Use of strobilurin-type compounds for combating phytopathogenic fungi containing amino acid substituted F129L in mitochondrial cytochrome b protein that confer resistance to Qo inhibitor XV

Abstract

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

Description

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

[0002] As used herein, "Qo inhibitor" includes any substance capable of reducing and / or inhibiting respiration by binding to the ubiquinol oxidation center of the cytochrome bc 1 complex in the mitochondrion. The oxidation center is typically located on the outer side of the inner mitochondrial membrane. Many of these compounds are also referred to as strobilurin-type or strobilurin analog compounds.

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

[0004] QoI fungicides, commonly known as strobilurin-type fungicides (Sauter 2007: Chapter 13.2. Strobilurins and other complex III inhibitors. [Strobilurins and other complex III inhibitors] in: W.; Schirmer, U. (eds.) – Modern Crop Protection Compounds. [Modern Crop Protection Compounds] Volume 2. Wiley-VCH Verlag [Wiley-VCH Press] 457 - 495) are commonly used for controlling many fungal pathogens in crops. Qo inhibitors typically act by binding to the cytochrome bc1 It acts by binding to the ubiquinol oxidation center of the complex (electron transport complex III) to inhibit respiration. The oxidation center is located on the outer side of the inner mitochondrial membrane. Main examples of the use of QoIs include, for example, the use of strobilurin on wheat to control Septoria tritici (also known as Mycosphaerella graminicola), which is the cause of wheat leaf blotch. Unfortunately, the widespread use of such QoIs has led to the selection of mutant pathogens resistant to such QoIs (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 or Venturia inaequalis. A major part of the resistance to QoIs in agricultural use is attributed to the pathogen having a single amino acid residue substitution G143A in the cytochrome b gene of its cytochrome bc 1 complex (the target protein of QoIs), and these pathogens have been found to be controllable by specific QoIs (WO 2013 / 092224). Although several commercial QoI fungicides have also been widely used for the control of soybean rust, no single amino acid residue substitution G143A conferring resistance to QoI fungicides has been observed in the cytochrome b protein.

[0005] Instead, soybean rust has acquired different gene mutations in the cytochrome b gene, resulting in a single amino acid substitution F129L, which also confers resistance to QoI fungicides. The efficacy of conventional QoI fungicides used against soybean rust (i.e., pyraclostrobin, azoxystrobin, picoxystrobin, orysastrobin, dimoxystrobin, and metominostrobin) has been reduced to an extent that poses practical problems for agricultural practice (e.g., Klosowski et al. (2016) Pest Manag Sci 72, 1211 - 1215).

[0006] Although trifloxystrobin appears to be less affected by the F129L amino acid substitution, to the same extent as other QoI fungicides such as azoxystrobin and pyraclostrobin, trifloxystrobin is consistently less effective against fungal populations carrying the F129L QoI resistance mutation than against sensitive 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 against phytopathogenic fungi containing said F129L amino acid substitution.

[0008] Therefore, new methods are needed to control pathogen-induced diseases in crops, including plants infested with pathogens containing the F129L amino acid substitution in the mitochondrial cytochrome b protein that confers resistance to Qo inhibitors. In addition, in many cases, especially at low application rates, the fungicidal activity of known fungicidal strobilurin compounds is not satisfactory, particularly in cases where a high proportion of fungal pathogens contain mutations in the mitochondrial cytochrome b gene that confer resistance to Qo inhibitors. Furthermore, there is a continuing need for new fungicidal active compounds that are more effective, less toxic to mammals, less toxic to non-target organisms (such as birds, aquatic vertebrates and invertebrates, pollinating insects, arthropods); and / or are otherwise safer for the environment. Based on this, another object of the present invention is to provide compounds having improved activity against phytopathogenic fungi and / or a broader activity spectrum and / or even further reduced toxicity to non-target organisms (such as vertebrates and invertebrates). In many countries / regions, certain per- and polyfluoroalkyl substances (PFAS) have increasingly attracted the attention of regulatory authorities due to their potential toxicity and environmental persistence. PFAS have recently been redefined (OECD 2021, Reconciling Terminology of the Universe of Per-and Polyfluoroalkyl Substances: Recommendations and Practical Guidance [Unifying Terminology for Per- and Polyfluoroalkyl Substances: Recommendations and Practical Guidance], OECD Series on Risk Management [OECD Risk Management Series], No. 61, OECD Publishing [OECD Publishing], Paris: https: / / www.oecd.org / chemicalsafety / portal-perfluorinated-chemicals / terminology-per-and-polyfluoroalkyl-substances.pdf; Environ. Sci. Technol. [Environmental Science and Technology] 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 thereto), i.e., with at least one perfluorinated methyl group (–CF 3 ) or perfluorinated methylene group (–CF 2Any chemical of (–). Therefore, another object of the present invention is to provide compounds having improved activity and / or a broader activity spectrum against phytopathogenic fungi, which compounds have low PFAS restrictions or no PFAS restrictions and / or reduced environmental persistence.

[0009] Certain strobilurin-type compounds of formula I have been described in EP 370629 and WO 1998 / 23156. However, it has not been mentioned that these compounds inhibit fungal pathogens containing the F129L substitution in the mitochondrial cytochrome b protein that confers resistance to Qo inhibitors.

[0010] Additional strobilurin compounds and their use against phytopathogenic fungi containing the F129L amino acid substitution in the mitochondrial cytochrome b protein that confers resistance to Qo inhibitors are disclosed in WO 2021 / 153754, WO 2021 / 219386, WO 2021 / 219387, WO 2021 / 219388, WO 2021 / 219390 and WO 2021 / 249928.

[0011] The strobilurin-analogue compounds according to the present invention differ from the above-mentioned documents particularly in that they contain a specific combination of a halogen group attached ortho to the side chain defined herein as R 3 to the central benzene ring and an alkyl ether group attached to the oxime group of the side chain.

[0012] Accordingly, the present invention relates to compounds of formula I

[0013]

[0014] wherein

[0015] R 1 is selected from O and NH;

[0016] R 2 is selected from CH and N;

[0017] R 3 is selected from Cl, F and Br;

[0018] R is selected from 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;

[0019] m is an integer selected from 0 and 1;

[0020] Z is selected from phenyl and 5- or 6-membered heteroaryl,

[0021] wherein said heteroaryl contains 1, 2 or 3 heteroatoms selected from N, O and S in addition to carbon atoms,

[0022] and wherein Z is unsubstituted or bears 1, 2, 3 or up to the maximum number of identical or different groups R a :

[0023] R a is selected from 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 -cycloalkyl, phenyl and 5- or 6-membered heteroaryl;

[0024] wherein said heteroaryl contains 1, 2 or 3 heteroatoms selected from N, O and S in addition to carbon atoms,

[0025] wherein said phenyl and heteroaryl are directly or via an oxygen atom or via C 1-C 2 -alkyl linker bond,

[0026] and wherein R a is unsubstituted or bears 1, 2, 3 or up to the maximum number of identical or different groups R b :

[0027] R b is selected from halogen, CN, hydroxy, NO 2 , C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl,

[0028] R A , R B are each independently selected from hydrogen, C 1 -C 4 -alkyl and C 1 -C 4 -haloalkyl;

[0029] and their stereoisomeric and tautomeric forms, as well as their N-oxides and agriculturally acceptable salts.

[0030] Although the present invention will be described with reference to specific embodiments, the description should not be construed in a limiting sense.

[0031] Before describing in detail the exemplary embodiments of the present invention, definitions important for understanding the present invention are given. As used in this specification and the appended claims, unless the context clearly dictates otherwise, the singular forms "a / an" also include the corresponding plurals. In the context of the present invention, the terms "about" and "approximately" denote an interval of precision that will be understood by those skilled in the art to still ensure the technical effect of the recited feature. The term typically indicates a deviation of ±20%, preferably ±15%, more preferably ±10%, and even more preferably ±5% from the indicated numerical value. It should be understood that the term "comprising" is not limiting. For the purposes of the present invention, the term "consisting of" is considered a preferred embodiment of the term "consisting essentially of".

[0032] Unless otherwise specified, the following definitions are set forth to illustrate and define the meaning and scope of the various terms used to describe the invention herein and in the appended claims. These definitions should not be construed literally as they are not intended to be general definitions and are only relevant to this application.

[0033] The term "Compound I" refers to the compound of formula I. Similarly, this term also applies to all sub-formulas, for example, "Compound I.2" refers to the compound of formula I.2 or "Compound V" refers to the compound of formula V, etc.

[0034] When used in the context of selecting substituents for a variable, the term "independently" means that when more than one substituent is selected from the many possible substituents, those substituents may be the same or different.

[0035] The organic moieties or groups mentioned in the above definitions of variables are general terms for separate lists of individual group members. The term "C v -C w " indicates the number of carbon atoms possible in each case.

[0036] The term "halogen" refers to fluorine, chlorine, bromine, and iodine.

[0037] The term "C 1 -C 4 -alkyl" refers to a straight-chain or branched-chain saturated hydrocarbon group having 1 to 4 carbon atoms, such as methyl (CH 3 ), ethyl (C 2 H 5 ), propyl, 1-methylethyl (isopropyl), butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl. Similarly, "C 1 -C 3 -alkyl" refers to a straight-chain or branched-chain saturated hydrocarbon group having 1 to 3 carbon atoms, selected from methyl (CH 3 ), ethyl (C 2 H 5 ), propyl, 1-methylethyl (isopropyl).

[0038] The term "C 2 -C 4 -alkenyl" refers to a straight-chain or branched-chain unsaturated hydrocarbon group having 2 to 4 carbon atoms and a double bond at any position, such as vinyl, 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.

[0039] The term "C 2 -C 4 -alkynyl" refers to a straight-chain or branched-chain 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.

[0040] The term "C 1 -C 4"-Halogenoalkyl" means a straight-chain or branched alkyl group having 1 to 4 carbon atoms, where some or all of the hydrogen atoms in these groups can be replaced by halogen atoms as mentioned above, 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, CH 2 -C 2 F 5 、CF 2 -C 2 F 5 、CF(CF 3 ) 2 、1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl.

[0041] The term "-O-C 1 -C 4 -alkyl" means a straight-chain or branched alkyl group having 1 to 4 carbon atoms, which is bonded via oxygen at any position of the alkyl group, such as OCH 3 、OCH 2 CH 3 、O(CH 2 ) 2 CH 3 、1-methylethoxy, O(CH 2 ) 3 CH 3 、1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy.

[0042] The term "C 3 -C 6 -cycloalkyl" means a monocyclic saturated hydrocarbon group having 3 to 6 carbon ring members, such as cyclopropyl (C 3 H 5 )、cyclobutyl, cyclopentyl or cyclohexyl. The term "C 3 -C 6 -cycloalkenyl" means a monocyclic saturated hydrocarbon group having 3 to 6 carbon ring members and one or more double bonds.

[0043] The term "-C 1-C 3 -alkyl-C 3 -C 6 -cycloalkyl” means an alkyl group having 1 to 3 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl group is replaced by a cycloalkyl group having 3 to 6 carbon atoms.

[0044] The term "phenyl" means C 6 H 5 .

[0045] The term "5- or 6-membered heteroaryl" containing 1, 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S is to be understood to mean an aromatic heterocycle having 5 or 6 ring atoms. Examples include:

[0046] - 5-membered heteroaryl, which in addition to carbon atoms, for example, contains 1, 2 or 3 N atoms and / or one sulfur and / or one 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;

[0047] - 6-membered heteroaryl, which in addition to carbon atoms, for example, contains 1, 2, 3 or 4 N atoms as ring members, such as 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl.

[0048] The term "C 1 -C 2 -alkylene linker" means a divalent alkyl group, such as -CH 2 - or -CH 2 -CH 2 -, which is bound at one end to the core structure of formula I and at the other end to a specific substituent.

[0049] As used herein, "compound", particularly "Compound I" includes all stereoisomeric and tautomeric forms and mixtures thereof in all ratios, prodrugs, isotopic forms, its agriculturally acceptable salts, its N-oxides and S-oxides.

[0050] The term "stereoisomer" is a general term for all isomers of a single compound that differ only in the spatial orientation of their atoms. The term stereoisomers includes mirror-image isomers (enantiomers), mixtures of mirror-image isomers (racemates, racemic mixtures), geometric (cis / trans or E / Z) isomers (e.g., of formulae Ia, Ib and Ic and their sub-formulae), and isomers of compounds having more than one chiral center that are not mirror images of each other (diastereoisomers). The term "tautomer" refers to the coexistence of two (or more) compounds that differ only in the position of one (or more) mobile atoms and the electronic distribution, e.g., keto-enol tautomers. As used herein, the term "agriculturally acceptable salts" includes salts of the active compounds which are prepared with acids or bases, depending on the specific substituents found on the compounds described herein. "N-oxides" refer to oxides of the nitrogen atoms of nitrogen-containing heteroaryls or heterocycles. N-oxides can be formed in the presence of oxidizing agents (e.g., peroxides such as m-chloroperbenzoic acid or hydrogen peroxide). N-oxides refer to amine oxides, also known as amine-N-oxides, and are compounds containing an N→O bond.

[0051] With regard to the variables, the examples of the intermediates correspond to the examples of compound I.

[0052] Preference is given to those compounds I and, where applicable, also to the compounds of all sub-formulae provided herein (e.g., formulae I.1 and I.2), preferably to the stereoisomers of formula I depicted as formulae Ia, Ib and Ic and their corresponding sub-formulae (e.g., formula Ib.1), and preferably to intermediates such as compounds II, III, IV and V, where the substituents and variables (such as m, R 1 , R 2 , R 3 , R, R A , R B , R a and R b ) independently of one another or more preferably in combination (any possible combination of 2 or more substituents as defined herein) have the following meanings:

[0053] Also preferred are uses, methods, mixtures and compositions, where the definitions (such as phytopathogenic fungi, treatment, crop, compound II, further active ingredient, solvent, solid carrier) independently of one another or more preferably in combination have the following meanings and even more preferably in combination with the preferred meanings of the compounds I of the present invention (any possible combination of 2 or more definitions as provided herein):

[0054] One embodiment of the present invention relates to compound I, wherein R 1 is selected from O and NH; and R 2 is selected from CH and N, provided that when R1 In the case of NH, R 2 is N. More preferably, R 1 is NH. In particular, R 1 is NH and R 2 is N. Another embodiment relates to compound I, wherein R 1 is O and R 2 is CH.

[0055] According to another embodiment, R 3 is selected from Cl and F, particularly Cl. According to a further embodiment, R 3 is F. According to a further embodiment, R 3 is Br.

[0056] According to one embodiment, R is selected from methyl, ethyl, isopropyl, C 1 -C 2 -haloalkyl, cyclopropyl, CH 2 -cyclopropyl and (CH 2 ) 2 -cyclopropyl; more preferably selected from methyl, ethyl, isopropyl, CHF 2 , CF 3 , CH 2 CHF 2 , CH 2 CF 3 , cyclopropyl and CH 2 -cyclopropyl, even more preferably selected from methyl and ethyl, particularly methyl.

[0057] According to a further embodiment, m is 0 and these compounds have the formula I.1

[0058]

[0059] According to a further embodiment, m is 1 and these compounds have the formula I.B

[0060]

[0061] According to a further embodiment, Z is selected from phenyl and 5- or 6-membered heteroaryl, wherein said heteroaryl contains 1, 2 or 3 heteroatoms selected from N, O and S in addition to carbon atoms, and wherein Z is unsubstituted or bears 1, 2 or 3 identical or different groups R as defined herein a ; more preferably, Z is unsubstituted or bears 1 or 2 identical or different groups R as defined herein a ; in particular, Z is unsubstituted or bears 1 group R as defined herein a .

[0062] According to a further embodiment, Z is phenyl and wherein Z bears 1, 2 or 3 identical or different groups R as defined herein a ; more preferably, Z bears 1 or 2 identical or different groups R as defined herein a ; in particular, Z bears 1 group R as defined herein a . According to a further embodiment, Z is phenyl and wherein Z is unsubstituted or bears 1, 2 or 3 identical or different groups R as defined herein a ; more preferably, Z is unsubstituted or bears 1, 2 or 3 identical or different groups R selected from halogen a .

[0063] According to a further embodiment, Z is selected from pyridyl and thiazolyl and wherein Z is unsubstituted or bears 1, 2 or 3 identical or different groups R as defined herein a ; more preferably, Z is unsubstituted or bears 1 or 2 identical or different groups R as defined herein a ; in particular, Z is unsubstituted or bears 1 group R as defined herein a .

[0064] According to the above embodiments, R a is preferably selected from halogen, CN, 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 4 -cycloalkyl, -C 1 -C 2 -alkyl-C 3 -C 4 -cycloalkyl, -O-C 3 -C 4-cycloalkyl, phenyl and 5- or 6-membered heteroaryl, wherein said heteroaryl contains 1, 2 or 3 heteroatoms selected from N, O and S in addition to carbon atoms, and wherein said phenyl and heteroaryl are bonded directly or via an oxygen atom or via a C 1 -C 2 -alkylene linker.

[0065] Preferably, R a is selected from halogen, CN, C 1 -C 4 -alkyl, -O-C 1 -C 4 -alkyl, -C(=O)-C 1 -C 2 -alkyl, -C(=N-O-C 1 -C 4 -alkyl)-C 1 -C 4 -alkyl, C 3 -C 4 -cycloalkyl, -O-C 3 -C 4 -cycloalkyl, phenyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl and heteroaryl contain 1 or 2 heteroatoms selected from N, O and S in addition to carbon atoms, and wherein said phenyl, heterocycloalkyl and heteroaryl are bonded directly or via an oxygen atom or via a methylene linker.

[0066] More preferably, R a is selected from halogen, CN, C 1 -C 3 -alkyl, -O-C 1 -C 3 -alkyl, -C(=N-O-CH 3 )-CH 3 , C 3 -C 4 -cycloalkyl, -O-C 3 -C 4 -cycloalkyl, phenyl and 5- or 6-membered heteroaryl, wherein said heteroaryl contains 1 or 2 heteroatoms selected from N, O and S in addition to carbon atoms, and wherein said phenyl and heteroaryl are bonded directly or via an oxygen atom or via a methylene linker.

[0067] In particular, R a is selected from halogen, CN, C 1 -C 2 -alkyl, -O-C 1 -C 2 -alkyl, vinyl, ethynyl and -C(=N-O-CH 3 )-CH 3 .

[0068] According to a further embodiment, R a is selected from halogen, C 1 -C 2 -alkyl, -O-C 1 -C 2 -alkyl, wherein the aliphatic moiety is unsubstituted or bears 1, 2 or 3 identical or different groups R b selected from halogen.

[0069] According to the above embodiment of R a , the above-mentioned heteroaryl is a 5-membered heteroaryl, which contains 1 or 2 heteroatoms selected from N, O and S in addition to carbon atoms. Preferably, the heteroatoms are selected from N and O.

[0070] According to the above embodiment of R a , the aliphatic and cyclic moieties of R a are unsubstituted or bear 1, 2, 3 or up to the maximum number of identical or different groups R b selected from halogen, CN, 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; more preferably selected from halogen; even more preferably, only the cyclic moiety of R a is unsubstituted or bears 1, 2, 3 or up to the maximum number of identical or different groups R b selected from halogen, CN, 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; even more preferably, only the phenyl moiety of R a is unsubstituted or bears 1, 2, 3, 4 or 5 identical or different groups R b selected from halogen, CN, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, -O-C 1 -C 4 -alkyl and -O-C 1 -C4 - haloalkyl; in particular, said phenyl is unsubstituted or bears 1, 2 or 3 identical or different groups R b , which groups are selected from halogen, CN, C 1 -C 2 -alkyl, C 1 -C 2 -haloalkyl, -O-C 1 -C 2 -alkyl and -O-C 1 -C 2 -haloalkyl.

[0071] According to a further embodiment, m is 0 and Z is phenyl, which phenyl is unsubstituted or bears 1, 2 or 3 identical or different substituents R a , where R a is selected from halogen, C 1 -C 2 -alkyl and -O-C 1 -C 2 -alkyl, where the aliphatic moiety of R a is unsubstituted or bears 1, 2 or 3 identical or different groups R selected from halogen b .

[0072] According to a further embodiment, m is 1 and Z is phenyl, which phenyl is unsubstituted or bears 1, 2 or 3 identical or different substituents R a , where R a is selected from halogen, C 1 -C 2 -alkyl and -O-C 1 -C 2 -alkyl, where the aliphatic moiety of R a is unsubstituted or bears 1, 2 or 3 identical or different groups R selected from halogen b .

[0073] According to a further embodiment, Z is phenyl and bears two substituents R a , which two substituents are preferably in the following positions: 2, 3 (meaning one substituent is in position 2 and the other is in position 3); 2, 4; 2, 5; 3, 4 or 3, 5; even more preferably in positions 2, 3 or 2, 4.

[0074] According to a further embodiment, Z is phenyl and bears three substituents R a , which three substituents are preferably in positions 2, 3 and 4.

[0075] According to a further preferred embodiment, the invention relates to a compound of formula I, wherein:

[0076] R1 selected from O and NH; and

[0077] R 2 selected from CH and N;

[0078] R 3 selected from F, Cl and Br;

[0079] R is selected from C 1 -C 2 -alkyl and cyclopropyl;

[0080] m is an integer selected from 0 and 1;

[0081] Z is phenyl or pyridyl, which is unsubstituted or bears 1, 2 or 3 identical or different substituents R a :

[0082] R a selected from halogen, CN, C 1 -C 4 -alkyl and -O-C 1 -C 4 -alkyl,

[0083] and wherein R a is unsubstituted or bears 1, 2, 3 or up to the maximum number of identical or different groups R b :

[0084] R b selected from halogen;

[0085] as well as its stereoisomeric and tautomeric forms, and its N-oxides and agriculturally acceptable salts.

[0086] According to a further preferred embodiment, the present invention relates to a compound of formula I, wherein:

[0087] R 1 selected from O and NH; and

[0088] R 2 selected from CH and N;

[0089] R 3 selected from F, Cl and Br;

[0090] R is selected from C 1 -C 2 -alkyl;

[0091] m is an integer selected from 0 and 1;

[0092] Z is phenyl or pyridyl, which is unsubstituted or bears 1, 2 or 3 identical or different substituents R a :

[0093] R a is selected from halogen, CN, methyl and methoxy;

[0094] and its stereoisomers and tautomers, and its N-oxides and agriculturally acceptable salts.

[0095] According to a further preferred embodiment, the invention relates to a compound of formula I, wherein:

[0096] R 1 is selected from O and NH; and

[0097] R 2 is selected from CH and N, provided that when R 1 is NH, R 2 is N;

[0098] R 3 is selected from Cl and Br;

[0099] R is selected from C 1 -C 3 -alkyl;

[0100] m is an integer selected from 0 and 1;

[0101] Z is phenyl, which is unsubstituted or bears 1, 2 or 3 identical or different substituents R a :

[0102] R a is selected from 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 -C6 -cycloalkenyl, -C 1 -C 2 -alkyl-C 3 -C 6 -cycloalkyl, -O-C 3 -C 6 -cycloalkyl, phenyl and 5- or 6-membered heteroaryl,

[0103] wherein said heteroaryl contains 1, 2 or 3 heteroatoms selected from N, O and S in addition to carbon atoms,

[0104] wherein said phenyl and heteroaryl are bonded directly or via an oxygen atom or via a C 1 -C 2 -alkylene linker,

[0105] and wherein R a is unsubstituted or bears 1, 2, 3 or up to the maximum number of identical or different groups R b :

[0106] R b is selected from 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;

[0107] R A 、R B are each independently selected from the group consisting of hydrogen, C 1 -C 3 -alkyl and C 1 -C 3 -haloalkyl;

[0108] and their stereoisomeric and tautomeric forms, and their N-oxides and agriculturally acceptable salts.

[0109] According to a further preferred embodiment, the invention relates to a compound of formula I, wherein:

[0110] R 1 is selected from O and NH; and

[0111] R 2 is selected from CH and N, provided that when R 1 is NH, R 2 is N;

[0112] R 3 is selected from Cl and Br;

[0113] R is selected from C 1 -C 2 -alkyl;

[0114] m is an integer selected from 0 and 1;

[0115] Z is phenyl, which is unsubstituted or bears 1, 2 or 3 identical or different substituents R a :

[0116] R a is selected from halogen and C 1 -C 4 -alkyl, wherein R a is unsubstituted or bears 1, 2, 3 or up to the maximum number of identical or different groups R b :

[0117] R b is selected from halogen;

[0118] and its stereoisomeric and tautomeric forms, as well as its N-oxides and agriculturally acceptable salts.

[0119] According to a further preferred embodiment, the present invention relates to a compound of formula I, wherein:

[0120] R 1 is selected from O and NH; and

[0121] R 2 is selected from CH and N, provided that when R 1 is NH, R 2 is N;

[0122] R 3 is selected from Cl and Br;

[0123] R is selected from C 1 -C 2 -alkyl;

[0124] m is an integer selected from 0 and 1;

[0125] Z is phenyl, which is unsubstituted or bears 1, 2 or 3 identical or different substituents R a :

[0126] R a is selected from halogen and C 1 -C 4 -alkyl;

[0127] and its stereoisomeric and tautomeric forms, as well as its N-oxides and agriculturally acceptable salts.

[0128] According to a further embodiment, R 1 is NH and R 2 is N and m is 0, and wherein Z is unsubstituted or substituted by 1, 2 or 3 substituents R as defined herein a substituted, and these compounds have the formula I.A1:

[0129]

[0130] According to a further embodiment, R 1 is O and R 2 is N and m is 0, and wherein Z is unsubstituted or substituted by 1, 2 or 3 substituents R as defined herein a substituted, and these compounds have the formula I.A2:

[0131]

[0132] According to a further embodiment, R 1 is O and R 2 is CH and m is 0, and wherein Z is unsubstituted or substituted by 1, 2 or 3 substituents R as defined herein a substituted, and these compounds have the formula I.A3:

[0133]

[0134] According to a further embodiment, R 1 is NH and R 2 is N, m is 1, and wherein Z is unsubstituted or substituted by 1, 2 or 3 substituents R as defined herein a substituted, and these compounds have the formula I.B.1:

[0135]

[0136] According to a further embodiment, R 1 is O and R 2 is N and m is 1, and wherein Z is unsubstituted or substituted by 1, 2 or 3 substituents R as defined herein a substituted, and these compounds have the formula I.B.2:

[0137]

[0138] According to a further embodiment, R 1 is O and R 2 is CH and m is 1, and wherein Z is unsubstituted or substituted by 1, 2 or 3 substituents R as defined herein a substituted, and these compounds have the formula I.B.3:

[0139]

[0140] Preferably, R of Compound I 3 is one of the following groups 3-1 to 3-6:

[0141]

[0142] A particularly preferred embodiment of the present invention relates to Compound I, wherein R is one of the following groups 4-1 to 4-8:

[0143]

[0144] Preferably, Z in Compound I is one of the following groups Z-1 to Z-44:

[0145]

[0146] A particularly preferred embodiment of the present invention relates to Compound I, wherein R a is selected from one of the following groups a-1 to a-57:

[0147]

[0148] In an embodiment, Compound I has the formula I.A.1, wherein Z is phenyl (Z-1), R 3 is F, R and 0 to 3 R a substituents are in any row of Table A below, and these compounds are named I.A1.1-Z-1-A-1 to I.A.1.1-Z-1-A-2389.

[0149] In another embodiment, Compound I has the formula I.A.2, wherein Z is phenyl (Z-1), R 3 is F, R and 0 to 3 R a substituents are in any row of Table A below, and these compounds are named I.A.2.1-Z-1-A-1 to I.A2.1-Z-1-A-2389.

[0150] In another embodiment, Compound I has the formula I.A.3, wherein Z is phenyl (Z-1), R 3 is F, R and 0 to 3 R a substituents are in any row of Table A below, and these compounds are named I.A.3.1-Z-1-A-1 to I.A3.1-Z-1-A-2389.

[0151] In another embodiment, Compound I has the formula I.B.1, wherein Z is phenyl (Z-1), R 3 is F, R and 0 to 3 R aFor substituents according to any row of Table A below, these compounds are named as I.B.1.1-Z-1-A-1 to I.B1.1-Z-1-A-2389.

[0152] In another embodiment, Compound I has the formula I.B.2, where Z is phenyl (Z-1), R 3 is F, R and 0 to 3 R a For substituents according to any row of Table A below, these compounds are named as I.B.2.1-Z-1-A-1 to I.B.2.1-Z-1-A-2389.

[0153] In another embodiment, Compound I has the formula I.B.3, where Z is phenyl (Z-1), R 3 is F, R and 0 to 3 R a For substituents according to any row of Table A below, these compounds are named as I.B.3.1-Z-1-A-1 to I.B.3.1-Z-1-A-2389.

[0154] In another embodiment, Compound I has the formula I.A.1, where Z is phenyl (Z-1), R 3 is Cl, R and 0 to 3 R a For substituents according to any row of Table A below, these compounds are named as I.A1.2-Z-1-A-1 to I.A.1.2-Z-1-A-2389.

[0155] In another embodiment, Compound I has the formula I.A.2, where Z is phenyl (Z-1), R 3 is Cl, R and 0 to 3 R a For substituents according to any row of Table A below, these compounds are named as I.A.2.2-Z-1-A-1 to I.A2.2-Z-1-A-2389.

[0156] In another embodiment, Compound I has the formula I.A.3, where Z is phenyl (Z-1), R 3 is Cl, R and 0 to 3 R a For substituents according to any row of Table A below, these compounds are named as I.A.3.2-Z-1-A-1 to I.A3.2-Z-1-A-2389.

[0157] In another embodiment, Compound I has the formula I.B.1, where Z is phenyl (Z-1), R 3 is Cl, R and 0 to 3 R a For substituents according to any row of Table A below, these compounds are named as I.B.1.2-Z-1-A-1 to I.B.1.2-Z-1-A-2389.

[0158] In another embodiment, Compound I has the formula I.B.2, where Z is phenyl (Z-1), R 3 is Cl, and R and from 0 to 3 R a substituents are in any row of Table A below, and these compounds are named I.B.2.2-Z-1-A-1 to I.B.2.2-Z-1-A-2389.

[0159] In another embodiment, Compound I has the formula I.B.3, where Z is phenyl (Z-1), R 3 is Cl, and R and from 0 to 3 R a substituents are in any row of Table A below, and these compounds are named I.B.3.2-Z-1-A-1 to I.B.3.2-Z-1-A-2389.

[0160] In another embodiment, Compound I has the formula I.A.1, where Z is phenyl (Z-1), R 3 is Br, and R and from 0 to 3 R a substituents are in any row of Table A below, and these compounds are named I.A1.3-Z-1-A-1 to I.A.1.3-Z-1-A-2389.

[0161] In another embodiment, Compound I has the formula I.A.2, where Z is phenyl (Z-1), R 3 is Br, and R and from 0 to 3 R a substituents are in any row of Table A below, and these compounds are named I.A.2.3-Z-1-A-1 to I.A2.3-Z-1-A-2389.

[0162] In another embodiment, Compound I has the formula I.A.3, where Z is phenyl (Z-1), R 3 is Br, and R and from 0 to 3 R a substituents are in any row of Table A below, and these compounds are named I.A.3.3-Z-1-A-1 to I.A3.3-Z-1-A-2389.

[0163] In another embodiment, Compound I has the formula I.B.1, where Z is phenyl (Z-1), R 3 is Br, and R and from 0 to 3 R a substituents are in any row of Table A below, and these compounds are named I.B.1.3-Z-1-A-1 to I.B.1.3-Z-1-A-2389.

[0164] In another embodiment, Compound I has the formula I.B.2, where Z is phenyl (Z-1), R 3 is Br, and R and from 0 to 3 Ra The substituents are in any row of Table A below, and these compounds are named I.B.2.3-Z-1-A-1 to I.B.2.3-Z-1-A-2389.

[0165] In another embodiment, Compound I has the formula I.B.3, where Z is phenyl (Z-1), R 3 is Br, R and 0 to 3 R a The substituents are in any row of Table A below, and these compounds are named I.B.3.3-Z-1-A-1 to I.B.3.3-Z-1-A-2389.

[0166] Table A

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200]

[0201]

[0202]

[0203]

[0204]

[0205]

[0206] * refers to 3 fluorine substituents at positions 3, 4 and 5 of Z.

[0207] R a The "-" of refers to Z being unsubstituted.

[0208] In the examples, compound I has formula I.A.1, where Z is pyridin-4-yl (Z-4), R 3 is F, R and 0 or 1 R aThe substituents are in any row of Table O below, and these compounds are named I.A.1.1-Z-4-O-1 to I.A1.1-Z-4-O-150.

[0209] In another embodiment, compound I has the formula I.A.2, where Z is pyridin-4-yl (Z-4), R 3 is F, R and 0 or 1 R a The substituents are in any row of Table O below, and these compounds are named I.A.2.1-Z-4-O-1 to I.A2.1-Z-4-O-150.

[0210] In another embodiment, compound I has the formula I.A.3, where Z is pyridin-4-yl (Z-4), R 3 is F, R and 0 or 1 R a The substituents are in any row of Table O below, and these compounds are named I.A.3.1-Z-4-O-1 to I.A3.1-Z-4-O-150.

[0211] In another embodiment, compound I has the formula I.B.1, where Z is pyridin-4-yl (Z-4), R 3 is F, R and 0 or 1 R a The substituents are in any row of Table O below, and these compounds are named I.B.1.1-Z-4-O-1 to I.B1.1-Z-4-O-150.

[0212] In another embodiment, compound I has the formula I.B.2, where Z is pyridin-4-yl (Z-4), R 3 is F, R and 0 or 1 R a The substituents are in any row of Table O below, and these compounds are named I.B.2.1-Z-4-O-1 to I.B.2.1-Z-4-O-150.

[0213] In another embodiment, compound I has the formula I.B.3, where Z is pyridin-4-yl (Z-4), R 3 is F, R and 0 or 1 R a The substituents are in any row of Table O below, and these compounds are named I.B.3.1-Z-4-O-1 to I.B.3.1-Z-4-O-150.

[0214] In another embodiment, compound I has the formula I.A.1, where Z is pyridin-4-yl (Z-4), R 3 is Cl, R and 0 or 1 R a The substituents are in any row of Table O below, and these compounds are named I.A1.2-Z-4-O-1 to I.A.1.2-Z-4-O-150.

[0215] In another embodiment, Compound I has the formula I.A.2, where Z is pyridin-4-yl (Z-4), R 3 is Cl, and R and zero or one R a substituents are in any row of Table O below, and these compounds are named I.A.2.2-Z-4-O-1 to I.A2.2-Z-4-O-150.

[0216] In another embodiment, Compound I has the formula I.A.3, where Z is pyridin-4-yl (Z-4), R 3 is Cl, and R and zero or one R a substituents are in any row of Table O below, and these compounds are named I.A.3.2-Z-4-O-1 to I.A3.2-Z-4-O-150.

[0217] In another embodiment, Compound I has the formula I.B.1, where Z is pyridin-4-yl (Z-4), R 3 is Cl, and R and zero or one R a substituents are in any row of Table O below, and these compounds are named I.B.1.2-Z-4-O-1 to I.B.1.2-Z-4-O-150.

[0218] In another embodiment, Compound I has the formula I.B.2, where Z is pyridin-4-yl (Z-4), R 3 is Cl, and R and zero or one R a substituents are in any row of Table O below, and these compounds are named I.B.2.2-Z-4-O-1 to I.B.2.2-Z-4-O-150.

[0219] In another embodiment, Compound I has the formula I.B.3, where Z is pyridin-4-yl (Z-4), R 3 is Cl, and R and zero or one R a substituents are in any row of Table O below, and these compounds are named I.B.3.2-Z-4-O-1 to I.B.3.2-Z-4-O-150.

[0220] In another embodiment, Compound I has the formula I.A.1, where Z is pyridin-4-yl (Z-4), R 3 is Br, and R and zero or one R a substituents are in any row of Table O below, and these compounds are named I.A1.3-Z-4-O-1 to I.A.1.3-Z-4-O-150.

[0221] In another embodiment, Compound I has the formula I.A.2, where Z is pyridin-4-yl (Z-4), R 3 is Br, and R and 0 or 1 R a substituents are in any row of Table O below, and these compounds are named I.A.2.3-Z-4-O-1 to I.A2.3-Z-4-O-150.

[0222] In another embodiment, Compound I has the formula I.A.3, where Z is pyridin-4-yl (Z-4), R 3 is Br, and R and 0 or 1 R a substituents are in any row of Table O below, and these compounds are named I.A.3.3-Z-4-O-1 to I.A3.3-Z-4-O-150.

[0223] In another embodiment, Compound I has the formula I.B.1, where Z is pyridin-4-yl (Z-4), R 3 is Br, and R and 0 or 1 R a substituents are in any row of Table O below, and these compounds are named I.B.1.3-Z-4-O-1 to I.B.1.3-Z-4-O-150.

[0224] In another embodiment, Compound I has the formula I.B.2, where Z is pyridin-4-yl (Z-4), R 3 is Br, and R and 0 or 1 R a substituents are in any row of Table O below, and these compounds are named I.B.2.3-Z-4-O-1 to I.B.2.3-Z-4-O-150.

[0225] In another embodiment, Compound I has the formula I.B.3, where Z is pyridin-4-yl (Z-4), R 3 is Br, and R and 0 or 1 R a substituents are in any row of Table O below, and these compounds are named I.B.3.3-Z-4-O-1 to I.B.3.3-Z-4-O-150.

[0226] Table O

[0227]

[0228]

[0229] In an embodiment, Compound I has the formula I.A.1, where Z is pyridin-3-yl (Z-3), R 3 is F, and R and 0 or 1 R aThe substituents are in any row of Table P below, and these compounds are named I.A.1.1-Z-3-P-1 to I.A1.1-Z-3-P-150.

[0230] In another embodiment, compound I has the formula I.A.2, where Z is pyridin-3-yl (Z-3), R 3 is F, R and 0 or 1 R a The substituents are in any row of Table P below, and these compounds are named I.A.2.1-Z-3-P-1 to I.A2.1-Z-3-P-150.

[0231] In another embodiment, compound I has the formula I.A.3, where Z is pyridin-3-yl (Z-3), R 3 is F, R and 0 or 1 R a The substituents are in any row of Table P below, and these compounds are named I.A.3.1-Z-3-P-1 to I.A3.1-Z-3-P-150.

[0232] In another embodiment, compound I has the formula I.B.1, where Z is pyridin-3-yl (Z-3), R 3 is F, R and 0 or 1 R a The substituents are in any row of Table P below, and these compounds are named I.B.1.1-Z-3-P-1 to I.B1.1-Z-3-P-150.

[0233] In another embodiment, compound I has the formula I.B.2, where Z is pyridin-3-yl (Z-3), R 3 is F, R and 0 or 1 R a The substituents are in any row of Table P below, and these compounds are named I.B.2.1-Z-3-P-1 to I.B.2.1-Z-3-P-150.

[0234] In another embodiment, compound I has the formula I.B.3, where Z is pyridin-3-yl (Z-3), R 3 is F, R and 0 or 1 R a The substituents are in any row of Table P below, and these compounds are named I.B.3.1-Z-3-P-1 to I.B.3.1-Z-3-P-150.

[0235] In another embodiment, compound I has the formula I.A.1, where Z is pyridin-3-yl (Z-3), R 3 is Cl, R and 0 or 1 R a The substituents are in any row of Table P below, and these compounds are named I.A1.2-Z-3-P-1 to I.A.1.2-Z-3-P-150.

[0236] In another embodiment, Compound I has the formula I.A.2, where Z is pyridin-3-yl (Z-3), R 3 is Cl, and R and zero or one R a substituents are in any row of Table P below, and these compounds are named I.A.2.2-Z-3-P-1 to I.A2.2-Z-3-P-150.

[0237] In another embodiment, Compound I has the formula I.A.3, where Z is pyridin-3-yl (Z-3), R 3 is Cl, and R and zero or one R a substituents are in any row of Table P below, and these compounds are named I.A.3.2-Z-3-P-1 to I.A3.2-Z-3-P-150.

[0238] In another embodiment, Compound I has the formula I.B.1, where Z is pyridin-3-yl (Z-3), R 3 is Cl, and R and zero or one R a substituents are in any row of Table P below, and these compounds are named I.B.1.2-Z-3-P-1 to I.B.1.2-Z-3-P-150.

[0239] In another embodiment, Compound I has the formula I.B.2, where Z is pyridin-3-yl (Z-3), R 3 is Cl, and R and zero or one R a substituents are in any row of Table P below, and these compounds are named I.B.2.2-Z-3-P-1 to I.B.2.2-Z-3-P-150.

[0240] In another embodiment, Compound I has the formula I.B.3, where Z is pyridin-3-yl (Z-3), R 3 is Cl, and R and zero or one R a substituents are in any row of Table P below, and these compounds are named I.B.3.2-Z-3-P-1 to I.B.3.2-Z-3-P-150.

[0241] In another embodiment, Compound I has the formula I.A.1, where Z is pyridin-3-yl (Z-3), R 3 is Br, and R and zero or one R a substituents are in any row of Table P below, and these compounds are named I.A1.3-Z-3-P-1 to I.A.1.3-Z-3-P-150.

[0242] In another embodiment, compound I has the formula I.A.2, where Z is pyridin-3-yl (Z-3), R 3 is Br, and R and 0 or 1 R a substituents are in any row of Table P below, and these compounds are named I.A.2.3-Z-3-P-1 to I.A2.3-Z-3-P-150.

[0243] In another embodiment, compound I has the formula I.A.3, where Z is pyridin-3-yl (Z-3), R 3 is Br, and R and 0 or 1 R a substituents are in any row of Table P below, and these compounds are named I.A.3.3-Z-3-P-1 to I.A3.3-Z-3-P-150.

[0244] In another embodiment, compound I has the formula I.B.1, where Z is pyridin-3-yl (Z-3), R 3 is Br, and R and 0 or 1 R a substituents are in any row of Table P below, and these compounds are named I.B.1.3-Z-3-P-1 to I.B.1.3-Z-3-P-150.

[0245] In another embodiment, compound I has the formula I.B.2, where Z is pyridin-3-yl (Z-3), R 3 is Br, and R and 0 or 1 R a substituents are in any row of Table P below, and these compounds are named I.B.2.3-Z-3-P-1 to I.B.2.3-Z-3-P-150.

[0246] In another embodiment, compound I has the formula I.B.3, where Z is pyridin-3-yl (Z-3), R 3 is Br, and R and 0 or 1 R a substituents are in any row of Table P below, and these compounds are named I.B.3.3-Z-3-P-1 to I.B.3.3-Z-3-P-150.

[0247] Table P

[0248]

[0249]

[0250] In an embodiment, compound I has the formula I.A.1, where Z is pyridin-2-yl (Z-2), R 3 is F, and R and 0 or 1 R aFor substituents according to any row of Table Q below, these compounds are named I.A.1.1-Z-2-Q-1 to I.A1.1-Z-2-Q-150.

[0251] In another embodiment, compound I has the formula I.A.2, where Z is pyridin-2-yl (Z-2), R 3 is F, R and 0 or 1 R a For substituents according to any row of Table Q below, these compounds are named I.A.2.1-Z-2-Q-1 to I.A2.1-Z-2-Q-150.

[0252] In another embodiment, compound I has the formula I.A.3, where Z is pyridin-2-yl (Z-2), R 3 is F, R and 0 or 1 R a For substituents according to any row of Table Q below, these compounds are named I.A.3.1-Z-2-Q-1 to I.A3.1-Z-2-Q-150.

[0253] In another embodiment, compound I has the formula I.B.1, where Z is pyridin-2-yl (Z-2), R 3 is F, R and 0 or 1 R a For substituents according to any row of Table Q below, these compounds are named I.B.1.1-Z-2-Q-1 to I.B1.1-Z-2-Q-150.

[0254] In another embodiment, compound I has the formula I.B.2, where Z is pyridin-2-yl (Z-2), R 3 is F, R and 0 or 1 R a For substituents according to any row of Table Q below, these compounds are named I.B.2.1-Z-2-Q-1 to I.B.2.1-Z-2-Q-150.

[0255] In another embodiment, compound I has the formula I.B.3, where Z is pyridin-2-yl (Z-2), R 3 is F, R and 0 or 1 R a For substituents according to any row of Table Q below, these compounds are named I.B.3.1-Z-2-Q-1 to I.B.3.1-Z-2-Q-150.

[0256] In another embodiment, compound I has the formula I.A.1, where Z is pyridin-2-yl (Z-2), R 3 is Cl, R and 0 or 1 R a For substituents according to any row of Table Q below, these compounds are named I.A1.2-Z-2-Q-1 to I.A.1.2-Z-2-Q-150.

[0257] In another embodiment, Compound I has the formula I.A.2, where Z is pyridin-2-yl (Z-2), R 3 is Cl, and R and zero or one R a substituents are in any row of Table Q below, and these compounds are named I.A.2.2-Z-2-Q-1 to I.A2.2-Z-2-Q-150.

[0258] In another embodiment, Compound I has the formula I.A.3, where Z is pyridin-2-yl (Z-2), R 3 is Cl, and R and zero or one R a substituents are in any row of Table Q below, and these compounds are named I.A.3.2-Z-2-Q-1 to I.A3.2-Z-2-Q-150.

[0259] In another embodiment, Compound I has the formula I.B.1, where Z is pyridin-2-yl (Z-2), R 3 is Cl, and R and zero or one R a substituents are in any row of Table Q below, and these compounds are named I.B.1.2-Z-2-Q-1 to I.B.1.2-Z-2-Q-150.

[0260] In another embodiment, Compound I has the formula I.B.2, where Z is pyridin-2-yl (Z-2), R 3 is Cl, and R and zero or one R a substituents are in any row of Table Q below, and these compounds are named I.B.2.2-Z-2-Q-1 to I.B.2.2-Z-2-Q-150.

[0261] In another embodiment, Compound I has the formula I.B.3, where Z is pyridin-2-yl (Z-2), R 3 is Cl, and R and zero or one R a substituents are in any row of Table Q below, and these compounds are named I.B.3.2-Z-2-Q-1 to I.B.3.2-Z-2-Q-150.

[0262] In another embodiment, Compound I has the formula I.A.1, where Z is pyridin-2-yl (Z-2), R 3 is Br, and R and zero or one R a substituents are in any row of Table Q below, and these compounds are named I.A1.3-Z-2-Q-1 to I.A.1.3-Z-2-Q-150.

[0263] In another embodiment, Compound I has the formula I.A.2, where Z is pyridin-2-yl (Z-2), and R 3 is Br, and R and zero or one R a substituents are in any row of Table Q below, and these compounds are named I.A.2.3-Z-2-Q-1 to I.A2.3-Z-2-Q-150.

[0264] In another embodiment, Compound I has the formula I.A.3, where Z is pyridin-2-yl (Z-2), and R 3 is Br, and R and zero or one R a substituents are in any row of Table Q below, and these compounds are named I.A.3.3-Z-2-Q-1 to I.A3.3-Z-2-Q-150.

[0265] In another embodiment, Compound I has the formula I.B.1, where Z is pyridin-2-yl (Z-2), and R 3 is Br, and R and zero or one R a substituents are in any row of Table Q below, and these compounds are named I.B.1.3-Z-2-Q-1 to I.B.1.3-Z-2-Q-150.

[0266] In another embodiment, Compound I has the formula I.B.2, where Z is pyridin-2-yl (Z-2), and R 3 is Br, and R and zero or one R a substituents are in any row of Table Q below, and these compounds are named I.B.2.3-Z-2-Q-1 to I.B.2.3-Z-2-Q-150.

[0267] In another embodiment, Compound I has the formula I.B.3, where Z is pyridin-2-yl (Z-2), and R 3 is Br, and R and zero or one R a substituents are in any row of Table Q below, and these compounds are named I.B.3.3-Z-2-Q-1 to I.B.3.3-Z-2-Q-150.

[0268] Table Q

[0269]

[0270]

[0271] These compounds I are substituted (2E)-2-[3-halo-2-[[(Z)-[2-(alkoxy)-1-aryl-ethylidene]amino]oxymethyl]phenyl]-2-methoxyimino-N-methyl-acetamide (Formula I.A.1), (2E)-2-[3-halo-2-[[(Z)-[1-(alkoxymethyl)-3-aryl-prop-2-ynylidene]amino]oxymethyl]phenyl]-2-methoxyimino-N-methyl-acetamide (Formula I.B.1), (2E)-2-[3-halo-2-[[(Z)-[2-(alkoxy)-1-(3-aryl)ethylidene]amino]oxymethyl]phenyl]-2-methoxyimino-methyl acetate (Formula I.A.2), (2E)-2-[3-halo-2-[[(Z)-[1-(alkoxymethyl)-3-(3-aryl)prop-2-ynylidene]amino]oxymethyl]phenyl]-2-methoxyimino-methyl acetate (Formula I.B.2), (E)-2-[3-halo-2-[[(Z)-[2-(alkoxy)-1-(3-aryl)ethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoic acid methyl ester (Formula I.A.3) and (E)-2-[3-halo-2-[[(Z)-[1-(alkoxymethyl)-3-(3-aryl)prop-2-ynylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoic acid methyl ester (Formula I.B.3) and their stereoisomers (e.g., depicted by Formulas Ia, Ib and Ic below).

[0272] Accordingly, the present invention also relates to the stereoisomers depicted below: the E / E isomer of Formula Ia:

[0273]

[0274] the Z / E isomer of Formula Ib:

[0275]

[0276] and the Z / Z isomer of Formula Ic:

[0277]

[0278] Accordingly, the present invention also relates to compounds Ia wherein R 1 is NH and R 2 is N, these compounds having Formula Ia.1 or Ia.2, relates to compounds Ia wherein R 1 is O and R 2 is N, these compounds having Formula Ia.3 or Ia.4, and relates to compounds Ia wherein R 1 is O and R 2 is CH, these compounds having Formula Ia.5 or Ia.6:

[0279]

[0280] The present invention further relates to compounds Ib in which R 1 is NH and R 2 is N, and these compounds have the formula Ib.1 or Ib.2, and relates to compounds Ib in which R 1 is O and R 2 is N, and these compounds have the formula Ib.3 or Ib.4, and relates to compounds Ib in which R 1 is O and R 2 is CH, and these compounds have the formula Ib.5 or Ib.6:

[0281]

[0282] The present invention further relates to compounds Ic in which R 1 is NH and R 2 is N, and these compounds have the formula Ic.1, and relates to compounds Ic in which R 1 is O and R 2 is N, and these compounds have the formula Ic.2, and relates to compounds Ic in which R 1 is O and R 2 is CH, and these compounds have the formula Ic.3:

[0283]

[0284]

[0285] In 2389 embodiments, compound I has the formula Ia.1, where Z is phenyl (Z-1), R 3 is F, R and 0 to 3 R a substituents are in any row of Table A above, and these compounds are named Ia.1.1-Z-1-A-1 to Ia.1.1-Z-1-A-2389.

[0286] In another 2389 embodiments, compound I has the formula Ia.2, where Z is phenyl (Z-1), R 3 is F, R and 0 to 3 R a substituents are in any row of Table A below, and these compounds are named Ia.2.1-Z-1-A-1 to Ia.2.1-Z-1-A-2389.

[0287] In another 2389 embodiments, compound I has the formula Ia.3, where Z is phenyl (Z-1), R 3 is F, R and 0 to 3 R aThe substituents are in any row of Table A below, and these compounds are named Ia.3.1-Z-1-A-1 to Ia.3.1-Z-1-A-2389.

[0288] In a further 2389 embodiments, compound I has the formula Ia.4, where Z is phenyl (Z-1), R 3 is F, R and 0 to 3 R a The substituents are in any row of Table A below, and these compounds are named Ia.4.1-Z-1-A-1 to Ia.4.1-Z-1-A-2389.

[0289] In a further 2389 embodiments, compound I has the formula Ia.5, where Z is phenyl (Z-1), R 3 is F, R and 0 to 3 R a The substituents are in any row of Table A below, and these compounds are named Ia.5.1-Z-1-A-1 to Ia.5.1-Z-1-A-2389.

[0290] In a further 2389 embodiments, compound I has the formula Ia.6, where Z is phenyl (Z-1), R 3 is F, R and 0 to 3 R a The substituents are in any row of Table A below, and these compounds are named Ia.6.1-Z-1-A-1 to Ia.6.1-Z-1-A-2389.

[0291] In a further 2389 embodiments, compound I has the formula Ia.1, where Z is phenyl (Z-1), R 3 is Cl, R and 0 to 3 R a The substituents are in any row of Table A above, and these compounds are named Ia.1.2-Z-1-A-1 to Ia.1.2-Z-1-A-2389.

[0292] In a further 2389 embodiments, compound I has the formula Ia.2, where Z is phenyl (Z-1), R 3 is Cl, R and 0 to 3 R a The substituents are in any row of Table A below, and these compounds are named Ia.2.2-Z-1-A-1 to Ia.2.2-Z-1-A-2389.

[0293] In a further 2389 embodiments, compound I has the formula Ia.3, where Z is phenyl (Z-1), R 3 is Cl, R and 0 to 3 R a The substituents are in any row of Table A below, and these compounds are named Ia.3.2-Z-1-A-1 to Ia.3.2-Z-1-A-2389.

[0294] In an additional 2389 embodiments, Compound I has the formula Ia.4, where Z is phenyl (Z-1), R 3 is Cl, and R and 0 to 3 R a substituents are in any row of Table A below, and these compounds are named Ia.4.2-Z-1-A-1 to Ia.4.2-Z-1-A-2389.

[0295] In an additional 2389 embodiments, Compound I has the formula Ia.5, where Z is phenyl (Z-1), R 3 is Cl, and R and 0 to 3 R a substituents are in any row of Table A below, and these compounds are named Ia.5.2-Z-1-A-1 to Ia.5.2-Z-1-A-2389.

[0296] In an additional 2389 embodiments, Compound I has the formula Ia.6, where Z is phenyl (Z-1), R 3 is Cl, and R and 0 to 3 R a substituents are in any row of Table A below, and these compounds are named Ia.6.2-Z-1-A-1 to Ia.6.2-Z-1-A-2389.

[0297] In an additional 2389 embodiments, Compound I has the formula Ia.1, where Z is phenyl (Z-1), R 3 is Br, and R and 0 to 3 R a substituents are in any row of Table A above, and these compounds are named Ia.1.3-Z-1-A-1 to Ia.1.3-Z-1-A-2389.

[0298] In an additional 2389 embodiments, Compound I has the formula Ia.2, where Z is phenyl (Z-1), R 3 is Br, and R and 0 to 3 R a substituents are in any row of Table A below, and these compounds are named Ia.2.3-Z-1-A-1 to Ia.2.3-Z-1-A-2389.

[0299] In an additional 2389 embodiments, Compound I has the formula Ia.3, where Z is phenyl (Z-1), R 3 is Br, and R and 0 to 3 R a substituents are in any row of Table A below, and these compounds are named Ia.3.3-Z-1-A-1 to Ia.3.3-Z-1-A-2389.

[0300] In an additional 2,389 embodiments, Compound I has the formula Ia.4, where Z is phenyl (Z-1), R 3 is Br, and R and from 0 to 3 R a substituents are in any row of Table A below, and these compounds are named Ia.4.3-Z-1-A-1 to Ia.4.3-Z-1-A-2,389.

[0301] In an additional 2,389 embodiments, Compound I has the formula Ia.5, where Z is phenyl (Z-1), R 3 is Br, and R and from 0 to 3 R a substituents are in any row of Table A below, and these compounds are named Ia.5.3-Z-1-A-1 to Ia.5.3-Z-1-A-2,389.

[0302] In an additional 2,389 embodiments, Compound I has the formula Ia.6, where Z is phenyl (Z-1), R 3 is Br, and R and from 0 to 3 R a substituents are in any row of Table A below, and these compounds are named Ia.6.3-Z-1-A-1 to Ia.6.3-Z-1-A-2,389.

[0303] In an additional 2,389 embodiments, Compound I has the formula Ib.1, where Z is phenyl (Z-1), R 3 is F, and R and from 0 to 3 R a substituents are in any row of Table A above, and these compounds are named Ib.1.1-Z-1-A-1 to Ib.1.1-Z-1-A-2,389.

[0304] In an additional 2,389 embodiments, Compound I has the formula Ib.2, where Z is phenyl (Z-1), R 3 is F, and R and from 0 to 3 R a substituents are in any row of Table A below, and these compounds are named Ib.2.1-Z-1-A-1 to Ib.2.1-Z-1-A-2,389.

[0305] In an additional 2,389 embodiments, Compound I has the formula Ib.3, where Z is phenyl (Z-1), R 3 is F, and R and from 0 to 3 R a substituents are in any row of Table A below, and these compounds are named Ib.3.1-Z-1-A-1 to Ib.3.1-Z-1-A-2,389.

[0306] In an additional 2,389 embodiments, Compound I has the formula Ib.4, where Z is phenyl (Z-1), R 3 is F, and R and from 0 to 3 Ra For any row of Table A below, these compounds are named Ib.4.1-Z-1-A-1 to Ib.4.1-Z-1-A-2389.

[0307] In an additional 2389 embodiments, Compound I has the formula Ib.5, where Z is phenyl (Z-1), R 3 is F, R and 0 to 3 R a For any row of Table A below, these compounds are named Ib.5.1-Z-1-A-1 to Ib.5.1-Z-1-A-2389.

[0308] In an additional 2389 embodiments, Compound I has the formula Ib.6, where Z is phenyl (Z-1), R 3 is F, R and 0 to 3 R a For any row of Table A below, these compounds are named Ib.6.1-Z-1-A-1 to Ib.6.1-Z-1-A-2389.

[0309] In an additional 2389 embodiments, Compound I has the formula Ib.1, where Z is phenyl (Z-1), R 3 is Cl, R and 0 to 3 R a For any row of Table A above, these compounds are named Ib.1.2-Z-1-A-1 to Ib.1.2-Z-1-A-2389.

[0310] In an additional 2389 embodiments, Compound I has the formula Ib.2, where Z is phenyl (Z-1), R 3 is Cl, R and 0 to 3 R a For any row of Table A below, these compounds are named Ib.2.2-Z-1-A-1 to Ib.2.2-Z-1-A-2389.

[0311] In an additional 2389 embodiments, Compound I has the formula Ib.3, where Z is phenyl (Z-1), R 3 is Cl, R and 0 to 3 R a For any row of Table A below, these compounds are named Ib.3.2-Z-1-A-1 to Ib.3.2-Z-1-A-2389.

[0312] In an additional 2389 embodiments, Compound I has the formula Ib.4, where Z is phenyl (Z-1), R 3 is Cl, R and 0 to 3 R aThe substituents are in any row of Table A below, and these compounds are named Ib.4.2-Z-1-A-1 to Ib.4.2-Z-1-A-2389.

[0313] In a further 2389 embodiments, compound I has the formula Ib.5, where Z is phenyl (Z-1), R 3 is Cl, R and 0 to 3 R a The substituents are in any row of Table A below, and these compounds are named Ib.5.2-Z-1-A-1 to Ib.5.2-Z-1-A-2389.

[0314] In a further 2389 embodiments, compound I has the formula Ib.6, where Z is phenyl (Z-1), R 3 is Cl, R and 0 to 3 R a The substituents are in any row of Table A below, and these compounds are named Ib.6.2-Z-1-A-1 to Ib.6.2-Z-1-A-2389.

[0315] In a further 2389 embodiments, compound I has the formula Ib.1, where Z is phenyl (Z-1), R 3 is Br, R and 0 to 3 R a The substituents are in any row of Table A above, and these compounds are named Ib.1.3-Z-1-A-1 to Ib.1.3-Z-1-A-2389.

[0316] In a further 2389 embodiments, compound I has the formula Ib.2, where Z is phenyl (Z-1), R 3 is Br, R and 0 to 3 R a The substituents are in any row of Table A below, and these compounds are named Ib.2.3-Z-1-A-1 to Ib.2.3-Z-1-A-2389.

[0317] In a further 2389 embodiments, compound I has the formula Ib.3, where Z is phenyl (Z-1), R 3 is Br, R and 0 to 3 R a The substituents are in any row of Table A below, and these compounds are named Ib.3.3-Z-1-A-1 to Ib.3.3-Z-1-A-2389.

[0318] In a further 2389 embodiments, compound I has the formula Ib.4, where Z is phenyl (Z-1), R 3 is Br, R and 0 to 3 R a The substituents are in any row of Table A below, and these compounds are named Ib.4.3-Z-1-A-1 to Ib.4.3-Z-1-A-2389.

[0319] In an additional 2389 embodiments, Compound I has the formula Ib.5, where Z is phenyl (Z-1), R 3 is Br, and R and 0 to 3 R a substituents are in any row of Table A below, and these compounds are named Ib.5.3-Z-1-A-1 to Ib.5.3-Z-1-A-2389.

[0320] In an additional 2389 embodiments, Compound I has the formula Ib.6, where Z is phenyl (Z-1), R 3 is Br, and R and 0 to 3 R a substituents are in any row of Table A below, and these compounds are named Ib.6.3-Z-1-A-1 to Ib.6.3-Z-1-A-2389.

[0321] In an additional 2389 embodiments, Compound I has the formula Ic.1, where Z is phenyl (Z-1), R 3 is F, and R and 0 to 3 R a substituents are in any row of Table A above, and these compounds are named Ic.1.1-Z-1-A-1 to Ic.1.1-Z-1-A-2389.

[0322] In an additional 2389 embodiments, Compound I has the formula Ic.2, where Z is phenyl (Z-1), R 3 is F, and R and 0 to 3 R a substituents are in any 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.

[0323] In an additional 2389 embodiments, Compound I has the formula Ic.3, where Z is phenyl (Z-1), R 3 is F, and R and 0 to 3 R a substituents are in any row of Table A below, and these compounds are named Ic.3.1-Z-1-A-1 to Ic.3.1-Z-1-A-2389.

[0324] In an additional 2389 embodiments, Compound I has the formula Ic.4, where Z is phenyl (Z-1), R 3 is F, and R and 0 to 3 R a substituents are in any row of Table A below, and these compounds are named Ic.4.1-Z-1-A-1 to Ic.4.1-Z-1-A-2389.

[0325] In an additional 2389 embodiments, Compound I has the formula Ic.5, where Z is phenyl (Z-1), R3 is F, R and 0 to 3 Rs a The substituents are in any row of Table A below, and these compounds are named Ic.5.1-Z-1-A-1 to Ic.5.1-Z-1-A-2389.

[0326] In a further 2389 embodiments, compound I has the formula Ic.6, wherein Z is phenyl (Z-1), R 3 is F, R and 0 to 3 Rs a The substituents are in any row of Table A below, and these compounds are named Ic.6.1-Z-1-A-1 to Ic.6.1-Z-1-A-2389.

[0327] In a further 2389 embodiments, compound I has the formula Ic.1, wherein Z is phenyl (Z-1), R 3 is Cl, R and 0 to 3 Rs a The substituents are in any row of Table A above, and these compounds are named Ic.1.2-Z-1-A-1 to Ic.1.2-Z-1-A-2389.

[0328] In a further 2389 embodiments, compound I has the formula Ic.2, wherein Z is phenyl (Z-1), R 3 is Cl, R and 0 to 3 Rs a The substituents are in any 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.

[0329] In a further 2389 embodiments, compound I has the formula Ic.3, wherein Z is phenyl (Z-1), R 3 is Cl, R and 0 to 3 Rs a The substituents are in any 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.

[0330] In a further 2389 embodiments, compound I has the formula Ic.4, wherein Z is phenyl (Z-1), R 3 is Cl, R and 0 to 3 Rs a The substituents are in any row of Table A below, and these compounds are named Ic.4.2-Z-1-A-1 to Ic.4.2-Z-1-A-2389.

[0331] In a further 2389 embodiments, compound I has the formula Ic.5, wherein Z is phenyl (Z-1), R 3 is Cl, R and 0 to 3 Rs aThe substituents are in any row of Table A below, and these compounds are named Ic.5.2-Z-1-A-1 to Ic.5.2-Z-1-A-2389.

[0332] In a further 2389 embodiments, compound I has the formula Ic.6, where Z is phenyl (Z-1), R 3 is Cl, R and 0 to 3 R a The substituents are in any row of Table A below, and these compounds are named Ic.6.2-Z-1-A-1 to Ic.6.2-Z-1-A-2389.

[0333] In a further 2389 embodiments, compound I has the formula Ic.1, where Z is phenyl (Z-1), R 3 is Br, R and 0 to 3 R a The substituents are in any row of Table A above, and these compounds are named Ic.1.3-Z-1-A-1 to Ic.1.3-Z-1-A-2389.

[0334] In a further 2389 embodiments, compound I has the formula Ic.2, where Z is phenyl (Z-1), R 3 is Br, R and 0 to 3 R a The substituents are in any row of Table A below, and these compounds are named Ic.2.3-Z-1-A-1 to Ic.2.3-Z-1-A-2389.

[0335] In a further 2389 embodiments, compound I has the formula Ic.3, where Z is phenyl (Z-1), R 3 is Br, R and 0 to 3 R a The substituents are in any 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.

[0336] In a further 2389 embodiments, compound I has the formula Ic.4, where Z is phenyl (Z-1), R 3 is Br, R and 0 to 3 R a The substituents are in any row of Table A below, and these compounds are named Ic.4.3-Z-1-A-1 to Ic.4.3-Z-1-A-2389.

[0337] In a further 2389 embodiments, compound I has the formula Ic.5, where Z is phenyl (Z-1), R 3 is Br, R and 0 to 3 R a The substituents are in any row of Table A below, and these compounds are named Ic.5.3-Z-1-A-1 to Ic.5.3-Z-1-A-2389.

[0338] In an additional 2389 embodiments, Compound I has the formula Ic.6, where Z is phenyl (Z-1), R 3 is Br, R and from 0 to 3 R a substituents are in any row of Table A below, and these compounds are named Ic.6.3-Z-1-A-1 to Ic.6.3-Z-1-A-2389.

[0339] The compounds according to the invention comprise the isomers depicted in formulae I, Ia, Ib and Ic. Preferably, the compounds according to the invention comprise more than 50% of the stereoisomers depicted in formula I and less than 50% of the stereoisomers depicted in formulae Ia, Ib and Ic. Preferably, the compounds according to the invention comprise more than 80% of the stereoisomers depicted in formula I and less than 20% of the stereoisomers depicted in formulae Ia, Ib and Ic. Preferably, the compounds according to the invention comprise more than 90% of the stereoisomers depicted in formula I and less than 10% of the stereoisomers depicted in formulae Ia, Ib and Ic. Preferably, the compounds according to the invention comprise more than 95% of the stereoisomers depicted in formula I and less than 5% of the stereoisomers depicted in formulae Ia, Ib and Ic. Preferably, the compounds according to the invention comprise more than 98% of the stereoisomers depicted in formula I and less than 2% of the stereoisomers depicted in formulae Ia, Ib and Ic. Preferably, the compounds according to the invention comprise more than 99% of the stereoisomers depicted in formula I and less than 1% of the stereoisomers depicted in formulae Ia, Ib and Ic. Preferably, the compounds according to the invention comprise more than 99.5% of the stereoisomers depicted in formula I and less than 0.5% of the stereoisomers depicted in formulae Ia, Ib and Ic.

[0340] According to another embodiment, the compounds according to the invention comprise the stereoisomers depicted in formula I and formula Ia. Preferably, the compounds according to the invention comprise more than 50% of the stereoisomers depicted in formula I and less than 50% of the stereoisomers depicted in formula Ia. Preferably, the compounds according to the invention comprise more than 80% of the stereoisomers depicted in formula I and less than 20% of the stereoisomers depicted in formula Ia. Preferably, the compounds according to the invention comprise more than 90% of the stereoisomers depicted in formula I and less than 10% of the stereoisomers depicted in formula Ia. Preferably, the compounds according to the invention comprise more than 95% of the stereoisomers depicted in formula I and less than 5% of the stereoisomers depicted in formula Ia. Preferably, the compounds according to the invention comprise more than 99% of the stereoisomers depicted in formula I and less than 1% of the stereoisomers depicted in formula Ia. Preferably, the compounds according to the invention comprise more than 99.5% of the stereoisomers depicted in formula I and less than 0.5% of the stereoisomers depicted in formula Ia. According to a further embodiment, the compounds according to the invention are substantially stereoisomerically pure stereoisomers as depicted in formula I.

[0341] Synthesis

[0342] The compounds can be obtained by various routes similar to known prior art methods (such as EP 463488, WO 2021 / 153754, WO 2021 / 219386, WO 2021 / 219387, WO 2021 / 219388, WO 2021 / 219390 and WO 2021 / 249928), and advantageously, as shown in Schemes 1 to 4 and in the following Examples section. Scheme 1 A suitable method is illustrated in:

[0343]

[0344] It starts with the conversion of a 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 a temperature of 60 °C to 100 °C (preferably about 65 °C). In the case of obtaining an E / Z mixture, the isomers can be separated by known purification techniques (such as column chromatography, crystallization, distillation, etc.). Then, under basic conditions using, for example, sodium hydride, cesium carbonate or potassium carbonate as the base, and an organic solvent such as dimethylformamide (DMF) or acetonitrile (AcN), preferably cesium carbonate as the base and AcN as the solvent, the coupling with intermediate IV is carried out at room temperature (RT) of about 24 °C, where X is a leaving group such as halogen, tosylate and mesylate, preferably X is Cl or Br. This general procedure is also applicable to the preparation of compounds of formula I where Z is not phenyl and / or m is 1. Where R 1 is O, the ester compound I can be converted to the amide of formula I where R 1 is NH by reacting with methylamine (preferably 40% aqueous solution) using tetrahydrofuran (THF) as the solvent at RT. In the case of obtaining an E / Z mixture, the isomers can be separated by known purification techniques (such as column chromatography, crystallization, distillation, etc.). Thus, in addition to the E / Z isomers (such as (2E)-2 - methoxyimino - 2 - [2 - [[(Z)-[2 - methoxy - 1-(2,4 - difluorophenyl)ethylidene]amino]oxymethyl]-3 - chloro - phenyl]-N - methyl - acetamide), these procedures can also be used to provide the corresponding E / E, Z / E and Z / Z isomers of formula Ia, Ib and Ic (such as (2E)-2 - methoxyimino - 2 - [2 - [[(E)-[2 - methoxy - 1-(2,4 - difluorophenyl)ethylidene]amino]oxymethyl]-3 - chloro - phenyl]-N - methyl - acetamide, (2Z)-2 - methoxyimino - 2 - [2 - [[(E)-[2 - methoxy - 1-(2,4 - difluorophenyl)ethylidene]amino]oxymethyl]-3 - bromo - phenyl]-N - methyl - acetamide and (2Z)-2 - methoxyimino - 2 - [2 - [[(Z)-[2 - methoxy - 1-(2,4 - difluorophenyl)ethylidene]amino]oxymethyl]-3 - chloro - phenyl]-N - methyl - acetamide).

[0345] Another general method for preparing compound I is depicted in Scheme 2 :

[0346]

[0347] The intermediate IV is reacted with N-hydroxysuccinimide VI using a base such as triethylamine in DMF. The reaction temperature is generally from 50 °C to 70 °C, preferably about 70 °C. The conversion to the corresponding O-benzylhydroxylamine, i.e., intermediate VIII, is achieved at 25 °C by removing the phthalimide group, preferably using hydrazine hydrate in methanol as the solvent. Alternatively, removal of the phthalimide group using methylamine in methanol as the solvent at 25 °C can afford intermediate IX. Intermediate VIII and intermediate IX can be condensed with a ketone at a temperature of 50 °C to 65 °C using acetic acid or pyridine in methanol as the solvent. Alternatively, THF can be used as the solvent and condensation can be carried out with titanium(IV) ethoxide (Ti(OEt) 4 ) at about 70 °C. The desired product is usually accompanied by an unwanted isomer, which can be removed, for example, by column chromatography, crystallization.

[0348] A general method for preparing intermediate IV is shown in Scheme 3 :

[0349]

[0350] Compound XI can be obtained from X by lithium-halogen exchange or by generating a Grignard reagent and further reacting with dimethyl oxalate or chloromethyl oxalate in the presence of a solvent. Preferred solvents are THF, 2-methyl-THF, and the temperature can be between -70 °C and -78 °C. The conversion of intermediate XI to intermediate XII can be achieved using N-methylhydroxylamine hydrochloride and a base such as pyridine or NaAc in a polar solvent such as methanol. The reaction temperature is preferably about 65 °C. An E / Z mixture is usually obtained, and the isomers can be separated by purification techniques known in the art (e.g., column chromatography, crystallization). Bromination of intermediate XII provides the desired intermediate compound IV, where R 1 is O and R 2 =N. This reaction of intermediate XII with N-bromosuccinimide (NBS) is carried out in a solvent such as carbon tetrachloride, chlorobenzene, AcN, using a radical initiator such as 1,1'-azobis(cyclohexanecarbonitrile) or azobisisobutyronitrile, at a temperature of 70 °C to 100 °C. The preferred radical initiator is 1,1'-azobis(cyclohexanecarbonitrile), the preferred solvent is chlorobenzene and the preferred temperature is 80 °C.

[0351] The synthesis of compounds containing different substituents R 3 follows a similar sequence to that in Scheme 3, where R 3 is bromine. Intermediate III and intermediate IV (where R 3The coupling of (wherein is bromine) provides Compound I as described above. Using standard chemical reactions, such as the Suzuki or Stille reaction, the bromine group can be converted into, for example, other R 3 substituents, such as cycloalkyl, alkoxy, and alkenyl. Further conversions, such as that of vinyl, provide Compound I with other R 3 substituents, such as ethyl, CN, and haloalkyl.

[0352] Most of the ketones of general formula II are commercially available. However, for those that are not, the preparation of these ketones is carried out in-house using methods known in the prior art. The various methods known in the literature for synthesizing these ketones are depicted in Scheme 4 as follows:

[0353]

[0354] Ketone II can be obtained from the corresponding halogen-containing precursor XIV, where X is preferably bromine or iodine. Lithium-halogen exchange is carried out in Compound XIV using n-butyllithium (J Org Chem [Journal of Organic Chemistry], 1998, 63(21), 7399 - 7407) or the corresponding Grignard reagent is synthesized using THF as a solvent (Nature Comm [Nature Communications], 2017, 8(1), 1 - 7), and then reacted with N-methoxy-N-methylalkoxyacetamide at about -70 °C to -78 °C to provide Ketone II.

[0355] Compound I and its compositions are respectively suitable as fungicides, effectively against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, especially fungi from the classes Plasmodiophoromycetes, Peronosporomycetes (synonym Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes (synonym Fungi imperfecti). They can be used as foliar fungicides, seed dressing fungicides, and soil fungicides in crop protection.

[0356] Compound I and its compositions are preferably useful for controlling phytopathogenic fungi on the following plants: various cultivated plants, such as cereals, for example wheat, rye, barley, triticale, oats or rice; sugar beet, for example sugar beet or fodder beet; fruits, such as pomaceous fruits (apples, pears, etc.), stone fruits (for example plums, peaches, almonds, cherries) or soft fruits, also known as berries (strawberries, raspberries, blackberries, currants, etc.); leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olive, sunflower, coconut, cacao bean, castor oil plant, oil palm, peanut or soybean; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruits, such as oranges, lemons, grapefruits or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, gourds or paprika; laurel plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as maize, soybean, rape, sugar cane or oil palm; maize; tobacco; nuts; coffee; tea; bananas; grapevines (table grapes and wine grapes); hops; turf; stevia (also known as stevia rebaudiana); natural rubber plants; or ornamental and forest plants, such as flowers, shrubs, broad-leaved trees or evergreens (conifers, eucalyptus, etc.); plant propagation material, such as seeds; and crop material of these plants.

[0357] More preferably, compound I and its compositions are used for controlling fungi on the following plants: field crops, such as potatoes, sugar beet, tobacco, wheat, rye, barley, oats, rice, maize, cotton, soybeans, rape, beans, sunflowers, coffee or sugar cane; fruits; vines; ornamental plants; or vegetables, such as cucumbers, tomatoes, kidney beans or pumpkins.

[0358] The term "plant propagation material" is to be understood as meaning all generative parts of plants, such as seeds; and vegetative plant material which can be used for plant propagation, such as cuttings and tubers (for example potatoes). This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, buds and other parts of plants; including seedlings and young plants which are transplanted after germination or after emergence from the soil.

[0359] Preferably, plant propagation material is treated with compound I and its compositions respectively for controlling fungi on the following plants: cereals, such as wheat, rye, barley and oats; rice, maize, cotton and soybeans.

[0360] According to the present invention, all of the above-mentioned cultivated plants are to be understood as including all species, subspecies, variants, varieties and / or hybrids belonging to the respective cultivated plants, including but not limited to winter and spring varieties, in particular cereals such as wheat and barley, and oilseed rape, for example winter wheat, spring wheat, winter barley, etc., further including dwarf, semi-dwarf and fully dwarf varieties and / or hybrids with reduced height and thicker and shorter stems, such as dwarf maize (also known as "smart maize"), semi-dwarf wheat and dwarf rice.

[0361] Maize, also known as Indian corn or Zea mays, includes all kinds of maize, such as feed maize and sweet maize. According to the present invention, it includes all Zea mays or maize subspecies and / or variants, in particular floury maize (Zea mays var. amylacea), popcorn (Zea mays var. everta), dent maize (Zea mays var. indentata), flint maize (Zea mays var. indurata), sweet maize (Zea mays var. saccharata and var. rugosa), waxy maize (Zea mays var. ceratina), high amylose maize (amylomaize) (high amylose Zea mays variant), pod maize or wild maize (Zea mays var. tunicata) and striped maize (Zea mays var. japonica).

[0362] Most soybean cultivars can be classified into indeterminate and determinate growth habits, while wild soybean (Glycine soja) (the wild ancestor of soybean) is indeterminate (PNAS [Proceedings of the National Academy of Sciences of the United States of America] 2010, 107(19) 8563 - 8568). Indeterminate growth habit (maturity groups, MG 00 to MG 4.9) is characterized by the continuation of vegetative growth after the start of flowering, while determinate soybean varieties (MG 5 to MG 8) characteristically have completed most of their vegetative growth at the start of flowering. According to the present invention, it includes all soybean cultivars or varieties, in particular indeterminate and determinate cultivars or varieties.

[0363] The term "cultivated plant" shall be understood to include plants that have been modified by mutagenesis or genetic engineering in order to confer new traits on the plant or to modify existing traits. Mutagenesis includes random mutagenesis using X-rays or mutagenic chemicals and also includes targeted mutagenesis to generate 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 generate modifications in the plant genome that cannot be readily obtained by crossing, mutagenesis or natural recombination in the natural environment. Typically, one or more genes are integrated into the genome of the plant in order to add traits or to improve or modify traits. These integrated genes are also referred to as transgenes, and plants containing such transgenes are referred to as transgenic plants. The plant transformation process typically gives rise to a number of transformation events that differ in the genomic loci into which the transgene has been integrated. A plant containing a specific transgene at a specific genomic locus is typically described as containing a specific "event", which is designated by a specific event name. Traits that have been introduced into plants or that have been modified include herbicide tolerance, insect resistance, increased yield, and tolerance to abiotic conditions such as drought.

[0364] Herbicide tolerance has been generated by using mutagenesis and genetic engineering. Plants that have been made tolerant to acetolactate synthase (ALS) inhibitor herbicides by mutagenesis and breeding are available, for example, under the name 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) has been generated by using transgenes.

[0365] The use of Compound I and its compositions on cultivated plants can result in effects that are specific to a cultivated plant containing a particular transgene or event. These effects may involve alterations in growth behavior or altered resistance to biotic or abiotic stress factors. Such effects may particularly include increased yield, increased resistance or tolerance to insect, nematode, fungal, bacterial, mycoplasma, viral or viroid pathogens, and early vigour, early maturity or delayed maturity, cold or heat tolerance, and altered amino acid or fatty acid profiles or contents.

[0366] Compound I and its compositions are particularly suitable, respectively, for controlling the causative pathogens of the following plant diseases:

[0367] Species of Albugo (white rust) on ornamental plants, vegetables (e.g., A. candida), and sunflowers (e.g., A. tragopogonis); species of Alternaria (alternaria leaf spot) on vegetables (e.g., A. dauci or A. porri), rape (A. brassicicola or A. brassicae), sugar beet (A. tenuis), fruits (e.g., A. grandis), rice, soybeans, potatoes, and tomatoes (e.g., A. solani, A. grandis, or A. alternata), tomatoes (e.g., A. solani or A. alternata), and wheat (e.g., A. triticina); species of Aphanomyces on sugar beet and vegetables; species of Ascochyta on cereals and vegetables, such as A. tritici (anthracnose) on wheat and A. hordei on barley; Aureobasidium zeae (synonym Kapatiella zeae) on maize; species of Bipolaris and Drechslera (sexual form: species of Cochliobolus), such as southern leaf blight (D. maydis) or northern leaf blight (B. zeicola) on maize, such as spot blotch (B. sorokiniana) on cereals, and such as B. oryzae on rice and turfgrass; Blumeria (formerly known as Erysiphe graminis) on cereals (e.g., wheat or barley) (powdery mildew); Botrytis cinerea (sexual form: Botryotinia fuckeliana: gray mold) on fruits and berries (e.g., strawberries), vegetables (e.g., lettuce, carrots, celery, and cabbage); Botrytis squamosa or Botrytis allii on the onion family, rape, ornamental plants (e.g., B. elliptica), vines, forest plants, and wheaton Allium spp. (e.g., downy mildew: Peronospora destructor); Bremia lactucae (downy mildew) on lettuce; Ceratocystis (synonym Ophiostoma) species (rot or wilt) on broad-leaved and evergreen trees, e.g., Ceratocystis ulmi (Dutch elm disease) on elm; Cercospora species (Cercospora leaf spot) on maize (e.g., gray leaf spot: Cercospora zeae-maydis), rice, sugar beet (e.g., Cercospora beticola), sugar cane, vegetables, coffee, soybean (e.g., Cercospora sojina or Cercospora kikuchii) and rice; Cladobotryum (synonym Dactylium) species (e.g., Cladobotryum mycophilum (formerly known as Dactylium dendroides, teleomorph: Nectria albertinii, Nectriarosella synonym Hypomyces rosellus)) on mushrooms; Cladosporium species on tomato (e.g., Cladosporium fulvum: leaf mold) and cereals, e.g., Cladosporium herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helminthosporium or Bipolaris) species (leaf spot) on maize (Cochliobolus carbonum), cereals (e.g., Cochliobolus sativus, anamorph: Bipolaris sorokiniana) and rice (e.g., Cochliobolus miyabeanus, anamorph: Bipolaris oryzae); Colletotrichum species on cotton (e.g., Colletotrichum gossypii), maize (e.g., Colletotrichum graminicola: anthracnose stalk rot), soft fruits, potato (e.g., Colletotrichum coccodes: black dot), beans (e.g., Colletotrichum lindemuthianum), soybean (e.g., Colletotrichum truncatum or Colletotrichum gloeosporioides), vegetables (e.g., Colletotrichum lagenarium or Colletotrichum capsici), fruits (e.g., Colletotrichum acutatum)acutatum)), coffee (e.g., Colletotrichum coffeanum or C. kahawae), and Colletotrichum on various crops (sexual stage: Glomerella species (anthracnose); Corticium species, e.g., C. sasakii on rice (sheath blight)); Corynespora cassiicola on soybean, cotton, and ornamental plants (leaf spot); Cycloconium species, e.g., C. oleaginum on olive trees; Cylindrocarpon species on fruit trees, vines (e.g., C. liriodendri, sexual stage: Neonectria liriodendri: black foot disease) and ornamental plants (e.g., fruit tree canker or young vine decline, sexual stage: Nectria or Neonectria species); Dematophora on soybean (sexual stage: Rosellinia necatrix) (root and stem rot); Diaporthe species, e.g., D. phaseolorum on soybean (damping-off); Drechslera (synonym Helminthosporium, sexual stage: Pyrenophora) species on maize, cereals such as barley (e.g., D. teres on barley, net blotch) and wheat (e.g., D. tritici-repentis: tan spot), rice, and turfgrass; Esca disease (dieback, apoplexia) on vines caused by Formitiporia (synonyms Phellinus punctata, F. mediterranea, Phaeomoniella chlamydospora (formerly known as Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum, and / or Botryosphaeria obtusa); Elsinoë pyri on pome fruits, Elsinoë veneta on soft fruits (anthracnose), and Elsinoë on vines (Elsinoe species on Ampelina (anthracnose); Entyloma oryzae on rice (leaf smut); Epicoccum species on wheat (black mold); Erysiphe species (powdery mildew) on sugar beet (E. betae), vegetables such as peas (E. pisi), cucurbits such as gourds (e.g., E. cichoracearum), cabbage, rape (e.g., E. cruciferarum); Eutypa lata on fruit trees, vines and ornamental woods (Eutypa rot or dieback, anamorph: Cytosporina lata, synonym Libertella blepharis); Exserohilum (synonym Helminthosporium) on maize (e.g., E. turcicum); Fusarium species (sexual form: Gibberella) on various plants (wilt, root rot or stem rot), such as F. graminearum or F. culmorum on cereals (e.g., wheat or barley) (root rot, scab or head blight), F. oxysporum on tomato, and F. solani (f.sp. glycines, now synonym F. virguliforme), F. tucumaniae and F. brasiliense, each causing sudden death syndrome on soybean, and F. verticillioides on maize; Gaeumannomyces graminis on cereals (e.g., wheat or barley) and maize (take-all); Gibberella species on cereals (e.g., G. zeae) and rice (e.g., G. fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cottonon gossypii); Grain staining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium species on Rosaceae plants and junipers, such as Gymnosporangium sabinae (rust) on pears; species of Helminthosporium (synonym: Drechslera, teleomorph: Cochliobolus) on maize, cereals, potatoes and rice; Hemileia species, such as Hemileia vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (synonym: Cladosporium vitis) on vines; Macrophomina phaseolina (synonym: phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (synonym: Fusarium nivale) (pink snow mold) on cereals (e.g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia species, such as Monilinia laxa, Monilinia fructicola and Monilinia fructigena (synonym: Monilia species: blossom blight and twig blight, brown rot) on stone fruits and other Rosaceae plants; Mycosphaerella species on cereals, bananas, soft fruits and ground nuts, such as Mycosphaerella graminicola (anamorph: Zymoseptoria tritici, formerly known as Septoria tritici: Septoria leaf blotch) on wheat or Mycosphaerella fijiensis (synonym: Pseudocercospora fijiensis: black Sigatoka disease) on bananas and Mycosphaerella musicola, Mycosphaerella arachidicola (synonym: Mycosphaerella arachidis or Cercospora arachidis) on peanuts, Mycosphaerella pisi on peas and Mycosphaerella brassiciola on brassicas; on cabbages (e.g. PeronosporaSpecies of Peronospora (downy mildew) on Brassica spp. (e.g., Peronospora parasitica on Brassica oleracea), rape (e.g., Peronospora parasitica on Brassica napus), onion (e.g., Peronospora destructor on Allium cepa), tobacco (Peronospora tabacina on Nicotiana tabacum), and soybean (e.g., Peronospora manshurica on Glycine max); Phakopsora pachyrhizi and Phakopsora meibomiae on soybean (soybean rust); Species of Phialophora, such as on vines (e.g., Phialophora tracheiphila and Phialophora tetraspora) and soybean (e.g., Phialophora gregata on Glycine max: stem rot); Phoma lingam (synonyms Leptosphaeria biglobosa and Leptosphaeria maculans: root and stem rot) on rape and cabbage and Phoma betae on sugar beet (root rot, leaf spot, and damping-off), and Phoma zeae-maydis (synonym Phyllostica zeae) on maize; Species of Phomopsis on sunflower, vines (e.g., Phomopsis viticola on Vitis vinifera: can and leaf spot) and soybean (e.g., Phomopsis phaseoli on Glycine max, teleomorph: Diaporthe phaseolorum: stem rot); Physoderma maydis on maize (brown spot); Species of Phytophthora (wilt, root, leaf, fruit, and stem rot) on various plants such as red pepper and gourd (e.g., Phytophthora capsici), soybean (e.g., Phytophthora megasperma, synonym Phytophthora sojae), potato and tomato (e.g., Phytophthora infestans: late blight), and broad-leaved trees (e.g., Phytophthora ramorum: sudden oak death); Plasmodiophora brassicae on cabbage, rape, radish, and other plants (club root); Species of Plasmopara, such as Plasmopara viticola on vines (grapevine downy mildew) and Plasmopara halstedii on sunflower; Species of Podosphaera (powdery mildew) on Rosaceae plants, hops, pome fruits, and soft fruits, such as Podosphaera leucotricha on apple and Podosphaera xanthii on gourd;Polymyxa species on, for example, cereals such as barley and wheat (P. graminis) and sugar beet (P. betae), and the virus diseases transmitted thereby; Pseudocercosporella herpotrichoides (synonyms Oculimacula yallundae, O. acuformis: eyespot, teleomorph: Tapesia yallundae) on cereals (e.g., wheat or barley); Pseudoperonospora (downy mildew) on various plants, e.g., P. cubensis on cucurbits or P. humili on hops; Pseudopezicula tracheiphila (red fire disease or rotbrenner, anamorph: Phialophora) on vines; Puccinia species (rust) on various plants, e.g., P. triticina (brown rust or leaf rust) on cereals such as, for example, wheat, barley or rye, 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 (citrus rust) on sugar cane and P. asparagi on asparagus; Pyrenopeziza species, e.g., P. brassicae on oilseed rape; Pyrenophora (anamorph: Drechslera tritici-repentis) on wheat (tan spot) or P. teres (net blotch) on barley; Pyricularia species, e.g., P. oryzae on rice (teleomorph: Magnaporthe grisea: rice blast) and P. grisea on turfgrass and cereals; Pythium species (damping-off) on turfgrass, rice, maize, wheat, cotton, oilseed rape, sunflower, soybean, sugar beet, vegetables and many other plants (e.g., P. ultimum or P. aphanidermatum) and P. oligandrum on mushroomsoligandrum); Ramularia species, such as Ramularia collo-cygni on barley (Ramularia leaf spot, physiological leaf spot), Ramularia areola on cotton (teleomorph: Mycosphaerella areola), and Ramularia beticola on sugar beet; Rhizoctonia species on cotton, rice, potato, turfgrass, maize, oilseed rape, potato, sugar beet, vegetables, and many other plants, such as Rhizoctonia solani on soybean (root and stem rot), Rhizoctonia solani on rice (sheath blight), or Rhizoctonia cerealis on wheat or barley (Rhizoctonia spring leaf blight); Rhizopus stolonifer on strawberry, carrot, cabbage, vine, and tomato (black mold, soft rot); Rhynchosporium secalis and Rhynchosporium commune on barley, rye, and triticale (scald); Sarocladium oryzae and Sarocladium attenuatum on rice (sheath rot); Sclerotinia species on vegetables (Sclerotinia minor and Sclerotinia sclerotiorum) and field crops, such as oilseed rape, sunflower (e.g., Sclerotinia), and soybean (stem rot or white mold), Sclerotium rolfsii (synonym Athelia rolfsii) on soybean, peanut, vegetables, maize, cereals, and ornamental plants; Septoria species on various plants, such as Septoria glycines on soybean (brown spot), Septoria tritici on wheat (synonym Zymoseptoria tritici, Septoria leaf spot), and S. (synonym Stagonospora nodorum) on cereals (Stagonospora blotch); Uncinula necator on vine (synonym Erysiphe) (powdery mildew, anamorph: Oidium tuckeri); maize (e.g., Setosphaeria turcicaturcicum), synonym Helminthosporium turcicum) and Setosphaeria species on turfgrass (leaf blight); Sphacelotheca species on maize, sorghum and sugarcane (smut) (e.g., Sphacelotheca reiliana, synonym Ustilago reiliana: head smut); Sphaerotheca fuliginea on cucurbits (synonym Podosphaera xanthii: powdery mildew); Spongospora subterranea on potato (powdery scab) and virus diseases transmitted thereby; Stagonospora species on cereals, e.g., Stagonospora nodorum on wheat (Stagonospora leaf blotch, sexual form: Leptosphaeria [synonym Phaeosphaeria nodorum]), synonym Septoria nodorum); Synchytrium endobioticum on potato (potato wart disease); Taphrina species, e.g., Taphrina deformans on peach (leaf curl) and Taphrina pruni on plum (plumpocket); Thielaviopsis species on tobacco, pome fruits, vegetables, soybeans and cotton (black root rot), e.g., Thielaviopsis basicola (synonym Chalara elegans); Tilletia species on cereals (common bunt or stinking smut), such as Tilletia tritici on wheat (synonym T. caries, common bunt) and Tilletia controversa on wheat (dwarf bunt); Trichoderma harzianum on mushrooms; Typhula incarnata on barley or wheat (grey snow mold); Urocystis species, e.g., Urocystis occulta on rye (stem smut); vegetables such as beans (e.g., Uromyces appendiculatus, synonym Uromyces phaseoli), sugar beet (e.g., Uromyces betae or U.species of Uromyces (rust) on beticola)) and legumes (e.g., Uromyces vignae, Uromyces pisi, Uromyces viciae-fabae, and Uromyces fabae); species of Ustilago (loose smut) on cereals (e.g., Ustilago nuda and Ustilago avenae), maize (e.g., Ustilago maydis: corn smut), and sugarcane; species of Venturia (scab) on apples (e.g., Venturia inaequalis) and pears; and species of Verticillium (wilt) on various plants such as fruit and ornamental plants, vines, soft fruits, vegetables, and field crops, e.g., Verticillium longisporum on rapeseed, and Verticillium dahliae on strawberries, rapeseed, potatoes, and. Compound I and its compositions are particularly suitable, respectively, for controlling the pathogenic agents of the following plant diseases: rust fungi (from the order Puccinales) on various plants, preferably rust fungi on soybeans and cereals, more preferably selected from: Phakopsora pachyrhizi and Phakopsora meibomiae, which cause Asian soybean rust on soybeans; Puccinia graminis, which causes stem rust or black rust on cereals; Puccinia triticina (synonym Puccinia recondita), which causes brown rust or leaf rust on wheat; Puccinia striiformis, which causes yellow rust or stripe rust on wheat; Puccinia hordei, which causes leaf rust on barley; Puccinia sorghi, which causes common corn rust; and Puccinia polysora, which causes southern corn leaf rust.

[0368] Accordingly, the present invention also relates to a method for treating phytopathogenic rust fungi (from the order Puccinales), the method comprising: treating, therapeutically and / or prophylactically, infected plants at a dosage rate of 50 to 200 g / ha with an agrochemical composition comprising at least one compound of formula I, said plants being at risk of being infested with said phytopathogenic rust fungi, and / or applying said agrochemical composition to said phytopathogenic fungi, more preferably, in said method, said plants are selected from soybeans and cereals.

[0369] In addition, compound I and its compositions are each particularly suitable for controlling other pathogenic agents of plant diseases caused by phytopathogenic fungi, at least a part of their populations having acquired the F129L mutation in the cytochrome b gene that confers resistance to Qo inhibitors: Alternaria solani, which causes early blight on Solanaceae plants; Pyrenophora teres, which causes net blotch of barley; Pyrenophora tritici-repentis, which causes brown spot, yellow leaf spot, yellow leaf blight or helminthosporiosis on cereals; and Rhizoctonia solani, which causes various plant diseases such as root rot, wilt and nematode diseases on various plants.

[0370] In addition, compound I and its compositions are each particularly suitable for controlling the pathogenic agents of the following plant diseases: mildew on specialty crops, soybeans, rapeseed and sunflowers (e.g., Botrytis cinerea on strawberries and vines, Sclerotinia sclerotiorum, Sclerotinia minor and Sclerotium rolfsii on rapeseed, sunflowers and soybeans); Fusarium diseases on cereals (e.g., Fusarium culmorum and Fusarium graminearum on wheat); downy mildew on specialty crops (e.g., Plasmopara viticola on vines, Phytophthora infestans on potatoes); powdery mildew on specialty crops and cereals (e.g., Uncinula necator on vines, species of Erysiphe on various specialty crops, Blumeria graminis on cereals); and leaf spot on cereals, soybeans and corn (e.g., Septoria tritici and Septoria nodorum on cereals, Septoria glycines on soybeans, species of Cercospora on corn and soybeans).

[0371] It has been observed that populations of phytopathogenic fungi consisting apparently entirely of non-resistant strains can readily develop resistance. These compounds can also be applied under such conditions as to completely prevent the formation of resistance and the spread of resistant strains. In this regard, it is useful that they also have strong activity against non-resistant phytopathogenic fungi.

[0372] Fungicide-resistant strains of various phytopathogenic fungi have been reported, and strains resistant to one or more fungicides from various mode-of-action classes are observed by target-site mutations in the genes of the corresponding proteins (e.g., QoI (C3, according to FRAC convention, details available at www.frac.info), quinone outside inhibitor (QoSI; C8), and quinone inside inhibitor (QiI; C4): CytB target protein; sterol demethylation inhibitor (DMI, G1): Cyp51 / Erg11; carboxamide (CAA, H5): CesA3; succinate dehydrogenase inhibitor (SDHI, C2): SdhB, SdhC, and SdhD; dicarboximide (E3): Os-1 (including Bos1, Daf1, etc.); ketoreductase inhibitor (KRI; class III SBI; G3): Erg27; and oxysterol-binding protein inhibitor (OSBPI; F9): ORP1).

[0373] Examples of mutation sites in genes encoding such target proteins are depicted in Table M, which result in single amino acid exchanges, deletions, or insertions listed in the corresponding target protein sequences, thereby conferring resistance to certain fungicides in phytopathogenic fungi (see also Pest Manag Sci 72(8) 2016:1449–1459).

[0374] Table M

[0375]

[0376]

[0377]

[0378]

[0379]

[0380]

[0381]

[0382]

[0383] * Based on alignment with a reference sequence from Phytophthora infestans; ** G54E / K / R / V / W indicates the possibility of five different amino acid changes at position 54; Δ indicates amino acid deletion; # refers to amino acid insertion.

[0384] Thus, compound I is particularly suitable for controlling fungicide-resistant strains of plant pathogenic fungi as described in Table M. Such strains may have one or more resistances resulting from one or more mutations (including but not limited to the mutations listed in Table M) in one or more genes encoding target proteins of various fungicides and / or resistance resulting from overexpression of the corresponding target proteins.

[0385] In addition, certain fungal strains may have developed so-called multidrug resistance, which ultimately leads to broad cross-resistance to many structurally and functionally unrelated compounds. "Multidrug resistance" (MDR), also known as "pleiotropic drug resistance" (PDR), describes a resistance phenomenon that is usually caused by overexpression of certain membrane transporters, resulting in increased activity of efflux pumps that export certain substrates (e.g., mycotoxins and 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 or the corresponding mRNA. The measured amount of mRNA can be, for example, 2-fold, 5-fold, 20-fold, up to 100-fold or more relative to the amount of mRNA of the corresponding fungicide-sensitive wild-type fungus.

[0386] The compound I of the present invention can be used for controlling plant diseases caused by multidrug-resistant (MDR) fungi. Multidrug-resistant fungi can also have one or more resistances resulting from one or more mutations (including but not limited to the mutations listed in Table M) in one or more genes encoding target proteins of various fungicides and / or resistance resulting from overexpression of the target proteins. Thus, compound I is also particularly suitable for controlling such multidrug-resistant fungi.

[0387] According to another embodiment of the present invention, the present invention also relates to the use of the compound of formula I for combating plant pathogenic fungi containing a mutation in the mitochondrial cytochrome b gene that confers 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 a mutation in the mitochondrial cytochrome b gene that confers resistance to Qo inhibitors, the method comprising: treating with an effective amount of at least one compound I or a composition containing the compound plant pathogenic fungi containing a mutation in the mitochondrial cytochrome b gene that confers resistance to Qo inhibitors, or materials, plants, soil or seeds at risk of being attacked by plant pathogenic fungi containing a mutation in the mitochondrial cytochrome b gene that confers resistance to Qo inhibitors.

[0388] The term "phytopathogenic fungus containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors" shall be understood to mean that at least 10% of the fungal isolates to be controlled contain a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, more preferably at least 30%, even more preferably at least 50%, and most preferably at least 75% (in particular between 90% and 100%) of the fungi.

[0389] It has been observed under field conditions that phytopathogenic fungal populations apparently consisting of non-resistant strains can readily develop resistance. These compounds can also be applied under such conditions so as to completely prevent the formation of resistance and the spread of resistant strains. In this regard, it is useful that they also have strong activity against non-resistant phytopathogenic fungi.

[0390] According to another embodiment, a method for combating phytopathogenic fungi comprises: a) identifying a phytopathogenic fungus containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors as defined herein, or a material, plant, soil or seed at risk of being infested by such phytopathogenic fungi; and b) treating said fungus or material, plant, soil or seed with an effective amount of at least one compound I or a composition comprising the compound.

[0391] According to another embodiment of the invention, the invention also relates to a method for combating phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, the method comprising: treating with an effective amount of at least one compound I or a composition comprising the compound a phytopathogenic fungus in which at least 10% contains a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, or a material, plant, soil or seed at risk of being infested by a phytopathogenic fungus containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors; 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 conferring resistance to Qo inhibitors.

[0392] According to one embodiment of the use and method for combating phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, the mutation in the mitochondrial cytochrome b gene of these phytopathogenic fungi is G143A.

[0393] The mutation G143A in the cytochrome b (cytb, also known as cob) gene shall mean any substitution of a nucleotide in codon 143 encoding "G" (glycine; e.g., GGT, GGC, GGA, or GGG) that results in a codon encoding "A" (alanine; e.g., GCT, GCC, GCA, or GCG). For example, substituting the second nucleotide 'G' in codon 143 of the cytochrome b gene with 'C' (GGT to GCT) results in a single amino acid substitution from G (glycine) to A (alanine) at position 143 in the cytochrome b protein (Cytb) (G143A). In the present invention, the mutation G143A in the cytochrome b gene shall be understood as a single amino acid substitution from G (glycine) to A (alanine) at position 143 in the cytochrome b protein (G143A).

[0394] According to a further embodiment, plant pathogenic fungi containing a mutation in the mitochondrial cytochrome b gene that confers resistance to Qo inhibitors, wherein the mutation in the mitochondrial cytochrome b gene of these plant pathogenic fungi is G143A, are selected from the group consisting of Alternaria alternata, Blumeria graminis, Pyriculania oryzae (also known as Magnaporthe grisea), Septoria tritici (also known as Mycosphaerella graminicola), Mycosphaerella fijiensis, Venturia inaequalis, Pyrenophora teres, Pyrenophora tritici-repentis, and Plasmopara viticola, particularly Septoria tritici.

[0395] According to another embodiment of the use and method 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 these plant pathogenic fungi is F129L.

[0396] The mutation F129L in the cytochrome b (cytb, also known as cob) gene shall mean any substitution of a nucleotide in codon 129 encoding "F" (phenylalanine; e.g., TTT or TTC) that results in a codon encoding "L" (leucine; e.g., TTA, TTG, CTT, CTC, CTA, or CTG). For example, substituting the first nucleotide 'T' in codon 129 of the cytochrome b gene with 'C' (TTT to CTT) results in a single amino acid substitution from F (phenylalanine) to L (leucine) at position 129 in the cytochrome b protein (F129L). In the present invention, the mutation F129L in the cytochrome b gene shall be understood as a single amino acid substitution from F (phenylalanine) to L (leucine) at position 129 in the cytochrome b protein (F129L).

[0397] Many other phytopathogenic fungi have acquired the F129L mutation in the cytochrome b gene that confers resistance to Qo inhibitors, such as rust fungi, in particular soybean rust fungi (Phakopsora pachyrhizi and Phakopsora meibomiae) and fungi from the genera Alternaria, Pyrenophora, and Rhizoctonia. Preferred fungal species are Alternaria solani, Phakopsora pachyrhizi, Phakopsora meibomiae, Pyrenophora teres, Pyrenophora tritici-repentis, and Rhizoctonia solani; in particular Phakopsora pachyrhizi.

[0398] In one aspect, the present invention relates to a method for protecting plants vulnerable to and / or attacked by phytopathogenic fungi that contain the amino acid substitution F129L in the mitochondrial cytochrome b protein that confers resistance to Qo inhibitors, the method comprising applying to the plants at least one compound of formula I or a composition comprising at least one compound of formula I, treating the plant propagation material of the plants with at least one compound of formula I or a composition comprising at least one compound of formula I, and / or applying to the phytopathogenic fungi at least one compound of formula I or a composition comprising at least one compound of formula I.

[0399] According to another embodiment, a method for combating phytopathogenic fungi comprises: a) identifying a phytopathogenic fungus as defined herein that contains the amino acid substitution F129L in the mitochondrial cytochrome b protein that confers resistance to Qo inhibitors, or a material, plant, soil, or seed at risk of being infested by these phytopathogenic fungi; and b) treating the fungus or the material, plant, soil, or plant propagation material with an effective amount of at least one compound of formula I or a composition comprising the compound.

[0400] The term "phytopathogenic fungus that contains the amino acid substitution F129L in the mitochondrial cytochrome b protein that confers resistance to Qo inhibitors" should be understood to mean that at least 10% of the fungal isolates to be controlled contain such an F129L substitution in the mitochondrial cytochrome b protein that 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 between 90% and 100%; in particular between 95% and 100%.

[0401] Compound I and its compositions are also suitable for controlling harmful microorganisms in the protection of stored products or harvested crops and in the protection of materials.

[0402] The term "stored products or harvests" shall be understood to mean natural substances of plant or animal origin and their processed forms required for long-term protection. Stored products of plant origin, such as stalks, leaves, tubers, seeds, fruits or grains, can be protected in the freshly harvested state or in processed forms such as pre-dried, moistened, crushed, ground, pressed or baked (such processing is also referred to as post-harvest treatment). Also falling under the definition of stored products is wood, whether in the form of logs, such as construction timber, transmission towers and fences, or in the form of finished products, such as furniture or objects made of wood. Stored products of animal origin are hides, leather, furs, hairs, etc. Preferably, "stored products" shall be understood to mean natural substances of plant origin and their processed forms, more preferably fruits and their processed forms, such as pome fruits, stone fruits, soft fruits and citrus fruits and their processed forms, wherein the application of compound I and its compositions can also prevent adverse effects such as decay, discoloration or mildew.

[0403] The term "protection of materials" shall be understood to mean protection techniques and non-living materials such as adhesives, glues, wood, paper, cardboard, textiles, leather, paint dispersions, plastics, cooling lubricants, fibres, or fabrics against infestation and destruction by harmful microorganisms such as fungi and bacteria.

[0404] When used for the protection of materials or stored products, the amount of the active substance applied depends on the type of application area and the desired effect. The amount usually applied for the protection of materials is 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active substance per cubic metre of the treated material.

[0405] Compound I and its compositions can be used separately to improve the health of plants. The present invention also relates to a method for improving the health of plants by treating plants, their propagation materials and / or the places where plants are growing or will grow with effective amounts of compound I and its compositions separately.

[0406] The term "plant health" shall be understood to mean the condition of plants and / or their products, which is determined by a number of criteria, either alone or in combination with each other, such as yield (e.g., increased biomass and / or increased content of valuable components), plant vigour (e.g., improved plant growth and / or greener leaves ("greening effect")), quality (e.g., improved content or composition of certain components) and tolerance to abiotic and / or biotic stress. The criteria for the plant health condition determined above can be interdependent or can influence each other.

[0407] Compound I is used as such or in the form of a composition by treating fungi, plants, plant propagation materials (such as seeds); soil, surfaces, materials or rooms with a fungicidally effective amount of the active substance to protect them from fungal attack. The application can be carried out before and after the plants, plant propagation materials (such as seeds), soil, surfaces, materials or rooms are infected with fungi.

[0408] The agrochemical composition contains a fungicidally effective amount of Compound I. The term "fungicidally effective amount" means an amount of the composition or Compound I that is sufficient to control harmful fungi on cultivated plants, or for the protection of stored products or harvested crops, or for the protection of materials, and that does not cause substantial damage to the treated plants, treated stored products or harvested crops, or to the 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 crops or materials to be treated, the climatic conditions and the specific Compound I used.

[0409] Plant propagation materials can be prophylactically treated with Compound I itself or a composition containing at least one Compound I at the time of planting or transplanting or before planting or transplanting.

[0410] When used in plant protection, depending on the type of desired effect, the amount of the active substance applied is 0.001 to 2 kg / ha, preferably 0.005 to 2 kg / ha, more preferably 0.05 to 0.9 kg / ha, and especially 0.1 to 0.75 kg / ha.

[0411] In the treatment of plant propagation materials (such as seeds), for example by dusting, coating or soaking, an amount of the active substance of generally 0.1 to 1000 g, preferably 1 to 1000 g, more preferably 1 to 100 g and most preferably 5 to 100 g per 100 kg of plant propagation materials (preferably seeds) is required.

[0412] The user generally applies the agrochemical composition by means of a pre-metering device, a knapsack sprayer, a spray tank, a spraying aircraft, or an irrigation system. Generally, the agrochemical composition is made up with water, buffer solutions, and / or other adjuvants to the desired application concentration, and thus a ready-to-use spray liquid or agrochemical composition according to the invention is obtained. Generally, 20 to 2000 liters, preferably 50 to 400 liters of the ready-to-use spray liquid are applied per hectare of agricultural usable area.

[0413] Compounds I and compositions containing them can be applied in combination with or by using smart farming technologies such as precision farming, remote and proximal imaging and image recognition, or smart farm site management programs. Such technologies typically include models, for example computer programs such as the following, which support the user by considering information from various sources to increase the quality and yield of the harvested material, reduce pest damage, including prediction of pest pressure and intelligent application of crop protection products, ensure environmental protection, support rapid and reliable agronomic decision-making, reduce the use of fertilizers and crop protection products, reduce product residues in consumer goods, increase the spatial and temporal precision of agronomic measures, automate processes, and enable traceability of measures. Commercially available systems including agronomic models are for example FieldScripts TM (The Climate Corporation) TM (BASF SE) TM (John Deere & Company).

[0414] Compound I, its N-oxides and salts can be converted into agrochemical compositions of common types, such as solutions, emulsions, suspensions, dusts, powders, pastes, granules, tablets, capsules, and mixtures thereof. Examples of composition types (see also "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Edition, 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, tablets, wettable powders or dusts (e.g., WP, SP, WS, DP, DS), tablets (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), insecticidal products (e.g., LN), and gel formulations (e.g., GF) for treating plant propagation materials such as seeds. These compositions are prepared in a known manner, such 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 auxiliaries and at least one compound I.

[0415] Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, fungicides, antifreezes, antifoaming agents, colorants, tackifiers, and binders.

[0416] Suitable solvents and liquid carriers are water and organic solvents such as medium to high boiling mineral oil fractions, for example kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cycloaliphatic and aromatic hydrocarbons such as toluene, paraffin wax, tetrahydronaphthalene and alkylated naphthalenes; alcohols such as ethanol, propanol, butanol, benzyl alcohol, cyclohexanol, diols; DMSO; ketones such as cyclohexanone; esters such as lactate, carbonate, fatty acid esters, γ-butyrolactone; fatty acids; phosphonates; amines; amides such as N-methylpyrrolidone, fatty acid dimethylamide; and mixtures thereof.

[0417] 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 vegetable origin such as cereal flour, bark powder, wood powder, nut shell powder and mixtures thereof.

[0418] Suitable surfactants are surface-active compounds such as anionic, cationic, non-ionic 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, Volume 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Edition or North American Edition).

[0419] Suitable anionic surfactants are the alkali metal salts, alkaline earth metal salts or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl sulfonates, diphenyl sulfonates, α-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, dodecylbenzene and tridecylbenzene sulfonates, naphthalene and alkylnaphthalene sulfonates, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids, oils, ethoxylated alkylphenols, alcohols, ethoxylated alcohols or fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.

[0420] Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, glycosyl surfactants, polymeric surfactants and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters that have been alkoxylated with 1 to 50 equivalents of alkylene oxide. Ethylene oxide and / or propylene oxide can be used for alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerides or glycerol monoesters. Examples of glycosyl surfactants are sorbitan, ethoxylated sorbitan, sucrose and glucose esters or alkyl polyglucosides. Examples of polymeric surfactants are homologues or copolymers of vinylpyrrolidone, vinyl alcohol or vinyl acetate.

[0421] Suitable cationic surfactants are quaternary ammonium surfactants, such as quaternary ammonium compounds having one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkyl betaines and imidazolines. Suitable block polymers are A-B or A-B-A type block polymers containing polyethylene oxide and polypropylene oxide blocks, or A-B-C type block polymers containing alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are polyacrylic acid or alkali metal salts of polyacid comb polymers. Examples of polybases are polyvinylamine or polyethylenamine.

[0422] Suitable adjuvants are compounds that themselves have negligible or even no pesticidal activity and can enhance the biological properties of Compound I against the target. Examples are surfactants, mineral oils or vegetable oils and other auxiliaries, such as those listed in Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, Chapter 5. Suitable thickeners are polysaccharides (such as xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates and silicates. Suitable fungicides are bronopol and isothiazolone derivatives, such as alkyl isothiazolones and benzisothiazolones. Suitable antifreezes are ethylene glycol, propylene glycol, urea and glycerol. Suitable defoamers are silicones, long-chain alcohols, and salts of fatty acids. Suitable colorants (such as red, blue, or green) are poorly water-soluble pigments and water-soluble dyes. Examples are inorganic colorants (such as iron oxide, titanium oxide, iron hexacyanoferrate) and organic colorants (such as alizarin colorants, azo colorants and phthalocyanine colorants). Suitable thickening agents or binders are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylates, biological waxes or synthetic waxes, and cellulose ethers.

[0423] Agrochemical compositions generally contain an active substance (such as at least one compound I) in an amount of between 0.01% and 95% by weight, preferably between 0.1% and 90% by weight, more preferably between 1% and 70% by weight, and especially between 10% and 60% by weight. Agrochemical compositions generally contain at least one adjuvant in an amount of between 5% and 99.9% by weight, preferably between 10% and 99.9% by weight, more preferably between 30% and 99% by weight, and especially between 40% and 90% by weight. The active substance (such as compound I) is used with a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectra).

[0424] For the purpose of treating plant propagation materials, especially seeds, solutions for seed treatment (LS), suspension emulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually used. After dilution 2 to 10 times, the concentration of the active substance in the ready-to-use preparation of the composition in question is 0.01% to 60% by weight, preferably 0.1% to 40% by weight. Application can be carried out before sowing or during sowing. Methods for applying compound I and its compositions to plant propagation materials, especially seeds, respectively, include seed dressing, coating, granulation, dusting, soaking and in-furrow application methods. Preferably, compound I or its composition is applied to plant propagation materials separately by a method that does not induce germination, such as by seed dressing, granulation, coating and dusting.

[0425] Various types of oils, wetting agents, adjuvants, fertilizers or micronutrients, and additional pest control agents (such as fungicides, growth regulators, herbicides, insecticides, safeners) can be added to compound I or its composition as a premix, or added just before use (tank mix). These reagents can be admixed with the composition according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

[0426] A pesticidal agent is generally a chemical or biological agent (such as a pesticidal active ingredient, compound, composition, virus, bacterium, antimicrobial agent or disinfectant) that prevents, incapacitates, kills or otherwise frustrates pests by its effect. Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms) and microorganisms that damage property, cause nuisances, spread diseases or are vectors of diseases. The term "pesticidal agent" also includes plant growth regulators that alter the expected growth, flowering or reproductive rate of plants; defoliants that cause leaves or other foliage to drop from plants, usually to facilitate harvesting; desiccants that promote the drying of living tissue (such as the above-ground parts of unwanted plants); plant activators that activate plant physiological functions to defend against certain pests; safeners that reduce the unwanted herbicidal effects of pesticidal agents on crop plants; and plant growth promoters that affect plant physiological functions, for example, to enhance plant growth, biomass, yield or any other quality parameter of the harvestable items of crop plants.

[0427] Biopesticidal agents are defined as pesticidal agents based on microorganisms (bacteria, fungi, viruses, nematodes, etc.) or in the form of natural products (compounds such as metabolites, proteins or extracts from biological or other natural sources) (U.S. Environmental Protection Agency: http: / / www.epa.gov / pesticides / biopesticides / ). Biopesticidal agents fall into two main categories, microbial and biochemical pesticidal agents:

[0428] (1) Microbial pesticidal agents consist of bacteria, fungi or viruses (and usually include metabolites produced by bacteria and fungi). Entomopathogenic nematodes are also classified as microbial pesticidal agents, although they are multicellular.

[0429] (2) Biochemical pesticidal agents are naturally occurring substances that control pests or provide other crop protection uses as defined below, but are relatively non-toxic to mammals.

[0430] Mixing compound I or a composition containing them in the form of a fungicidal use with other fungicides often results in an expansion of the fungicidal activity spectrum or prevents the development of fungicide resistance. In addition, in many cases, a synergistic effect (synergistic mixture) is obtained.

[0431] The following list of pesticidal agents II that can be used in combination with compound I is intended to illustrate possible combinations but does not limit them:

[0432] A) Respiratory inhibitors

[0433] - At Q o Site Complex III inhibitors (QoI, C3, FRAC convention; www.frac.info): Azoxystrobin (A.1.1), Jiaxiangjunzhi (A.1.2), Dingxiangjunzhi (A.1.3), Kresoxim-methyl (A.1.4), Enestroburin (A.1.5), Enoxastrobin (A.1.6), Fenoxystrobin / Flufenoxystrobin (A.1.7), Fluoxastrobin (A.1.8), Kresoxim-methyl (A.1.9), Mandestrobin (A.1.10), Fenpyrazamine (A.1.11), Trifloxystrobin (A.1.12), Picoxystrobin (A.1.13), Pyraclostrobin (A.1.14), Pyribencarb (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), Pyribenzoxim (A.1.19), Triclopyricarb / Chlorodincarb (A.1.20), Famoxadone (A.1.21), Fenamidone (A.1.21), Methyl-N-[2-[(1,4-dimethyl-5-phenyl-pyrazol-3-yl)oxymethyl]phenyl]-N-methoxy-carbamate (A.1.22), Tebuconazole (A.1.25; member of MoA subgroup A), (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (A.1.34), (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (A.1.35), Pyridaben (A.1.36), Pyflubumide (A.1.37), 2-(o-((2,5-dimethylphenyl-oxymethylene)phenyl)-3-methoxy-acrylic acid methyl ester (A.1.38);

[0434] - At Q i Site Complex III inhibitors (QiI, C4): Cyazofamid (A.2.1), Indaziflam (A.2.2), 2-methylpropanoic acid [(6S,7R,8R)-8-benzyl-3-[(3-hydroxy-4-methoxypyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl] ester (A.2.3), Fenpicoxamid (A.2.4), Picoxystrobin (A.2.5), Metarylpicoxamid (A.2.6);

[0435] - Complex II inhibitors (SDHI, C2): carboxin (A.3.1), bixafen (A.3.2), boscalid (A.3.3), boscalid (A.3.4), oxycarboxin (A.3.5), furametpyr (A.3.6), fluxapyroxad (A.3.7), flutolanil (A.3.8), fluopyram (A.3.9), fupyradifurone (A.3.10), isofetamid (A.3.11), isopyrazam (A.3.12), triticonazole (A.3.13), oxycarboxin oxide (A.3.14), sedaxane (A.3.15), pydiflumetofen (A.3.16), penflufen (A.3.17), fluxametamide (A.3.18), cyclopyrimorate (A.3.19), tecloftalam (A.3.20), thifluzamide (A.3.21), inpyrfluxam (A.3.22), pyrapropoyne (A.3.23), fluindapyr (A.3.28), N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (A.3.29), (E)-methyl 2-[2-[(5-cyano-2-methylphenoxy)methyl]phenyl]-3-methoxyprop-2-enoate (A.3.30), isoflucypram (A.3.31), 2-(difluoromethyl)-N-(1,1,3-trimethyl-inden-4-yl)pyridine-3-carboxamide (A.3.32), 2-(difluoromethyl)-N-[(3R)-1,1,3-trimethylinden-4-yl]pyridine-3-carboxamide (A.3.33), 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethylinden-4-yl)pyridine-3-carboxamide (A.3.34), 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethylinden-4-yl]pyridine-3-carboxamide (A.3.35), 2-(difluoromethyl)-N-(1,1-dimethyl-3-propylinden-4-yl)pyridine-3-carboxamide (A.3.36), 2-(difluoromethyl)-N-[(3R)-1,1-dimethyl-3-propylinden-4-yl]pyridine-3-carboxamide (A.3.37), 2-(difluoromethyl)-N-(3-isobutyl-1,1-dimethylinden-4-yl)pyridine-3-carboxamide (A.3.38), 2-(difluoromethyl)-N-[(3R)-3-isobutyl-1,1-dimethylinden-4-yl]pyridine-3-carboxamide (A.3.39), triflumizole (A.3.24);

[0436] - Other respiratory inhibitors: diflufenican (A.4.1); nitro-phenyl derivatives: binapacryl (A.4.2), dinobuton (A.4.3), dinocap (A.4.4), fluazinam (A.4.5), dicofol (A.4.6), ferimzone (A.4.7); organo-metallic compounds: triphenyltin salts, e.g., triphenyltin acetate (A.4.8), triphenyltin chloride (A.4.9) or triphenyltin hydroxide (A.4.10); silthiofam (A.4.11);

[0437] - Quinone outside inhibitor strobilurin binding type (QoSI; C8): amisulbrom (A.5.1);

[0438] B) Sterol biosynthesis inhibitors (SBI fungicides)

[0439] -C14 Demethylase Inhibitors (DMI, G1): Triazoles: Propiconazole (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), Imibenconazole (B.1.14), Iprovalicarb (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), Tricyclazole (B.1.29), Uniconazole (B.1.30), 2-(2,4-Difluorophenyl)-1,1-difluoro-3-(tetrazol-1-yl)-1-[5-[4-(2,2,2-trifluoroethoxy)phenyl]-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), Fluopyram (B.1.33), Ipfentrifluconazole (B.1.37), Chlorfluzolam (B.1.38), (2R)-2-[4-(4-Chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, (2S)-2-[4-(4-Chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, 2-(Chloromethyl)-2-methyl-5-(p-tolylmethyl)-1-(1,2,4-triazol-1-ylmethyl)cyclopentanol (B.1.43); Imidazoles: Imazalil (B.1.44), Fenarimol (B.1.45), Prochloraz (B.1.46), Triflumizole (B.1.47); Pyrimidines, Pyridines, Piperazines: Chlorophenylpyrimidine alcohol (B.1.49), Pyrifenox (B.1.50), Triforine (B.1.51), [3-(4-Chloro-2-fluorophenyl)-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), methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propionate (B.1.56), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propanoic acid (B.1.57);

[0440] -δ14-reductase inhibitors (G2): 4-dodecyl-2,6-dimethylmorpholine (aldimorph) (B.2.1), dodemorph (B.2.2), dodemorph acetate (B.2.3), fenpropimorph (B.2.4), pyrifenox (B.2.5), fenpropidin (B.2.6), tridemorph (B.2.7), spiroxamine (B.2.8);

[0441] -3-ketoreductase inhibitors: fenhexamid (B.3.1), amisulbrom (B.3.2);

[0442] -other sterol biosynthesis inhibitors: etaconazole (B.4.1);

[0443] C) Nucleic acid synthesis inhibitors

[0444] -RNA polymerase I inhibitors (A1): benalaxyl (C.1.1), benalaxyl-M (C.1.2), kiralaxyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (C.1.5), ofurace (C.1.6), oxadixyl (C.1.7);

[0445] -other nucleic acid synthesis inhibitors (A2 to A5): hymexazol (C.2.1), octhilinone (C.2.2), oxolinic acid (C.2.3), ethirimol besylate (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: iproquilon (C.2.9), fluquinconazole (C.2.10);

[0446] D) Cell division and cytoskeleton inhibitors

[0447] - Microtubulin polymerization inhibitors (MBC, B1): Benomyl (D.1.1), Carbendazim (D.1.2), Fuberidazole (D1.3), Thiabendazole (D.1.4), Thiophanate-methyl (D.1.5), Pyridachlometyl (D.1.6), N-Ethyl-2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]butanamide (D.1.8), N-Ethyl-2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]-2-methylthio-acetamide (D.1.9), 2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]-N-(2-fluoroethyl)butanamide (D.1.10), 2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]-N-(2-fluoroethyl)-2-methoxy-acetamide (D.1.11), 2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]-N-propyl-butanamide (D.1.12), 2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]-2-methoxy-N-propyl-acetamide (D.1.13), 2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]-2-methylthio-N-propyl-acetamide (D.1.14), 2-[(3-ethynyl-8-methyl-6-quinolinyl)oxy]-N-(2-fluoroethyl)-2-methylthio-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);

[0448] - Other cell division inhibitors (B2 to B7): Diethofencarb (D.2.1), Ethaboxam (D.2.2), Fenpropimorph (D.2.3), Fluopicolide (D.2.4), Zoxamide (D.2.5), Metrafenone (D.2.6), Pyriofenone (D.2.7), Cyenopyrac (D.2.8); Fluxapyroxad (D.2.9);

[0449] E) Amino acid and protein synthesis inhibitors

[0450] - Methionine synthesis inhibitors (D1): Cyprodinil (E.1.1), Fenarimol (E.1.2), Pyrimethanil (E.1.3);

[0451] - Protein synthesis inhibitors (D2 to D5): Blasticidin-S (E.2.1), Kasugamycin (E.2.2), Kasugamycin hydrochloride hydrate (E.2.3), Validamycin (E.2.4), Streptomycin (E.2.5), Oxytetracycline (E.2.6);

[0452] F) Signal transduction inhibitors

[0453] - MAP / Histidine Kinase Inhibitors (E2 and E3): Iprodione (F.1.2), Procymidone (F.1.3), Vinclozolin (F.1.4), Fludioxonil (F.1.5);

[0454] - Unknown Mechanism (E1): Quinoxyphen (F.2.1), Propoxyquinoline (F.2.2);

[0455] G) Lipid and Membrane Synthesis Inhibitors

[0456] - Phospholipid Biosynthesis Inhibitors (F2): Blasticidin-S (G.1.1), IBP (G.1.2), Kitazin P (G.1.3), Isoprothiolane (G.1.4);

[0457] - Lipid Peroxidation (F3): Dichlofluanid (G.2.1), PCNB (G.2.2), Tecnazene (G.2.3), Tolclofos-methyl (G.2.4), Biphenyl (G.2.5), Chloroneb (G.2.6), Etridiazole (G.2.7);

[0458] - Compounds Affecting Cell Membrane Permeability and Fatty Acids (F4): Propamocarb (G.4.1);

[0459] Oxysterol-binding protein inhibitors (OSBPIs, F9): flutianil (G.5.1), fluoxapiprolin (G.5.3), 4-[1-[2-[3-difluoromethyl-5-methyl-pyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphthalen-1-yl-pyridine-2-carboxamide (G.5.4), 4-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphthalen-1-yl-pyridine-2-carboxamide (G.5.5), 4-[1-[2-[3-(difluoromethyl)-5-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphthalen-1-yl-pyridine-2-carboxamide (G.5.6), 4-[1-[2-[5-cyclopropyl-3-(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphthalen-1-yl-pyridine-2-carboxamide (G.5.7), 4-[1-[2-[5-methyl-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphthalen-1-yl-pyridine-2-carboxamide (G.5.8), 4-[1-[2-[5-(difluoromethyl)-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphthalen-1-yl-pyridine-2-carboxamide (G.5.9), 4-[1-[2-[3,5-bis(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphthalen-1-yl-pyridine-2-carboxamide (G.5.10), (4-[1-[2-[5-cyclopropyl-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]-N-tetrahydronaphthalen-1-yl-pyridine-2-carboxamide (G.5.11);

[0460] H) Inhibitors with multi-site action

[0461] - 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);

[0462] - Thiocarbamates and dithiocarbamates (M03): ferric dimethyldithiocarbamate (H.2.1), mancozeb (H.2.2), maneb (H.2.3), metam sodium (H.2.4), metiram (H.2.5), zinc methyldithiocarbamate (H.2.6), thiram (H.2.7), zinc dithiocarbamate (H.2.8), zinc dimethyldithiocarbamate (H.2.9), thiazole (H.2.10);

[0463] - Organochlorine 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, tecnazene (H.3.10), tolylfluanid (H.3.11);

[0464] - 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), guazatine amine (H.4.6), guazatine triacetate (H.4.7), guazatine octylbenzene sulfonate (H.4.8), dithianon (H.4.9), 2,6 - dimethyl - 1H,5H - [1,4]dithieno[2,3 - c:5,6 - c']dipyrrole - 1,3,5,7(2H,6H) - tetrone (H.4.10), isazofos (H.4.11), sulfallate (H.4.12), pyridaben (H.4.13);

[0465] I) Cell wall synthesis inhibitors

[0466] - Glucan synthesis inhibitor: validamycin (I.1.1); Chitin synthase inhibitor (H4): polyoxin B (I.1.2);

[0467] - Melanin synthesis inhibitors (I1 to I3): Trihydroxynaphthalene reductase inhibitors (MBI - R; I1) pyroquilon (I.2.1), tricyclazole (I.2.2); Dehydratase inhibitors (MBI - D, I2); Carpropamid (I.2.3), diclocymet (I.2.4), cymoxanil (I.2.5); Polyketide synthase inhibitors (MBI - P, I3): tolprocarb (I.2.6);

[0468] - Cellulose synthase inhibitor (H5): dimethomorph (I.3.1), flumorph (I.3.2), mandipropamid (I.3.3), pyrimorph (I.3.4), benthiavalicarb - isopropyl (I.3.5), propineb (I.3.6), valifenalate (I.3.7);

[0469] J) Plant defense inducers (P1 to P8)

[0470] - Benzo-S-methyl arsonate (J.1.1), thiabendazole (J.1.2), isothiazolinamine (J.1.3), tiadinil (J.1.4), prohexadione-calcium (J.1.5); Phosphonates: etridiazole (J.1.6), fosetyl-aluminum (J.1.7), phosphorous acid and its salts (J.1.8), potassium bicarbonate or sodium bicarbonate (J.1.9), 4-cyclopropyl-N-(2,4-dimethoxyphenyl)-1,3-thiazole-5-carboxamide (J.1.10), calcium phosphonate (J.1.11), potassium phosphonate (J.1.12), dichlofluanid (J.1.13);

[0471] K) Mode of action unknown (U, unknown):

[0472] -Bronopol (K.1.1), cyflufenamid (K.1.3), cymoxanil (K.1.4), dazomet (K.1.5), iminoctadine (K.1.6), pyridinitril (K.1.8), barban (K.1.9), barban - methyl sulfate (K.1.10), diphenylamine (K.1.11), cloethocarb (K.1.12), flumetover (K.1.14), flumetylsulforim (K.1.60), sulfanilamide (K.1.15), fluopyram (K.1.16), harpin protein (K.1.17), trichloromethylpyridine (K.1.19), phthalide (K.1.20), copper quinolate (K.1.22), seboctylamine (K.1.61), tebufloquin (K.1.24), tetrachloroisophthalodinitrile (K.1.25), azoxystrobin (K.1.26), N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methylformamidine (K.1.27), N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methylformamidine (K.1.28), N'-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine (K.1.29), N'-(5-bromo-6-indan-2-yloxy-2-methyl-3-pyridyl)-N-ethyl-N-methyl-formamidine (K.1.30), N'-[5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methyl-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.31), N'-[5-bromo-6-(4-isopropylcyclohexyloxy)-2-methyl-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.32), N'-[5-bromo-2-methyl-6-(1-phenylethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.33), N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilyl-propoxy)phenyl)-N-ethyl-N-methylformamidine (K.1.34), N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilyl-propoxy)-phenyl)-N-ethyl-N-methyl-formamidine (K.1.35), 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide (K.1.36), 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (picoxystrobin) (K.1.37), 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (K.1.38), 5-chloro-1-(4,6-dimethoxypyrimidin-2-yl)-2-methyl-1H-benzimidazole (K.1.39), ethyl (Z)-3-amino-2-cyano-3-phenylprop-2-enoate (K.1.40), tebuconazole (K.1.41), N-[6-[[(Z)-[(1-methyltetrazol-5-yl)phenylmethylene]amino]oxymethyl]-2-pyridinyl]pentylcarbamate (K.1.42), N-[6-[[(Z)-[(1-methyltetrazol-5-yl)phenylmethylene]amino]oxymethyl]-2-pyridinyl]but-3-ynylcarbamate (K.1.43), thiabendazole (K.1.48), bromothalonil (K.1.49), 2-(6-benzyl-2-pyridinyl)quinazoline (K.1.50), 2-[6-(3-fluoro-4-methoxyphenyl)-5-methyl-2-pyridinyl]quinazoline (K.1.51), N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylformamidine (K.1.53), amisulbrom (K.1.54), N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridinyl]-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), [MoA recommended: Class II histone deacetylase inhibitor], N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]thiobenzamide (K.1.59), N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide (K.1.60; WO2018 / 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]phenyl]methyl]-3,3,3-trifluoropropanamide (K.1.66), 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]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), 1 - [[4 - [5 - (trifluoromethyl)-1,2,4 - oxadiazol - 3 - yl]phenyl]methyl]pyrazole - 4 - carboxylic acid ethyl ester (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-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.1.91), 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-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylformamidine (K.1.95), N'-[2-chloro-4-[(4-methoxyphenyl)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-methyl-phenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide (K.1.101), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (K.1.102), 6-chloro-3-(3-chloro-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (K.1.103), N-[2-(2-bromo-4-methyl-phenyl)-2,2-difluoro-ethyl]-6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide (K.1.104);.

[0473] L) Biopesticides

[0474] L1) Microbial pest control agents with fungicidal, bactericidal, virucidal, and / or plant defense activator activities: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, Bacillus amyloliquefaciens, Bacillus amyloliquefaciens subsp. plantarum (also known as Bacillus velezensis), Bacillus megaterium, Bacillus mojavensis, Bacillus mycoides, Bacillus pumilus, Bacillus simplex, Bacillus salarius, Bacillus subtilis, Bacillus subtilis var. amyloliquefaciens, Bacillus velezensis, Candida oleophila, Candida saitoana, Clavibacter michiganensis (phage), Coniothyrium minitans, Cryptocline parasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonostachys rosea f. catenulate (also known as Gliocladium catenulatum), Gliocladium roseum, Lysobacter antibioticus, Lysobacter enzymogenes, Metschnikowia fructicola, Microdochium dimerum, Microsphaeropsis arundinis, Muscodor albus, Paenibacillus alvei, Paenibacillus epiphyticus, Paenibacillus polymyxa, Pantoea agglomerans, Penicillium bilaiae, Phellinus igniarius, Pseudomonas spp., Pseudomonas chlororaphis, Pseudozyma flocculosa, Pichia anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces griseoviridis, Streptomyces lydicus, Streptomyces violaceoniger, Talaromyces flavus, Trichoderma asperelloides, Trichoderma asperellum, Trichoderma atroviride, Trichoderma apical, Trichoderma gamosum, Trichoderma harmatum, Trichoderma harzianum, Trichoderma polysporum, Trichoderma stromaticum, Trichoderma virens, Trichoderma viride, Typhula phacorrhiza, Ulocladium oudemansii, Verticillium dahliae, Zucchini yellow mosaic virus (avirulent strain);

[0475] L2) Biochemical pest control agents with fungicidal, bactericidal, virucidal, and / or plant defense activator activities: Harpin protein, Reynoutria japonica extract;

[0476] L3) Microbial pest control agents with insecticidal, acaricidal, molluscicidal and / or nematicidal activity: Agrobacterium radiobacter, Bacillus cereus, Bacillus firmus, Bacillus thuringiensis, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. israelensis, Bacillus thuringiensis subsp. galleriae, Bacillus thuringiensis subsp. kurstaki, Bacillus thuringiensis subsp. tenebrionis, Beauveria bassiana, Beauveria brongniartii, Burkholderia species, Chromobacterium subtsugae, Cydia pomonella granulovirus (CpGV), Cryptophlebia leucotreta granulovirus (CrleGV), Flavobacterium species, Helicoverpa armigera nucleopolyhedrovirus (HearNPV), Helicoverpa zea nucleopolyhedrovirus (HzNPV), Helicoverpa zea single nucleocapsid nucleopolyhedrovirus (HzSNPV), Heterorhabditis bacteriophora, Isaria fumosorosea, Lecanicillium longisporum, Lecanicillium muscarium, Metarhizium anisopliae, Metarhizium anisopliae var. anisopliae, Metarhizium anisopliae var. acridum, Nomuraea rileyi, Paecilomyces fumosoroseus, Paecilomyces lilacinus, Paenibacillus popilliae, Pasteuria species, Pasteuria penetrans, Pasteuria ramosa, Pasteuria thornea, Pasteuria usgae, Pseudomonas fluorescens, Spodoptera litura nucleopolyhedrovirus (SpliNPV), Steinernema carpocapsae, Steinernema feltiae, Steinernema sawfly, Streptomyces gilvosporeus, Streptomyces microflavus;

[0477] L4) Biochemical pest control agents with insecticidal, acaricidal, molluscicidal, pheromonal and / or nematicidal activity: L-carvone, citral, (E,Z)-7,9-dodecadien-1-yl acetate, ethyl formate, (E,Z)-ethyl 2,4-decadienoate (pear ester), (Z,Z,E)-7,11,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavandulyl senecioate, cis-jasmone, 2-methyl-1-butanol, methyleugenol, methyl jasmonate, (E,Z)-2,13-octadecadien-1-ol, (E,Z)-2,13-octadecadien-1-yl acetate, (E,Z)-3,13-octadecadien-1-ol, (R)-1-octen-3-ol, termite pheromone (pentatermanone), (E,Z,Z)-3,8,11-tetradecatrien-1-yl 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, Quillay extract;

[0478] L5) Microbial pest control agents with plant stress reduction, plant growth regulator, plant growth promotion and / or yield increase activity: Azospirillum amazonense, Azospirillum brasilense, Azospirillum lipoferum, Azospirillum iraquense, Azospirillum halopraeferens, Bradyrhizobium spp., Bradyrhizobium elkanii, Bradyrhizobium japonicum, Bradyrhizobium liaoningense, Bradyrhizobium lupini, Delftia acidovorans, Arbuscular mycorrhizal fungi, Mesorhizobium spp., Rhizobium leguminosarum biovar phaseoli, Rhizobium leguminosarum biovar trifolii, Rhizobium leguminosarum biovar viciae, Rhizobium tropici and Sinorhizobium meliloti;

[0479] O) Insecticides from classes O.1 to O.29

[0480] 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, XMC, xylylcarb, triazamate; acephate, azamethiphos, coumaphos, crotoxyphos, dichlofenthion, dimethoate, ethion, EPN, ethoprophos, fenamiphos, fenthion, fosthiazate, heptenophos, imicyafos, isopropylamine phosphate, O-(methoxyaminothio-phosphoryl) isopropyl salicylate, isoxathion, malathion, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, pyrethrins, pyriproxyfen, pyridaphenthion, quinalphos, sulprofos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, vamidothion;

[0481] O.2 GABA-gated chloride channel antagonists: endosulfan, chlordane; ethiprole, fipronil, butene-fipronil, pyrafluprole, pyriprole;

[0482] O.3 Sodium channel modulators: acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, k-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, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, flumethrin, heptaflumethrin, imiprothrin, metofluthrin, metofluthrin, epsilon-methoxychlor, permethrin, phenothrin, propargite, propalphuthrin, pyrethrum, resmethrin, silafluofen, heptafluthrin, k-heptafluthrin, tetrafluoromethrin, tetramethrin, tetramethrin, tetramethrin, tetrachlorvinphos, methoxychlor;

[0483] 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-pentylideneamino-guanidine; 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, bixafen, flufenerim;

[0484] O.5 Allosteric activators of nicotinic acetylcholine receptors: spinosad, spinetoram;

[0485] O.6 Chloride channel activators: abamectin, emamectin benzoate, ivermectin, lepimectin, milbemycin;

[0486] O.7 Juvenile hormone mimics: hydroprene, kinoprene, methoprene; fenoxycarb, pyriproxyfen;

[0487] O.8 Various non-specific (multisite) inhibitors: methyl bromide and other alkyl halides; chloropicrin, sulfuryl fluoride, borax, tartar emetic;

[0488] O.9 Chordotonal organ TRPV channel modulators: cyenopyrafen, pymetrozine, flupyradifurone;

[0489] O.10 Mite growth inhibitors: clofentezine, hexythiazox, flufenzine; etoxazole;

[0490] O.11 Microbial disruptors of the insect midgut membrane: Bacillus thuringiensis, Bacillus sphaericus, and the insecticidal proteins they produce: Bacillus thuringiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, Bacillus thuringiensis subsp. tenebrionis, Bt crop proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34 / 35Ab1;

[0491] O.12 Mitochondrial ATP synthase inhibitors: diafenthiuron; azocyclotin, cyhexatin, fenbutatin oxide, propargite, chlorfenson;

[0492] O.13 Oxidative phosphorylation uncouplers interfering via the proton gradient: chlorfenapyr, DNOC, sulfluramid;

[0493] O.14 Nicotinic acetylcholine receptor (nAChR) channel blockers: bensultap, cartap, thiocyclam, bisultap;

[0494] O.15 Chitin biosynthesis inhibitor type 0: bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, flupyrazofos, chlorbenzuron, tralomethrin;

[0495] O.16 Chitin biosynthesis inhibitor type 1: buprofezin;

[0496] O.17 Molting disruptors: cyromazine;

[0497] O.18 Ecdysone receptor agonists: methoxyfenozide, tebufenozide, halofenozide, furanfenozide, chromafenozide;

[0498] O.19 Octopamine receptor agonists: amitraz;

[0499] O.20 Mitochondrial complex III electron transport inhibitors: hydramethylnon, acequinocyl, fluacrypyrim, bifenazate;

[0500] O.21 Mitochondrial complex I electron transport inhibitors: fenazaquin, flubenzimine, pyridaben, pyrimidifen, tolfenpyrad, flufenerim; rotenone;

[0501] 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]hydrazinecarboxamide, N-[4-chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chloro-2-pyridyl)-3-(fluoromethoxy)-1H-pyrazole-5-carboxamide, 2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]hydrazinecarboxamide;

[0502] O.23 Acetyl-CoA carboxylase inhibitors: spirodiclofen, spiromesifen, spirotetramat, methoprene, spirodiclofen, 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1,4-dioxo-9-aza-dispiro[4.2.4.2]tetradec-11-en-10-one, dispirotetramat;

[0503] O.24 Mitochondrial complex IV electron transport inhibitors: aluminium phosphide, calcium phosphide, phosphine, zinc phosphide, cyanide;

[0504] O.25 Mitochondrial complex II electron transport inhibitors: cyenopyrafen, butylpyridaben, etoxazole, pyraclostrobin;

[0505] O.28 Ryanodine receptor modulators: chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide, flubendiamide, (R)-3-chloro-N 1 -{2-methyl-4-[1,2,2,2–tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}-N 2 -(1-methyl-2-methylsulfonylethyl)phthalamide, (S)-3-chloro-N 1 -{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-λ4-sulfanylidene)carbamoyl]phenyl]-2-(3-chloropyridin-2-yl)-5-(trifluoromethyl)pyrazole-3-carboxamide; N-[4-chloro-2-[(diethyl-λ4-sulfanylidene)carbamoyl]-6-methylphenyl]-2-(3-chloropyridin-2-yl)-5-(trifluoromethyl)pyrazole-3-carboxamide; N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide; 3-chloro-1-(3-chloropyridin-2-yl)-N-[2,4-dichloro-6-[[(1-cyano-1-methylethyl)amino]carbonyl]phenyl]-1H-pyrazole-5-carboxamide; tetrachlorantraniliprole; tetraniliprole; thiodicarb; N-[4-chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chloropyridin-2-yl)-3-(fluoromethoxy)-1H-pyrazole-5-carboxamide; chlorantraniliprole; N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide;

[0506] O.29 Chordotonal organ modulator: flonicamid;

[0507] O.30 GABA-gated chloride channel allosteric modulators: broflanilide, chlorantraniliprole, isoxazid;

[0508] O.33 Calcium-activated potassium channel modulator: acynonapyr;

[0509] O.34 Mitochondrial complex III electron transport inhibitor at the Qi site: flometoquin;

[0510] O.UN Insecticidal compounds with unknown or uncertain mode of action: afoxolaner, azadirachtin, amidoflumet, bromopropylate, chlorbromuron, chinomethionat, cryolite, cyproflanilid, dichlorothymid, dicofol, flupyradifurone, flufenerim, flutolanil, fluralaner, metaldehyde, oxydemethon-methyl, pyridalyl, piperonyl butoxide, pyridalyl, tioxazafen, trifluenfuronate, umifoxolaner, 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1,4-dioxo-9-aza-dispiro[4.2.4.2]tetradec-11-en-10-one, 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-methyl-benzoyl)amino]-N-[2,6-dichloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]-2-fluoro-benzamide, N-[5-[[[2-chloro-6-cyano-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]amino]carbonyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide, N-[5-[[[2-bromo-6-chloro-4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]phenyl]amino]carbonyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide, N-[5-[[[2-bromo-6-chloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]amino]carbonyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide, 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-methyl-benzamide, 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-cyano-phenyl]-4-cyano-2-methyl-benzamide, 4-cyano-N-[2-cyano-5-[[[2,6-dichloro-4-[1,2,2,2-Tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]amino]carbonyl]phenyl]-2-methyl-benzamide, active substance based on Bacillus firmus (Votivo, I-1582); fluopyram; 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-cyano-phenyl]-4-cyano-2-methyl-benzamide; 4-Cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)-propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; 4-Cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; N-[5-[[2-bromo-6-chloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; 2-(1,3-dioxolan-2-yl)-6-[2-(3-pyridyl)-5-thiazolyl]-pyridine; 2-[6-[2-(5-fluoro-3-pyridyl)-5-thiazolyl]-2-pyridyl]-pyrimidine; 2-[6-[2-(3-pyridyl)-5-thiazolyl]-2-pyridyl]-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-pyridyl)methyl]-1,2,3,5,6,7-hexahydro-5-methoxy-7-methyl-8-nitro-imidazo[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-pyridyl)methyl]-1,2,3,5,6,7-hexahydro-5-methoxy-7-methyl-8-nitro-imidazo[1,2-a]pyridine; 2-(3-pyridyl)-N-(2-pyrimidinylmethyl)-2H-indazole-5-carboxamide; chlorantraniliprole; 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-(2,2,2-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-(2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carboxamide, N-[4-Chloro-3-[(1-cyanocyclopropyl)carbamoyl]phenyl]-2-methyl-5-(2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carboxamide; Benzpyrimoxan; Tigolaner; Oxasulfuron; [(2S,3R,4R,5S,6S)-3,5-Dimethoxy-6-methyl-4-propoxytetrahydropyran-2-yl]-N-[4-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]carbamate; [(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-(2,2,2-pentafluoroethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]carbamate; [(2S,3R,4R,5S,6S)-3,4,5-Trimethoxy-6-methyltetrahydropyran-2-yl]-N-[4-[1-[4-(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]methylidenehydrazino]thiazolidin-4-one, (2Z)-3-(2-Isopropylphenyl)-2-[(E)-[4-[1-[4-(2,2,2-pentafluoroethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]methylidenehydrazino]thiazolidin-4-one, (2Z)-3-(2-Isopropylphenyl)-2-[(E)-[4-[1-[4-(2,2,2-pentafluoroethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]methylidenehydrazino]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]pyridin-2-yl]imidazo[1,2-a]pyridine-8-carbonitrile, 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-(trifluoromethyl)imidazo[4,5-c]pyridine, 2-(6-bromo-3-ethylsulfonyl-imidazo[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; Fluvalinate, N-[3-chloro-1-(3-pyridyl)pyrazol-4-yl]-2-methylsulfonyl-propionamide, Triflumizole; N-[4-chloro-3-[(1-cyanocyclopropyl)carbamoyl]phenyl]-2-methyl-4-methylsulfonyl-5-(1,1,2,2,2-pentafluoroethyl)pyrazole-3-carboxamide, Cyflumetofen, Chlorantraniliprole; 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-trifluoroethylthio)phenyl]imino-3-(2,2,(2-Trifluoroethyl)thiazolidin-4-one, indoxacarb, N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-3-methylsulfonyl-propanamide, 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.,

[0511] The active substance known as component 2, its preparation and its activity against harmful fungi, for example, are known (see: https: / / pesticidecompendium.bcpc.org / ); these substances are commercially available. Compounds described by IUPAC nomenclature, their preparation and their pesticidal activity are also known (see Can. J. Plant Sci. [Canadian Journal of Plant Science] 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031; EP-A 226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941; EP-A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP-A 1201 648; EP-A 1 122 244, JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; US 3,296,272; US 3,325,503; WO 98 / 46608; WO 99 / 14187; WO 99 / 24413; WO 99 / 27783; WO00 / 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 / 139271, 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, CN 1907024, CN1456054, CN 103387541, CN 1309897, WO 12 / 84812, CN 1907024, WO 09094442, WO 14 / 60177, WO 13 / 116251, WO 08 / 013622, WO 15 / 65922, WO 94 / 01546, EP 2865265, WO 07 / 129454, WO 12 / 165511, WO 11 / 081174, WO 13 / 47441, WO 16 / 156241, WO 16 / 162265). Some compounds are identified by their CAS Registry Numbers, which are divided into three parts by hyphens, the first part consisting of two to seven digits, the second part consisting of two digits, and the third part consisting of a single digit.;

[0512] According to the present invention, the solid material (dry matter) of a biopesticide (except for oils such as neem oil) is considered to be the active ingredient (obtained, for example, after drying or evaporation of the extraction or suspension medium in the case of a liquid formulation of a microbial pesticide). The weight ratios and percentages used for biological extracts such as quillaia extracts are based on the total weight of the dry content (solid material) of the respective extracts.

[0513] The total weight ratio of a composition containing at least one microbial pesticide in the form of live microbial cells (including dormant forms) can be determined by calculating the total weight of the corresponding active ingredient using the amount of CFU of the corresponding microorganism with the following equation: 1×10 10 CFU is equal to the total weight of one gram of the corresponding active ingredient. Colony forming unit is a measure of live microbial cells. In addition, "CFU" can also be understood as the number of (juvenile) individual nematodes in the case of nematode biopesticides such as Steinernema feltiae.

[0514] In a binary mixture, the weight ratio of component 1) to component 2) generally depends on the properties of the components used, and generally it is in the range of 1:10,000 to 10,000:1, often in the range of 1:100 to 100:1, frequently in the range of 1:50 to 50:1, preferably in the range of 1:20 to 20:1, more preferably in the range of 1:10 to 10:1, even more preferably in the range of 1:4 to 4:1, and especially in the range of 1:2 to 2:1. According to a further embodiment, the weight ratio of component 1) to component 2) is generally in the range of 1000:1 to 1:1, often in the range of 100:1 to 1:1, frequently in the range of 50:1 to 1:1, preferably in the range of 20:1 to 1:1, more preferably in the range of 10:1 to 1:1, even more preferably in the range of 4:1 to 1:1, and especially in the range of 2:1 to 1:1. According to a further embodiment, the weight ratio of component 1) to component 2) is generally in the range of 20,000:1 to 1:10, often in the range of 10,000:1 to 1:1, frequently in the range of 5,000:1 to 5:1, preferably in the range of 5,000:1 to 10:1, more preferably in the range of 2,000:1 to 30:1, even more preferably in the range of 2,000:1 to 100:1, and especially in the range of 1,000:1 to 100:1. According to a further embodiment, the weight ratio of component 1) to component 2) is generally in the range of 1:1 to 1:1000, often in the range of 1:1 to 1:100, frequently in the range of 1:1 to 1:50, preferably in the range of 1:1 to 1:20, more preferably in the range of 1:1 to 1:10, even more preferably in the range of 1:1 to 1:4, and especially in the range of 1:1 to 1:2. According to a further embodiment, the weight ratio of component 1) to component 2) is generally in the range of 10:1 to 1:20,000, often in the range of 1:1 to 1:10,000, frequently in the range of 1:5 to 1:5,000, preferably in the range of 1:10 to 1:5,000, more preferably in the range of 1:30 to 1:2,000, even more preferably in the range of 1:100 to 1:2,000, and especially in the range of 1:100 to 1:1,000.

[0515] In a ternary mixture, i.e. a composition comprising component 1) and component 2) and compound III (component 3), the weight ratio of component 1) to component 2) depends on the properties of the active substances used, and generally it is in the range of 1:100 to 100:1, frequently in the range of 1:50 to 50:1, preferably in the range of 1:20 to 20:1, more preferably in the range of 1:10 to 10:1, and especially in the range of 1:4 to 4:1, and the weight ratio of component 1) to component 3) is generally in the range of 1:100 to 100:1, frequently in the range of 1:50 to 50:1, preferably in the range of 1:20 to 20:1, more preferably in the range of 1:10 to 10:1, and especially in the range of 1:4 to 4:1. If desired, any additional active component is added to component 1) in a ratio of 20:1 to 1:20. These ratios are also suitable for mixtures applied by seed treatment.

[0516] When a mixture containing a microbial pestcide is used for crop protection, the application rate ranges from 1×10 6 to 5×10 16 (or greater) CFU / ha, preferably from 1×10 8 to 1×10 13 CFU / ha, and even more preferably from 1×10 9 to 5×10 15 CFU / ha, and especially from 1×10 12 to 5×10 14 CFU / ha. In the case of nematodes as microbial pestcides (such as Steinernema feltiae), the application rate ranges are often from 1×10 5 to 1×10 12 (or greater), preferably from 1×10 8 to 1×10 11 , more preferably from 5×10 8 to 1×10 10 individuals (such as in the form of eggs, larvae or any other living stage, preferably in the non-reproductive (infetive) larval stage) / ha.

[0517] When a mixture containing a microbial pestcide is used for seed treatment, the application rate ranges are generally from 1×10 6 to 1×10 12 (or greater) CFU / seed, preferably from 1×10 6 to 1×10 9 CFU / seed. In addition, the application rate ranges for seed treatment are generally from 1×10 7 to 1×10 14 (or greater) CFU / 100 kg of seeds, preferably from 1×10 9 to 1×10 12 CFU / 100 kg of seeds.

[0518] Preferably, a mixture containing at least one active substance as component 2), the at least one active substance being selected from group A) in Q oComplex III inhibitors 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); particularly 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).

[0519] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from the complex III inhibitors in group A) at Q i Complex III inhibitors at the site, more preferably selected from compounds (A.2.1), (A.2.3), (A.2.4) and (A.2.6); particularly selected from (A.2.3), (A.2.4) and (A.2.6).

[0520] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from the complex II inhibitors in group A), more preferably selected from compounds (A.3.2), (A.3.3), (A.3.4), (A.3.7), (A.3.9), (A.3.11), (A.3.12), (A.3.15), (A.3.16), (A.3.17), (A.3.18), (A.3.19), (A.3.20), (A.3.21), (A.3.22), (A.3.23), (A.3.24), (A.3.28), (A.3.31), (A.3.32), (A.3.33), (A.3.34), (A.3.35), (A.3.36), (A.3.37), (A.3.38) and (A.3.39); particularly 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).

[0521] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from other respiratory inhibitors and QoSI in group A), more preferably selected from compounds (A.4.5) and (A.5.1); in particular (A.5.1).

[0522] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from C14-demethylase inhibitors in group B), more preferably selected from compounds (B.1.4), (B.1.5), (B.1.8), (B.1.10), (B.1.11), (B.1.12), (B.1.13), (B.1.17), (B.1.18), (B.1.21), (B.1.22), (B.1.23), (B.1.25), (B.1.26), (B.1.29), (B.1.33), (B.1.34), (B.1.37), (B.1.38), (B.1.43), (B.1.46), (B.1.53), (B.1.54) and (B.1.55); in particular selected from (B.1.5), (B.1.8), (B.1.10), (B.1.17), (B.1.22), (B.1.23), (B.1.25), (B.1.33), (B.1.34), (B.1.37), (B.1.38), (B.1.43) and (B.1.46).

[0523] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from δ14-reductase inhibitors in group B), more preferably selected from compounds (B.2.4), (B.2.5), (B.2.6) and (B.2.8); in particular (B.2.4).

[0524] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from phenylamide and acyl amino acid fungicides in group C), more preferably selected from 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).

[0525] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from other nucleic acid synthesis inhibitors in group C), more preferably selected from compounds (C.2.6), (C.2.7), (C.2.8), (C.2.9) and (C.2.10); in particular (C.2.9) and (C.2.10).

[0526] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from group D), more preferably selected from compounds (D.1.1), (D.1.2), (D.1.5), (D.2.4) and (D.2.6); particularly selected from (D.1.2), (D.1.5) and (D.2.6).

[0527] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from group E), more preferably selected from compounds (E.1.1), (E.1.3), (E.2.2) and (E.2.3); particularly (E.1.3).

[0528] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from group F), more preferably selected from compounds (F.1.2), (F.1.4) and (F.1.5).

[0529] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from group G), more preferably selected from 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); particularly selected from (G.5.1) and (G.5.3).

[0530] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from group H), more preferably selected from 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); particularly selected from (H.2.2), (H.2.5), (H.3.2), (H.4.9) and (H.4.10).

[0531] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from group I), more preferably selected from compounds (I.2.2), (I.2.5), (I.3.1), (I.3.3) and (I.3.6); particularly (I.3.1).

[0532] Also preferred is a mixture comprising at least one active substance as component 2), said at least one active substance being selected from group J), more preferably selected from compounds (J.1.2), (J.1.5), (J.1.8), (J.1.11) and (J.1.12); particularly (J.1.5).

[0533] Also preferably, a mixture comprising at least one active substance as component 2), the at least one active substance being selected from group K), more preferably selected from compounds (K.1.41), (K.1.42), (K.1.57), (K.1.58) and (K.1.59); particularly selected from (K.1.41), (K.1.57), (K.1.58) and (K.1.59).

[0534] Any of the above mixtures comprises as component 1) preferably compound I explicitly disclosed herein, for example in a table, and even more preferably compound I selected from the following list of compounds: I.A1.1-Z-1-A-1 to I.A.1.1-Z-1-A-2389, I.A.2.1-Z-1-A-1 to I.A.2.1-Z-1-A-2389, I.A.3.1-Z-1-A-1 to I.A.3.1-Z-1-A-2389, I.A1.2-Z-1-A-1 to I.A.1.2-Z-1-A-2389, I.A.2.2-Z-1-A-1 to I.A.2.2-Z-1-A-2389, I.A.3.2-Z-1-A-1 to I.A.3.2-Z-1-A-2389, I.A1.3-Z-1-A-1 to I.A.1.3-Z-1-A-2389, I.A.2.3-Z-1-A-1 to I.A.2.3-Z-1-A-2389, I.A.3.3-Z-1-A-1 to I.A.3.3-Z-1-A-2389, I.B1.1-Z-1-A-1 to I.B.1.1-Z-1-A-2389, I.B.2.1-Z-1-A-1 to I.B.2.1-Z-1-A-2389, I.B.3.1-Z-1-A-1 to I.B.3.1-Z-1-A-2389, I.B1.2-Z-1-A-1 to I.B.1.2-Z-1-A-2389, I.B.2.2-Z-1-A-1 to I.B.2.2-Z-1-A-2389, I.B.3.2-Z-1-A-1 to I.B.3.2-Z-1-A-2389, I.B1.3-Z-1-A-1 to I.B.1.3-Z-1-A-2389, I.B.2.3-Z-1-A-1 to I.B.2.3-Z-1-A-2389 and I.B.3.3-Z-1-A-1 to I.B.3.3-Z-1-A-2389; and particularly preferably compound I selected from the example compound numbers 1 to 128 in Table S.

[0535] The biopesticides from group L1) and / or L2) may also have insecticidal, acaricidal, molluscicidal, pheromonal, nematicidal, plant stress reducing, plant growth regulating, plant growth promoting and / or yield increasing activity. The biopesticides from group L3) and / or L4) may also have fungicidal, bactericidal, virucidal, plant defense activating, plant stress reducing, plant growth regulating, plant growth promoting and / or yield increasing activity. The biopesticides from group L5) may also have fungicidal, bactericidal, virucidal, plant defense activating, insecticidal, acaricidal, molluscicidal, pheromonal and / or nematicidal activity.

[0536] Microbial biopesticides, in particular those from groups L1), L3) and L5), include not only isolated pure cultures of the corresponding microorganisms as defined herein, but also their cell-free extracts, their suspensions in whole broth cultures and metabolite-containing media, or purified metabolites obtained from whole broth cultures of the microorganisms.

[0537] Many of these biopesticides are deposited under the accession numbers mentioned herein (prefixes such as ATCC or DSM refer to the initials of the corresponding culture collections, for details see, for example, http: / / www.wfcc.info / ccinfo / collection / by_acronym / ), are mentioned in the literature, are registered and / or are commercially available: a mixture of Aureobasidium pullulans DSM14940 and DSM 14941 was isolated in 1989 in Constance, Germany (e.g., blastospores, from ) of bio-ferm GmbH, Austria), Azospirillum brasilense Sp245 was initially isolated at least before 1980 in the wheat-growing region of southern Brazil (Passo Fundo) (BR 11005; e.g., from Gramíneas) of BASF Agricultural Specialties Ltd., Brazil), Azospirillum brasilense strains Ab-V5 and Ab-V6 (e.g., AzoMax from Novozymes BioAg Produtos papra Agricultura Ltda., QuattroBarras, Brazil or Simbiose- Plant Soil 331, 413 - 425, 2010), Bacillus amyloliquefaciens strain AP - 188 (NRRL B - 50615 and B - 50331; US 8,445,255); Bacillus amyloliquefaciens subsp. plantarum strains, which were sometimes formerly referred to as Bacillus subtilis and have recently been reclassified as Bacillus velezensis together with B. methylotrophicus (Int. J. Syst. Evol. Microbiol. [International Journal of Systematic and Evolutionary Microbiology] 66, 1212–1217, 2016): Bacillus amyloliquefaciens subsp. plantarum or Bacillus velezensis D747 isolated from the air in Kikukawa, Japan (US20130236522 A1; FERM BP - 8234; e.g., Double Nickel from Certis LLC, USA TM 55WDG), Bacillus amyloliquefaciens subsp. plantarum or Bacillus velezensis FZB24 isolated from soil in Brandenburg, Germany (also known as SB3615; DSM 96 - 2; J. Plant Dis. Prot. [Journal of Plant Diseases and Protection] 105, 181 - 197, 1998; e.g., ) from AbiTEP GmbH, Germany), Bacillus amyloliquefaciens subsp. plantarum or Bacillus velezensis FZB42 isolated from soil in Brandenburg, Germany (DSM 23117; J. Plant Dis. Prot. [Journal of Plant Diseases and Protection] 105, 181 - 197, 1998; e.g., 42), Bacillus amyloliquefaciens subsp. plantarum or Bacillus velezensis MBI600 (also known as 1430; NRRL B - 50595; US2012 / 0149571A1) isolated from Vicia faba in Sutton Bonington, Nottinghamshire, UK at least before 1988; e.g., ) from BASF Corp., USA), Bacillus amyloliquefaciens subsp. plantarum or Bacillus velezensis QST - 713 (NRRL B - 21661) isolated from a peach orchard in California, USA in 1995; e.g., MAX), Bacillus amyloliquefaciens subsp. plantarum or Bacillus velezensis TJ1000 (also known as 1BE; ATCC BAA-390; CA 2471555 A1) isolated in 1992 in South Dakota, USA, e.g., QuickRoots from TJ Technologies, Watertown, SD, USA TM ); Bacillus firmus CNCM I-1582, a variant of the parental strain EIP-N1 isolated from soil in the Central Region of Israel (CNCM I-1556) (WO 2009 / 126473, US 6,406,690; e.g., from Bayer CropScience LP, USA ), Bacillus pumilus GHA 180 isolated from the rhizosphere of apple trees in Mexico (IDAC 260707-01; e.g., PRO- from Premier Horticulture, Quebec, Canada BX), Bacillus pumilus INR-7, also known as BU-F22 and BU-F33, isolated at least prior to 1993 from cucumbers infected with Erwinia tracheiphila (NRRL B-50185, NRRL B-50153; US 8,445,255), Bacillus pumilus KFP9F isolated at least prior to 2008 from the rhizosphere of grass in South Africa (NRRL B-50754; WO 2014 / 029697; e.g., BAC-UP or FUSION-P from BASF Agricultural Specialities (Pty) Ltd., South Africa), Bacillus pumilus QST 2808 isolated in 1998 from soil collected in Pohnpei, Federated States of Micronesia (NRRL B-30087; e.g., from Bayer CropScience LP, USA or Plus), Bacillus simplex ABU 288 (NRRL B-50304; US8,445,255), also known as UD 1022 or UD10-22, Bacillus subtilis FB17 was isolated from red beet root in North America (ATCCPTA-11857; System. Appl. Microbiol. [System and Applied Microbiology] 27, 372-379, 2004; US2010 / 0260735; WO 2011 / 109395); Bacillus thuringiensis subsp. aizawai ABTS-1857 was isolated in 1987 from soil taken from a lawn in Ephraim, Wisconsin, USA (also known as ABG-6346; ATCC SD-1372; e.g., from BioFa AG, Münsingen, Germany ), Bacillus thuringiensis subsp. kurstaki ABTS-351 is equivalent to HD-1 isolated in 1967 from diseased black larvae of the cotton bollworm in Brownsville, Texas, USA (ATCC SD-1275; e.g., from Valent BioSciences, IL, USA DF), Bacillus thuringiensis subsp. kurstaki SB4 was isolated from the larval cadavers of the African sugarcane borer (E. saccharina) (NRRL B-50753; e.g., Beta from BASF Agricultural Products (Pty) Ltd., South Africa ), Bacillus thuringiensis subsp. tenebrionis NB-176-1, a mutant of strain NB-125, was isolated from the dead pupae of the beetle Tenebrio molitor in 1982 (DSM 5480; EP 585 215B1; e.g., from Valent BioSciences, Switzerland ), Beauveria bassiana GHA (ATCC74250; e.g., from Laverlam Int. Corp., USA 22WGP), Beauveria bassiana JW-1 (ATCC 74040; e.g., from CBC (Europe) S.r.l., Italy ), Beauveria bassiana PPRI 5339 was isolated from the larvae of the tortoise beetle Conchyloctenia punctata (NRRL 50757; e.g., from BASF Agricultural Products (Pty) Ltd., South Africa ) The Bradyrhizobium elkanii strain SEMIA 5019 (also known as 29W) was isolated in Rio de Janeiro, Brazil and SEMIA 587 was isolated in 1967 in the State of Rio Grande do Sul, from an area previously inoculated with North American isolates and has been used for commercial inoculants since 1968 (Appl. Environ. Microbiol. [Applied and Environmental Microbiology] 73(8), 2635, 2007; e.g., GELFIX 5 from BASF Agricultural Products Ltd., Brazil), and Bradyrhizobium japonicum 532c was isolated from a field in Wisconsin, USA (Nitragin 61A152; Can. J. Plant Sci. [Canadian Journal of Plant Sciences] 70, 661 - 666, 1990; e.g., (Super), Bradyrhizobium japonicum E-109 variant of strain USDA 138 (INTA E109, SEMIA 5085; Eur. J. Soil Biol. [European Journal of Soil Biology] 45, 28 - 35, 2009; Biol. Fertil. Soils [Biology and Fertility of Soils] 47, 81–89, 2011); Bradyrhizobium japonicum strains known to be deposited at SEMIA by Appl. Environ. Microbiol. [Applied and Environmental Microbiology] 73(8), 2635, 2007: Bradyrhizobium japonicum SEMIA 5079 was isolated from soil by Embrapa-Cerrados in the Cerrados region of Brazil and has been used for commercial inoculants since 1992 (CPAC 15; e.g., GELFIX 5 or ADHERE 60 from BASF Agricultural Products Ltd., Brazil), Bradyrhizobium japonicum SEMIA 5080 was obtained under laboratory conditions by Embrapa-Cerrados in Brazil and has been used for commercial inoculants since 1992 and is a natural variant of SEMIA 586 (CB1809) originally isolated in the United States (CPAC 7; e.g., GELFIX 5 or ADHERE 60 from BASF Agricultural Products Ltd., Brazil); Burkholderia species A396 was isolated from soil in Nikko, Japan in 2008 (NRRL B-50319; WO 2013 / 032693; Marrone Bio Innovations, Inc., USA), Coniothyrium minitans CON / M / 91-08 was isolated from Brassica napus (WO 1996 / 021358; DSM 9660; e.g., WG, WG), harpin (α-β) protein (Science [Science] 257, 85 - 88, 1992; e.g., Messenger from Plant HealthCare plc, U.K.) TM or HARP-N-Tek), Helicoverpa armigera nucleopolyhedrovirus (HearNPV) (J. Invertebrate Pathol [Journal of Invertebrate Pathology]. 107, 112 - 126, 2011; e.g., from Koppert, Brazil from AgBiTech Pty Ltd., Queensland, Australia Max), Helicoverpa zea single nucleocapsid nucleopolyhedrovirus (HzSNPV) (e.g., from Certis USA LLC ), Helicoverpa zea nucleopolyhedrovirus ABA-NPV-U (e.g., from AgBiTech Pty Ltd., Queensland, Australia ), Heterorhabditis bacteriophora (e.g., from BASF Agricultural Specialities Limited, UK G), Isaria fumosorosea Apopka-97 isolated from mealybugs on Begonia fimbristipula in Apopka, Florida, USA (ATCC 20874; Biocontrol Science Technol [Biocontrol Science and Technology]. 22(7), 747-761, 2012; e.g., PFR-97 from Certis USA LLC TM or ), Metarhizium anisopliae var. anisopliae F52, also known as 275 or V275, isolated from Cydia pomonella in Austria (DSM 3884, ATCC 90448; e.g., Novozymes Biologicals BioAg Group, Canada), Metschnikowia fructicola 277 isolated from grapes in central Israel (US 6,994,849; NRRL Y-30752; e.g., previously from Agrogreen of Israel ), Paecilomyces lilacinus 251 isolated from infected nematode eggs in the Philippines (AGAL 89 / 030550; WO1991 / 02051; Crop Protection [Crop Protection] 27, 352-361, 2008; e.g., from Bayer CropScience AG of Germany and from Certis USA LLC ), Bacillus alvei NAS6G6 was isolated from the rhizosphere of grass roots in South Africa at least before 2008 (WO 2014 / 029697; NRRL B-50755; for example, BAC-UP from BASF Agricultural Products (Pty) Ltd., South Africa), Paenibacillus strains isolated from soil samples from various European regions including Germany: Paenibacillus adhaerens Lu17015 (WO 2016 / 020371; DSM 26971), Paenibacillus polymyxa subsp. plantarum Lu16774 (WO 2016 / 020371; DSM 26969), Paenibacillus polymyxa subsp. plantarum strain Lu17007 (WO 2016 / 020371; DSM 26970); Pasteuria nishizawae Pn1 was isolated from a soybean field in Illinois, USA in the mid-2000s (ATCC SD-5833; Federal Register 76(22), 5808, February 2, 2011; for example, Clariva from Syngenta Crop Protection, LLC, USA TM PN), Penicillium bilaiae (also known as P. bilaii) strains ATCC 18309 (= ATCC 74319), ATCC 20851 and / or ATCC 22348 (= ATCC 74318) were originally isolated from soil in Alberta, Canada (Fertilizer Res. 39, 97-103, 1994; Can. J. Plant Sci. 78(1), 91-102, 1998; US5,026,417, WO 1995 / 017806; for example, Jump from Novozymes Biopharmaceuticals BioAg Group, Canada ), Reynoutria japonica extract (EP 0307510 B1; for example, SC from Marrone BioInnovations, Davis, CA, USA or ) from Bayer CropScience AG, Germany), Steinernema carpocapsae (for example, ) from BASF Agricultural Products (Pty) Ltd., UK), Steinernema feltiae (for example, from BASF Agricultural Products (Pty) Ltd., UK and ), Streptomyces microflavus NRRL B-50550 (WO2014 / 124369; Bayer CropScience AG, Germany), Trichoderma asperelloides JM41R isolated in South Africa (NRRL 50759; also known as Trichoderma viride; e.g., from BASF Agricultural Products (Pty) Ltd., South Africa ), Trichoderma harzianum T-22 also known as KRL-AG2 (ATCC 20847; BioControl 57, 687-696, 2012; e.g., from BioEngineering, Inc., USA or SabrEx from Advanced Biological Marketing Inc., Van Wert, OH, USA TM ).

[0538] According to another embodiment of the mixture, the at least one pesticidal agent II is selected from groups L1) to L5):

[0539] L1) Microbial pest control agents 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), Bacillus amyloliquefaciens subsp. plantarum D747 (L.1.3), Bacillus amyloliquefaciens subsp. plantarum FZB24 (L.1.4), Bacillus amyloliquefaciens subsp. plantarum FZB42 (L.1.5), Bacillus amyloliquefaciens subsp. plantarum MBI600 (L.1.6), Bacillus amyloliquefaciens subsp. QST-713 (L.1.7), Bacillus amyloliquefaciens subsp. TJ1000 (L.1.8), Bacillus pumilus GB34 (L.1.9), Bacillus pumilus GHA 180 (L.1.10), Bacillus pumilus INR-7 (L.1.11), Bacillus pumilus KFP9F (L.1.12), Bacillus pumilus QST 2808 (L.1.13), Bacillus simplex ABU 288 (L.1.14), Bacillus subtilis FB17 (L.1.15), Coniothyrium minitans CON / M / 91-08 (L.1.16), Metschnikowia fructicola NRRL Y-30752 (L.1.17), Paenibacillus alvei NAS6G6 (L.1.18), Paenibacillus epiphyticus Lu17015 (L.1.25), Paenibacillus polymyxa subsp. plantarum Lu16774 (L.1.26), Paenibacillus polymyxa subsp. strain Lu17007 (L.1.27), Penicillium bilaiae ATCC 22348 (L.1.19), Penicillium bilaiae ATCC 20851 (L.1.20), Penicillium bilaiae ATCC 18309 (L.1.21), Streptomyces microflavus NRRLB-50550 (L.1.22), Trichoderma asperelloides JM41R (L.1.23), Trichoderma harzianum T-22 (L.1.24);

[0540] L2) Biochemical pest control agents with fungicidal, bactericidal, virucidal and / or plant defense activator activity: harpins (L.2.1), Reynoutria maxima extract (L.2.2);

[0541] L3) Microbial pest control agents with insecticidal, acaricidal, molluscicidal and / or nematicidal activity: Bacillus firmus I-1582 (L.3.1); Bacillus thuringiensis subsp. aizawai ABTS-1857 (L.3.2), Bacillus thuringiensis subsp. kurstaki ABTS-351 (L.3.3), Bacillus thuringiensis subsp. kurstaki SB4 (L.3.4), Bacillus thuringiensis subsp. tenebrionis NB-176-1 (L.3.5), Beauveria bassiana GHA (L.3.6), Beauveria bassiana JW-1 (L.3.7), Beauveria bassiana PPRI 5339 (L.3.8), Burkholderia species A396 (L.3.9), Helicoverpa armigera nucleopolyhedrovirus (HearNPV) (L.3.10), Helicoverpa zea nucleopolyhedrovirus (HzNPV) ABA-NPV-U (L.3.11), Helicoverpa zea single nucleocapsid 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), Steinernema feltiae (L.3.19);

[0542] L4) Biochemical pest control agents with insecticidal, acaricidal, molluscicidal, pheromonal and / or nematicidal activity: cis-jasmone (L.4.1), methyl jasmonate (L.4.2), Quillaja saponaria extract (L.4.3);

[0543] L5) Microbial pest control agents with plant stress reduction, plant growth regulator, plant growth promotion and / or yield increase activity: Azospirillum brasilense Ab-V5 and Ab-V6 (L.5.1), Azospirillum brasilense Sp245 (L.5.2), Bradyrhizobium elkanii SEMIA 587 (L.5.3), Bradyrhizobium elkanii SEMIA 5019 (L.5.4), Bradyrhizobium japonicum 532c (L.5.5), Bradyrhizobium japonicum E-109 (L.5.6), Bradyrhizobium japonicum SEMIA 5079 (L.5.7), Bradyrhizobium japonicum SEMIA 5080 (L.5.8).

[0544] Furthermore, the present invention relates to agrochemical compositions comprising a mixture of the following: 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, if desired, at least one suitable adjuvant.

[0545] Furthermore, the present invention relates to agrochemical compositions comprising a mixture of the following: 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, if desired, at least one suitable adjuvant.

[0546] Also preferred are mixtures comprising a biopesticide as pesticidal agent II (component 2), which biopesticide is selected from groups L1), L3) and L5), preferably selected from the strains represented above as (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.5.5), (L.5.6), (L.5.7), (L.5.8); (L.4.2) and (L.4.1); even more preferably selected from (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), (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 treating propagation material, i.e. for seed treatment purposes, and are equally suitable for soil treatment. These seed treatment mixtures are particularly suitable for crops such as cereals, maize and leguminous plants such as soybeans.

[0547] Also preferred are mixtures comprising a biopesticide as pesticidal agent II (component 2), which biopesticide is selected from group L1), L3) and L5), preferably selected from the strains designated above as (L1.1), (L1.2), (L1.3), (L1.6), (L1.7), (L1.9), (L1.11), (L1.12), (L1.13), (L1.14), (L1.15), (L1.17), (L1.18), (L1.22), (L1.23), (L1.24), (L1.25), (L1.26), (L1.27), (L2.2); (L3.2), (L3.3), (L3.4), (L3.5), (L3.6), (L3.7), (L3.8), (L3.10), (L3.11), (L3.12), (L3.13), (L3.14), (L3.15), (L3.18), (L3.19); (L4.2), even more preferably selected from (L1.2), (L1.7), (L1.11), (L1.13), (L1.14), (L1.15), (L1.18), (L1.23), (L3.3), (L3.4), (L3.6), (L3.7), (L3.8), (L3.10), (L3.11), (L3.12), (L3.15) and (L4.2). These mixtures are particularly suitable for the foliar treatment of cultivated plants, preferably vegetables, fruits, vines, cereals, maize and leguminous crops such as soybeans.

[0548] Compositions comprising mixtures of active ingredients can be prepared by customary means, for example by the means given for the compositions of compound I.

[0549] When live microorganisms such as pesticidal agents II from groups L1), L3) and L5) form part of the composition, such compositions can be prepared by customary means (for example H.D. Burges: Formulation of Microbial Biopesticides, Springer, 1998; WO 2008 / 002371, US 6,955,912, US 5,422,107).

[0550] Example

[0551] Synthesis process

[0552] Example 1: Methyl (2E)-2-[3-chloro-2-[[(Z)-[1-(4-fluorophenyl)-2-methoxyethylidene]amino]oxymethyl]phenyl]-2-methoxyiminoacetate (No. 1)Step 1

[0553] Step 2 1-(4-Fluorophenyl)-2-methoxy-ethanone

[0554]

[0555] In N 2 and at -70 °C, N,2-dimethoxy-N-methyl-acetamide (3.15 g, 23.68 mmol) in THF (10 mL) was added to a solution of 4-fluorophenylmagnesium bromide (2 M) (11.2 mL, 22.55 mmol) in THF (10 mL), and the mixture was stirred for 2 h in N 2 and at -70 °C. TLC (petroleum ether:ethyl acetate (PE:EtOAc) = 5:1) showed completion of the reaction. The reaction mixture was quenched at -60 °C with aqueous HCl solution (0.5 M) (34 mL), extracted with EtOAc (60 mL × 3), dried over Na 2 SO 4 and concentrated, and purified by column (PE:EtOAc = 90:10) to give 1-(4-fluorophenyl)-2-methoxy-ethanone as a yellow oil (2 g, 52%). 1 1H NMR: (400 MHz, CHCl 3 -d) δ (ppm) = 7.97 - 8.02 (m, 2H), 7.12 - 7.18 (m, 2H), 4.67 (s, 2H), 3.51 (s, 3H).

[0556] Step 3 1-(4-Fluorophenyl)-2-methoxy-ethanone oxime

[0557]

[0558] At 20 °C, NaAc (0.97 g, 11.9 mmol) and NH 2 OH·HCl (0.82 g, 11.9 mmol) were added to a solution of 1-(4-fluorophenyl)-2-methoxy-ethanone (1 g, 5.95 mmol) in MeOH (20 mL), and the reaction was stirred for 1 h in N 2 and at 20 °C. TLC (PE:EtOAc = 5:1) showed completion of the reaction. Two batches of parallel reactions were combined. The resulting solution was filtered and the filtrate was poured into water (30 mL), extracted with EtOAc (30 mL × 3), dried over Na 2 SO 4 and concentrated, and purified by column (PE:EtOAc = 10:1) to give 1-(4-fluorophenyl)-2-methoxy-ethanone oxime as a yellow oil (1.5 g, 69%).1 1H NMR: (400 MHz, DMSO-d 6 ) 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).

[0559] Step 4 (2-Bromo-6-chloro-phenyl)methanol

[0560]

[0561] At 0 °C, NaBH 4 (18.8 g, 495.4 mmol) was added to a solution of 2-bromo-6-chlorobenzaldehyde (90 g, 412.8 mmol) in MeOH (1 L) and THF (500 mL), and the mixture was stirred at 0 °C for 1 h. TLC (PE:EtOAc = 10:1) showed the reaction was complete. The reaction mixture was quenched with H 2 O (1 L) and extracted with dichloromethane (DCM) (500 mL × 3). The organic layer was dried over Na 2 SO 4 and concentrated to give (2-bromo-6-chloro-phenyl)methanol (90 g, yield: 99.1%) as a yellow solid. 1 1H NMR: (400 MHz, CHCl 3 -d) δ = 7.52 (d, J = 8.00 Hz, 1H), 7.38 (d, J = 8.00 Hz, 1H), 7.06 - 7.17 (m, 1H), 4.99 (d, J = 7.00 Hz, 2H), 2.16 (t, J = 7.00 Hz, 1H).

[0562] Step 5 1-Bromo-3-chloro-2-(methoxymethyl)benzene

[0563]

[0564] At 0 °C, NaH (about 60%) (19.7 g, 493 mmol) was added to a solution of (2-bromo-6-chloro-phenyl)methanol (90 g, 411 mmol) in DMF (1 L), and the mixture was stirred at 0 °C for 1 h. At 0 °C, MeI (70 g, 493 mmol) was added to the mixture, and the mixture was stirred at 0 °C for another 1 h. TLC (PE:EtOAc = 10:1) showed the reaction was complete. The reaction mixture was quenched with H 2 O (1 L), extracted with EtOAc (500 mL × 3), and washed with brine (500 mL × 2). The organic layer was dried over Na 2 SO 4It was dried, concentrated, and purified by column (PE:EtOAc = 10:1) to obtain 1-bromo-3-chloro-2-(methoxymethyl)benzene as a yellow solid (65 g, yield: 67.6%). 1 H NMR: (400 MHz, CHCl 3 -d): δ = 7.52 (dd, J = 8.03, 1.13 Hz, 1H), 7.37 (dd, J = 8.09, 1.07 Hz, 1H), 7.11 (t, J = 8.03 Hz, 1H), 4.76 (s, 2H), 3.46 (s, 3H).

[0565] Step 6 [3-Chloro-2-(methoxymethyl)phenyl]magnesium bromide

[0566]

[0567] At 40 °C to 50 °C, 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 I 2 (2.1 g, 8.3 mmol) in THF (150 mL), and the mixture was stirred at 45 °C for 2 h. TLC (PE:EtOAc = 20:1) showed the reaction was complete. The resulting solution was used directly for the next step.

[0568] Step 7 Methyl 2-[3-chloro-2-(methoxymethyl)phenyl]-2-oxoacetate

[0569]

[0570] At -40 °C, a solution of [3-chloro-2-(methoxymethyl)phenyl]magnesium bromide (450 mL, 278 mmol) was added to a solution of dimethyl oxalate (66 g, 556 mmol) in toluene (500 mL), and the mixture was stirred at -40 °C for 2 h. TLC (PE^:EtOAc = 10:1) showed the reaction was complete. The reaction mixture was quenched with aqueous NH 4 Cl solution (500 mL) and extracted with EtOAc (500 mL × 3). The organic layer was dried over Na 2 SO 4 It was dried, concentrated, and purified by column (PE:EtOAc = 10:1) to obtain methyl 2-[3-chloro-2-(methoxymethyl)phenyl]-2-oxoacetate as a yellow solid (40 g, yield: 59.5%). 1 H NMR: (400 MHz, CHCl 3-d): δ = 7.50 (d, J = 7.75 Hz, 1H), 7.29 - 7.41 (m, 2H), 4.71 (s, 2H), 3.90 - 3.94 (s, 3H), 3.30 (s, 3H).

[0571] Step 8 (2E)-2-[3-Chloro-2-(methoxymethyl)phenyl]-2-methoxyimino-acetic acid methyl ester

[0572]

[0573] To a solution of methyl 2-[3-chloro-2-(methoxymethyl)phenyl]-2-oxo-acetate (40 g, 165 mmol) in MeOH (40 mL) was added MeONH 2 .HCl (27.4 g, 330 mmol), and the mixture was stirred at 80 °C for 3 h. TLC (PE:EtOAc = 5:1) showed the reaction was complete. The reaction mixture was quenched with H 2 O (400 mL), and extracted with DCM (400 mL × 3). The organic layer was dried over Na 2 SO 4 and concentrated to give methyl (2E)-2-[3-chloro-2-(methoxymethyl)phenyl]-2-methoxyimino-acetate (44.5 g, yield: 99.5%) as a yellow oil. 1 1H NMR: (400 MHz, CHCl 3 -d): δ = 7.41 - 7.50 (m, 1H), 7.28 - 7.34 (m, 1H), 7.09 (dd, J = 7.63, 1.00 Hz, 1H), 4.64 (s, 2H), 4.01 - 4.07 (m, 3H), 3.85 - 3.96 (m, 3H), 3.25 - 3.41 (m, 3H).

[0574] Step 9 (2E)-2-[2-(Bromomethyl)-3-chloro-phenyl]-2-methoxyimino-acetic acid methyl ester

[0575]

[0576] 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 (approx. 33%) (120 g, 493 mmol), and the mixture was stirred at 35 °C for 16 h. TLC (PE:EtOAc = 5:1) showed the reaction was complete. The reaction mixture was quenched with H 2Quenched with O (800 mL), and extracted with DCM (800 mL × 3). The organic layer was dried over Na 2 SO 4 and concentrated to give methyl (2E)-2-[2-(bromomethyl)-3-chloro-phenyl]-2-methoxyimino-acetate as a yellow solid (27 g, yield: 51.6%). 1 H NMR: (400 MHz, CHCl 3 -d): δ = 7.48 (dd, J = 8.03, 1.13 Hz, 1H), 7.34 (t, J = 7.84 Hz, 1H), 7.06 (dd, J = 7.65, 1.13 Hz, 1H), 4.44 (br s, 2H), 4.08 (s, 3H), 3.90 (s, 3H).

[0577] Example 2: (2E)-2-[3-chloro-2-[[(Z)-[1-(4-fluorophenyl)-2-methoxyethylidene]amino]oxymethyl]phenyl]-2-methoxyimino-N-methylacetamide (No. 2) Methyl (2E)-2-[3-chloro-2-[[(Z)-[1-(4-fluorophenyl)-2-methoxy-ethylidene]amino]oxymethyl]phenyl]-2-methoxyimino-acetate

[0578]

[0579] To a solution of 1-(4-fluorophenyl)-2-methoxy-ethanone oxime (7.9 g, 43.2 mmol) in MeCN (100 mL) was added methyl (2E)-2-[2-(bromomethyl)-3-chloro-phenyl]-2-methoxyimino-acetate (14.5 g, 45.3 mmol) and Cs 2 CO 3 (28 g, 86.4 mmol), and the mixture was stirred at 15 °C for 2 h. LCMS showed the reaction was complete. The reaction mixture was quenched with H 2 O (100 mL), and extracted with EtOAc (100 mL × 3). The organic layer was dried over Na 2 SO 4 and concentrated, purified by HPLC, and lyophilized to give the title compound as a yellow solid (15 g, yield: 82.3%). 1 H NMR: (400 MHz, CHCl 3 -d): δ = 7.59 - 7.67 (m, 2H), 7.48 (dd, J = 8.09, 0.94 Hz, 1H), 7.34 (t, J = 7.84 Hz, 1H), 7.06 - 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).

[0580] Example 3: Methyl (2E)-2-[2-[[(Z)-[1-(2-bromophenyl)-2-methoxyethylidene]amino]oxymethyl]-3-chlorophenyl]-2-methoxyiminoacetate Step 1

[0581]

[0582] To a solution of methyl (2E)-2-[3-chloro-2-[[(Z)-[1-(4-fluorophenyl)-2-methoxyethylidene]amino]oxymethyl]phenyl]-2-methoxyiminoacetate (5.5 g, 13.0 mmol) in THF (80 mL) was added MeNH 2 (approx. 30% aqueous solution) (12.2 g, 118.0 mmol), and the mixture was stirred at 15 °C for 2 h. TLC (PE:EtOAc = 3:1) showed completion of the reaction. The reaction mixture was concentrated to give the title compound as a yellow solid (5.3 g, yield: 96.7%). 1 H NMR: (400 MHz, CHCl 3 -d): δ = 7.59 - 7.67 (m, 2H), 7.46 (dd, J = 8.00, 1.00 Hz, 1H), 7.34 (t, J = 7.88 Hz, 1H), 7.11 (dd, J = 7.63, 1.00 Hz, 1H), 6.99 - 7.07 (m, 2H), 6.78 (br d, J = 4.25 Hz, 1H), 5.07 - 5.43 (m, 2H), 4.52 (s, 2H), 3.93 (s, 3H), 3.26 (s, 3H), 2.85 (d, J = 5.00 Hz, 3H).

[0583] Step 2 Step 3

[0584] Example 4: Methyl (2E)-2-[3-chloro-2-[[(Z)-(2-methoxy-1-phenylethylidene)amino]oxymethyl]phenyl]-2-methoxyiminoacetate (No. 3) 1-(2-Bromophenyl)-2-methoxy-ethanone

[0585]

[0586] To a solution of 1-bromo-2-iodobenzene (50 g, 0.177 mol) in THF (500 mL) at 0 °C was added isopropylMgCl (2 M) (97 mL, 0.194 mol), and the mixture was stirred at N 2 and 0 °C for 0.5 h. Then N,2-dimethoxy-N-methyl-acetamide (28.2 g, 0.212 mol) in THF (50 mL) was added, and the mixture was stirred at N 2 and 0 °C for 2 h. TLC (PE:EtOAc = 3:1) showed completion of the reaction. The reaction mixture was quenched with aqueous HCl (0.5 M) (500 mL), extracted with EtOAc (500 mL × 3), and dried over Na 2 SO4 It was dried, concentrated, and purified by column (PE:EtOAc = 9:1) to obtain 1-(2-bromophenyl)-2-methoxy-ethanone as a yellow oil (33 g, 81.7%). 1 H NMR: (400 MHz, CHCl 3 -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).

[0587] Example 5: (2E)-2-[3-chloro-2-[[(Z)-(2-methoxy-1-phenylethylidene)amino]oxymethyl]phenyl]-2-methoxyimino-N-methylacetamide (No. 4) 1-(2-bromophenyl)-2-methoxy-ethanone oxime

[0588]

[0589] To a solution of 1-(2-bromophenyl)-2-methoxy-ethanone (10 g, 0.044 mol) in MeOH (100 mL) was added NaAc (7.2 g, 0.088 mmol) and NH 2 OH·HCl (6 g, 0.088 mmol). The reaction was stirred at N 2 and 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 and dried over Na 2 SO 4 and concentrated, and purified by column (PE:EtOAc = 9:1) to obtain 1-(2-bromophenyl)-2-methoxy-ethanone oxime as a yellow solid (8.8 g, 81.9%). 1H NMR: (400 MHz, CHCl 3 -d) δ = 7.51 (d, J = 7.91 Hz, 1H), 7.26 (d, J = 4.27 Hz, 2H), 7.14 - 7.20 (m, 1H), 4.57 (s, 2H), 3.21 (s, 3H).

[0590] Example 6: Methyl (E)-2-[3-bromo-2-[[(Z)-[3-(4-fluorophenyl)-1-(methoxymethyl)prop-2-ynylidene]amino]oxymethyl]phenyl]-3-methoxyprop-2-enoate (No. 8) (2E)-2-[2-[[(Z)-[1-(2-bromophenyl)-2-methoxy-ethylidene]amino]oxymethyl]-3-chloro-phenyl]-2-methoxyimino-acetic acid methyl ester

[0591]

[0592] To a solution of 1-(2-bromophenyl)-2-methoxy-ethanone oxime (9.5 g, 0.039 mol) in MeCN (150 mL) was added methyl (2E)-2-[2-(bromomethyl)-3-chloro-phenyl]-2-methoxyimino-acetate (12.5 g, 0.038 mmol) and Cs 2 CO 3 (26.6 g, 0.082 mmol). The reaction mixture was stirred at N 2 and 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 (PE:EtOAc = 9:1) to give the title compound as a yellow solid (14 g, 74.3%). 1 H NMR: (400 MHz, CHCl 3 -d) δ = 7.56 (dd, J = 7.88, 0.63 Hz, 1H), 7.48 (dd, J = 8.13, 1.00 Hz, 1H), 7.28 - 7.39 (m, 3H), 7.19 - 7.25 (m, 1H), 7.11 (dd, J = 7.63, 1.00 Hz, 1H), 5.21 (br s, 2H), 4.53 (s, 2H), 4.04 (s, 3H), 3.72 (s, 3H), 3.23 (s, 3H).

[0593] Step 1 Step 2

[0594]

[0595] To a solution of methyl (2E)-2-[2-[[(Z)-[1-(2-bromophenyl)-2-methoxyethylidene]amino]oxymethyl]-3-chloro-phenyl]-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]-dichloropalladium(II) (Pd(dppf)Cl 2 )(2.2 g, 0.003 mol). The reaction mixture was stirred at N 2 and 100 °C for 24 h. TLC (PE:EtOAc = 3:1) showed the reaction was complete. The reaction was filtered and poured into water (100 mL), extracted with EtOAc (100 mL × 3), washed with brine (50 mL × 3) and dried over Na 2 SO 4It was dried, concentrated, and purified by column (PE:EtOAc = 9:1) to give the title compound as a yellow oil (10 g, 82.3%). 1 H NMR: (400 MHz, CHCl 3 -d) δ = 7.63 (dd, J = 6.63, 2.88 Hz, 2H), 7.48 (d, J = 8.00 Hz, 1H), 7.30 - 7.39 (m, 4H), 7.09 (d, J = 7.50 Hz, 1H), 5.25 (br s, 2H), 4.55 (s, 2H), 4.01 (s, 3H), 3.73 (s, 3H), 3.27 (s, 3H).

[0596] Step 3 Step 4

[0597]

[0598] 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 2 (approx. 30% aqueous solution) (12.5 g, 0.12 mol), and the mixture was stirred at N 2 and 20 °C for 16 h. TLC (PE:EtOAc = 3:1) showed the reaction was complete. The reaction was concentrated and purified by column (PE:EtOAc = 4:1) to give the title compound as a white solid (4 g, 82.7%). 1 H NMR: (400 MHz, CHCl 3 -d) δ = 7.63 (dd, J = 6.63, 3.00 Hz, 2H), 7.42 - 7.51 (m, 1H), 7.29 - 7.39 (m, 4H), 7.08 - 7.16 (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).

[0599] Step 5 Step 6

[0600] Example 7: Methyl (E)-2-[3-chloro-2-[[(Z)-[3-(4-fluorophenyl)-1-(methoxymethyl)prop-2-ynylidene]amino]oxymethyl]phenyl]-3-methoxyprop-2-enoate (No. 5) Methyl 2-(3-bromo-2-methylphenyl)-2-oxoacetate

[0601]

[0602] Under N 2At 0 °C, isopropylmagnesium chloride (2 M) (37 mL, 74.2 mmol) was added dropwise to a mixture of 1-bromo-3-iodo-2-methyl-benzene (20.28 g, 68.3 mmol) in THF (200 mL), and the mixture was stirred at 0 °C for 0.5 h. CuI (14.3 g, 75.1 mmol) was added in portions at 20 °C, and the mixture was stirred at 25 °C for 1 h. Then, under N 2 and the reaction mixture was added to methyl 2-chloro-2-oxo-acetate (12.55 g, 102.4 mmol) in THF (250 mL) at -70 °C. The mixture was gradually warmed to 25 °C and stirred for 15 h. TLC (PE:EtOAc = 5:1) showed the reaction was complete. The two batches of parallel reactions were combined. The reaction solution was quenched with aqueous NH 2 Cl (1 L) at 0 °C and extracted with EtOAc (500 mL × 2). The combined organic phases were washed with brine (500 mL), dried over Na 4 SO 2 filtered, concentrated and purified by column (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. 4 H NMR: (400 MHz, CHCl 1 -d) δ = 7.74 - 7.84 (m, 1H) 7.58 (d, J = 7.75 Hz, 1H) 7.20 (t, J = 7.88 Hz, 1H) 3.97 (s, 3H) 2.61 (s, 3H). 3 -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)。

[0603] 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) (E)-Methyl 2-(3-bromo-2-methyl-phenyl)-3-methoxy-prop-2-enoate

[0604]

[0605] Under N 2 and 0 °C, lithium bis(trimethylsilyl)amide (LiHMDS) (1 M) (50 mL, 50.0 mmol) was added dropwise to a solution of methoxymethyltriphenylphosphonium bromide (17 g, 50.0 mmol) in THF (180 mL), and the mixture was stirred at 0 °C for 1 h. Then, methyl 2-(3-bromo-2-methyl-phenyl)-2-oxo-acetate (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) showed the reaction was complete. The two batches of parallel reactions were combined. The reaction solution was quenched with NH 4The reaction mixture was quenched with an aqueous solution of Cl (1 L) and extracted with MTBE (500 mL×3). The combined organic phases were washed with brine (500 mL), dried over Na 2 SO 4 , filtered, concentrated and purified by column chromatography (PE:EtOAc = 85:15) to give methyl (E)-2-(3-bromo-2-methylphenyl)-3-methoxyprop-2-enoate (19 g, yield: 80%) as a yellow solid. 1 1H NMR: (400 MHz, CDCl 3 3) δ = 7.57 (s, 1H) 7.51 (dd, J = 7.07, 2.19 Hz, 1H) 7.00 - 7.11 (m, 2H) 3.84 (s, 3H) 3.71 (s, 3H) 2.26 (s, 3H).

[0606] Example 9: Methyl (E)-2-[3-chloro-2-[[(Z)-[3-(4-fluorophenyl)-1-(methoxymethyl)prop-2-ynylidene]amino]oxymethyl]phenyl]-3-methoxyprop-2-enoate (No. 7) Methyl (E)-2-[3-bromo-2-(bromomethyl)phenyl]-3-methoxyprop-2-enoate

[0607]

[0608] To a solution of methyl (E)-2-(3-bromo-2-methylphenyl)-3-methoxyprop-2-enoate (11 g, 38.6 mmol) in cyclohexane (220 mL) at N 2 and 85 °C was added azobis(isobutyronitrile) (AIBN) (0.63 g, 3.86 mmol), followed by the addition of NBS (20.6 g, 115.8 mmol). The mixture was stirred at 85 °C for 16 h. HPLC showed that 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 phases were washed with brine (500 mL), dried over Na 2 SO 4 , filtered and concentrated. The residue was purified by silica gel column chromatography (PE:EtOAc = 85:15) to give methyl (E)-2-[3-bromo-2-(bromomethyl)phenyl]-3-methoxyprop-2-enoate (16.7 g, yield: 59%) as a yellow solid. 1 1H NMR: (400 MHz, CDCl 3 3) δ = 7.65 (s, 1H) 7.55 - 7.60 (m, 1H) 7.15 - 7.20 (m, 1H) 7.09 (dd, J = 7.63, 1.13 Hz, 1H) 4.55 (br, 2H) 3.85 (s, 3H) 3.71 (s, 3H).

[0609] Step 14-(4-Fluorophenyl)-1-methoxy-but-3-yn-2-one

[0610]

[0611] At -78 °C, n-BuLi (2.5 M) (88 mL, 218.7 mmol) was added dropwise to a solution of 4-fluorophenylacetylene (25 g, 208.3 mmol) in THF (300 mL), and the mixture was stirred at -78 °C for 1 h. At -78 °C, N,2-dimethoxy-N-methyl-acetamide (33.2 g, 250 mmol) in THF (50 mL) was added to the mixture, and the mixture was stirred at -78 °C for 2 h. TLC (PE:EtOAc = 5:1) showed that the reaction was complete. The reaction mixture was quenched with water (500 mL), extracted with EtOAc (200 mL × 3), dried over Na 2 SO 4 and concentrated, and purified by column (PE:EtOAc = 5:1) to give 4-(4-fluorophenyl)-1-methoxy-but-3-yn-2-one as a yellow oil (35 g, 87.5%). 1 1H NMR: (400 MHz, CHCl 3 -d) δ = 7.60 (dd, J = 8.78, 5.27 Hz, 2H), 7.03 - 7.16 (m, 2H), 4.26 (s, 2H), 3.52 (s, 3H).

[0612] Step 2 4-(4-Fluorophenyl)-1-methoxy-but-3-yn-2-one oxime

[0613]

[0614] At 15 °C, NaAc (29.9 g, 365 mmol) was added to a solution of NH 2 OH·HCl (25 g, 365.0 mmol) in MeOH (350 mL), and the mixture was stirred at N 2 and 15 °C for 0.5 h. Then, at 15 °C, 4-(4-fluorophenyl)-1-methoxy-but-3-yn-2-one (35 g, 182 mmol) in 2-MeTHF (50 mL) was added to the mixture, 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 Na 2 SO 4It was dried, concentrated, and purified by column (PE:EtOAc = 3:1) to obtain 4-(4-fluorophenyl)-1-methoxy-but-3-yn-2-one oxime as a yellow solid (17 g, 45.1%). 1 H NMR: (400 MHz, CHCl 3 -d) δ = 7.49 - 7.58 (m, 2H), 7.05 (t, J = 8.76 Hz, 2H), 4.40 (s, 2H), 3.50 (s, 3H).

[0615] Step 3 (E)-2-[3-bromo-2-[[(Z)-[3-(4-fluorophenyl)-1-(methoxymethyl)prop-2-ynylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoic acid methyl ester

[0616]

[0617] At N 2 and 20 °C, 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) was added (E)-2-(3-bromo-2-methylphenyl)-3-methoxy-prop-2-enoic acid methyl ester (6.33 g, 0.017 mol) and K 2 CO 3 (5.04 g, 0.037 mol). The mixture was stirred at N 2 and 80 °C for 16 h. TLC (PE:EtOAc = 3:1) and LCMS showed 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) and dried over Na 2 SO 4 dried, concentrated and purified by column (PE:EtOAc = 85:15), triturated with n-hexane (20 mL) and filtered to obtain the title compound as a white solid (4.7 g, 28%). 1H NMR (400 MHz, CHCl 3 -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) 3.43 (s, 3H).

[0618] Step 4 Example 10: Methyl (E)-2-[3-chloro-2-[[(Z)-[1-(2-chlorophenyl)-2-methoxyethylidene]amino]oxymethyl]phenyl]-3-methoxyprop-2-enoate (No. 15)

[0619]

[0620] 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 (2E)-2-[2-(bromomethyl)-3-chloro-phenyl]-2-methoxyimino-acetic acid methyl ester (17.8 g, 55.8 mmol) and Cs 2 CO 3 (33.1 g, 101.4 mmol). The reaction mixture was stirred at N 2 and 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 Na 2 SO 4 and concentrated, and purified by HPLC, freeze-dried to give the title compound as a yellow solid (11 g, 48.6%). 1 H NMR: (400 MHz, CHCl 3 -d) δ = 7.50 - 7.55 (m, 2H), 7.48 (dd, J = 8.07, 1.06 Hz, 1H), 7.36 (t, J = 7.82 Hz, 1H), 7.10 (dd, J = 7.63, 1.00 Hz, 1H), 7.03 (t, J = 8.69 Hz, 2H), 4.99 - 5.42 (dr, 2H), 4.24 (s, 2H), 4.06 (s, 3H), 3.87 (s, 3H), 3.43 (s, 3H).

[0621] Step 1 Step 2

[0622]

[0623] To a solution of (E)-2-[3-chloro-2-[[(Z)-[3-(4-fluorophenyl)-1-(methoxymethyl)prop-2-ynylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoic acid methyl ester (5.5 g, 12.3 mmol) in THF (60 mL) was added MeNH 2 (approx. 30% aqueous solution) (12.7 g, 123 mmol). The reaction mixture was stirred at N 2 and 20 °C for 2 h. LCMS showed the reaction was complete. The reaction mixture was concentrated to give the title compound as a yellow solid (5.2 g, 95.0%). 1 H NMR: (400 MHz, CHCl 3-d) δ = 7.49 - 7.55 (m, 2H), 7.47 (d, J = 8.07 Hz, 1H), 7.35 (t, J = 7.89 Hz, 1H), 7.11 (d, J = 7.58 Hz, 1H), 7.04 (t, J = 8.62 Hz, 2H), 6.83 (br d, J = 4.16 Hz, 1H), 5.00 - 5.50 (m, 2H), 4.24 (s, 2H), 3.97 (s, 3H), 3.42 (s, 3H), 2.92 (d, J = 5.01 Hz, 3H).

[0624] Step 3 ​

[0625] ​ Methyl 2-(3-chloro-2-methylphenyl)-2-oxoacetate

[0626]

[0627] At N 2 and 0 °C, isopropyl MgCl (2 M) (76.0 mL, 151.0 mmol) was added dropwise to a mixture of 1-chloro-3-iodo-2-methylbenzene (36.5 g, 144.0 mmol) in THF (360 mL). The mixture was stirred at N 2 and 0 °C for 0.5 h. Then, CuI (30.2 g, 159.0 mmol) was added portionwise at 20 °C, and the mixture was stirred at 25 °C for 1 h. Then, at N 2 under, the reaction mixture was added dropwise to methyl 2-chloro-2-oxoacetate (26.5 g, 216 mol) in THF (530 mL) at -70 °C. The mixture was gradually warmed to 25 °C and stirred for 15 h. TLC (PE:EtOAc = 5:1) showed the reaction was complete. The two batches of parallel reactions were combined. The reaction solution was quenched with an aqueous NH 4 Cl solution (1 L) at 0 °C and extracted with EtOAc (500 mL × 2). The combined organic phases were washed with brine (500 mL), dried over Na 2 SO 4 , filtered, concentrated and purified by column (PE:EtOAc = 9:1) to give methyl 2-(3-chloro-2-methylphenyl)-2-oxoacetate as a yellow solid (30 g, yield: 49%). 1 HNMR: (400 MHz, CHCl 3 -d) δ = 7.60 (d, J = 8.00 Hz, 1H) 7.54 (dd, J = 7.75, 0.88 Hz, 1H) 7.27 (m, 1H) 3.97 (s, 3H) 2.58 (s, 3H).

[0628] ​ Methyl (E)-2-(3-chloro-2-methylphenyl)-3-methoxyprop-2-enoate

[0629]

[0630] At N 2 and 0 °C, lithium bis(trimethylsilyl)amide (1 M) (85 mL, 84.5 mmol) was added dropwise to a solution of methoxymethyltriphenylphosphonium bromide (29 g, 84.5 mmol) in THF (300 mL), 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) showed the reaction was complete. Two batches were combined. The reaction solution was quenched with aqueous NH 4 Cl (1 L) at 0 °C, and extracted with MTBE (500 mL × 3). The combined organic phases were washed with brine (500 mL), dried over Na 2 SO 4 , filtered, concentrated and purified by column (PE:EtOAc = 85:15) to give methyl (E)-2-(3-chloro-2-methylphenyl)-3-methoxyprop-2-enoate (22 g, yield: 65%) as a yellow solid. 1 1H NMR: (400 MHz, CDCl 3 3) δ = 7.58 (s, 1H) 7.32 (dd, J = 7.94, 1.06 Hz, 1H) 7.13 (t, J = 7.82 Hz, 1H) 7.03 (dd, J = 7.63, 1.13 Hz, 1H) 3.84 (s, 3H) 3.71 (s, 3H) 2.23 (s, 3H).

[0631] ​ Methyl (E)-2-[2-(bromomethyl)-3-chlorophenyl]-3-methoxyprop-2-enoate

[0632]

[0633] At N 2At 85 °C, AIBN (0.75 g, 4.61 mmol) was added to a solution of methyl (E)-2-(3-chloro-2-methylphenyl)-3-methoxyprop-2-enoate (11 g, 46.1 mmol) in cyclohexane (220 mL), and then NBS (24.6 g, 138.2 mmol) was added. The mixture was stirred at 85 °C for 16 h. HPLC showed that 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 phases were washed with brine (500 mL), dried over Na 2 SO 4 , filtered and concentrated. The residue was purified by column (PE:EtOAc = 85:15) to give methyl (E)-2-[2-(bromomethyl)-3-chlorophenyl]-3-methoxyprop-2-enoate (20 g, yield: 68%) as a yellow solid. 1 1H NMR: (400 MHz, CDCl 3 3) δ = 7.66 (s, 1H) 7.38 (dd, J = 8.07, 1.19 Hz, 1H) 7.27 (m, 1H) 7.06 (dd, J = 7.63, 1.25 Hz, 1H) 4.36 - 4.66 (s, 2H) 3.85 (s, 3H) 3.72 (s, 3H).

[0634] ​ Methyl (E)-2-[3-chloro-2-[[(Z)-[3-(4-fluorophenyl)-1-(methoxymethyl)prop-2-ynylidene]amino]oxymethyl]phenyl]-3-methoxyprop-2-enoate

[0635]

[0636] To a solution of 4-(4-fluorophenyl)-1-methoxybut-3-yn-2-one oxime (5 g, 24.1 mmol) in MeCN (100 mL) was added methyl (E)-2-[2-(bromomethyl)-3-chlorophenyl]-3-methoxyprop-2-enoate (7.68 g, 24.1 mmol) and Cs 2 2CO 3 3 (15.6 g, 48 mmol). The reaction mixture was stirred at N 2 2 and 20 °C for 4 h. TLC (PE:EtOAc = 3:1) showed that the reaction was complete. The reaction was filtered, and the filtrate was concentrated and purified by column (PE:EtOAc = 8:1) and HPLC to give the title compound (5.2 g, 48.7%) as a yellow oil. 1 1H NMR: (400 MHz, CDCl 3-d) δ = 7.59 (s, 1H), 7.49 - 7.55 (m, 2H), 7.40 (dd, J = 8.00, 1.25 Hz, 1H), 7.30 (t, J = 7.82 Hz, 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).

[0637] ​ ​

[0638]

[0639] ​ 1-(2-Chlorophenyl)-2-methoxy-ethanone

[0640] Cool 2.9 mL (5.75 mmol) of isopropylmagnesium chloride (2.0 molar, in tetrahydrofuran) to -5 °C. Add 1-bromo-2-chloro-benzene (1 g, 5.23 mmol), and stir the reaction for 1 h. Add dropwise over 5 min a solution of N,2-dimethoxy-N-methyl-acetamide (0.695 g, 6.2 mmol) in 1 mL of THF. Continue stirring the reaction at -5 °C for 1 h. Monitor the completion of the reaction by TLC (20% EtOAc in heptane). Then quench the reaction with aqueous ammonium chloride solution (10 mL) and extract with methyl-tert-butyl ether (MTBE) (3 × 10 mL), wash with brine and dry over Na 2 SO 4 Dry. Evaporate the solvent in vacuo to give 0.8 g of 1-(2-chlorophenyl)-2-methoxy-ethanone as a pale yellow liquid, which is used in the next step without further purification. Yield (crude): 82.9%. 1 1H NMR (500 MHz, DMSO-d 6 ) 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).

[0641] ​ 1(Z)-(2-Chlorophenyl)-2-methoxy-ethanone oxime

[0642] Dissolve crude 1-(2-chlorophenyl)-2-methoxy-ethanone (0.8 g, 4.33 mmol) in 8 mL of methanol. Add NaAc (0.711 g, 8.66 mmol) and hydroxylamine hydrochloride (0.452 g, 6.499 mmol). Heat the reaction mixture to 50 °C and stir for 2 h. Dilute the reaction with water (8 mL) and extract with DCM (3 × 8 ml). Wash the organic layer with brine and dry over Na 2 SO 4 dry, filter, and evaporate 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 ratio of 75:25. Purify the Z-isomer by flash column chromatography (15%-20% EtOAc in heptane). Yield: 0.450 g, 52%. 1(Z)-(2-Chlorophenyl)-2-methoxy-ethanone oxime, the desired isomer (52%). 1 H NMR (500 MHz, DMSO-d 6 ) 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).

[0643] ​ (E)-Methyl 2-[3-chloro-2-[[(Z)-[1-(2-chlorophenyl)-2-methoxy-ethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoate

[0644] To a solution of 1(Z)-(2-chlorophenyl)-2-methoxy-ethanone oxime (1 g, 5.01 mmol) in 10 mL of AcN, add cesium carbonate (3.2 g, 10.02 mmol) and (E)-methyl 2-[2-(bromomethyl)-3-chloro-phenyl]-3-methoxy-prop-2-enoate (1.6 g, 5.01 mmol), and stir the reaction mixture at RT for 16 h. Dilute the reaction with water (10 mL) and extract with MTBE (3 × 1 mL). Separate the organic layer and wash with brine, dry over Na 2 SO 4 dry, filter, then evaporate in vacuo and purify by flash chromatography (15%-20% EtOAc in heptane) to give the title compound as a white solid. Yield: 1.4 g 63.7%. 1 H NMR (500 MHz, DMSO-d 6)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).

[0645] Example 11: (E)-2-[3-chloro-2-[[(Z)-[2-methoxy-1-(2,4,6-trifluorophenyl)ethylidene]amino]oxy methyl]phenyl]-3-methoxy-prop-2-enoic acid methyl ester (No. 12)

[0646]

[0647] Step 1: 2-Methoxy-1(Z)-(2,4,6-trifluorophenyl)ethanone oxime

[0648] Diisopropylamine (16.85 g, 0.17 mol) in 100 mL of THF was cooled to 0 °C. To this, 60 mL of n-butyllithium solution (2.5 M, in heptane, 0.15 mol) was added dropwise while maintaining the temperature at 0 °C. The reaction was further stirred for 15 min and then cooled to -78 °C. 1,3,5-Trifluorobenzene (20 g, 0.15 mol) in 50 mL of THF was added to the reaction mixture over 30 min. The reaction was stirred at -78 °C for 1 h. At -78 °C, N,2-Dimethoxy-N-methyl-acetamide (24.19 g, 0.18 mol) in 50 mL of THF was added dropwise thereto over 1 h. The reaction was stirred at the same temperature for 1 h and quenched with 200 mL of 1N aqueous HCl. The organic layer was separated and the aqueous layer was washed with 200 mL of MTBE. The organic layers were combined and washed with brine, dried over Na 2 SO 4 dried and concentrated in vacuo to give 18 g of crude 2-methoxy-1-(2,4,6-trifluorophenyl)ethanone. The crude material 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 h. The reaction was cooled to RT and the solvent was evaporated in vacuo to half the volume. The residue was diluted with 200 mL of water and extracted with DCM (100 mL × 2). The organic layers were combined and washed with brine (2 × 30 mL), dried over Na 2 SO 4 dried and concentrated in vacuo. The crude material 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 (500 MHz, DMSO-d 6) δ = 11.93 (s, 1H), 7.34–7.18 (m, 2H), 4.45 (s, 2H), 3.18 (s, 3H).

[0649] Step 2: (E)-2-[3-Chloro-2-[[(Z)-[2-methoxy-1-(2,4,6-trifluorophenyl)ethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoic acid methyl ester

[0650] To a solution of methyl (E)-2-[2-(bromomethyl)-3-chloro-phenyl]-3-methoxy-prop-2-enoate (5 g, 0.016 mol) in AcN (40 mL) was added cesium carbonate (10.19 g, 0.031 mol), and the mixture was stirred at RT for 10 min. 2-Methoxy-1-(2,4,6-trifluorophenyl)acetone oxime (3.49 g, 0.016 mol) in 10 ml of AcN was added to the reaction mixture, and the mixture was stirred at RT for an additional 16 h. The reaction mass was filtered and concentrated in vacuo, and purified by column chromatography (0%-20% EtOAc 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 (500 MHz, DMSO-d 6 ) δ = 7.69 (s, 1H), 7.47 (dd, J = 8.1, 1.3 Hz, 1H), 7.38 (t, J = 7.8 Hz, 1H), 7.28 (dd, J = 9.3, 7.9 Hz, 2H), 7.12 (dd, J = 7.6, 1.3 Hz, 1H), 5.13 (s, 2H), 4.32 (s, 2H), 3.80 (s, 3H), 3.57 (s, 3H), 3.14 (s, 3H).

[0651] Example 12: (E)-2-[3-chloro-2-[[(Z)-[1-(3-fluorophenyl)-2-methoxy-ethylidene]amino]oxymeth yl]phenyl]-3-methoxy-prop-2-enoic acid methyl ester (No. 14)

[0652]

[0653] Step 1: 1-(3-Fluorophenyl)-2-methoxy-ethanone

[0654] 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 min until the color of iodine disappeared. A solution of 1-bromo-3-fluoro-benzene (1 g, 5.7143 mmol) in 2 mL of THF was added dropwise, and the mixture was stirred at 50 °C for 1 h. 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 h. The reaction was quenched with saturated NH 4 Cl aqueous solution (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 Na 2 SO 4 and concentrated in vacuo to give 1-(3-fluorophenyl)-2-methoxy-ethanone. Yield: 1 g (crude). 1 1H NMR (500 MHz, DMSO-d 6 ) δ = 7.5–7.8 (m, 4H), 4.80 (s, 2H), 3.36 (s, 3H).

[0655] Step 2: 1(Z)-(3-fluorophenyl)-2-methoxy-ethanone oxime

[0656] To a solution of 1-(3-fluorophenyl)-2-methoxy-ethanone (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, 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 1H NMR (500 MHz, DMSO-d 6 ) δ = 11.76 (s, 1H), 7.54–7.16 (m, 4H), 4.57 (s, 2H), 3.3 (s, 3H).

[0657] Step 3: (E)-2-[3-chloro-2-[[(Z)-[1-(3-fluorophenyl)-2-methoxy-ethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoic acid methyl ester

[0658] Under RT, 1(Z)-(3-fluorophenyl)-2-methoxy-acetophenone oxime (1 g, 5.45 mmol) and cesium carbonate (3.5 g, 10.91 mmol) were stirred in 3 mL of AcN for 10 min. (E)-Methyl 2-[2-(bromomethyl)-3-chloro-phenyl]-3-methoxy-prop-2-enoate (1.725 g, 5.45 mmol) in 7 mL of AcN was added thereto, and the mixture was stirred for 16 h. The reaction was diluted with water (10 mL) and extracted with MTBE (10 mL × 2). The organic layer was washed with brine and dried over Na 2 SO 4 , concentrated in vacuo, and purified by column chromatography using 0%-20% EtOAc in heptane as the eluent to obtain the title compound. Yield: 1.7 g (75%). 1 HNMR (500 MHz, DMSO-d 6 ) δ = 7.72 (s, 1H), 7.48–7.34 (m, 5H), 7.27–7.21 (m, 1H), 7.12 (dd, J = 7.6, 1.3 Hz, 1H), 5.17 (s, 2H), 4.48 (s, 2H), 3.82 (s, 3H), 3.59 (s, 3H), 3.16 (s, 3H).

[0659] Example 13: (E)-2-[3-chloro-2-[[(Z)-[1-(4-fluorophenyl)-2-methoxy-ethylidene]amino]oxymeth yl]phenyl]-3-methoxy-prop-2-enoic acid methyl ester (No. 9)

[0660]

[0661] Step 1: 1-(4-fluorophenyl)-2-methoxy-acetophenone

[0662] A 1 M THF solution of 140 mL of phenylmagnesium bromide was cooled to 0 °C. 10 g of 2-methoxyacetonitrile (0.14 mol) was added, and the reaction was warmed to RT and stirred for 2 h. 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 Na 2 SO 4 , and concentrated in vacuo to obtain 1-(4-fluorophenyl)-2-methoxy-acetophenone. Yield (crude): 19 g, 81.5%. 1 H NMR (500 MHz, DMSO-d 6 ) δ = 7.93–7.79 (m, 1H), 7.75–7.61 (m, 1H), 7.44–7.31 (m, 2H), 4.66 (d, J = 2.9 Hz, 2H), 1.14 (dt, J = 10.9, 7.0 Hz, 3H).

[0663] Step 2: 1(Z)-(4-Fluorophenyl)-2-methoxy-acetophenone oxime

[0664] To a solution of 1-(4-fluorophenyl)-2-methoxy-acetophenone (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 NaOH solution (0.951 g, in 2 mL of water, 23.78 mmol), and the reaction was heated to 50 °C and stirred for 3 h. HPLC of the reaction mixture showed a ratio of Z-isomer to E-isomer of 4:1. Methanol was removed in vacuo, and the reaction was extracted with DCM (3 × 15 mL). The solvent was removed in vacuo, and the crude material was purified by column chromatography to give 1(Z)-(4-fluorophenyl)-2-methoxy-acetophenone oxime. Yield: 1.70 g, 80%. 1 H NMR (500 MHz, DMSO-d 6 ) δ = 11.58 (s, 1H), 7.67 (m, 2H), 7.22 (m, 2H), 4.6 (s, 2H), 3.2 (s, 3H).

[0665] Step 3: (E)-2-[3-Chloro-2-[[(Z)-[1-(4-fluorophenyl)-2-methoxy-ethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoic acid methyl ester

[0666] To a solution of 1(Z)-(4-fluorophenyl)-2-methoxy-acetophenone oxime (5 g, 27.29 mmol) in AcN (50 mL) was added cesium carbonate (17.79 g, 54.59 mmol), and the mixture was stirred for 10 min. To this was added (E)-2-[2-(bromomethyl)-3-chloro-phenyl]-3-methoxy-prop-2-enoic acid methyl ester (8.27 g, 27.29 mmol), and the mixture was stirred at RT for 16 h. 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 Na 2 SO 4 and concentrated in vacuo. The crude mixture was purified by column chromatography using (0%-20% EtOAc in heptane) to give the title compound. Yield: 5.2 g, 45.25%. LCMS (R t : 2.29 min, M+: 422); 1 H NMR (500 MHz, DMSO-d 6) 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, 1.4 Hz, 1H), 5.14 (s, 2H), 4.47 (s, 2H), 3.81 (s, 3H), 3.59 (s, 3H), 3.15 (s, 3H).

[0667] Example 14: (E)-2-[3-bromo-2-[[(Z)-[1-(4-fluorophenyl)-2-methoxy-ethylidene]amino]oxymeth yl]phenyl]-3-methoxy-prop-2-enoic acid methyl ester (No. 10)

[0668]

[0669] To a solution of 1(Z)-(4-fluorophenyl)-2-methoxy-ethanone oxime (5 g, 27.29 mmol) in AcN (50 mL) was added Cs 2 CO 3 (17.79 g, 54.59 mmol), and the mixture was stirred for 10 min. To this was added methyl (E)-2-[2-(bromomethyl)-3-bromophenyl]-3-methoxy-prop-2-enoate (9.88 g, 27.29 mmol), and the mixture was stirred at RT for 16 h. 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 Na 2 SO 4 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 min, M+1: 466). 1 1H NMR (500 MHz, DMSO-d 6 ) 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).

[0670] Example 15: (E)-2-[3-chloro-2-[[(Z)-[1-(2-fluorophenyl)-2-methoxy-ethylidene]amino]oxymeth yl]phenyl]-3-methoxy-prop-2-enoic acid methyl ester (No. 13)

[0671]

[0672] Step 1: 1-(2-Fluorophenyl)-2-methoxy-ethanone

[0673] Dissolve 1-bromo-2-fluorobenzene (10 g, 57.14 mmol) in 50 mL of THF and cool to 0 °C. Add dropwise a 2 M THF solution of isopropylmagnesium chloride (34.2 mL, 68.57 mmol), maintaining the temperature at 0 °C. Stir the mixture for an additional 1 h. Add dropwise over 15 min a THF solution (20 mL) of N,2-dimethoxy-N-methyl-acetamide (10 g, 68.57 mmol). Warm the reaction to 5 °C and stir for 2 h. Then quench the reaction mixture with 20% aqueous ammonium chloride solution (500 mL) and extract with MTBE (250 mL × 2). Combine the organic layers, dry over Na 2 SO 4 and concentrate to give 1-(2-fluorophenyl)-2-methoxy-ethanone as a colorless oil. Yield: 9.0 g (crude), 93.16%. 1 1H NMR (500 MHz, DMSO-d 6 ) δ = 7.93–7.79 (m, 1H), 7.75–7.61 (m, 1H), 7.44–7.31 (m, 2H), 4.66 (d, J = 2.9 Hz, 2H), 1.14 (dt, J = 10.9, 7.0 Hz, 3H).

[0674] Step 2: 1(Z)-(2-fluorophenyl)-2-methoxy-ethanone oxime

[0675] Under N 2 to a solution of 1-(2-fluorophenyl)-2-methoxy-ethanone (10 g, 59.47 mmol) in methanol (100 mL), add NaAc (9.75 g, 118.93 mmol) and hydroxylamine hydrochloride (8.26 g, 118.93 mmol). Stir the mixture at 50 °C for 4 h. HPLC shows a ratio of two isomers of 9:1. Concentrate the reaction mixture in vacuo to 50 mL, quench with water (200 mL) and extract with DCM (500 mL). Wash the organic layer with brine (500 mL), dry over Na 2 SO 4 and concentrate. Purify the crude mixture by column chromatography (20% EtOAc in heptane) to give 1(Z)-(2-fluorophenyl)-2-methoxy-ethanone oxime. Yield: 6.0 g, 55.08%. 1 1H NMR (500 MHz, DMSO-d 6 ) δ = 11.69 (s, 1H), 7.44 (dtd, J = 14.4, 7.5, 1.8 Hz, 2H), 7.28–7.15 (m, 2H), 4.52 (d, J = 1.0 Hz, 2H), 3.16 (s, 3H).

[0676] Step 3: (E)-Methyl 2-[3-chloro-2-[[(Z)-[1-(2-fluorophenyl)-2-methoxyethylidene]amino]oxymethyl]phenyl]-3-methoxyprop-2-enoate

[0677] At RT, 1(Z)-(2-fluorophenyl)-2-methoxyacetophenone oxime (4.0 g, 21.84 mmol) and cesium carbonate (14.23 g, 43.67 mmol) were stirred in 40 mL of AcN for 10 min. To this was added (E)-methyl 2-[2-(bromomethyl)-3-chlorophenyl]-3-methoxyprop-2-enoate (6.97 g, 21.84 mmol) in 10 mL of AcN, and the reaction was stirred for 16 h. The reaction was diluted with water (10 mL) and extracted with MTBE (50 mL × 2). The organic layer was washed with brine, dried over Na 2 SO 4 dried, 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 min; M+1, 421.85). 1 1H NMR (500 MHz, DMSO-d 6 ) δ = 7.70 (s, 1H), 7.50–7.40 (m, 2H), 7.42–7.31 (m, 2H), 7.28–7.19 (m, 2H), 7.12 (dd, J = 7.6, 1.3 Hz, 1H), 5.14 (s, 2H), 4.40 (d, J = 1.1 Hz, 2H), 3.80 (s, 3H), 3.58 (s, 3H), 3.11 (s, 3H).

[0678] Example 16: (E)-2-[3-chloro-2-[[(Z)-(2-methoxy-1-phenyl-ethylidene)amino]oxymethyl]benz yl]-3-methoxy-prop-2-enoic acid methyl ester (No. 11)

[0679]

[0680] Step 1: 2-Methoxy-1-phenyl-ethanone

[0681] A solution of 70 mL of phenylmagnesium bromide in THF (1 M in THF) was cooled to 0 °C. To this was added 5 g (70 mmol) of 2-methoxyacetonitrile, and the reaction was stirred at 10 °C for 1 h. 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 Na 2 SO 4Dry and concentrate in vacuo to obtain a light yellow liquid of 2-methoxy-1-phenyl-ethanone. Yield (crude): 10 g, 77%. 1 H NMR (500 MHz, DMSO-d 6 ) δ = 7.93 (dt, J = 8.2, 1.1 Hz, 2H), 7.65 (tdd, J = 7.8, 2.5, 1.2 Hz, 1H), 7.53 (tt, J = 7.7, 1.6 Hz, 2H), 4.79 (s, 2H), 3.38 (d, J = 1.5 Hz, 3H).

[0682] Step 2: 2-Methoxy-1(Z)-phenyl-ethanone oxime

[0683] Dissolve 10 g (66.59 mmol) of 2-methoxy-1-phenyl-ethanone in 80 mL of methanol. Add dropwise thereto an aqueous sodium hydroxide solution (5.32 g, in 20 mL of water, 133.18 mmol), and stir at RT for 10 min. Add 6.94 g (99.89 mmol) of hydroxylamine hydrochloride, and stir the reaction mixture at 60 °C for 2 h. Monitor the reaction by HPLC, which shows the consumption of the starting material and the formation of an 80:20 ratio of isomers. Remove methanol in vacuo, and extract the reaction mass with DCM (2 × 80 mL). Separate the organic layer, dry over Na 2 SO 4 Dry and concentrate in vacuo. Purify the crude material thus obtained by column chromatography to obtain 2-methoxy-1(Z)-phenyl-ethanone oxime (7.0 g, 63.6%). 1 H NMR (500 MHz, DMSO-d 6 ) 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).

[0684] Step 3: (E)-2-[3-Chloro-2-[[(Z)-(2-methoxy-1-phenyl-ethylidene)amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoic acid methyl ester

[0685] To a solution of 2-methoxy-1(Z)-phenyl-ethanone 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-chloro-phenyl]-3-methoxy-prop-2-enoate (12.34 g, 36.32 mmol). The reaction mixture was stirred at RT for 16 h. TLC (20% EtOAc in heptane) showed completion of the reaction. The reaction mixture was quenched with water (150 mL) and extracted with EtOAc (100 mL × 2). The organic phase was separated, washed with brine (100 mL), dried over Na 2 SO 4 , concentrated in vacuo, and purified by column chromatography to afford the title compound. Yield: 9.9 g (61.42%). LCMS (R t : 2.23 min; M+H, 404.3), 1 1H 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 = 0.9 Hz, 3H).

[0686] Example 17: (E)-2-[3-chloro-2-[[(Z)-[2-methoxy-1-(2-pyridyl)ethylidene]amino]oxymeth yl]phenyl]-3-methoxy-prop-2-enoic acid methyl ester (No. 129)

[0687]

[0688] Step 1:

[0689] To a solution of 2-iodopyridine (3.0 g, 14.6 mmol) in THF (30 mL) at 0 °C was added dropwise i-PrMgCl (2 M) (8.0 ml, 16.0 mmol), and the mixture was stirred at N 2 2 and 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 the mixture was stirred at 0 °C - 20 °C for 4 h. TLC (PE:EtOAc = 1:1) showed completion of the reaction. The reaction was quenched with aqueous NH 4 4Cl (100 ml) and extracted with EtOAc (50 ml × 3). The organic layer was washed with brine (50 ml × 2) and dried over Na 2 SO 4Drying. The residue was concentrated and purified by column (PE:EtOAc = 6:4) to give 2-methoxy-1-(2-pyridyl)ethanone as a yellow oil (2.1 g, 95.4%). 1 H NMR: (400 MHz, CDCl 3 ) δ = 8.58 - 8.66 (m, 1H) 8.05 (dt, J = 7.82, 0.97 Hz, 1H) 7.85 (td, J = 7.75, 1.75 Hz, 1H) 7.49 (ddd, J = 7.60, 4.78, 1.25 Hz, 1H) 5.04 (s, 2H) 3.54 (s, 3H).

[0690] Step 2:

[0691] At 25 °C, NaOAC (2.28 g, 27.8 mmol) and NH 2 OH·HCl (1.94 g, 27.8 mmol) were added to a solution of 2-methoxy-1-(2-pyridyl)ethanone (2.1 g, 13.9 mmol) in MeOH (25 mL). The reaction mixture was stirred at N 2 and 25 °C for 2 h. TLC (PE:EtOAc = 1:1) showed the reaction was complete. The reaction was quenched with aqueous NH 4 Cl solution (100 ml) and extracted with EtOAc (50 ml × 3). The organic layer was washed with brine (50 ml × 2) and dried over Na 2 SO 4 The residue was concentrated and purified by column (PE:EtOAc = 1:1) to give 2-methoxy-1-(2-pyridyl)ethanone oxime as a yellow oil (1 g, 43.3%). 1 H NMR: (400 MHz, MeOH-d 4 ) δ = 8.65 (dd, J = 4.88, 0.75 Hz, 1H) 7.81 (d, J = 8.00 Hz, 1H) 7.69 (td, J = 7.75, 1.75 Hz, 1H) 7.27 (s, 1H) 4.83 (s, 2H) 3.41 (s, 3H).

[0692] Step 3:

[0693] At 25 °C, methyl (E)-2-[2-(bromomethyl)-3-chloro-phenyl]-3-methoxy-prop-2-enoate (1.15 g, 3.6 mmol) and Cs 2 CO 3(1.96 g, 6.0 mmol). The reaction mixture was stirred at N 2 and 25 °C for 2 h. TLC (PE:EtOAc = 3:1) showed the reaction was complete. The reaction was quenched with aqueous NH 4 Cl (20 ml) and extracted with EtOAc (20 ml × 3). The organic layer was washed with brine (20 ml × 2) and dried over Na 2 SO 4 . The residue was concentrated and purified by preparative HPLC to give the title compound as a white solid (0.7 g, 57.8%). 1 1H NMR: (400 MHz, CDCl 3 ) δ = 8.63 (d, J = 4.38 Hz, 1H) 7.82 (d, J = 8.00 Hz, 1H) 7.68 (td, J = 7.75, 1.63 Hz, 1H) 7.59 (s, 1H) 7.40 (dd, J = 8.00, 1.13 Hz, 1H) 7.27 - 7.31 (m, 1H) 7.25 (ddd, J = 7.44, 5.00, 1.06 Hz, 1H) 7.09 (dd, J = 7.63, 1.00 Hz, 1H) 5.33 (s, 2H) 4.69 (s, 2H) 3.79 (s, 3H) 3.65 (s, 3H) 3.32 (s, 3H).

[0694] Example 18: (E)-2-[3-chloro-2-[[(Z)-[1-(3,5-difluoro-2-pyridyl)-2-methoxy-ethylidene]amin o]oxymethyl]phenyl]-3-methoxy-prop-2-enoic acid methyl ester (No. 130)

[0695]

[0696] Step 1:

[0697] Under N 2 , t-BuONO (8.7 g, 84.6 mmol) was added 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. The mixture was warmed to 20 °C and stirred at N 2 and 60 °C 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) and washed with aqueous Na 2 SO 3 (200 mL) and brine (100 ml), dried over Na 2 SO 4Dry and concentrate. The residue was purified by column (PE:EtOAc = 9:1) and concentrated to give 3,5-difluoro-2-iodopyridine as a white solid (4.4 g, 47.8%). 1 H NMR: (400 MHz, CDCl 3 ) δ = 8.24 (d, J = 2.38 Hz, 1H) 7.16 (ddd, J = 7.88, 6.94, 2.56 Hz, 1H).

[0698] Step 2:

[0699] At 0 °C, i-PrMgCl (2 M) (10.1 mL, 20.2 mmol) was added dropwise to a solution of 3,5-difluoro-2-iodopyridine (4.43 g, 18.4 mmol) in THF (40 mL), and the mixture was stirred at 0 °C for 30 min. Then, at 0 °C, N,2-dimethoxy-N-methyl-acetamide (3.18 g, 23.9 mmol) in THF (2 mL) was added to the solution, and the mixture was stirred at N

[0700] and 0 °C - 20 °C for 3 h. TLC (PE:EtOAc = 3:1) showed the reaction was complete. The reaction mixture was quenched with aqueous NH 2 Cl (100 mL), extracted with EtOAc (50 mL × 3) and washed with brine (100 mL). The organic layer was dried over Na 4 SO 2 and concentrated. The residue was purified by column (PE:EtOAc = 85:15) to give 1-(3,5-difluoro-2-pyridyl)-2-methoxy-ethanone as a yellow solid (2 g, 58.6%). 4 H NMR: (400 MHz, CDCl 1 ) δ = 8.37 (d, J = 2.25 Hz, 1H) 7.33 (ddd, J = 10.13, 8.07, 2.31 Hz, 1H) 4.88 (s, 2H) 3.53 (s, 3H). 3 ) δ = 8.37 (d, J = 2.25 Hz, 1H) 7.33 (ddd, J = 10.13, 8.07, 2.31 Hz, 1H) 4.88 (s, 2H) 3.53 (s, 3H).

[0701] Step 3:

[0702] At N 2 and 20 °C, NaOAc (1.75 g, 21.4 mmol) was added to a solution of 1-(3,5-difluoro-2-pyridyl)-2-methoxy-ethanone (2.0 g, 10.7 mmol) and NH 2 OH.HCl (1.5 g, 21.4 mmol) in MeOH (20 mL). The mixture was stirred at N 2Stir at 30 °C for 2 h. TLC (PE:EtOAc = 3:1) showed the reaction was complete. Quench the mixture with H 2 O (100 mL) and extract with EtOAc (50 mL × 3). Wash the organic layer with brine (50 mL) and dry over Na 2 SO 4 . Concentrate the residue and purify by column (PE:EtOAc = 82:18) to give 1-(3,5-difluoro-2-pyridyl)-2-methoxy-ethanone oxime as a yellow solid (1.92 g, 89%). 1 H NMR (400 MHz, CDCl 3 ) δ = 8.42 (br d, J = 2.38 Hz, 1H) 7.28 - 7.32 (m, 1H) 4.76 (s, 2H) 3.36 (s, 3H).

[0703] Step 4:

[0704] At N 2 and 20 °C, add methyl (E)-2-[2-(bromomethyl)-3-chloro-phenyl]-3-methoxy-prop-2-enoate (0.79 g, 2.48 mmol) and Cs 2 CO 3 (1.61 g, 4.95 mmol) to a solution of 1-(3,5-difluoro-2-pyridyl)-2-methoxy-ethanone oxime (0.5 g, 2.48 mmol) in MeCN (10 mL). Stir the mixture at N 2 and 20 °C for 16 h. TLC (PE:EtOAc = 3:1) and LCMS showed the reaction was complete. Quench the mixture with H 2 O (50 mL) and extract with EtOAc (50 mL × 3). Wash the organic layer with brine (50 mL) and dry over Na 2 SO 4 . Concentrate the residue and purify by column (PE:EtOAc = 85:15) to give the title compound as a yellow solid (0.5 g, 46.2%). 1 H NMR (400 MHz, MeOH-d) δ = 8.39 (d, J = 2.38 Hz, 1H) 7.67 (s, 1H) 7.60 - 7.66 (m, 1H) 7.37 - 7.43 (m, 1H) 7.31 (t, J = 7.82 Hz, 1H) 7.08 (dd, J = 7.57, 1.19 Hz, 1H) 5.26 (s, 2H) 4.55 (s, 2H) 3.81 (s, 3H) 3.65 (s, 3H) 3.22 (s, 3H).

[0705] Examples 19 and 20: (E)-2-[3-chloro-2-[[(Z)-[1-(5-fluoro-2-pyridyl)-2-methoxy-ethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoic acid methyl ester (No. 131) and (E)-2-[3-chloro-2-[[(E)-[1-(5- fluoro-2-pyridyl)-2-methoxy-ethylidene]amino]oxymethyl]phenyl]-3-methoxy-prop-2-enoic acid methyl ester (No. 132)

[0706]

[0707] Step 1:

[0708] To a solution of 5-fluoropyridin-2-amine (2 g, 17.8 mmol) in CH 2 I 2 (50 mL) was added CuI (3.7 g, 19.6 mmol), t-BuNO 2 (2 g, 19.6 mmol) and I 2 (4.9 g, 19.6 mmol). The reaction was stirred at N 2 and 85 °C for 20 min. TLC (PE:EtOAc = 3:1) showed completion of the reaction. The two batches were combined. The reaction mixture was concentrated and purified by column (PE:EtOAc = 9:1) to give 5-fluoro-2-iodopyridine as a yellow solid (1.8 g, 45%). 1 H NMR: (400 MHz, MEOH-d4) δ = 8.31 (d, J = 3.13 Hz, 1H), 7.85 (dd, J = 8.69, 4.31 Hz, 1H), 7.35 (td, J = 8.57, 3.13 Hz, 1H).

[0709] Step 2:

[0710] To a solution of 5-fluoro-2-iodopyridine (3.6 g, 16.1 mmol) in THF (40 mL) at 0 °C was added i-PrMgCl (2 M) (8.5 mL, 17.0 mmol), and the mixture was stirred at N 2 and 0 °C for 1 h. Then, at 0 °C, N,2-dimethoxy-N-methyl-acetamide (2.3 g, 17.7 mmol) in THF (10 mL) was added to the solution. The reaction was stirred at N 2 and 0 °C for 1 h. TLC (PE:EtOAc = 5:1) showed completion of the reaction. The reaction mixture was quenched with aqueous NH 4 Cl (50 mL), extracted with EtOAc (30 mL × 3), dried over Na 2 SO 4 and concentrated, and purified by column (PE:EtOAc = 6:1) to give 1-(5-fluoro-2-pyridyl)-2-methoxy-ethanone as a yellow solid (1.5 g, 55%). 11H NMR (400 MHz, MeOH-d4) δ = 8.55 (d, J = 2.75 Hz, 1H), 8.12 (dd, J = 8.76, 4.63 Hz, 1H), 7.76 (td, J = 8.57, 2.75 Hz, 1H), 5.01 (s, 2H), 3.50 (s, 3H).

[0711] Step 3:

[0712] To a solution of 1-(5-fluoro-2-pyridyl)-2-methoxy-ethanone (1.5 g, 8.87 mmol) in MeOH (30 mL) was added NaOAc (1.45 g, 17.7 mmol) and NH 2 OH·HCl (1.22 g, 17.7 mmol). The reaction was stirred at N 2 and 20 °C for 1 h. TLC (PE:EtOAc = 3:1) showed the reaction was complete. The reaction was poured into water (50 mL) and extracted with EtOAc (30 mL × 3), dried over Na 2 SO 4 and 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 (

[0713] H NMR showed Z:E = 4:1) (0.9 g, 55%). 1 1H NMR: (400 MHz, MeOH-d4) δ = 8.44 (d, J = 2.88 Hz, 1H), 7.90 (dd, J = 8.88, 4.50 Hz, 1H), 7.59 (td, J = 8.63, 3.00 Hz, 1H), 4.73 (s, 2H), 3.34 (s, 3H). 1

[0714] Step 4:

[0715] At 20 °C, 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-chloro-phenyl]-3-methoxy-prop-2-enoate (1.7 g, 5.29 mmol) and Cs 2 CO 3 (3.45 g, 10.61 mmol). The reaction mixture was stirred at N(3.45 g, 10.61 mmol). The reaction mixture was stirred at N 2 and 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 (NH4 HCO 3 ) Purification gave methyl (E)-2-[3-chloro-2-[[(Z)-[1-(5-fluoro-2-pyridyl)-2-methoxyethylidene]amino]oxymethyl]phenyl]-3-methoxyprop-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-methoxyprop-2-enoate (250 mg, 11.2%) as a yellow solid.

[0716] 1 H NMR: For compound 131 (400 MHz, CDCl 3 ): δ = 8.46 (d, J = 2.75 Hz, 1H), 7.85 (dd, J = 8.82, 4.57 Hz, 1H), 7.59 (s, 1H), 7.35 - 7.43 (m, 2H), 7.28 - 7.32 (m, 1H), 7.09 (dd, J = 7.63, 1.13 Hz, 1H), 5.32 (s, 2H), 4.65 (s, 2H), 3.80 (s, 3H), 3.65 (s, 3H), 3.31 (s, 3H).

[0717] 1 H NMR: For compound No. 132 (400 MHz, MeOH-d4): δ = 8.50 (d, J = 2.88 Hz, 1H), 7.97 (dd, J = 8.82, 4.69 Hz, 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, 1.25 Hz, 1H), 5.21 (s, 2H), 4.43 (s, 2H), 3.76 (s, 3H), 3.58 (s, 3H), 3.26 (s, 3H).

[0718] Intermediates: (E)-2-[2-(bromomethyl)-3-chloro-phenyl]-3-methoxy-prop-2-enoic acid methyl ester and (E)-2-[3- bromo-2-(bromomethyl)phenyl]-3-methoxy-prop-2-enoic acid methyl ester

[0719]

[0720] Step 1: Methyl 2-(3-halo-2-methylphenyl)-2-oxoacetate

[0721] At nitrogen and 0 °C, isopropylmagnesium chloride (2 M in THF) (16.6 mL, 33.34 mmol) was added dropwise to a solution of 1-chloro-3-iodo-2-methylbenzene (9.0 g, 30.31 mmol) in THF (90 mL), and the mixture was stirred for 30 min. The reaction was warmed to 20 °C and CuI (5.78 g, 30.31 mmol) was added in portions. The reaction mixture was stirred at RT for 1 h. The resulting reaction mixture was transferred to a solution of methyl 2-chloro-2-oxo-acetate (4.45 g, 36.37 mol) in THF (180 mL) maintained at -25 °C under nitrogen. The reaction mass was gradually warmed to 25 °C and stirred for 15 h. The reaction was cooled to 0 °C, quenched with saturated aqueous ammonium chloride (100 mL), and extracted with MTBE (500 mL × 2). The combined organic layers were washed with brine (500 mL), dried over Na 2 SO 4 dried, filtered, concentrated in vacuo and purified by column chromatography (0%-10% EtOAc in heptane) to give methyl 2-(3-chloro-2-methyl-phenyl)-2-oxo-acetate as a yellow oil. Yield: 5.0 g, 66%. 1 H NMR (500 MHz, DMSO-d 6 ) δ = 7.78 (m, 1H), 7.70 (m, 1H), 7.48–7.41 (m, 1H), 3.91 (s, 3H), 2.47 (s, 3H).

[0722] Methyl 2-(3-bromo-2-methyl-phenyl)-2-oxo-acetate was synthesized in a similar manner in 64% yield. 1 H NMR (500 MHz, DMSO-d 6 ) δ = 7.94 (dd, J = 8.0, 1.3 Hz, 1H), 7.73 (dd, J = 7.8, 1.3 Hz, 1H), 7.35 (t, J = 7.9 Hz, 1H), 3.91 (s, 3H), 2.49 (s, 3H).

[0723] Step 2: (E)-Methyl 2-(3-halo-2-methyl-phenyl)-3-methoxy-prop-2-enoate

[0724] In N 2At 0 °C, a 1 M THF solution of lithium bis(trimethylsilyl)amide (43 mL) was added dropwise to a solution of methoxymethyl(triphenyl)phosphonium chloride (14.6 g, 42.79 mmol) in THF (150 mL). 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 completion of the reaction. 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 phases were washed with brine (500 mL), dried over Na 2 SO 4 , 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 (500 MHz, DMSO-d 6 ) δ = 7.68 (s, 1H), 7.36 (m, 1H), 7.18 (t, J = 7.8 Hz, 1H), 7.03 (m, 1H), 3.84 (s, 3H), 3.63 (s, 3H), 2.12 (s, 3H).

[0725] Methyl (E)-2-(3-bromo-2-methyl-phenyl)-3-methoxy-prop-2-enoate was synthesized in a similar manner with a yield of 58.6%. 1 H NMR (500 MHz, DMSO-d 6 ) 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).

[0726] Step 3: Methyl (E)-2-[3-halo-2-(bromomethyl)phenyl]-3-methoxy-prop-2-enoate

[0727] In N 2At 80 °C, azobisisobutyronitrile (0.5 g, 3.15 mmol) was added to a solution of methyl (E)-2-(3-chloro-2-methylphenyl)-3-methoxyprop-2-enoate (9 g, 37.49 mmol) in cyclohexane (180 mL), and then NBS (16.8 g, 94.69 mmol) was added. The mixture was stirred at 80 °C for 16 h. TLC (20% EtOAc in heptane) showed completion of the reaction. The reaction mixture was quenched with water (500 mL) and extracted with MTBE (500 mL × 3). The combined organic phases were washed with brine (500 mL), dried over Na 2 SO 4 , 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-methoxyprop-2-enoate as a yellow solid. Yield: 7.5 g, 63%. 1 H NMR (500 MHz, DMSO-d 6 ) δ = 7.76 (s, 1H), 7.47 (m, 1H), 7.36 (t, J = 7.9 Hz, 1H), 7.09 (m, 1H), 4.52 (s, 2H), 3.84 (s, 3H), 3.62 (s, 3H).

[0728] Methyl (E)-2-[3-bromo-2-(bromomethyl)phenyl]-3-methoxyprop-2-enoate was synthesized in a similar manner with a yield of 65.4%. 1 H NMR (500 MHz, DMSO-d 6 ) δ = 7.75 (s, 1H), 7.63 (dd, J = 8.0, 1.3 Hz, 1H), 7.27 (t, J = 7.8 Hz, 1H), 7.13 (dd, J = 7.6, 1.3 Hz, 1H), 4.60 (s, 2H), 3.84 (s, 4H), 3.62 (s, 4H).

[0729] Table L: LCMS method

[0730]

[0731]

[0732]

[0733] The LCMS method used in Table S is shown in the LCMS column.

[0734] Table S:

[0735]

[0736]

[0737]

[0738]

[0739]

[0740]

[0741]

[0742]

[0743]

[0744]

[0745]

[0746]

[0747]

[0748]

[0749]

[0750]

[0751]

[0752]

[0753]

[0754]

[0755]

[0756]

[0757] Biological research greenhouse and detached leaf test

[0758] Dissolve the compound in a mixture of acetone and / or dimethyl sulfoxide and the ethoxylated alkylphenol-based wetting agent / emulsifier Wettol in a solvent-emulsifier ratio (by volume) of 99:1 to obtain a total volume of 5 ml. Subsequently, add water to a total volume of 100 ml. Then dilute this stock solution with the solvent-emulsifier-water mixture to the final concentrations given in the table below.

[0759] Use Example 1. Protective control of soybean rust on soybeans caused by Phakopsora pachyrhizi (PHAKPA P2)

[0760] Spray the leaves of potted soybean seedlings with the previously described spray solution containing the active ingredient or its mixture at the concentrations described below until run-off. Allow the plants to air dry. Grow the test plants in a greenhouse at 23 °C - 27 °C and a relative humidity between 60% and 80% for 2 days. Then inoculate the plants with spores of Phakopsora pachyrhizi. The strain used contains the amino acid substitution F129L in the mitochondrial cytochrome b protein that confers resistance to Qo inhibitors. To ensure successful artificial inoculation, transfer the plants to a humid chamber at a relative humidity of approximately 95% and 20 °C to 24 °C for 24 h. Grow the test plants in a greenhouse at 23 °C to 27 °C and a relative humidity between 60% and 80% for up to 14 days. The extent of fungal attack on the leaves is visually assessed as the percentage of diseased leaf area, and the disease level of the untreated control is typically higher than 85%.

[0761] Use Example 2. Protective control of soybean rust on soybeans caused by Phakopsora pachyrhizi (PHAKPA P6)

[0762] Spray the leaves of potted soybean seedlings with the previously described spray solution containing the active ingredient at the concentrations described below until run-off. Allow the plants to air dry. Grow the test plants in a greenhouse at 23 °C - 27 °C and a relative humidity between 60% and 80% for six days. Then inoculate the plants with spores of Phakopsora pachyrhizi. The strain used contains the amino acid substitution F129L in the mitochondrial cytochrome b protein that confers resistance to Qo inhibitors. To ensure successful artificial inoculation, transfer the plants to a humid chamber at a relative humidity of approximately 95% and 23 °C to 27 °C for 24 h. Grow the test plants in a greenhouse at 23 °C to 27 °C and a relative humidity between 60% and 80% for up to 14 days. The extent of fungal attack on the leaves is visually assessed as the percentage of diseased leaf area, and the disease level of the untreated control is typically higher than 85%.

[0763] Use Example 3. Therapeutic control of brown rust on wheat caused by Puccinia recondita (PUCCRT K4)

[0764] Sow the spores of *Puccinia recondita* on the first two developed leaves of potted wheat seedlings. To ensure the success of artificial inoculation, transfer the plants to a humid chamber without light, with a relative humidity of 95% to 99% and a temperature of 20°C to 24°C, for 24 h. For the next 3 days, cultivate the plants in a greenhouse at 20°C to 24°C with a relative humidity between 65% and 70%. Then spray the plants with the previously described spray solution containing the active ingredient or its mixture at the concentration described below until runoff. Allow the plants to air dry. Then cultivate the test plants in a greenhouse at 20°C to 24°C with a relative humidity between 65% and 70% for 5 to 7 days. The degree of fungal attack on the leaves is visually evaluated as the percentage of the diseased leaf area, and the disease level of the untreated control is usually between 80% and 100%.

[0765] Use Example 4. Preventive control of brown rust on wheat caused by Puccinia recondita (PUCCRT P7)

[0766] Spray the first two developed leaves of potted wheat seedlings with the previously described spray solution containing the active ingredient or its mixture at the concentration described below until runoff. Seven days later, sow the spores of *Puccinia recondita* on the plants. To ensure the success of artificial inoculation, transfer the plants to a humid chamber without light, with a relative humidity of 95% to 99% and a temperature of 20°C to 24°C, for 24 h. Then cultivate the test plants in a greenhouse at 20°C to 24°C with a relative humidity between 65% and 70% for 9 to 11 days. The degree of fungal attack on the leaves is visually evaluated as the percentage of the diseased leaf area, and the disease level of the untreated control is usually between 80% and 100%.

[0767] Table 1: Use Examples 1 and 2

[0768]

[0769]

[0770]

[0771]

[0772]

[0773]

[0774]

[0775]

[0776]

[0777]

[0778]

[0779]

[0780]

[0781]

[0782]

[0783] Table 2: Use Examples 3 and 4

[0784]

[0785]

[0786]

[0787]

[0788]

[0789]

[0790]

[0791]

[0792]

[0793]

[0794]

[0795]

[0796]

[0797]

[0798] Comparative test

[0799] Microtest

[0800] The active compound was formulated separately as a stock solution at a concentration of 10,000 ppm in dimethyl sulfoxide. The stock solutions were mixed proportionally, pipetted onto a microtiter plate (MTP), and diluted with water to the specified concentration. Then, a spore suspension of one of the following fungal phytopathogens in an aqueous solution of malt was added for the corresponding use example:

[0801] Use example 5: Alternaria solani (ALTESO)

[0802] Use example 6: Botrytis cinerea (BOTRCI)

[0803] Use example 7: Cercospora sojina (CERCSO)

[0804] Use example 8: Colletotrichum orbiculare (COLLLA)

[0805] Use example 9: Leptosphaeria nodorum (LEPTNO)

[0806] Use example 10: Pyrenophora teres (PYRNTE), which contains the amino acid substitution F129L in the mitochondrial cytochrome b protein that confers resistance to Qo inhibitors

[0807] Use example 11: Sclerotinia sclerotiorum (SCLESC), using ultrasonic solutes from the filter membrane

[0808] These plates were placed in a water vapor-saturated chamber at a temperature of 18 °C. Using an absorption photometer, the MTP was measured at 405 nm 7 days after inoculation.

[0809] The measured parameters were compared with the growth rate (100%) of the control variant without the active compound and the blank value without fungi to determine the relative growth rate (%) of the pathogen in the corresponding active compound.

[0810] Table 3: Comparison 1 regarding use examples 6, 9, and 11

[0811]

[0812] The results in Table 3 show that, compared with the compound with a methyl group at the same position, the specific alkyl ether group linked to the oxime group improves the fungicidal activity against various phytopathogenic fungi.

[0813] Table 4: Comparison 2 regarding use examples 6 and 7

[0814]

[0815] Table 5: Comparison 3 Regarding the Use of Example 8

[0816]

[0817] Table 6: Comparison 4 Regarding the Use of Examples 5 and 11

[0818]

[0819] Table 7: Comparison 5 Regarding the Use of Examples 6, 9, and 11

[0820]

[0821] Table 8: Comparison 6 Regarding the Use of Example 7

[0822]

[0823] Table 9: Comparison 7 Regarding the Use of Examples 7, 8, and 9

[0824]

[0825] Table 10: Comparison 8 Regarding the Use of Example 9

[0826]

[0827]

[0828] Table 11: Comparison 9 Regarding the Use of Example 10

[0829]

[0830] Table 12: Comparison 10 Regarding the Use of Examples 7 and 10

[0831]

[0832] Table 13: Comparison 11 Regarding the Use of Examples 8 and 10

[0833]

[0834] The results in Tables 4 to 13 show that, compared to the compounds with a methyl group at the same position, the specific halogen substituent R attached to the benzene ring 3 has improved fungicidal activity against various phytopathogenic fungi, including those phytopathogenic fungi that contain the amino acid substitution F129L in the mitochondrial cytochrome b protein that confers resistance to Qo inhibitors.

Claims

1. A compound of formula I wherein R 1 selected from O and NH; R 2 Selected from CH and N; R 3 selected from Cl, F, and Br; R is selected from 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 a 5- or 6-membered heteroaryl, wherein said heteroaryl contains 1, 2 or 3 heteroatoms selected from N, O and S in addition to carbon atoms, and wherein Z is unsubstituted or bears 1, 2, 3 or up to the maximum number of identical or different groups R a : R a Selected from 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 -cycloalkyl, phenyl and 5- or 6-membered heteroaryl; wherein said heteroaryl contains 1, 2 or 3 heteroatoms selected from N, O and S in addition to carbon atoms, wherein the phenyl and heteroaryl are bonded directly or via an oxygen atom or via a C 1 -C 2 -alkylene linker, and wherein R a is unsubstituted or bears 1, 2, 3 or up to the maximum number of identical or different radicals R b : R b Selected from halogen, CN, hydroxy, NO 2 , C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, R A and R B are each independently selected from hydrogen, C 1 -C 4 -alkyl, and C 1 -C 4 -haloalkyl; and its stereoisomers and tautomeric forms, as well as its N-oxides and agriculturally acceptable salts.

2. The compound according to claim 1, wherein in formula I, R 1 is selected from O and NH; and R 2 is selected from CH and N, provided that when R 1 is NH, R 2 is N.

3. The compound according to claim 1 or claim 2, wherein in formula I, m is 0.

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

5. The compound according to any one of claims 1 to 4, wherein in formula I, R is selected from C 1 -C 3 -alkyl.

6. A compound according to any one of claims 1 to 5, wherein in formula I, Z is phenyl and wherein Z is unsubstituted or bears 1, 2 or 3 identical or different groups R a .

7. A compound according to any one of claims 1 to 6, wherein in formula I, R a is selected from 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 -cycloalkyl, phenyl and 5- or 6-membered heteroaryl, wherein said heteroaryl contains 1, 2 or 3 heteroatoms selected from N, O and S in addition to carbon atoms, wherein said phenyl and heteroaryl are bonded directly or via an oxygen atom or via a C 1 -C 2 -alkylene linker, and wherein R a is unsubstituted or bears 1, 2, 3 or up to the maximum number of identical or different groups R b : R b Selected from 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 and R B are each independently selected from the group consisting of: hydrogen, C 1 -C 3 -alkyl, and C 1 -C 3 -haloalkyl.

8. The compound according to claim 7, wherein in formula I, R a is selected from halogen and C 1 -C 4 -alkyl, wherein R a is unsubstituted or bears 1, 2, 3 or up to the maximum number of identical or different groups R b , wherein R b is selected from halogen.

9. The compound according to claim 8, wherein in formula I, R a is selected from halogen and C 1 -C 4 -alkyl.

10. An agrochemical composition comprising an adjuvant and at least one compound of formula I or its stereoisomers or agriculturally acceptable salts or tautomeric forms or N-oxides as described in any one of claims 1 to 8.

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

12. A method for combating phytopathogenic fungi, the method comprising: therapeutically and / or prophylactically treating a plant or plant propagation material of said plant at risk of being infested with said phytopathogenic fungi with at least one compound of formula I as described in any one of claims 1 to 8 or an agrochemical composition as described in claim 9, and / or applying to said phytopathogenic fungi at least one compound of formula I as described in any one of claims 1 to 8 or an agrochemical composition as described in claim 9.

13. The method according to claim 11, which is used for combating phytopathogenic fungi containing the amino acid substitution F129L in mitochondrial cytochrome b protein that confers resistance to Qo inhibitors, the method comprising: therapeutically and / or prophylactically treating a plant or plant propagation material of said plant at risk of being infested with said phytopathogenic fungi with an effective amount of at least one compound of formula I as described in any one of claims 1 to 8 or an agrochemical composition as described in claim 9, and / or applying to said phytopathogenic fungi an effective amount of at least one compound of formula I as described in any one of claims 1 to 8 or an agrochemical composition as described in claim 9.

14. The use according to claim 10 or the method according to claim 11 or 12, wherein these phytopathogenic fungi contain the amino acid substitution F129L in mitochondrial cytochrome b protein that confers resistance to Qo inhibitors.

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

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