pat. No. 8,445,255); B. amyloliquefaciens sp. plantarum spp. plantarum strains (formerly sometimes called B. subtilis, now classified as B. velezensis together with B. methylotrophicus and B. velezensis) (Int. J.Syst. Evol. Microbiol. 66, 1212-1217, 2016): Bassp. plantarum or B. velezensis D747 isolated from the air of Kikugawa City, Japan (U.S. Patent Application Publication No. 20130236522A1; FERM BP-8234; e.g., Double Nickel™ 55 WDG from Certis LLC, USA), Bassp. plantarum or B. velezensis FZB24 isolated from soil in Brandenburg, Germany (also called SB3615; DSM96-2; J. Plant Dis. Prot. 105, 181-197, 1998; e.g., Novozyme Taegro® from Biologics, Inc., USA), Bassp. plantarum or B. velezensis FZB42 isolated from soil from Brandenburg, Germany (DSM 23117; J. Plant Dis. Prot. 105, 181-197, 1998; e.g., RhizoVital® 42 from AbiTEP GmbH, Germany), Bassp. plantarum or B. velezensis MBI600 (also called 1430; NRRL B-50595; U.S. Patent Application Publication No. 2012 / 0149571 A1; e.g., BASF Integral® from Bayer Crop Science LP, USA), Ba subsp. plantarum (B. plantarum) isolated from a peach orchard in California, USA in 1995, or B. velezensis QST-713 (NRRL B-21661; e.g., Serenade® MAX from Bayer Crop Science LP, USA), Ba subsp. plantarum (B.a.ssp.plantarum) or B. velezensis TJ1000 (also called 1BE; ATCC BAA-390; Canadian Patent Application Publication No. 2471555A1; e.g., QuickRoots™ from TJ Technologies, Watertown, SD, USA); B. firmus CNCM I-1582 (a mutant of the parent strain EIP-N1 (CNCM I-1556) isolated from soil in the central plains of Israel) (WO 2009 / 126473, U.S. Patent No. 6,406,690; e.g., Votivo™ from Bayer CropScience LP, USA), B. pumilus GHA 180 (IDAC 260707-01; e.g., Premier) isolated from the rhizosphere of apple trees in Mexico. B. pumilus INR-7 (also referred to as BU-F22 and BU-F33), isolated at least before 1993 from cucumber plants infested with Erwinia tracheiphila (NRRL B-50185, NRRL B-50153; U.S. Pat. No. 8,445,255), B. pumilus KFP9F, isolated at least before 2008 from the rhizosphere of grasses in South Africa (NRRL B-50754; WO 2014 / 029697; e.g., BAC-UP or FUSION-P from BASF Agricultural Specialties (Pty) Ltd., South Africa), B. pumilus QST 2808 was isolated from soil collected in Pohnpei, Federated States of Micronesia in 1998 (NRRL B-30087; e.g., Sonata® or Ballad® Plus from Bayer Crop Science LP, USA), B. simplex (B.simplex ABU 288 (NRRL B-50304; U.S. Pat. No. 8,445,255), B. subtilis FB17 (also called UD 1022 or UD 10-22) isolated from red beet roots in North America (ATCC PTA-11857; System. Appl. Microbiol. 27, 372-379, 2004; U.S. Patent Application Publication No. 2010 / 0260735; WO 2011 / 109395); B. thuringiensis ssp. aizawai ABTS-1857 (also called ABG-6346; ATCC SD-1372; e.g., BioFa, Inc.), isolated in 1987 from soil collected from turfgrass in Ephraim, Wisconsin, USA. XenTari® from AG, Muensingen, Germany), Bt subsp. kurstaki ABTS-351 (ATCC SD-1275; e.g., Dipel® DF from Valent BioSciences, IL, USA), identical to HD-1 isolated in 1967 from infected black cotton bollworms in Brownsville, Texas, USA, Bt subsp. kurstaki SB4 (NRRL B-50753; e.g., Beta from BASF Agricultural Specialties (Pty) Ltd., South Africa), isolated from the larval carcasses of E. saccharina, Bt subsp. kurstaki SB5 (NRRL B-50753; e.g., Beta from BASF Agricultural Specialties (Pty) Ltd., South Africa, Bt subsp. kurstaki SB6 (NRRL B-50753; e.g., Beta from BASF Agricultural Specialties (Pty) Ltd., South Africa), Bt subsp. kurstaki SB7 (NRRL B-50753; e.g., Beta from BASF Agricultural Specialties (Pty) Ltd., South Africa), Bt subsp. kurstaki SB8 (NRRL B-50753; e.g., Beta from BASF Agricultural Specialties (Pty) Ltd., South Africa), Bt subsp. kurstaki SB9 ...1 (NRRL B-50753; e.g., Beta from BASF Agricultural Specialties (Pty) Ltd., South Africa), Bt subsp. kur Pro®), Bt subsp. tenebrionis NB-176-1 (a mutant of the wild-type strain NB-125 isolated in 1982 from dead pupae of the mealworm beetle Tenebrio molitor) (DSM 5480; European Patent No. 585215 B1; e.g., Novodor® from Valent BioSciences, Switzerland), Beauveria bassiana GHA (ATCC 74250; e.g., Laverlam Int. Corp.BotaniGard® 22WGP from Rio Grande do Sul, USA), B. bassiana JW-1 (ATCC 74040; e.g., Naturalis® from CBC (Europe) Srl, Italy), B. bassiana PPRI 5339 (NRRL 50757; e.g., BroadBand® from BASF Agricultural Specialties (Pty) Ltd., South Africa) isolated from larvae of the tortoise leaf beetle Conchyloctenia punctata, Bradyrhizobium elkanii strain SEMIA 5019 (also called 29W) isolated in Rio de Janeiro, Brazil, and from an area previously inoculated with North American isolates from Rio Grande do Sul, Brazil. SEMIA 587, isolated in Sul in 1967 and used in commercial inoculants since 1968 (Appl. Environ. Microbiol. 73(8), 2635, 2007; e.g., GELFIX 5 from BASF Agricultural Specialties Ltd., Brazil), B. japonicum 532c, isolated in the USA from a field in Wisconsin (Nitragin 61A152; Can. J. Plant. Sci. 70, 661-666, 1990; e.g., in Rhizoflo®, Histick®, and Hicoat® Super from BASF Agricultural Specialties Ltd., Canada), B. japonicum E-109 variant of USDA 138 strain (INTA E109, SEMIA 5085; Eur. J. Soil Biol. 45, 28-35, 2009; Biol. Fertil. Soils 47, 81-89, 2011); B. japonicum (B.japonicum strain: SEMIA 5079 (CPAC 15; e.g., GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil), isolated by Embrapa-Cerrados from soil in the Cerrados region of Brazil and used in commercial inoculants since 1992, originally from the USA; B. japonicum SEMIA 5080 (CPAC7; e.g., GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil), a natural variant of SEMIA 586 (CB1809) isolated in 2008; Burkholderia sp. A396 (NRRL B-50319; WO 2013 / 032693; Marrone Bio Innovations, Inc., USA), isolated from soil in Nikko, Japan in 2008; Coniothyrium minitans CON / M / 91-08 (WO 1996 / 021358; DSM 9660; e.g., Bayer CropScience), isolated from rapeseed. Contans® WG, Intercept® WG from AgBiTech, Germany), Harpin (alpha-beta) protein (Science 257, 85-88, 1992; e.g., Messenger® or HARP-N Tek from Plant Health Care plc, UK), Helicoverpa armigera nuclear polyhedrosis virus (HearNPV) (J. Invertebrate Pathol. 107, 112-126, 2011; e.g., Helicovex® from Adermatt Biocontrol, Switzerland; Diplomata® from Koppert, Brazil; Vivus® Max from AgBiTech Pty Ltd., Queensland, Australia), Helicoverpa zea single-capsid nuclear polyhedrosis virus (HzSNPV) (e.g., Certis Gemstar® from AgBiTech Pty Ltd., LLC, USA), Helicoverpa zea nuclear polyhedrosis virus ABA-NPV-U (e.g., AgBiTech Pty Ltd.Heligen® from Queensland, Australia), Heterorhabditis bacteriophora (e.g., Nemasys® G from BASF Agricultural Specialties Limited, UK), Isaria fumosorosea Apopka-97 (ATCC 20874; Biocontrol Science Technol. 22(7), 747-761, 2012; e.g., PFR-97™ or PreFeRal® from Certis LLC, USA) isolated from mealybugs on Sanguinea gynura in Apopka, Florida, USA, and Metarhizium anisopliae var. anisopliae isolated from codling moth in Austria.anisopliae F52 (also called 275 or V275) (DSM 3884, ATCC 90448; e.g., Met52®, Novozymes Biologicals BioAg Group, Canada), Metschnikowia fructicola 277 isolated from grapevines in central Israel (U.S. Pat. No. 6,994,849; NRRL Y-30752; e.g., formerly Shemer®, from Agrogreen, Israel), and Paecilomyces ilacinus 251 isolated from infected nematode eggs in the Philippines (AGAL 89 / 030550; WO 1991 / 02051; Crop Protection 27, 352-361, 2008; e.g., Bayer CropScience). AG, Germany and MeloCon® from Certis, USA), Paenibacillus alvei NAS6G6 isolated from the rhizosphere of grasses in South Africa at least before 2008 (WO 2014 / 029697; NRRL B-50755; e.g., BAC-UP from BASF Agricultural Specialties (Pty) Ltd., South Africa), Paenibacillus strains isolated from soil samples from various locations in Europe, including Germany: P. epiphyticus Lu17015 (WO 2016 / 020371; DSM 26971), P. polymyxa subsp. plantarum (P. polymyxa ssp. plantarum) Lu16774 (WO 2016 / 020371; DSM 26969), Pp subsp. plantarum (Pps sp. plantarum) strain Lu17007 (WO 2016 / 020371; DSM 26970); Illinois, USPasteuria nishizawae Pn1 (ATCC SD-5833; Federal Register 76(22), 5808, February 2, 2011; e.g., Clariva™ PN from Syngenta Crop Protection, LLC, USA), which was isolated from a soybean field in the mid-2000s in A. aureus, and Penicillium bilaiae (also known as P. bilaii) strains ATCC 18309 (=ATCC 74319), ATCC 20851, and / or ATCC 22348 (=ATCC 74318), originally isolated from soil in Alberta, Canada (Fertilizer Res. 39, 97-103, 1994; Can. J. Plant Res. Sci. 78(1), 91-102, 1998; U.S. Pat. No. 5,026,417; WO 1995 / 017806; e.g., Jump Start®, Provide® from Novozymes Biologicals BioAg Group, Canada), Reynoutria sachalinensis extract (European Patent No. 0307510B1; e.g., Regalia® SC from Marrone BioInnovations, Davis, CA, USA or Milsana® from BioFa AG, Germany), Steinernema carpocapsae (e.g., Millenium® from BASF Agricultural Specialties Limited, UK), S. feltiae (e.g., BioWorks, Inc.Nemashield® from BASF Agricultural Specialties Limited, UK; Nemasys® from BASF Agricultural Specialties Limited, UK), Streptomyces microflavus NRRL B-50550 (WO 2014 / 124369; Bayer CropScience, Germany), Trichoderma asperelloides JM41R isolated in South Africa (NRRL 50759; also known as T. fertile; e.g., Trichoplus® from BASF Agricultural Specialties (Pty) Ltd., South Africa), T. harzianum T-22 (also known as KRL-AG2) (ATCC 20847; BioControl 57, 687-696, 2012; e.g., BioWorks Plantshield® from Advanced Biological Marketing Inc., Van Wert, OH, USA or SabrEx™ from Advanced Biological Marketing Inc., Van Wert, OH, USA.

[0347] According to another embodiment of the mixture, at least one pesticide II is selected from the groups L1) to L5): L1) Microbial pesticides with fungicidal, bactericidal, virucidal and / or plant defense activator activity: Aureobasidium pullulans DSM 14940 and DSM 14941 (L1.1), Bacillus amyloliquefaciens AP-188 (L.1.2), B. amyloliquefaciens ssp. plantarum D747 (L.1.3), B. amyloliquefaciens ssp. plantarum FZB24 (L.1.4), B. amyloliquefaciens plantarum) FZB42 (L.1.5), B. amyloliquefaciens ssp. plantarum MBI600 (L.1.6), B. amyloliquefaciens ssp. plantarum QST-713 (L.1.7), B. amyloliquefaciens ssp. plantarum TJ1000 (L.1.8), B. pumilus GB34 (L.1.9), B. pumilus GHA 180 (L.1.10), B. pumilus INR-7 (L.1.11), B. pumilus KFP9F (L.1.12), B. pumilus QST 2808 (L.1.13), B. simplex ABU 288 (L.1.14), B. subtilis FB17 (L.1.15), Coniothyrium minitans CON / M / 91-08 (L.1.16), Metschnikowia fructicola NRRL Y-30752 (L.1.17), Paenibacillus alvei (Paenibacillus alvei) NAS6G6 (L.1.18), P. epiphyticus (P.epiphyticus Lu17015 (L.1.25), P. polymyxa ssp. plantarum Lu16774 (L.1.26), Ppssp. plantarum strain Lu17007 (L.1.27), Penicillium bilaiae ATCC 22348 (L.1.19), P. bilaiae ATCC 20851 (L.1.20), Penicillium bilaiae ATCC 18309 (L.1.21), Streptomyces microflavus NRRL B-50550 (L.1.22), Trichoderma asperelloides JM41R (L.1.23), T. harzianum T-22 (L.1.24); L2) Biochemical pesticides with fungicidal, bactericidal, virucidal and / or plant defense activator activity: harpin protein (L.2.1), Reynoutria sachalinensis extract (L.2.2); L3) Microbial pesticides with insecticidal, acaricidal, molluscicidal and / or nematicidal activity: Bacillus firmus I-1582 (L.3.1), B. thuringiensis ssp. aizawai ABTS-1857 (L.3.2), Bt subsp. kurstaki ABTS-351 (L.3.3), Bt subsp. kurstaki SB4 (L.3.4), Bt subsp. tenebrionis NB-176-1 (L.3.5), Beauveria bassiana bassiana GHA (L.3.6), B. bassiana JW-1 (L.3.7), B. bassiana PPRI 5339 (L.3.8), Burkholderia sp. A396 (L.3.9), Helicoverpa armigera nucleopolyhedrovirus (HearNPV) (L.3.10), Helicoverpa zea nucleopolyhedrovirus (HzNPV) ABA-NPV-U (L.3.11), Helicoverpa zea single capsid nucleopolyhedrovirus (HzNPV) ABA-NPV-U (L.3.12), Helicoverpa zea single capsid nucleopolyhedrovirus (HzNPV) ABA-NPV-U (L.3.13), Helicoverpa zea single capsid nucleopolyhedrovirus (HzNPV) ABA-NPV-U (L.3.14), Helicoverpa zea single capsid nucleopolyhedrovirus (HzNPV) ABA-NPV-U (L.3.15), Helicoverpa zea single capsid nucleopolyhedrovirus (HzNPV) ABA-NPV-U (L.3.16), Helicoverpa zea single capsid nucleopolyhedrovirus (HzNPV) ABA-NPV-U (L.3.17), Helicoverpa zea single capsid nucleopolyhedrovirus (HzNPV) ABA-NPV-U (L.3.18), Helicoverpa zea single capsid nucleopolyhedrovirus (HzNPV) ABA-NPV-U (L.3.19), Helicoverpa zea single capsid nucleopolyhedrovirus (HzNPV) ABA-NPV-U (L.3.20), Helicoverpa zea single capsid nucleopolyhedrovirus ( nucleopolyhedrovirus (HzSNPV) (L.3.12), Heterohabditis bacteriophora (L.3.13), Isaria fumosorosea Apopka-97 (L.3.14), Metarhizium anisopliae var. anisopliae F52 (L.3.15), Paecilomyces lilacinus 251 (L.3.16), Pasteuria nishizawae Pn1 (L.3.17), Steinernema carpocapsae (L.3.18), S. feltiae (L.3.19);. L4) Biochemical pesticides with insecticidal, acaricidal, molluscicidal, pheromone and / or nematicidal activity; cis-jasmone (L.4.1), methyl jasmonate (L.4.2), Quillaja extract (L.4.3); L5) Microbial pesticides with plant stress-reducing activity, plant growth regulator activity, plant growth-promoting activity and / or yield-enhancing activity: Azospirillum brasilense Ab-V5 and Ab-V6 (L.5.1), A. brasilense Sp245 (L.5.2), Bradyrhizobium elkanii SEMIA 587 (L.5.3), B. elkanii SEMIA 5019 (L.5.4), B. japonicum 532c (L.5.5), B. japonicum E-109 (L.5.6), B. japonicum SEMIA 5079 (L.5.7), B. japonicum SEMIA 5080 (L.5.8) is selected from.

[0348] The present invention further relates to an agrochemical composition comprising a mixture of at least one compound I (component 1) and at least one biopesticide selected from group L) (component 2), in particular at least one biopesticide selected from groups L1) and L2), as described above, and optionally at least one suitable adjuvant.

[0349] The present invention further relates to an agrochemical composition comprising a mixture of at least one compound I (component 1) and at least one biopesticide selected from group L) (component 2), in particular at least one biopesticide selected from groups L3) and L4), as described above, and optionally at least one suitable adjuvant.

[0350] As pesticide II (component 2) there is used a compound selected from the group L1), L3) and L5), preferably (L.1.2), (L.1.3), (L.1.4), (L.1.5), (L.1.6), (L.1.7), (L.1.8), (L.1.10), (L.1.11), (L.1.12), (L.1.13), (L.1.14), (L .1.15), (L.1.17), (L.1.18), (L.1.19), (L.1.20), (L.1.21), (L.1.25), (L.1.26), (L. 1.27), (L.3.1); (L.3.9), (L.3.16), (L.3.17), (L.5.1), (L.5.2), (L.5.3), (L.5.4), (L (L.5.5), (L.5.6), (L.5.7), (L.5.8); (L.4.2) and (L.4.1), and even more preferably (L.1.2), (L.1.6), (L.1.7), (L.1.8), (L.1.11), (L.1.12), (L.1.13), (L.1.14), (L.1.15). Also preferred are mixtures containing a biopesticide selected from (L.1.18), (L.1.19), (L.1.20), (L.1.21), (L.3.1); (L.3.9), (L.3.16), (L.3.17), (L.5.1), (L.5.2), (L.5.5), (L.5.6); (L.4.2) and (L.4.1). These mixtures are particularly suitable for the treatment of propagation material, i.e., seed treatment purposes, as well as for soil treatment. These seed treatment mixtures are particularly suitable for crops such as cereals, corn, and legumes such as soybeans.

[0351] As pesticide II (component 2) there is used a compound selected from the group L1), L3) and L5), preferably (L1.1), (L.1.2), (L.1.3), (L.1.6), (L.1.7), (L.1.9), (L.1.11), (L.1.12), (L.1.13), (L.1.14), (L.1.15), (L.1.16), (L.1.17), (L.1.18), (L.1.19), (L.120), (L.121), (L.122), (L.123), (L.124), (L.125), (L.126), (L.127), (L.128), (L.129), (L.130), (L.131), (L.132), (L.133), (L.134), (L.13 .17), (L.1.18), (L.1.22), (L.1.23), (L.1.24), (L.1.25), (L.1.26), (L.1.27), (L .2.2);(L.3.2), (L.3.3), (L.3.4), (L.3.5), (L.3.6), (L.3.7), (L.3.8), (L.3.10) , (L.3.11), (L.3.12), (L.3.13), (L.3.14), (L.3.15), (L.3.18), (L.3.19); (L.4.2), and even more preferably selected from the strains indicated above as (L.1.2), (L.1.7), (L.1.11), (L.1.13), (L.1.14). Also preferred are mixtures comprising a biopesticide selected from (L.1.15), (L.1.18), (L.1.23), (L.3.3), (L.3.4), (L.3.6), (L.3.7), (L.3.8), (L.3.10), (L.3.11), (L.3.12), (L.3.15) and (L.4.2). These mixtures are particularly suitable for the foliar treatment of cultivated plants, preferably vegetables, fruits, vines, cereals, and legumes such as maize and soybeans.

[0352] Compositions containing the mixture of active ingredients can be prepared by conventional means, for example those given for the compositions of Compound I.

[0353] When live microorganisms form part of the composition, such as pesticides II from groups L1), L3) and L5), such compositions can be prepared by conventional means (e.g., HD Burgess: Formulation of Microbial Biopesticides, Springer, 1998; WO 2008 / 002371; U.S. Pat. No. 6,955,912; U.S. Pat. No. 5,422,107). [Example]

[0354] Synthesis Process Example 1: Methyl (2E)-2-[3-chloro-2-[[(Z)-[1-(4-fluorophenyl)-2-methoxyethylidene]amino]oxymethyl]phenyl]-2-methoxyimino-acetate (No. 1) Step 1: 1-(4-fluorophenyl)-2-methoxyethanone [ka] A solution of 4-fluorophenylmagnesium bromide (2 M) (11.2 mL, 22.55 mmol) in THF (10 mL) was added to a solution of N,2-dimethoxy-N-methylacetamide (3.15 g, 23.68 mmol) in THF (10 mL) at −70° C. under N and stirred at −70° C. for 2 h under N. TLC (petroleum ether:ethyl acetate (PE:EtOAc) = 5:1) showed the reaction was complete. The reaction mixture was quenched at −60° C. with aqueous HCl (0.5 M) (34 mL), extracted with ethyl acetate (60 mL × 3), dried over NaSO, and purified by column chromatography (PE:EtOAc = 90:10) to give 1-(4-fluorophenyl)-2-methoxyethanone (2 g, 52%) as a yellow oil. 1 H NMR:(400MHz,CHCL3-d)δ(ppm)=7.97-8.02(m,2H),7.12-7.18(m,2H),4.67(s,2H),3.51(s,3H).

[0355] Step 2: 1-(4-fluorophenyl)-2-methoxyethanone oxime [ka] To a solution of 1-(4-fluorophenyl)-2-methoxyethanone (1 g, 5.95 mmol) in MeOH (20 mL) was added NaAc (0.97 g, 11.9 mol) and NH2OH.HCl (0.82 g, 11.9 mol) at 20 °C, and the reaction was stirred under N2 at 20 °C for 1 h. TLC (PE: EtOAc = 5:1) showed the reaction was complete. Two batches of parallel reactions were combined. The resulting solution was filtered, and the filtrate was poured into water (30 mL), extracted with ethyl acetate (30 mL × 3), dried over Na2SO4, and purified by column chromatography (PE: EtOAc = 10:1) to give 1-(4-fluorophenyl)-2-methoxyethanone oxime (1.5 g, 69%) as a yellow oil. 1 H NMR:(400MHz,DMSO-d6)δ=11.56(s,1H),7.64-7.70(m,2H),7.18-7.24(m,2H),4.56(s,2H),3.21(s,3H).

[0356] Step 3: (2-Bromo-6-chloro-phenyl)methanol [ka] To a solution of 2-bromo-6-chlorobenzaldehyde (90 g, 412.8 mmol) in MeOH (1 L) and THF (500 mL) was added NaBH (18.8 g, 495.4 mmol) at 0 °C and stirred at 0 °C for 1 h. TLC (PE: EtOAc = 10:1) showed the reaction was complete. The reaction mixture was quenched with HO (1 L) and extracted with dichloromethane (DCM) (500 mL × 3). The organic layer was dried over NaSO and concentrated to give (2-bromo-6-chloro-phenyl)methanol (90 g, yield: 99.1%) as a yellow solid. 1 H NMR:(400MHz,CHCl3-d)δ=7.52(d,J=8.00Hz,1H),7.38(d,J=8.00Hz,1H),7.06-7.17(m,1H),4.99(d,J=7.00Hz,2H),2.16(t,J=7.00Hz,1H).

[0357] Step 4: 1-Bromo-3-chloro-2-(methoxymethyl)benzene [ka] To a solution of (2-bromo-6-chlorophenyl)methanol (90 g, 411 mmol) in DMF (1 L) was added NaH (ca. 60%) (19.7 g, 493 mmol) at 0 °C and stirred at 0 °C for 1 h. To the mixture was added MeI (70 g, 493 mmol) at 0 °C and stirred at 0 °C for another 1 h. TLC (PE: EtOAc = 10:1) showed that the reaction was complete. The reaction mixture was quenched with HO (1 L), extracted with EtOAc (500 mL × 3), and washed with brine (500 mL × 2). The organic layer was dried over NaSO, concentrated, and purified by column chromatography (PE: EtOAc = 10:1) to give 1-bromo-3-chloro-2-(methoxymethyl)benzene (65 g, yield: 67.6%) as a yellow solid. 1 H NMR:(400MHz,CHCl3-d):δ=7.52(dd,J=8.03,1.13Hz,1H),7.37(dd,J=8.09,1.07Hz,1H),7.11(t,J=8.03Hz,1H),4.76(s,2H),3.46(s,3H).

[0358] Step 5: [3-chloro-2-(methoxymethyl)phenyl]magnesium bromide [ka] A solution of 1-bromo-3-chloro-2-(methoxymethyl)benzene (65 g, 278 mmol) in THF (300 mL) was added to a solution of Mg (8 g, 333 mmol) and I2 (2.1 g, 8.3 mmol) in THF (150 mL) at 40-50 °C and stirred at 45 °C for 2 h. TLC (PE: EtOAc = 20:1) showed the reaction was complete. The resulting solution was used directly in the next step.

[0359] Step 6: Methyl-2-[3-chloro-2-(methoxymethyl)phenyl]-2-oxo-acetate [ka] To a solution of dimethyl oxalate (66 g, 556 mmol) in toluene (500 mL), [3-chloro-2-(methoxymethyl)phenyl]magnesium bromide (450 mL, 278 mmol) was added at −40° C., and the mixture was stirred at −40° C. for 2 hours. TLC (PE: EtOAc = 10:1) showed that the reaction was complete. The reaction mixture was quenched with aqueous NH4Cl (500 mL) and extracted with EtOAc (500 mL × 3). The organic layer was dried over Na2SO4, concentrated, and purified by column chromatography (PE: EtOAc = 10:1) to give methyl-2-[3-chloro-2-(methoxymethyl)phenyl]-2-oxoacetate (40 g, yield: 59.5%) as a yellow solid. 1 H NMR:(400MHz,CHCl3-d):δ=7.50(d,J=7.75Hz,1H),7.29-7.41(m,2H),4.71(s,2H),3.90-3.94(s,3H),3.30(s,3H).

[0360] Step 7: Methyl-(2E)-2-[3-chloro-2-(methoxymethyl)phenyl]-2-methoxyimino-acetate [ka] To a solution of methyl-2-[3-chloro-2-(methoxymethyl)phenyl]-2-oxoacetate (40 g, 165 mmol) in MeOH (40 mL) was added MeONH2.HCl (27.4 g, 330 mmol) and stirred at 80 °C for 3 h. TLC (PE: EtOAc = 5:1) showed the reaction was complete. The reaction mixture was quenched with HO (400 mL) and extracted with DCM (400 mL × 3). The organic layer was dried over Na2SO4 and concentrated to give methyl-(2E)-2-[3-chloro-2-(methoxymethyl)phenyl]-2-methoxyiminoacetate (44.5 g, yield: 99.5%) as a yellow oil. 1H NMR:(400MHz,CHCl3-d):δ=7.41-7.50(m,1H),7.28-7.34(m,1H),7.09(dd,J=7.63, 1.00Hz,1H),4.64(s,2H),4.01-4.07(m,3H),3.85-3.96(m,3H),3.25-3.41(m,3H).

[0361] Step 8: Methyl-(2E)-2-[2-(bromomethyl)-3-chlorophenyl]-2-methoxyimino-acetate [ka] To a solution of methyl-(2E)-2-[3-chloro-2-(methoxymethyl)phenyl]-2-methoxyimino-acetate (44.5 g, 164 mmol) in DCM (1 L) was added HBr / AcOH (ca. 33%) (120 g, 493 mmol) and stirred at 35 °C for 16 h. TLC (PE: EtOAc = 5:1) showed the reaction was complete. The reaction mixture was quenched with HO (800 mL) and extracted with DCM (800 mL × 3). The organic layer was dried over NaSO and concentrated to give methyl-(2E)-2-[2-(bromomethyl)-3-chlorophenyl]-2-methoxyimino-acetate (27 g, 51.6% yield) as a yellow solid. 1 H NMR:(400MHz,CHCl3-d):δ=7.48(dd,J=8.03,1.13Hz,1H),7.34(t,J=7.84Hz,1H),7.06(dd,J=7.65,1.13Hz,1H),4.44(br s,2H),4.08(s,3H),3.90(s,3H).

[0362] Step 9: Methyl (2E)-2-[3-chloro-2-[[(Z)-[1-(4-fluorophenyl)-2-methoxyethylidene]amino]oxymethyl]phenyl]-2-methoxyimino-acetate [ka] To a solution of 1-(4-fluorophenyl)-2-methoxyethanone oxime (7.9 g, 43.2 mmol) in MeCN (100 mL) was added methyl-(2E)-2-[2-(bromomethyl)-3-chlorophenyl]-2-methoxyiminoacetic acid (14.5 g, 45.3 mmol) and CsCO (28 g, 86.4 mmol), followed by stirring at 15 °C for 2 h. LCMS showed the reaction was complete. The reaction mixture was quenched with HO (100 mL) and extracted with EtOAc (100 mL × 3). The organic layer was dried over NaSO, concentrated, purified by HPLC, and lyophilized to give the title compound (15 g, yield: 82.3%) as a yellow solid. 1 H NMR:(400MHz,CHCl3-d):δ=7.59-7.67(m,2H),7.48(dd,J=8.09,0.94Hz,1H),7.34(t,J=7.84Hz,1H),7.0 6-7.11(m,1H),6.99-7.06(m,2H),5.12-5.32(m,2H),4.53(s,2H),4.01(s,3H),3.74(s,3H),3.26(s,3H).

[0363] Example 2: (2E)-2-[3-chloro-2-[[(Z)-[1-(4-fluorophenyl)-2-methoxyethylidene]amino]oxymethyl]phenyl]-2-methoxyimino-N-methylacetamide (No. 2) [ka] To a solution of methyl (2E)-2-[3-chloro-2-[[(Z)-[1-(4-fluorophenyl)-2-methoxyethylidene]amino]oxymethyl]phenyl]-2-methoxyimino-acetate (5.5 g, 13.0 mmol) in THF (80 mL) was added MeNH2 (ca. 30% aqueous solution) (12.2 g, 118.0 mmol) and stirred at 15 °C for 2 h. TLC (PE: EtOAc = 3:1) showed the reaction was complete. The reaction mixture was concentrated to give the title compound (5.3 g, yield: 96.7%) as a yellow solid. 1H NMR:(400MHz,CHCl3-d):δ=7.59-7.67(m,2H),7.46(dd,J=8.00,1.00Hz,1H),7. 34(t,J=7.88Hz,1H),7.11(dd,J=7.63,1.00Hz,1H),6.99-7.07(m,2H),6.78(br d,J=4.25Hz,1H),5.07-5.43(m,2H),4.52(s,2H),3.93(s,3H),3.26(s,3H),2.85(d,J=5.00Hz,3H).

[0364] Example 3: Methyl-(2E)-2-[2-[[(Z)-[1-(2-bromophenyl)-2-methoxyethylidene]amino]oxymethyl]-3-chlorophenyl]-2-methoxyimino-acetate Step 1: 1-(2-bromophenyl)-2-methoxyethanone [ka] To a solution of 1-bromo-2-iodobenzene (50 g, 0.177 mol) in THF (500 mL) was added isopropyl MgCl (2 M) (97 mL, 0.194 mol) at 0 °C and stirred under N at 0 °C for 0.5 h. Then, N,2-dimethoxy-N-methylacetamide (28.2 g, 0.212 mol) in THF (50 mL) was added and stirred under N at 0 °C for 2 h. TLC (PE: EtOAc = 3:1) showed the reaction was complete. The reaction mixture was quenched with aqueous HCl (0.5 M) (500 mL), extracted with EtOAc (500 mL × 3), dried over NaSO, concentrated, and purified by column chromatography (PE: EtOAc = 9:1) to give 1-(2-bromophenyl)-2-methoxy-ethanone (33 g, 81.7%) as a yellow oil. 1 H NMR:(400MHz,CHCl3-d)δ=7.50-7.55(m,1H),7.27-7.33(m,2H),7.21-7.26(m,1H),4.46(s,2H),3.40(s,3H).

[0365] Step 2: 1-(2-bromophenyl)-2-methoxyethanone oxime [ka] To a solution of 1-(2-bromophenyl)-2-methoxyethanone (10 g, 0.044 mol) in MeOH (100 mL) was added NaAc (7.2 g, 0.088 mmol) and NHOH.HCl (6 g, 0.088 mmol). The reaction was stirred under N at 50 °C for 3 h. TLC (PE: EtOAc = 3:1) showed the reaction was complete. The reaction was poured into water (200 mL), extracted with EtOAc (100 mL × 3), washed with brine, dried over NaSO, concentrated, and purified by column chromatography (PE: EtOAc = 9:1) to give 1-(2-bromophenyl)-2-methoxyethanone oxime (8.8 g, 81.9%) as a yellow solid. 1H NMR:(400MHz,CHCl3-d)δ=7.51(d,J=7.91Hz,1H),7.26(d,J=4.27Hz,2H),7.14-7.20(m,1H),4.57(s,2H),3.21(s,3H).

[0366] Step 3: Methyl-(2E)-2-[2-[[(Z)-[1-(2-bromophenyl)-2-methoxyethylidene]amino]oxymethyl]-3-chlorophenyl]-2-methoxyimino-acetate [ka] To a solution of 1-(2-bromophenyl)-2-methoxyethanone oxime (9.5 g, 0.039 mol) in MeCN (150 mL) was added methyl (2E)-2-[2-(bromomethyl)-3-chlorophenyl]-2-methoxyiminoacetate (12.5 g, 0.038 mmol) and CsCO (26.6 g, 0.082 mmol). The reaction mixture was stirred under N at 20 °C for 16 h. TLC (PE: EtOAc = 3:1) showed the reaction was complete. The reaction was filtered, and the filtrate was concentrated and purified by column chromatography (PE: EtOAc = 9:1) to give the title compound (14 g, 74.3%) as a yellow solid. 1H NMR:(400MHz,CHCl3-d)δ=7.56(dd,J=7.88,0.63Hz,1H),7.48(dd,J=8.13,1.00Hz ,1H),7.28-7.39(m,3H),7.19-7.25(m,1H),7.11(dd,J=7.63,1.00Hz,1H),5.21(br s,2H),4.53(s,2H),4.04(s,3H),3.72(s,3H),3.23(s,3H).

[0367] Example 4: Methyl-(2E)-2-[3-chloro-2-[[(Z)-(2-methoxy-1-phenylethylidene)amino]oxymethyl]phenyl]-2-methoxyimino-acetate (No. 3) [ka] To a solution of methyl (2E)-2-[2-[[(Z)-[1-(2-bromophenyl)-2-methoxyethylidene]amino]oxymethyl]-3-chlorophenyl]-2-methoxyimino-acetate (14.5 g, 0.03 mol) in 1,4-dioxane (150 mL) was added triethylsilane (10.4 g, 0.09 mol), CsF (9.1 g, 0.06 mol), and [1,1'-bis-(diphenylphosphino)-ferrocene]-dichloro-palladium(II) (Pd(dppf)Cl) (2.2 g, 0.003 mol). The reaction mixture was stirred at 100 °C under N for 24 h. TLC (PE: EtOAc = 3:1) showed the reaction was complete. The reaction was filtered, poured into water (100 mL), extracted with EtOAc (100 mL × 3), washed with brine (50 mL × 3), dried over Na2SO4, concentrated and purified by column (PE: EtOAc = 9:1) to give the title compound (10 g, 82.3%) as a yellow oil. 1 H NMR:(400MHz,CHCl3-d)δ=7.63(dd,J=6.63,2.88Hz,2H),7.48(d,J=8.00Hz,1H),7.30-7.39(m,4H),7.09(d,J=7.50Hz,1H),5.25(br s,2H),4.55(s,2H),4.01(s,3H),3.73(s,3H),3.27(s,3H).

[0368] Example 5: (2E)-2-[3-chloro-2-[[(Z)-(2-methoxy-1-phenylethylidene)amino]oxymethyl]phenyl]-2-methoxyimino-N-methylacetamide (No. 4) [ka] To a solution of methyl-(2E)-2-[3-chloro-2-[[(Z)-(2-methoxy-1-phenylethylidene)amino]oxymethyl]phenyl]-2-methoxyiminoacetate (4.9 g, 0.012 mol) in THF (50 mL) was added MeNH (ca. 30% aqueous solution) (12.5 g, 0.12 mol), and the mixture was stirred under N at 20 °C for 16 h. TLC (PE: EtOAc = 3:1) showed the reaction was complete. The reaction was concentrated and purified by column chromatography (PE: EtOAc = 4:1) to give the title compound (4 g, 82.7%) as a white solid. 1 H NMR:(400MHz,CHCl3-d)δ=7.63(dd,J=6.63,3.00Hz,2H),7.42-7.51(m,1H),7.29-7.39(m,4H),7.08-7.1 6(m,1H),6.71-6.84(m,1H),5.03-5.51(m,2H),4.54(s,2H),3.93(s,3H),3.27(s,3H),2.74-2.92(m,3H).

[0369] Example 6: Methyl-(E)-2-[3-bromo-2-[[(Z)-[3-(4-fluorophenyl)-1-(methoxymethyl)prop-2-ynylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (No. 8) Step 1: Methyl 2-(3-bromo-2-methylphenyl)-2-oxo-acetate [ka] To a mixture of 1-bromo-3-iodo-2-methyl-benzene (20.28 g, 68.3 mmol) in THF (200 mL) was added isopropyl MgCl (2 M) (37 mL, 74.2 mmol) dropwise at 0 °C under N. The mixture was stirred at 0 °C under N for 0.5 h. CuI (14.3 g, 75.1 mmol) was added in small portions at 20 °C, and the mixture was stirred at 25 °C for 1 h. The reaction mixture was then added to methyl-2-chloro-2-oxo-acetate (12.55 g, 102.4 mol) in THF (250 mL) at -70 °C under N. The mixture was gradually warmed to 25 °C and stirred for 15 h. TLC (PE: EtOAc = 5:1) indicated the reaction was complete. Two batches of parallel reactions were combined. The reaction solution was quenched with aqueous NH4Cl (1 L) at 0 °C and extracted with EtOAc (500 mL × 2). The combined organic phase was washed with brine (500 mL), dried over Na2SO4, filtered, concentrated, and purified by column chromatography (PE: EtOAc = 9:1) to give methyl-2-(3-bromo-2-methyl-phenyl)-2-oxo-acetate (21.4 g, yield: 61%) as a yellow oil. 1 H NMR:(400MHz,CHCl3-d)δ=7.74-7.84(m,1H)7.58(d,J=7.75Hz,1H)7.20(t,J=7.88Hz,1H)3.97(s,3H)2.61(s,3H).

[0370] Step 2: Methyl-(E)-2-(3-bromo-2-methylphenyl)-3-methoxy-prop-2-enoate [ka] To a solution of methoxymethyltriphenylphosphonium bromide (17 g, 50.0 mmol) in THF (180 mL), lithium bis(trimethylsilyl)amide (LiHMDS) (1 M) (50 mL, 50.0 mmol) was added dropwise at 0 °C under N2, and the mixture was stirred at 0 °C for 1 h. Then, methyl 2-(3-bromo-2-methylphenyl)-2-oxoacetate (10.7 g, 41.6 mmol) in THF (20 mL) was added dropwise, and the mixture was gradually warmed to 25 °C and stirred for 15 h. TLC (PE: EtOAc = 5:1) indicated the reaction was complete. Two parallel batches of the reaction mixture were combined. The reaction solution was quenched with aqueous NH4Cl (1 L) at 0 °C and extracted with MTBE (500 mL × 3). The combined organic phase was washed with brine (500 mL), dried over NaSO, filtered, concentrated and purified by column chromatography (PE: EtOAc = 85:15) to give methyl-(E)-2-(3-bromo-2-methylphenyl)-3-methoxy-prop-2-enoate (19 g, yield: 80%) as a yellow solid. 1 H NMR:(400MHz,CHCl3-d)δ=7.57(s,1H)7.51(dd,J=7.07,2.19Hz,1H)7.00-7.11(m,2H)3.84(s,3H)3.71(s,3H)2.26(s,3H).

[0371] Step 3: Methyl-(E)-2-[3-bromo-2-(bromomethyl)phenyl]-3-methoxy-prop-2-enoate [ka] To a solution of methyl-(E)-2-(3-bromo-2-methylphenyl)-3-methoxy-prop-2-enoate (11 g, 38.6 mmol) in cyclohexane (220 mL) was added azobis(isobutyronitrile) (AIBN) (0.63 g, 3.86 mmol), followed by the addition of NBS (20.6 g, 115.8 mmol) in small portions at 85 °C under N. The mixture was stirred at 85 °C for 16 h. HPLC showed the reaction was complete. Two batches of parallel reactions were combined. The reaction mixture was quenched with water (1 L) and extracted with EtOAc (500 mL × 3). The combined organic phase was washed with brine (500 mL), dried over NaSO, filtered, and concentrated. The residue was purified by silica gel column (PE: EtOAc = 85:15) to give methyl-(E)-2-[3-bromo-2-(bromomethyl)phenyl]-3-methoxy-prop-2-enoate (16.7 g, yield: 59%) as a yellow solid. 1 H NMR:(400MHz,CHCl3-d)δ=7.65(s,1H)7.55-7.60(m,1H)7.15-7.20(m,1H)7.09(dd,J=7.63,1.13Hz,1H)4.55(br,2H)3.85(s,3H)3.71(s,3H).

[0372] Step 4: 4-(4-fluorophenyl)-1-methoxy-but-3-yn-2-one [ka] To a solution of 4-fluorophenylacetylene (25 g, 208.3 mmol) in THF (300 mL), n-BuLi (2.5 M) (88 mL, 218.7 mmol) was added dropwise at −78°C and stirred at −78°C for 1 h. A solution of N,2-dimethoxy-N-methylacetamide (33.2 g, 250 mmol) in THF (50 mL) was added to the mixture at −78°C and stirred at −78°C for 2 h. TLC (PE: EtOAc = 5:1) showed the reaction was complete. The reaction mixture was quenched with water (500 mL), extracted with EtOAc (200 mL × 3), dried over NaSO, and purified by column chromatography (PE: EtOAc = 5:1) to give 4-(4-fluorophenyl)-1-methoxy-but-3-yn-2-one (35 g, 87.5%) as a yellow oil. 1 H NMR:(400MHz,CHCl3-d)δ=7.60(dd,J=8.78,5.27Hz,2H),7.03-7.16(m,2H),4.26(s,2H),3.52(s,3H).

[0373] Step 5: 4-(4-Fluorophenyl)-1-methoxy-but-3-yn-2-one oxime [ka] To a solution of NHOH.HCl (25 g, 365.0 mmol) in MeOH (350 mL) was added NaAc (29.9 g, 365 mmol) at 15 °C, and the mixture was stirred under N at 15 °C for 0.5 h. Then, 4-(4-fluorophenyl)-1-methoxy-but-3-yn-2-one (35 g, 182 mmol) in 2-MeTHF (50 mL) was added to the mixture at 15 °C, and the mixture was stirred at 15 °C for 3 h. TLC (PE: EtOAc = 3:1) showed that the reaction was complete. The reaction was poured into water (300 mL), extracted with DCM (300 mL × 3), dried over NaSO, concentrated, and purified by column chromatography (PE: EtOAc = 3:1) to give 4-(4-fluorophenyl)-1-methoxy-but-3-yn-2-one oxime (17 g, 45.1%) as a yellow solid. 1H NMR:(400MHz,CHCl3-d)δ=7.49-7.58(m,2H),7.05(t,J=8.76Hz,2H),4.40(s,2H),3.50(s,3H).

[0374] Step 6: Methyl-(E)-2-[3-bromo-2-[[(Z)-[3-(4-fluorophenyl)-1-(methoxymethyl)prop-2-ynylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate [ka] To a solution of 4-(4-fluorophenyl)-1-methoxy-but-3-yn-2-one oxime (3.6 g, 0.017 mol) in DMF (40 mL), methyl-(E)-2-(3-bromo-2-methylphenyl)-3-methoxy-prop-2-enoate (6.33 g, 0.017 mol) and K2CO3 (5.04 g, 0.037 mol) were added under N2 at 20 °C. The mixture was stirred at 80 °C under N2 for 16 h. TLC (PE: EtOAc = 3:1) and LCMS indicated that the reaction was complete. The mixture was filtered, and the filtrate was concentrated. Two batches of parallel reactions were combined. The residue was extracted with EtOAc (100 mL × 2). The organic layer was washed with brine (500 mL × 3), dried over Na2SO4, concentrated, purified by column chromatography (PE: EtOAc = 85:15), triturated with n-hexane (20 mL), and filtered to give the title compound (4.7 g, 28%) as a white solid. 1H NMR (400 MHz, CHCl3-d) δ = 7.56-7.63 (m, 2H), 7.48-7.55 (m, 2H), 7.22 (t, J = 7.82 Hz, 1H), 7.10-7.15 (m, 1H), 7.04 (t, J = 8.69 Hz, 2H), 5.24 (s, 2H), 4.26 (s, 2H), 3.83 (s, 3H), 3.70 (s, 3H), and 3.43 (s, 3H).

[0375] Example 7: Methyl-(E)-2-[3-chloro-2-[[(Z)-[3-(4-fluorophenyl)-1-(methoxymethyl)prop-2-ynylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (No. 5) [ka] To a solution of 4-(4-fluorophenyl)-1-methoxy-but-3-yn-2-one oxime (10.5 g, 50.7 mmol) in MeCN (100 mL) was added methyl-(2E)-2-[2-(bromomethyl)-3-chlorophenyl]-2-methoxyimino-acetate (17.8 g, 55.8 mmol) and CsCO (33.1 g, 101.4 mmol). The reaction mixture was stirred under N at 20 °C for 16 h. LCMS showed the reaction was complete. The reaction mixture was quenched with water (100 mL), extracted with EtOAc (100 mL × 3), dried over NaSO, concentrated, purified by HPLC, and lyophilized to give the title compound (11 g, 48.6%) as a yellow solid. 1 H NMR:(400MHz,CHCl3-d)δ=7.50-7.55(m,2H),7.48(dd,J=8.07,1.06Hz,1H),7.36(t,J=7.82Hz,1H),7.10(dd,J=7 .63,1.00Hz,1H),7.03(t,J=8.69Hz,2H),4.99-5.42(dr,2H),4.24(s,2H),4.06(s,3H),3.87(s,3H),3.43(s,3H).

[0376] Example 8: (2E)-2-[3-chloro-2-[[(Z)-[3-(4-fluorophenyl)-1-(methoxymethyl)prop-2-ynylidene]amino]oxymethyl]phenyl]-2-methoxyimino-N-methylacetamide (No. 6) [ka] To a solution of methyl-(E)-2-[3-chloro-2-[[(Z)-[3-(4-fluorophenyl)-1-(methoxymethyl)prop-2-ynylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (5.5 g, 12.3 mmol) in THF (60 mL) was added MeNH (ca. 30% aqueous solution) (12.7 g, 123 mmol). The reaction mixture was stirred under N at 20 °C for 2 hours. LCMS showed the reaction was complete. The reaction mixture was concentrated to give the title compound (5.2 g, 95.0%) as a yellow solid. 1H NMR:(400MHz,CHCl3-d)δ=7.49-7.55(m,2H),7.47(d,J=8.07Hz,1H),7.35(t,J=7.89Hz,1H),7.11(d,J=7.58Hz,1H),7.04(t,J=8.62Hz,2H),6.83(br d,J=4.16Hz,1H),5.00-5.50(m,2H),4.24(s,2H),3.97(s,3H),3.42(s,3H),2.92(d,J=5.01Hz,3H).

[0377] Example 9: Methyl (E)-2-[3-chloro-2-[[(Z)-[3-(4-fluorophenyl)-1-(methoxymethyl)prop-2-ynylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (No. 7) Step 1: Methyl-2-(3-chloro-2-methylphenyl)-2-oxo-acetate [ka] To a mixture of 1-chloro-3-iodo-2-methyl-benzene (36.5 g, 144.0 mmol) in THF (360 mL) was added isopropyl MgCl (2 M) (76.0 mL, 151.0 mmol) dropwise under N at 0 °C. The mixture was stirred under N at 0 °C for 0.5 h. CuI (30.2 g, 159.0 mmol) was then added portionwise at 20 °C, and the mixture was stirred at 25 °C for 1 h. The reaction mixture was then added dropwise to 2-chloro-2-oxomethyl acetate (26.5 g, 216 mol) in THF (530 mL) at -70 °C under N. The mixture was gradually warmed to 25 °C and stirred for 15 h. TLC (PE: EtOAc = 5:1) indicated the reaction was complete. Two batches of parallel reactions were combined. The reaction solution was quenched with aqueous NH4Cl (1 L) at 0 °C and extracted with EtOAc (500 mL × 2). The combined organic phase was washed with brine (500 mL), dried over Na2SO4, filtered, concentrated, and purified by column chromatography (PE: EtOAc = 9:1) to give methyl-2-(3-chloro-2-methyl-phenyl)-2-oxo-acetate (30 g, yield: 49%) as a yellow solid. 1 H NMR:(400MHz,CHCl3-d)δ=7.60(d,J=8.00Hz,1H)7.54(dd,J=7.75,0.88Hz,1H)7.27(m,1H)3.97(s,3H)2.58(s,3H).

[0378] Step 2: Methyl-(E)-2-(3-chloro-2-methylphenyl)-3-methoxy-prop-2-enoate [ka] To a solution of methoxymethyltriphenylphosphonium bromide (29 g, 84.5 mmol) in THF (300 mL), 1 M LiHMDS (85 mL, 84.5 mmol) was added dropwise at 0 °C under N2, and the mixture was stirred at 0 °C for 1 h. Then, methyl 2-(3-chloro-2-methylphenyl)-2-oxoacetate (15 g, 70.4 mmol) in THF (30 mL) was added dropwise at 0 °C, and the mixture was gradually warmed to 25 °C and stirred for 15 h. TLC (PE: EtOAc = 5:1) indicated the reaction was complete. The two batches were combined. The reaction solution was quenched with aqueous NH4Cl (1 L) at 0 °C and extracted with MTBE (500 mL × 3). The combined organic phase was washed with brine (500 mL), dried over NaSO, filtered, concentrated and purified by column chromatography (PE: EtOAc = 85:15) to give methyl-(E)-2-(3-chloro-2-methylphenyl)-3-methoxy-prop-2-enoate (22 g, yield: 65%) as a yellow solid. 1 H NMR:(400MHz,CHCl3-d)δ=7.58(s,1H)7.32(dd,J=7.94,1.06Hz,1H)7.13(t,J= 7.82Hz,1H)7.03(dd,J=7.63,1.13Hz,1H)3.84(s,3H)3.71(s,3H)2.23(s,3H).

[0379] Step 3: Methyl-(E)-2-[2-(bromomethyl)-3-chloro-phenyl]-3-methoxy-prop-2-enoate [ka] To a solution of methyl-(E)-2-(3-chloro-2-methylphenyl)-3-methoxy-prop-2-enoate (11 g, 46.1 mmol) in cyclohexane (220 mL) was added AIBN (0.75 g, 4.61 mmol), followed by NBS (24.6 g, 138.2 mmol) in small portions at 85 °C under N. The mixture was stirred at 85 °C for 16 h. HPLC showed the reaction was complete. Two batches of parallel reactions were combined. The reaction mixture was quenched with water (1 L) and extracted with EtOAc (500 mL × 3). The combined organic phase was washed with brine (500 mL), dried over NaSO, filtered, and concentrated. The residue was purified by column (PE: EtOAc = 85:15) to give methyl-(E)-2-[2-(bromomethyl)-3-chloro-phenyl]-3-methoxy-prop-2-enoate (20 g, yield: 68%) as a yellow solid. 1 H NMR:(400MHz,CHCl3-d)δ=7.66(s,1H)7.38(dd,J=8.07,1.19Hz,1H)7.27(m, 1H)7.06(dd,J=7.63,1.25Hz,1H)4.36-4.66(s,2H)3.85(s,3H)3.72(s,3H).

[0380] Step 4: Methyl-(E)-2-[3-chloro-2-[[(Z)-[3-(4-fluorophenyl)-1-(methoxymethyl)prop-2-ynylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate [ka] To a solution of 4-(4-fluorophenyl)-1-methoxy-but-3-yn-2-one oxime (5 g, 24.1 mmol) in MeCN (100 mL) was added methyl-(E)-2-[2-(bromomethyl)-3-chlorophenyl]-3-methoxy-prop-2-enoate (7.68 g, 24.1 mmol) and CsCO (15.6 g, 48 mmol). The reaction mixture was stirred under N at 20 °C for 4 h. TLC (PE: EtOAc = 3:1) showed the reaction was complete. The reaction was filtered, and the filtrate was concentrated and purified by column chromatography (PE: EtOAc = 8:1) and HPLC to give the title compound (5.2 g, 48.7%) as a yellow oil. 1 H NMR:(400MHz,CHCl3-d)δ=7.59(s,1H),7.49-7.55(m,2H),7.40(dd,J=8.00,1.25Hz,1H),7.30(t,J =7.82Hz,1H),7.00-7.11(m,3H),5.24(s,2H),4.25(s,2H),3.83(s,3H),3.71(s,3H),3.42(s,3H).

[0381] Example 10: Methyl-(E)-2-[3-chloro-2-[[(Z)-[1-(2-chlorophenyl)-2-methoxyethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (No. 15) [ka] Step 1: 1-(2-chlorophenyl)-2-methoxyethanone 2.9 mL (5.75 mmol) of isopropylmagnesium chloride (2.0 M in tetrahydrofuran) was cooled to -5 °C. 1-Bromo-2-chlorobenzene (1 g, 5.23 mmol) was added, and the reaction was stirred for 1 hour. To this, a 1 mL THF solution of N,2-dimethoxy-N-methylacetamide (0.695 g, 6.2 mmol) was added dropwise over 5 minutes. The reaction was continued to stir at -5 °C for 1 hour. Completion of the reaction was monitored by TLC (20% ethyl acetate in heptane). The reaction was then quenched with aqueous ammonium chloride (10 mL), extracted with methyl tert-butyl ether (MTBE) (3 × 10 mL), washed with brine, and dried over Na SO . The solvent was evaporated under vacuum to give 0.8 g of 1-(2-chlorophenyl)-2-methoxy-ethanone as a yellowish liquid, which was used in the next step without further purification. Yield (crude): 82.9%. 1 H NMR(500MHz,DMSO-d6)δ=7.69-7.62(m,1H),7.58-7.53(m,2H),7.49-7.43(m,1H),7.33-7.26(m,1H),4.57(s,2H),3.3(s,3H).

[0382] Step 2: 1(Z)-(2-chlorophenyl)-2-methoxyethanone oxime Crude 1-(2-chlorophenyl)-2-methoxy-ethanone (0.8 g, 4.33 mmol) was dissolved in 8 mL of methanol. NaAc (0.711 g, 8.66 mmol) was added, followed by hydroxylamine hydrochloride (0.452 g, 6.499 mmol). The reaction mixture was heated to 50 °C and stirred for 2 h. The reaction was diluted with water (8 mL) and extracted with DCM (3 × 8 mL). The organic layer was washed with brine, dried over NaSO, filtered, and evaporated in vacuo to give 0.8 g of a crude mixture of the Z- and E-isomers of 1-(2-chlorophenyl)-2-methoxy-ethanone oxime in a 75:25 ratio. The Z isomer was purified by flash column chromatography (15–20% EtOAc in heptane). Yield: 0.450 g, 52%. The desired isomer of 1(Z)-(2-chlorophenyl)-2-methoxy-ethanone oxime (52%).1 H NMR(500MHz,DMSO-d6)δ=11.56(s,1H),7.47(m,1H),7.42-7.39(m,1H),7.39-7.34(m,2H),4.53(s,2H),3.16(s,3H).

[0383] Step 3: Methyl-(E)-2-[3-chloro-2-[[(Z)-[1-(2-chlorophenyl)-2-methoxy-ethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate To a solution of 1(Z)-(2-chlorophenyl)-2-methoxyethanone oxime (1 g, 5.01 mmol) in 10 mL of AcN, cesium carbonate (3.2 g, 10.02 mmol) and methyl-(E)-2-[2-(bromomethyl)-3-chlorophenyl]-3-methoxy-prop-2-enoate (1.6 g, 5.01 mmol) were added, and the reaction mixture was stirred at room temperature for 16 h. The reaction mixture was diluted with water (10 mL) and extracted with MTBE (1 mL × 3). The organic layer was separated, washed with brine, dried over Na2SO4, filtered, and subsequently evaporated in vacuo. Purification by flash chromatography (15-20% EtOAc in heptane) afforded the title compound as a white solid. Yield: 1.4 g, 63.7%. 1 H NMR(500MHz,DMSO-d6)δ=7.70(s,1H),7.47(dd,2H),7.44-7.40(m,1H),7.39-7.34(m,2H),7 .31(dd,1H),7.12(d,1H),5.12(s,2H),4.41(s,2H),3.81(s,3H),3.58(s,3H),3.11(s,3H).

[0384] Example 11: Methyl-(E)-2-[3-chloro-2-[[(Z)-[2-methoxy-1-(2,4,6-trifluorophenyl)ethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (No. 12) [ka] Step 1: 2-Methoxy-1(Z)-(2,4,6-trifluorophenyl)ethanone oxime A solution of diisopropylamine (16.85 g, 0.17 mol) in 100 mL of THF was cooled to 0°C. To this was added 60 mL of n-butyllithium (2.5 M in heptane, 0.15 mol) dropwise, maintaining the temperature at 0°C. The reaction mixture was stirred for an additional 15 minutes and then cooled to -78°C. To this mixture was added a solution of 1,3,5-trifluorobenzene (20 g, 0.15 mol) in 50 mL of THF over 30 minutes. The reaction mixture was stirred at -78°C for 1 hour. To this mixture was added a solution of N,2-dimethoxy-N-methylacetamide (24.19 g, 0.18 mol) in 50 mL of THF dropwise over 1 hour at -78°C. The reaction mixture was stirred at the same temperature for 1 hour and then quenched with 200 mL of 1 N aqueous HCl. The organic layer was separated, and the aqueous layer was washed with 200 mL of MTBE. The organic layers were combined, washed with brine, dried over NaSO, and concentrated in vacuo to give 18 g of crude 2-methoxy-1-(2,4,6-trifluorophenyl)ethanone. The crude mass was dissolved in 230 mL of methanol, and 13.9 g (0.17 mol) of NaAc and 11.7 g (0.17 mol) of hydroxylamine hydrochloride were added. The mixture was heated to 50°C and stirred for 2 hours. The reaction was cooled to room temperature, and the solvent was evaporated in vacuo to half its volume. The residual mass was diluted with 200 mL of water and extracted with DCM (100 mL x 2). The organic layers were combined, washed with brine (2 x 30 mL), dried over NaSO, and concentrated in vacuo. The crude mass thus obtained was purified by column chromatography to give 10 g of 2-methoxy-1(Z)-(2,4,6-trifluorophenyl)ethanone oxime. Yield: 30%. 1 H NMR(500MHz,DMSO-d6)δ=11.93(s,1H),7.34-7.18(m,2H),4.45(s,2H),3.18(s,3H).

[0385] Step 2: Methyl-(E)-2-[3-chloro-2-[[(Z)-[2-methoxy-1-(2,4,6-trifluorophenyl)ethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate To a solution of methyl (E)-2-[2-(bromomethyl)-3-chlorophenyl]-3-methoxyprop-2-enoate (5 g, 0.016 mol) in AcN (40 mL) was added cesium carbonate (10.19 g, 0.031 mol) and stirred at room temperature for 10 minutes. 2-Methoxy-1-(2,4,6-trifluorophenyl)ethanone oxime (3.49 g, 0.016 mol) in 10 mL AcN was added to the reaction mixture and stirred at room temperature for an additional 16 hours. The reaction was filtered, concentrated in vacuo, and purified by column chromatography (0-20% ethyl acetate in heptane) to give 5.5 g of the title compound. Yield: 5.5 g (75%). LCMS: RT: 2.28 min (M+458.2). 1 H NMR(500MHz,DMSO-d6)δ=7.69(s,1H),7.47(dd,J=8.1,1.3Hz,1H),7.38(t,J=7.8Hz,1H),7.28(dd,J=9.3, 7.9Hz,2H),7.12(dd,J=7.6,1.3Hz,1H),5.13(s,2H),4.32(s,2H),3.80(s,3H),3.57(s,3H),3.14(s,3H).

[0386] Example 12: Methyl-(E)-2-[3-chloro-2-[[(Z)-[1-(3-fluorophenyl)-2-methoxy-ethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (No. 14) [ka] Step 1: 1-(3-fluorophenyl)-2-methoxyethanone Mg (0.153 g, 6.2 mmol) and iodine (0.001 g, 0.0057 mmol) in 5 mL of THF were heated to 50 °C and stirred for 5 minutes until the iodine color disappeared. A solution of 1-bromo-3-fluorobenzene (1 g, 5.7143 mmol) in 2 mL of THF was added dropwise and stirred at 50 °C for 1 hour. The reaction mixture was cooled to 0 °C, and 2-methoxyacetonitrile (0.48 g, 6.857 mmol) in 2 mL of THF was added. The temperature was raised to 10 °C and stirred for 1 hour. The reaction was quenched with saturated aqueous NH4Cl (5 mL) and extracted with MTBE (10 mL). The aqueous phase was separated and washed with 5 mL of MTBE. The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo to give 1-(3-fluorophenyl)-2-methoxy-ethanone. Yield: 1g (crude). 1 H NMR(500MHz,DMSO-d6)δ=7.5-7.8(m,4H),4.80(s,2H),3.36(s,3H).

[0387] Step 2: 1(Z)-(3-fluorophenyl)-2-methoxyethanone oxime To a solution of 1-(3-fluorophenyl)-2-methoxyethanone (1 g, 6.09 mmol) in 8 mL of MeOH was added NaAc (0.99 g, 12.18 mmol) in 2 mL of water, followed by hydroxylamine hydrochloride (0.84 g, 12.18 mmol). The reaction was heated to 50 °C and stirred for 2 h, then diluted with water (10 mL) and extracted with DCM. The aqueous layer was separated and washed with DCM (5 mL). The combined organic layers were concentrated in vacuo and purified by column chromatography to give 1(Z)-(3-fluorophenyl)-2-methoxy-ethanone oxime. Yield: 0.45 g (43%). 1 H NMR(500MHz,DMSO-d6)δ=11.76(s,1H),7.54-7.16(m,4H),4.57(s,2H),3.3(s,3H).

[0388] Step 3: Methyl-(E)-2-[3-chloro-2-[[(Z)-[1-(3-fluorophenyl)-2-methoxy-ethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate 1(Z)-(3-Fluorophenyl)-2-methoxy-ethanone oxime (1 g, 5.45 mmol) and cesium carbonate (3.5 g, 10.91 mmol) were stirred in 3 mL of AcN at room temperature for 10 minutes. To this was added methyl (E)-2-[2-(bromomethyl)-3-chlorophenyl]-3-methoxy-prop-2-enoate (1.725 g, 5.45 mmol) in 7 mL of AcN and stirred for 16 hours. The reaction was diluted with water (10 mL) and extracted with MTBE (10 mL × 2). The organic layer was washed with brine, dried over Na2SO4, concentrated in vacuo, and purified by column chromatography using 0-20% EtOAc in heptane as the eluent to give the title compound. Yield 1.7 g (75%). 1 H NMR(500MHz,DMSO-d6)δ=7.72(s,1H),7.48-7.34(m,5H),7.27-7.21(m,1H),7.12(dd ,J=7.6,1.3Hz,1H),5.17(s,2H),4.48(s,2H),3.82(s,3H),3.59(s,3H),3.16(s,3H).

[0389] Example 13: Methyl-(E)-2-[3-chloro-2-[[(Z)-[1-(4-fluorophenyl)-2-methoxyethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (No. 9) [ka] Step 1: 1-(4-fluorophenyl)-2-methoxyethanone 140 mL of a 1 M THF solution of 4-phenylmagnesium bromide was cooled to 0 °C. 10 g of 2-methoxyacetonitrile (0.14 mol) was added, and the reaction was warmed to room temperature and stirred for 2 hours. The reaction was quenched with 2 N HCl (100 mL) and extracted with ethyl acetate (100 mL × 2). The organic layer was separated, washed with brine, dried over Na2SO4, and concentrated in vacuo to give 1-(4-fluorophenyl)-2-methoxy-ethanone. Yield (crude): 19 g, 81.5%. 1 H NMR(500MHz,DMSO-d6)δ=7.93-7.79(m,1H),7.75-7.61(m,1H),7.44-7.31(m,2H),4.66(d,J=2.9Hz,2H),1.14(dt,J=10.9,7.0Hz,3H).

[0390] Step 2: 1(Z)-(4-fluorophenyl)-2-methoxyethanone oxime To a solution of 1-(4-fluorophenyl)-2-methoxyethanone (2.0 g, 11.89 mmol) in 15 mL of methanol was added hydroxylamine hydrochloride (1.15 g, 17.84 mmol). To this was added an aqueous solution of NaOH (0.951 g, 23.78 mmol in 2 mL of water), and the reaction was heated to 50° C. and stirred for 3 hours. HPLC of the reaction mass showed a 4:1 ratio of Z and E isomers. Methanol was removed in vacuo, and the reaction mass was extracted with DCM (3×15 mL). The solvent was removed in vacuo, and the crude mass was purified by column chromatography to give 1(Z)-(4-fluorophenyl)-2-methoxy-ethanone oxime. Yield: 1.70 g, 80%. 1 H NMR(500MHz,DMSO-d6)δ=11.58(s,1H),7.67(m,2H),7.22(m,2H),4.6(s,2H),3.2(s,3H).

[0391] Step 3: Methyl-(E)-2-[3-chloro-2-[[(Z)-[1-(4-fluorophenyl)-2-methoxy-ethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate To a solution of 1(Z)-(4-fluorophenyl)-2-methoxyethanone oxime (5 g, 27.29 mmol) in AcN (50 mL) was added cesium carbonate (17.79 g, 54.59 mmol) and stirred for 10 minutes. To this was added methyl (E)-2-[2-(bromomethyl)-3-chlorophenyl]-3-methoxy-prop-2-enoate (8.27 g, 27.29 mmol) and stirred at room temperature for 16 hours. The reaction mixture was filtered, then diluted with water and extracted with EtOAc (2 x 50 mL). The organic phases were combined, washed with brine, dried over Na2SO4, and concentrated in vacuo. The crude mixture was purified by column chromatography (0-20% EtOAc in heptane) to give the title compound. Yield: 5.2 g, 45.25%. LCMS (R t :2.29 minutes, M+:422); 1 H NMR(500MHz,DMSO-d6)δ=7.72(s,1H),7.68-7.58(m,2H),7.49-7.32(m,2H),7.28-7.17(m,2H) ,7.11(dd,J=7.6,1.4Hz,1H),5.14(s,2H),4.47(s,2H),3.81(s,3H),3.59(s,3H),3.15(s,3H).

[0392] Example 14: Methyl-(E)-2-[3-bromo-2-[[(Z)-[1-(4-fluorophenyl)-2-methoxyethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (No. 10) [ka] To a solution of 1(Z)-(4-fluorophenyl)-2-methoxyethanone oxime (5 g, 27.29 mmol) in AcN (50 mL) was added CsCO (17.79 g, 54.59 mmol) and stirred for 10 minutes. To this was added methyl-(E)-2-[2-(bromomethyl)-3-bromophenyl]-3-methoxy-prop-2-enoate (9.88 g, 27.29 mmol) and stirred at room temperature for 16 hours. The reaction mixture was filtered, then diluted with water and extracted with EtOAc (2 × 50 mL). The organic phases were combined, washed with brine, dried over NaSO, and concentrated in vacuo. The crude mixture was purified by column chromatography (0-20% EtOAc in heptane) to give the title compound. Yield: 6.85 g, 54.5%. LCMS (R t :2.23 minutes, M+1:466). 1 H NMR(500MHz,DMSO-d6)δ=7.6-7.8(m,2H),7.5-7.6(m,3H),7.0-7.3(m,3H),5.15(s,2H),4.48(s,2H),3.81(s,3H),3.59(s,3H),3.15(s,3H).

[0393] Example 15: Methyl-(E)-2-[3-chloro-2-[[(Z)-[1-(2-fluorophenyl)-2-methoxyethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (No. 13) [ka] Step 1: 1-(2-fluorophenyl)-2-methoxyethanone 1-Bromo-2-fluorobenzene (10 g, 57.14 mmol) was dissolved in 50 mL of THF and cooled to 0 °C. A 2 M solution of isopropylmagnesium chloride in THF (34.2 mL, 68.57 mmol) was added dropwise while maintaining the temperature at 0 °C. The mixture was stirred for an additional 1 h. A solution of N,2-dimethoxy-N-methylacetamide (10 g, 68.57 mmol) in THF (20 mL) was added dropwise over 15 min. The reaction was warmed to 5 °C and stirred for 2 h. The reaction mixture was then quenched with 20% aqueous ammonium chloride solution (500 mL) and extracted with MTBE (250 mL × 2). The organic layers were combined, dried over Na2SO4, and concentrated to give 1-(2-fluorophenyl)-2-methoxy-ethanone as a colorless oil. Yield: 9.0 g (crude), 93.16%. 1 H NMR(500MHz,DMSO-d6)δ=7.93-7.79(m,1H),7.75-7.61(m,1H),7.44-7.31(m,2H),4.66(d,J=2.9Hz,2H),1.14(dt,J=10.9,7.0Hz,3H).

[0394] Step 2: 1(Z)-(2-fluorophenyl)-2-methoxyethanone oxime To a solution of 1-(2-fluorophenyl)-2-methoxyethanone (10 g, 59.47 mmol) in methanol (100 mL) was added sodium acetate (9.75 g, 118.93 mmol) and hydroxylamine hydrochloride (8.26 g, 118.93 mmol) under N2. The mixture was stirred at 50 °C for 4 h. HPLC showed two isomers in a 9:1 ratio. The reaction mixture was concentrated to 50 mL in vacuo, quenched with water (200 mL), and extracted with DCM (500 mL). The organic layer was washed with brine (500 mL), dried over Na2SO4, and concentrated. The crude mixture was purified by column chromatography (20% EtOAc in heptane) to give 1(Z)-(2-fluorophenyl)-2-methoxy-ethanone oxime. Yield: 6.0 g, 55.08%. 1H NMR(500MHz,DMSO-d6)δ=11.69(s,1H),7.44(dtd,J=14.4,7.5,1.8Hz,2H),7.28-7.15(m,2H),4.52(d,J=1.0Hz,2H),3.16(s,3H).

[0395] Step 3: Methyl-(E)-2-[3-chloro-2-[[(Z)-[1-(2-fluorophenyl)-2-methoxy-ethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate 1(Z)-(2-Fluorophenyl)-2-methoxy-ethanone oxime (4.0 g, 21.84 mmol) and cesium carbonate (14.23 g, 43.67 mmol) were stirred in 40 mL of AcN at room temperature for 10 minutes. To this was added methyl (E)-2-[2-(bromomethyl)-3-chlorophenyl]-3-methoxy-prop-2-enoate (6.97 g, 21.84 mmol) in 10 mL of AcN and stirred for 16 hours. The reaction was diluted with water (10 mL) and extracted with MTBE (50 mL × 2). The organic layer was washed with brine, dried over Na2SO4, concentrated in vacuo, and purified by column chromatography (0-20% EtOAc in heptane) to give the title compound. Yield: 5.3 g, 54%. LCMS (R t :2.20 minutes; M+1, 421.85). 1 H NMR(500MHz,DMSO-d6)δ=7.70(s,1H),7.50-7.40(m,2H),7.42-7.31(m,2H),7.28-7.19(m,2H),7.1 2(dd,J=7.6,1.3Hz,1H),5.14(s,2H),4.40(d,J=1.1Hz,2H),3.80(s,3H),3.58(s,3H),3.11(s,3H).

[0396] Example 16: Methyl-(E)-2-[3-chloro-2-[[(Z)-(2-methoxy-1-phenylethylidene)amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (No. 11) [ka] Step 1: 2-Methoxy-1-phenylethanone A 70 mL THF solution of phenylmagnesium bromide (1 M in THF) was cooled to 0° C. To this was added 5 g (70 mmol) of 2-methoxyacetonitrile and stirred at 10° C. for 1 hour. The reaction was quenched with 2 N HCl (100 mL) and extracted with EtOAc (2×100 mL). The organic phase was separated, washed with brine, dried over Na2SO4, and concentrated in vacuo to give 2-methoxy-1-phenyl-ethanone as a pale yellow liquid. Yield (crude): 10 g, 77%. 1 H NMR(500MHz,DMSO-d6)δ=7.93(dt,J=8.2,1.1Hz,2H),7.65(tdd,J=7.8,2.5,1.2Hz,1H),7.53(tt,J=7.7,1.6Hz,2H),4.79(s,2H),3.38(d,J=1.5Hz,3H).

[0397] Step 2: 2-Methoxy-1(Z)-phenylethanone oxime 10 g (66.59 mmol) of 2-methoxy-1-phenylethanone was dissolved in 80 mL of methanol. To this was added dropwise aqueous sodium hydroxide solution (5.32 g, 133.18 mmol in 20 mL of water) and stirred at room temperature for 10 minutes. 6.94 g (99.89 mmol) of hydroxylamine hydrochloride was added, and the reaction mixture was stirred at 60 °C for 2 hours. The reaction was monitored by HPLC, which confirmed the consumption of the starting material and the formation of isomers in an 80:20 ratio. Methanol was removed in vacuo, and the reaction mass was extracted with DCM (2 × 80 mL). The organic layer was separated, dried over NaSO, and concentrated in vacuo. The crude material thus obtained was purified by column chromatography to give 2-methoxy-1(Z)-phenyl-ethanone oxime (7.0 g, 63.6%). 1 H NMR(500MHz,DMSO-d6)δ=11.57(s,1H),7.68-7.62(m,2H),7.42-7.34(m,3H),4.58(s,2H),3.23(s,3H).

[0398] Step 3: Methyl-(E)-2-[3-chloro-2-[[(Z)-(2-methoxy-1-phenylethylidene)amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate To a solution of 2-methoxy-1(Z)-phenylethanone oxime (6.0 g, 36.32 mmol) in AcN (60 mL) was added cesium carbonate (23.90 g, 72.64 mmol) and methyl (E)-2-[2-(bromomethyl)-3-chlorophenyl]-3-methoxy-prop-2-enoate (12.34 g, 36.32 mmol). The reaction mixture was stirred at room temperature for 16 hours. TLC (20% EtOAc in heptane) showed the reaction was complete. The reaction mixture was quenched with water (150 mL) and extracted with EtOAc (100 mL x 2). The organic phase was separated, washed with brine (100 mL), dried over Na2SO4, concentrated in vacuo, and purified by column chromatography to give the title compound. Yield: 9.9 g (61.42%). LCMS (R t :2.23 minutes; M+H, 404.3), 1 H NMR (500 MHz, DMSO-d 6 )δ=7.72(s,1H),7.59(m,2H),7.46(m,1H),7.41-7.32(m,4H),7.11(m,1H), 5.15(s,2H),4.47(s,2H),3.81(s,3H),3.59(s,3H),3.15(d,J=0.9Hz,3H).

[0399] Example 17: Methyl (E)-2-[3-chloro-2-[[(Z)-[2-methoxy-1-(2-pyridyl)ethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (No. 129) [ka] Step 1: To a solution of 2-iodopyridine (3.0 g, 14.6 mmol) in THF (30 mL) was added i-PrMgCl (2 M) (8.0 mL, 16.0 mmol) dropwise at 0 °C and stirred under N2 at 0 °C for 30 min. Then, N,2-dimethoxy-N-methyl-acetamide (2.5 g, 18.8 mmol) in THF (5 mL) was added to the solution and stirred at 0-20 °C for 4 h. TLC (PE: EtOAc = 1:1) showed the reaction was complete. The reaction was quenched with aqueous NH4Cl (100 mL) and extracted with EtOAc (50 mL × 3). The organic layer was washed with brine (50 mL × 2) and dried over Na2SO4. The residue was concentrated and purified by column (PE: EtOAc = 6:4) to give 2-methoxy-1-(2-pyridyl)ethanone (2.1 g, 95.4%) as a yellow oil. 1 H NMR:(400MHz,CDCl3)δ=8.58-8.66(m,1H)8.05(dt,J=7.82,0.97Hz,1H)7.85(td, J=7.75,1.75Hz,1H)7.49(ddd,J=7.60,4.78,1.25Hz,1H)5.04(s,2H)3.54(s,3H).

[0400] Step 2: To a solution of 2-methoxy-1-(2-pyridyl)ethanone (2.1 g, 13.9 mmol) in methanol (25 mL) was added NaOAC (2.28 g, 27.8 mmol) and NHOH.HCl (1.94 g, 27.8 mmol) at 25 °C. The reaction mixture was stirred under N at 25 °C for 2 h. TLC (PE: EtOAc = 1:1) showed the reaction was complete. The reaction was quenched with aqueous NHCl (100 mL) and extracted with EtOAc (50 mL × 3). The organic layer was washed with brine (50 mL × 2) and dried over NaSO. The residue was concentrated and purified by column chromatography (PE: EtOAc = 1:1) to give 2-methoxy-1-(2-pyridyl)ethanone oxime (1 g, 43.3%) as a yellow oil. 1H NMR: (400MHz,MeOH-d4)δ=8.65(dd,J=4.88,0.75Hz,1H)7.81(d,J=8.00Hz,1H)7.69(td,J=7.75,1.75Hz,1H)7.27(s,1H)4.83(s,2H)3.41(s,3H).

[0401] Step 3: To a solution of 2-methoxy-1-(2-pyridyl)ethanone oxime (0.5 g, 3.0 mmol) in MeCN (7 mL) was added methyl (E)-2-[2-(bromomethyl)-3-chlorophenyl]-3-methoxy-prop-2-enoate (1.15 g, 3.6 mmol) and CsCO (1.96 g, 6.0 mmol) at 25 °C. The reaction mixture was stirred under N at 25 °C for 2 h. TLC (PE: EtOAc = 3:1) showed the reaction was complete. The reaction was quenched with aqueous NHCl (20 mL) and extracted with EtOAc (20 mL × 3). The organic layer was washed with brine (20 mL × 2) and dried over NaSO. The residue was concentrated and purified by preparative HPLC to give the title compound (0.7 g, 57.8%) as a white solid. 1H NMR:(400MHz,CDCl3)δ=8.63(d,J=4.38Hz,1H)7.82(d,J=8.00Hz,1H)7.68(td,J=7.75,1.63Hz,1H)7.59(s,1H)7.40(dd,J=8.00,1.13Hz,1H)7. 27-7.31(m,1H)7.25(ddd,J=7.44,5.00,1.06Hz,1H)7.09(dd,J=7.63,1 .00Hz,1H)5.33(s,2H)4.69(s,2H)3.79(s,3H)3.65(s,3H)3.32(s,3H).

[0402] Example 18: Methyl (E)-2-[3-chloro-2-[[(Z)-[1-(3,5-difluoro-2-pyridyl)-2-methoxyethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (No. 130) [ka] Step 1: To a solution of 3,5-difluoropyridin-2-amine (5 g, 38.5 mmol) and CuI (14.7 g, 76.9 mmol) in MeCN (100 mL) cooled to 0 °C under N was added t-BuONO (8.7 g, 84.6 mmol). The mixture was warmed to 20 °C and stirred at 60 °C under N for 16 h. TLC (PE: EtOAc = 5:1) showed the reaction was complete. The reaction mixture was filtered, and the filtrate was concentrated. The mixture was extracted with EtOAc (100 mL × 2), washed with aqueous NaSO (200 mL) and brine (100 ml), dried over NaSO, and concentrated. The residue was purified by column chromatography (PE: EtOAc = 9:1) and concentrated to give 3,5-difluoro-2-iodopyridine (4.4 g, 47.8%) as a white solid. 1 H NMR:(400MHz,CDCl3)δ=8.24(d,J=2.38Hz,1H)7.16(ddd,J=7.88,6.94,2.56Hz,1H).

[0403] Step 2: To a solution of 3,5-difluoro-2-iodopyridine (4.43 g, 18.4 mmol) in THF (40 mL), i-PrMgCl (2 M) (10.1 mL, 20.2 mmol) was added dropwise at 0 °C and stirred at 0 °C for 30 min. Then, N,2-dimethoxy-N-methyl-acetamide (3.18 g, 23.9 mmol) in THF (2 mL) was added to the solution at 0 °C and stirred at 0–20 °C for 3 h under N2. TLC (PE: EtOAc = 3:1) showed the reaction was complete. The reaction mixture was washed with aqueous NH4Cl (100 mL), extracted with EtOAc (50 mL × 3), and washed with brine (100 mL). The organic layer was dried over Na2SO4 and concentrated. The residue was purified by column (PE: EtOAc = 85:15) to give 1-(3,5-difluoro-2-pyridyl)-2-methoxy-ethanone (2 g, 58.6%) as a yellow solid. 1 H NMR:(400MHz,CDCl3)δ=8.37(d,J=2.25Hz,1H)7.33(ddd,J=10.13,8.07,2.31Hz,1H)4.88(s,2H)3.53(s,3H).

[0404] Step 3: To a solution of 1-(3,5-difluoro-2-pyridyl)-2-methoxyethanone (2.0 g, 10.7 mmol) and NHOH.HCl (1.5 g, 21.4 mmol) in MeOH (20 mL) was added NaOAc (1.75 g, 21.4 mmol) at 20 °C under N. The mixture was stirred at 30 °C under N for 2 h. TLC (PE: EtOAc = 3:1) showed that the reaction was complete. The mixture was quenched with H2O (100 ml) and extracted with EtOAc (50 mL × 3). The organic layer was washed with brine (50 mL) and dried over Na2SO4. The residue was concentrated and purified by column chromatography (PE: EtOAc = 82:18) to give 1-(3,5-difluoro-2-pyridyl)-2-methoxyethanone oxime (1.92 g, 89%) as a yellow solid. 1 H NMR(400MHz,CDCl3)δ=8.42(br d,J=2.38Hz,1H)7.28-7.32(m,1H)4.76(s,2H)3.36(s,3H).

[0405] Step 4: To a solution of 1-(3,5-difluoro-2-pyridyl)-2-methoxy-ethanone oxime (0.5 g, 2.48 mmol) in MeCN (10 mL) was added methyl (E)-2-[2-(bromomethyl)-3-chlorophenyl]-3-methoxyprop-2-enoate (0.79 g, 2.48 mmol) and CsCO (1.61 g, 4.95 mmol) at 20 °C under N. The mixture was stirred at 20 °C under N for 16 h. TLC (PE: EtOAc = 3:1) and LCMS showed that the reaction was complete. The mixture was quenched with H0 (50 mL) and extracted with EtOAc (50 mL × 3). The organic layer was washed with brine (50 mL) and dried over NaSO. The residue was concentrated and purified by column (PE: EtOAc = 85:15) to give the title compound (0.5 g, 46.2%) as a yellow solid. 1 H NMR(400MHz,MeOH-d)δ.=8.39(d,J=2.38Hz,1H)7.67(s,1H)7.60-7.66(m,1H)7.37-7.43(m,1H)7.31(t, J=7.82Hz,1H)7.08(dd,J=7.57,1.19Hz,1H)5.26(s,2H)4.55(s,2H)3.81(s,3H)3.65(s,3H)3.22(s,3H).

[0406] Examples 19 and 20: Methyl (E)-2-[3-chloro-2-[[(Z)-[1-(5-fluoro-2-pyridyl)-2-methoxyethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (No. 131) and methyl (E)-2-[3-chloro-2-[[(E)-[1-(5-fluoro-2-pyridyl)-2-methoxyethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (No. 132) [ka] Step 1: To a solution of 5-fluoropyridin-2-amine (2 g, 17.8 mmol) in CHCl (50 mL) was added CuI (3.7 g, 19.6 mmol), t-BuNO (2 g, 19.6 mmol), and I (4.9 g, 19.6 mmol). The reaction was stirred at 85 °C under N for 20 min. TLC (PE: EtOAc = 3:1) showed the reaction was complete. The two batches were combined. The reaction mixture was concentrated and purified by column chromatography (PE: EtOAc = 9:1) to give 5-fluoro-2-iodo-pyridine (1.8 g, 45%) as a yellow solid. 1 H NMR:(400MHz,MEOH-d4)δ=8.31(d,J=3.13Hz,1H),7.85(dd,J=8.69,4.31Hz,1H),7.35(td,J=8.57,3.13Hz,1H).

[0407] Step 2: To a solution of 5-fluoro-2-iodopyridine (3.6 g, 16.1 mmol) in THF (40 mL) was added i-PrMgCl (2 M) (8.5 mL, 17.0 mmol) at 0 °C and stirred under N at 0 °C for 1 h. Then, N,2-dimethoxy-N-methylacetamide (2.3 g, 17.7 mmol) in THF (10 mL) was added to the solution at 0 °C. The reaction was stirred under N at 0 °C for 1 h. TLC (PE: EtOAc = 5:1) showed the reaction was complete. The reaction mixture was quenched with aqueous NH Cl (50 mL), extracted with EtOAc (30 mL × 3), dried over Na SO , concentrated, and purified by column chromatography (PE: EtOAc = 6:1) to give 1-(5-fluoro-2-pyridyl)-2-methoxy-ethanone (1.5 g, 55%) as a yellow solid. 1 H NMR(400MHz,MeOH-d4)δ=8.55(d,J=2.75Hz,1H),8.12(dd,J=8.76,4.63Hz,1H),7.76(td,J=8.57,2.75Hz,1H),5.01(s,2H),3.50(s,3H).

[0408] Step 3: To a solution of 1-(5-fluoro-2-pyridyl)-2-methoxyethanone (1.5 g, 8.87 mmol) in MeOH (30 mL) was added NaOAc (1.45 g, 17.7 mmol) and NHOH.HCl (1.22 g, 17.7 mmol). The reaction was stirred under N at 20 °C for 1 h. TLC (PE: EtOAc = 3:1) showed the reaction was complete. The reaction was poured into water (50 mL), extracted with EtOAc (30 mL × 3), dried over NaSO, concentrated, and purified by column (PE: EtOAc = 3:1) to give an E / Z mixture of 1-(5-fluoro-2-pyridyl)-2-methoxy-ethanone oxime as a yellow solid ( 1 H NMR showed Z:E=4:1) (0.9 g, 55%). 1 H NMR:(400MHz,MeOH-d4)δ=8.44(d,J=2.88Hz,1H),7.90(dd,J=8.88,4.50Hz,1H),7.59(td,J=8.63,3.00Hz,1H),4.73(s,2H),3.34(s,3H).

[0409] Step 4: To a solution of 1-(5-fluoro-2-pyridyl)-2-methoxy-ethanone oxime (0.97 g, 5.2 mmol) in MeCN (20 mL) was added methyl (E)-2-[2-(bromomethyl)-3-chlorophenyl]-3-methoxy-prop-2-enoate (1.7 g, 5.29 mmol) and CsCO (3.45 g, 10.61 mmol) at 20 °C. The reaction mixture was stirred under N at 20 °C for 3 h. TLC (PE: EtOAc = 3:1) showed the reaction was complete. The reaction was filtered, and the filtrate was concentrated and purified by column (PE: EtOAc = 4:1) and preparative HPLC (NH4HCO3) to give methyl (E)-2-[3-chloro-2-[[(Z)-[1-(5-fluoro-2-pyridyl)-2-methoxyethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (600 mg, 26.8%) as a yellow solid and methyl (E)-2-[3-chloro-2-[[(E)-[1-(5-fluoro-2-pyridyl)-2-methoxyethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate (250 mg, 11.2%) as a yellow solid. 1 H NMR:(400MHz,CDCl3)comp.131:δ=8.46(d,J=2.75Hz,1H),7.85(dd,J=8.82,4.57Hz,1H),7.59(s,1H),7.35-7.43(m,2 H),7.28-7.32(m,1H),7.09(dd,J=7.63,1.13Hz,1H),5.32(s,2H),4.65(s,2H),3.80(s,3H),3.65(s,3H),3.31(s,3H). Compound No. 132 1 H NMR:(400MHz,MeOH-d4):δ=8.50(d,J=2.88Hz,1H),7.97(dd,J=8.82,4.69Hz,1H),7.52-7.64(m,2H),7.34-7.41(m,1H) ),7.25-7.32(m,1H),7.06(dd,J=7.63,1.25Hz,1H),5.21(s,2H),4.43(s,2H),3.76(s,3H),3.58(s,3H),3.26(s,3H).

[0410] Intermediates: methyl-(E)-2-[2-(bromomethyl)-3-chloro-phenyl]-3-methoxy-prop-2-enoate and methyl-(E)-2-[3-bromo-2-(bromomethyl)phenyl]-3-methoxy-prop-2-enoate [ka] Step 1: Methyl 2-(3-halo-2-methylphenyl)-2-oxo-acetate To a solution of 1-chloro-3-iodo-2-methylbenzene (9.0 g, 30.31 mmol) in THF (90 mL) was added dropwise isopropylmagnesium chloride (2 M THF solution, 16.6 mL, 33.34 mmol) under nitrogen at 0°C and stirred for 30 minutes. The reaction mixture was warmed to 20°C, and CuI (5.78 g, 30.31 mmol) was added portionwise. The reaction mixture was stirred at room temperature for 1 hour. The resulting reaction mixture was transferred to a solution of methyl 2-chloro-2-oxoacetate (4.45 g, 36.37 mol) in THF (180 mL) kept at -25°C under nitrogen. The reaction mass was gradually warmed to 25°C and stirred for 15 hours. The reaction mixture was cooled to 0°C, quenched with saturated aqueous ammonium chloride (100 mL), and extracted with MTBE (500 mL x 2). The combined organic layers were washed with brine (500 mL), dried over NaSO, filtered, concentrated in vacuo, and purified by column chromatography (0-10% EtOAc in heptane) to give methyl 2-(3-chloro-2-methylphenyl)-2-oxo-acetate as a yellow oil. Yield: 5.0 g, 66%. 1 H NMR(500MHz,DMSO-d6)δ=7.78(m,1H),7.70(m,1H),7.48-7.41(m,1H),3.91(s,3H),2.47(s,3H).

[0411] Methyl 2-(3-bromo-2-methylphenyl)-2-oxo-acetate was also synthesized in a similar manner with a yield of 64%. 1H NMR(500MHz,DMSO-d6)δ=7.94(dd,J=8.0,1.3Hz,1H),7.73(dd,J=7.8,1.3Hz,1H),7.35(t,J=7.9Hz,1H),3.91(s,3H),2.49(s,3H).

[0412] Step 2: Methyl-(E)-2-(3-halo-2-methylphenyl)-3-methoxy-prop-2-enoate To a solution of methoxymethyl(triphenyl)phosphonium chloride (14.6 g, 42.79 mmol) in THF (150 mL) was added dropwise a 1 M solution of lithium bis(trimethylsilyl)amide (43 mL) in THF under N2 at 0 °C. The mixture was stirred at 0 °C for 1 h. A solution of methyl-2-(3-chloro-2-methyl-phenyl)-2-oxo-acetate (10 g, 38.9 mmol) in THF (20 mL) was added dropwise, and the mixture was gradually warmed to 25 °C and stirred for 15 h. TLC (20% EtOAc in heptane) showed the reaction was complete. The reaction was cooled to 0 °C, quenched with saturated aqueous ammonium chloride (500 mL), and extracted with MTBE (500 mL × 3). The combined organic phase was washed with brine (500 mL), dried over Na2SO4, filtered, concentrated in vacuo, and purified by column chromatography (20% EtOAc in heptane) to give methyl-(E)-2-(3-chloro-2-methyl-phenyl)-3-methoxy-prop-2-enoate as a yellow solid. Yield: 6.5 g, 57.5%. 1 H NMR(500MHz,DMSO-d6)δ=7.68(s,1H),7.36(m,1H),7.18(t,J=7.8Hz,1H),7.03(m,1H),3.84(s,3H),3.63(s,3H),2.12(s,3H).

[0413] Methyl-(E)-2-(3-bromo-2-methyl-phenyl)-3-methoxy-prop-2-enoate was also synthesized in a similar manner with a yield of 58.6%. 1H NMR(500MHz,DMSO-d6)δ=7.66(s,1H),7.51(m,1H),7.13-6.98(m,2H),3.82(s,3H),3.61(s,3H),2.13(s,3H).

[0414] Step 3: Methyl-(E)-2-[3-halo-2-(bromomethyl)phenyl]-3-methoxy-prop-2-enoate To a solution of methyl-(E)-2-(3-chloro-2-methylphenyl)-3-methoxy-prop-2-enoate (9 g, 37.49 mmol) in cyclohexane (180 mL) was added azobisisobutyronitrile (0.5 g, 3.15 mmol), followed by the addition of NBS (16.8 g, 94.69 mmol) in small portions at 80 °C under N. The mixture was stirred at 80 °C for 16 h. TLC (20% EtOAc in heptane) showed the reaction was complete. The reaction mixture was quenched with water (500 mL) and extracted with MTBE (500 mL × 3). The combined organic phase was washed with brine (500 mL), dried over NaSO, filtered, and concentrated in vacuo. The residue was purified by column chromatography (0-15% EtOAc in heptane) to give methyl-(E)-2-[3-chloro-2-(bromomethyl)phenyl]-3-methoxy-prop-2-enoate as a yellow solid. Yield: 7.5 g, 63%. 1 H NMR(500MHz,DMSO-d6)δ=7.76(s,1H),7.47(m,1H),7.36(t,J=7.9Hz,1H),7.09(m,1H),4.52(s,2H),3.84(s,3H),3.62(s,3H).

[0415] Methyl-(E)-2-[3-bromo-2-(bromomethyl)phenyl]-3-methoxy-prop-2-enoate was also synthesized in a similar manner with a yield of 65.4%. 1 H NMR(500MHz,DMSO-d6)δ=7.75(s,1H),7.63(dd,J=8.0,1.3Hz,1H),7.27(t,J=7 .8Hz,1H),7.13(dd,J=7.6,1.3Hz,1H),4.60(s,2H),3.84(s,4H),3.62(s,4H).

[0416] [Table 46]

[0417] [Table 47]

[0418] [Table 48]

[0419] [Table 49]

[0420] [Table 50]

[0421] [Table 51]

[0422] [Table 52]

[0423] [Table 53]

[0424] can be found on column LCMS using the LCMS method in Table S.

[0425] [Table 54]

[0426] [Table 55]

[0427] Table 56

[0428] Table 57

[0429] Table 58

[0430] Table 59

[0431] Table 60

[0432] Table 61

[0433] Table 62

[0434] Table 63

[0435] Table 64

[0436] Table 65

[0437] [Table 66]

[0438] [Table 67]

[0439] [Table 68]

[0440] [Table 69]

[0441] [Table 70]

[0442] [Table 71]

[0443] [Table 72]

[0444] biological research Greenhouse and cut leaf tests Compounds were dissolved in a mixture of acetone and / or dimethyl sulfoxide and Wettol, an ethoxylated alkylphenol-based wetting / emulsifier, at a solvent-to-emulsifier ratio (volume) of 99 to 1 to make a total volume of 5 ml. Water was then added to make 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.

[0445] Use Case 1. Protective control of soybean rust in soybeans caused by Phakopsora pachyrhizi (PHAKPA P2) The leaves of potted soybean seedlings were sprayed with the spray solution containing a concentrate of the active ingredient or mixtures thereof, as described below, until runoff. 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 artificial inoculation, the plants were transferred to a humidity 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 percent diseased leaf area; lesion levels in untreated controls were typically greater than 85%.

[0446] Use Case 2. Protective control of soybean rust in soybeans caused by Phakopsora pachyrhizi (PHAKPA P6) The leaves of potted soybean seedlings were sprayed with the spray solution containing the active ingredient concentrates described below until runoff. The plants were allowed to air dry. 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 artificial inoculation, the plants were transferred to a humidity chamber at 23-27°C and approximately 95% relative humidity for 24 hours. 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 percent diseased leaf area; lesion levels in untreated controls were typically greater than 85%.

[0447] Use Case 3. Curative control of wheat leaf rust caused by Puccinia recondita (PUCCRT K4) The first two expanded leaves of potted wheat seedlings were dusted with spores of Puccinia recondita. To ensure successful artificial inoculation, the plants were transferred to a humid chamber with 20-24°C temperature, 95-99% relative humidity, and a shading-free environment for 24 hours. They were then grown in a greenhouse chamber at 20-24°C and 65-70% relative humidity for three days. The plants were then sprayed to runoff with the spray solution containing a concentrate of the active ingredient or a mixture thereof, as described below. The plants were allowed to air dry. The test plants were then grown in a greenhouse chamber at 20-24°C and 65-70% relative humidity for five to seven days. The extent of fungal attack on the leaves was assessed visually as percent diseased leaf area; lesion levels in untreated controls were typically 80-100%.

[0448] Use Case 4. Preventive control of wheat leaf rust caused by Puccinia recondita (PUCCRT P7) The first two expanded leaves of potted wheat seedlings were sprayed to runoff with the spray solution containing the active ingredient or a mixture thereof as specified below. Seven days later, the plants were dusted with Puccinia recondita spores. To ensure successful artificial inoculation, the plants were transferred to a humid chamber with 20-24°C temperature, 95-99% relative humidity, and a 24-hour shading period. The test plants were then grown in a greenhouse chamber at 20-24°C and 65-70% relative humidity for 9-11 days. The extent of fungal attack on the leaves was assessed visually as percent diseased leaf area; lesion levels in untreated controls were typically 80-100%.

[0449] [Table 73]

[0450] Table 74

[0451] Table 75

[0452] Table 76

[0453] Table 77

[0454] Table 78

[0455] Table 79

[0456] Table 80

[0457] Table 81

[0458] Table 82

[0459] Table 83

[0460] Table 84

[0461] [Table 85]

[0462] [Table 86]

[0463] [Table 87]

[0464] [Table 88]

[0465] [Table 89]

[0466] [Table 90]

[0467] [Table 91]

[0468] [Table 92]

[0469] [Table 93]

[0470] Comparative Test Micro 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 in proportions, pipetted into microtiter plates (MTPs), and diluted with water to the specified concentrations. A spore suspension of one of the following fungal plant pathogens in aqueous biomalt was then added for each use case:

[0471] Usage example 5: Alternaria solani (ALTESO)

[0472] Usage example 6: Botrytis cinerea (BOTRCI)

[0473] Usage example 7: Cercospora sojina (CERCSO)

[0474] Usage example 8: Colletotrichum orbiculare (COLLLA)

[0475] Usage example 9: Leptosphaeria nodorum (LEPTNO)

[0476] Use Example 10: Drechslera teres (PYRNTE) containing the amino acid substitution F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors

[0477] Use Case 11: Sclerotinia sclerotiorum (SCLESC), solute with ultrasound from filter membrane

[0478] The plates were placed in a water vapor-saturated chamber at 18° C. The MTP was measured at 405 nm using an absorption photometer for 7 days after inoculation.

[0479] The measured parameters were compared with the growth of a control variant without active compound (100%) and a blank value without fungus to determine the relative growth in % of the pathogen for each active compound.

[0480] [Table 94]

[0481] The results in Table 3 show that specific alkyl ether groups attached to the oxime group improve fungicidal activity against a variety of plant pathogenic fungi compared to compounds bearing a methyl group at the same position.

[0482] [Table 95]

[0483] [Table 96]

[0484] [Table 97]

[0485] [Table 98]

[0486] [Table 99]

[0487] [Table 100]

[0488] [Table 101]

[0489] [Table 102]

[0490] [Table 103]

[0491] [Table 104]

[0492] [Table 105]

[0493] [Table 106]

[0494] The results in Tables 4-13 show the specific halogen substituents R attached to the phenyl ring. 3 have shown that, compared with compounds with a methyl group at the same position, it improves fungicidal activity against a variety of plant pathogenic fungi, including fungi containing the amino acid substitution F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors.

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 selected from Cl, F and Br; R is C １ ~C ３ Alkyl, C １ ~C ３ Haloalkyl, C ３ ~C ６ Cycloalkyl and C １ ~C ３ Alkyl-C ３ ~C ６ cycloalkyl; m is an integer selected from 0 and 1; Z is selected from phenyl and 5- or 6-membered heteroaryl; The heteroaryl contains, in addition to carbon atoms, 1, 2 or 3 heteroatoms selected from N, O and S, Z is unsubstituted or contains 1, 2, 3 or up to a maximum of the same or different groups R ａ and R ａ is halogen, CN, hydroxy, NR Ａ R Ｂ , C １ ~C ４ Alkyl, C ２ ~C ４ Alkenyl, C ２ ~C ４ Alkynyl, —O—C １ ~C ４ Alkyl, —C(═N—O—C １ ~C ４ alkyl)-C １ ~C ４ Alkyl, —C(═O)—C １ ~C ４ Alkyl, —C(═O)—O—C １ ~C ４ Alkyl, —C(═O)—NH—C １ ~C ４ Alkyl, —O—CH ２ -C(=N-O-C 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, —O—C ３ ~C ６ selected from cycloalkyl, phenyl, and 5- or 6-membered heteroaryl; The heteroaryl contains, in addition to carbon atoms, 1, 2 or 3 heteroatoms selected from N, O and S, The phenyl and heteroaryl may be directly or via an oxygen atom or C １ ~C ２ is attached via an alkylene linker, R ａ is unsubstituted or contains 1, 2, 3 or up to a maximum of the same or different groups R ｂ and R ｂ is halogen, CN, hydroxy, NO ２ , C １ ~C ４ Alkyl, C １ ~C ４ haloalkyl; R Ａ , R Ｂ are each independently hydrogen, C １ ~C ４ Alkyl and C １ ~C ４ haloalkyl) and the stereoisomers and tautomers thereof and in the form of their N-oxides and agriculturally acceptable salts.

2. In Formula I, R １ is selected from O and NH, and R ２ is selected from CH and N, with the proviso that R １ When is NH, R ２ The compound of claim 1 , wherein is N.

3. 3. The compound of claim 1, wherein in formula I, m is 0.

4. In Formula I, R ３ The compound according to any one of claims 1 to 3, wherein is selected from Cl and Br.

5. In Formula I, R is C １ ~C ３ The compound according to any one of claims 1 to 4, wherein the aryl group is selected from alkyl.

6. In formula I, Z is phenyl, Z is unsubstituted or contains one, two or three identical or different groups R ａ The compound according to any one of claims 1 to 5, having the formula:

7. In Formula I, R ａ is halogen, CN, -NR Ａ R Ｂ , C １ ~C ４ Alkyl, C ２ ~C ４ Alkenyl, C ２ ~C ４ Alkynyl, —O—C １ ~C ４ Alkyl, —C(═N—O—C １ ~C ４ alkyl)-C １ ~C ４ Alkyl, —C(═O)—C １ ~C ４ Alkyl, —O—CH ２ -C(=N-O-C 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, —O—C ３ ~C ６ and selected from cycloalkyl, phenyl and 5- or 6-membered heteroaryl, wherein the heteroaryl contains, in addition to carbon atoms, 1, 2 or 3 heteroatoms selected from N, O and S, and the phenyl and heteroaryl are bonded directly or via an oxygen atom or C １ ~C ２ is bonded via an alkylene linker; R ａ is unsubstituted or contains 1, 2, 3 or up to a maximum of the same or different groups R ｂ and R ｂ is halogen, CN, NH ２ , NO ２ , C １ ~C ４ Alkyl, C １ ~C ４ Haloalkyl, —O—C １ ~C ４ Alkyl and —O—C １ ~C ４ haloalkyl; R Ａ , R Ｂ are each independently hydrogen, C １ ~C ３ Alkyl and C １ ~C ３ The compound of any one of claims 1 to 6, selected from the group consisting of haloalkyl.

8. In Formula I, R ａ is a halogen and C １ ~C ４ alkyl, and R ａ is unsubstituted or contains 1, 2, 3 or up to a maximum of the same or different groups R ｂ and R ｂ The compound of claim 7, wherein is selected from halogen.

9. In Formula I, R ａ is a halogen and C １ ~C ４ 9. The compound of claim 8, wherein the alkyl is selected from the group consisting of aryl, aryl, arylsulfonyl ...

10. 9. An agrochemical composition comprising an adjuvant and at least one compound of formula I according to any one of claims 1 to 8 or in the form of a stereoisomer, or an agriculturally acceptable salt, or tautomer, or N-oxide thereof.

11. Use of a compound of formula I as defined in any one of claims 1 to 8 or an agrochemical composition as defined in claim 9 for combating phytopathogenic fungi.

12. 10. A method for combating phytopathogenic fungi, comprising curatively and / or preventively treating plants or plant propagation material of said plants at risk of lesions caused by said phytopathogenic fungi and / or applying to said phytopathogenic fungi at least one compound of formula I as defined in any one of claims 1 to 8 or an agrochemical composition as defined in claim 9.

13. 12. A method according to claim 11 for combating phytopathogenic fungi containing the amino acid substitution F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors, comprising curatively and / or preventively treating a plant or plant propagation material of said plant at risk of lesions by said phytopathogenic fungi 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 8 or an agrochemical composition as defined in claim 9.

14. 13. The use of claim 10 or the method of claim 11 or 12, wherein the plant pathogenic fungus contains the amino acid substitution F129L in the mitochondrial cytochrome b protein, which confers resistance to Qo inhibitors.

15. 14. The use according to claim 10 or 13 or the method according to any one of claims 11 to 13, wherein the phytopathogenic fungus is soybean rust (Phakopsora pachyrhizi and / or P. meibomiae).

Images