Use of strobilurin-type compounds for controlling phytopathogenic fungi containing an F129L amino acid substitution in the mitochondrial cytochrome B protein that confers resistance to QO inhibitors (IV)

Description

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

[0002] "Qo inhibitor," as used herein, includes any substance that is capable of diminishing and / or inhibiting respiration by binding to a ubihydroquinone oxidation center of a cytochrome bc 1 complex in mitochondria. The oxidation center is typically located on the outer side of the inner mitochrondrial membrane. Many of these compounds are also known as strobilurin-type or strobilurin analogue compounds.

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

[0004] Qol fungicides, often referred to as strobilurin-type fungicides (Sauter 2007: Chapter 13.2. Strobilurins and other complex Ill inhibitors. In: Krämer, W.; Schirmer, U. (Ed.) - Modern Crop Protection Compounds. Volume 2. Wiley-VCH Verlag 457-495), are conventionally used to control a number of fungal pathogens in crops. Qo inhibitors typically work by inhibiting respiration by binding to a ubihydroquinone oxidation center of a cytochrome bc 1 complex (electron transport complex III) in mitochondria. Said oxidation center is located on the outer side of the inner mitochrondrial membrane. A prime example of the use of Qols includes the use of, for example, strobilurins on wheat for the control of Septoria tritici (also known as Mycosphaerella graminicola), which is the cause of wheat leaf blotch. Unfortunately, widespread use of such Qols has resulted in the selection of mutant pathogens which are resistant to such Qols (Gisi et al., Pest Manag Sci 56, 833-841, (2000)). Resistance to Qols has been detected in several phytopathogenic fungi such as Blumeria graminis, Mycosphaerella fijiensis, Pseudoperonspora cubensis or Venturia inaequalis. The major part of resistance to Qols in agricultural uses has been attributed to pathogens containing a single amino acid residue substitution G143A in the cytochrome b gene for their cytochrome bc 1 complex, the target protein of Qols which have been found to be controlled by specific Qols (WO 2013 / 092224). Despite several commercial Qol fungicides have also been widely used in soybean rust control, the single amino acid residue substitution G143A in the cytochrome b protein conferring resistance to Qol fungicides was not observed.

[0005] Instead soybean rust acquired a different genetic mutation in the cytochrome b gene causing a single amino acid substitution F129L which also confers resistance against Qol fungicides. The efficacy of Qol fungicides used against soybean rust conventionally, i.e. pyraclostrobin, azoxystrobin, picoxystrobin, orysastrobin, dimoxystrobin and metominostrobin, has decreased to a level with practical problems for agricultural practice (e.g. Klosowski et al (2016) Pest Manag Sci 72, 1211-1215).

[0006] Although it seems that trifloxystrobin was less affected by the F129L amino acid substitution to the same degree as other Qol fungicides such as azoxystrobin and pyraclostrobin, trifloxystrobin was never as efficacious on a fungal population bearing the F129L Qol resistance mutation as on a sensitive population (Crop Protection 27, (2008) 427-435).

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

[0008] Thus, new methods are desirable for controlling pathogen induced diseases in crops comprising plants subjected to pathogens containing a F129L amino acid substitution in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors. Furthermore, in many cases, in particular at low application rates, the fungicidal activity of the known fungicidal strobilurin compounds is unsatisfactory, especially in case that a high proportion of the fungal pathogens contain a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors. Besides there is an ongoing need for new fungicidally active compounds which are more effective, less toxic and / or environmentally safer. Based on this, it was also an object of the present invention to provide compounds having improved activity and / or a broader activity spectrum against phytopathogenic fungi and / or even further reduced toxicity against non target organisms such as vertebrates and invertebrates.

[0009] The strobilurin-analogue compounds used to combat phytopathogenic fungi containing a F129L amino acid substitution in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors according to the present invention differ from trifloxystrobin inter alia by containing a specific group attached to the central phenyl ring in ortho position to the side chain defined herein as R 3< .

[0010] Any uses and methods according to the invention referred to in any part of the following text are to be understood as being of a non-therapeutic nature.

[0011] Accordingly, the present invention relates to the use of compounds of formula I wherein R 1< is selected from O and NH; R 2< is selected from CH and N, provided that R 2< is N in case R 1< is NH; R 3< is selected from halogen, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 1 -C 2 -monohaloalkyl, C 1 -C 2 -dihaloalkyl, monohalo-ethenyl, dihalo-ethenyl, C 3 -C 6 -cycloalkyl and -O-C 1 -C 4 -alkyl; R 4< is selected from C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, -C(=O)-C 1 -C 2 -alkyl, C 1 -C 4 -haloalkyl, C 2 -C 4 -haloalkenyl, -(C 1 -C 2 -alkyl)-O-(C 1 -C 2 -alkyl) and -CH 2 -cyclopropyl; R a< is selected from halogen, CN, -NR 5< R 6< , 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, 3- to 6-membered heterocycloalkyl, 3- to 6-membered heterocycloalkenyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl, heterocycloalkenyl and heteroaryl besides carbon atoms contain 1, 2 or 3 heteroatoms selected from N, O and S, wherein said phenyl, heterocycloalkyl, heterocycloalkenyl and heteroaryl are bound directly or via an oxygen atom or via a C 1 -C 2 -alkylene linker, and wherein the aliphatic and cyclic moieties of R a< are unsubstituted or carry 1, 2, 3, 4 or up to the maximum number of identical or different groups R b< : 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; R 5< , R 6< are independently of each other selected from the group consisting of H, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl and C 2 -C 4 -alkynyl; nis an integer selected from 0, 1, 2, 3, 4 and 5; and in form or stereoisomers and tautomers thereof, and the N-oxides and the agriculturally acceptable salts thereof, for combating phytopathogenic fungi containing an amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors.

[0012] The mutation F129L in the cytochrome b (cytb, also referred to as cob) gene shall mean any substitution of nucleotides of codon 129 encoding "F" (phenylalanine; e.g. TTT or TTC) that leads to a codon encoding "L" (leucine; e.g. TTA, TTG, TTG, CTT, CTC, CTA or CTG), for example the substitution of the first nucleotide of codon 129 'T' to 'C' (TTT to CTT), in the cytochrome b gene resulting in a single amino acid substitution in the position 129 from F (phenylalanine) to L (leucine) (F129L) in the cytochrome b protein (Cytb). In the present invention, the mutation F129L in the cytochrome b gene shall be understood to be a single amino acid substitution in the position 129 from F (phenylalanine) to L (leucine) (F129L) in the cytochrome b protein.

[0013] Many other phytopathogenic fungi acquired the F129L mutation in the cytochrome b gene conferring resistance to Qo inhibitors, such as rusts, in particular soybean rust (Phakopsora pachyrhizi and Phakopsora meibromiae) as well as fungi from the genera Alternaria, Pyrenophora and Rhizoctonia.

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

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

[0016] According to another embodiment, the method for combating phytopathogenic fungi, comprises: a) identifying the phytopathogenic fungi containing an amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors, or the materials, plants, the soil or seeds that are at risk of being diseased from phytopathogenic fungi as defined herein, and b) treating said fungi or the materials, plants, the soil or plant propagation material with an effective amount of at least one compound of formula I, or a composition comprising it thereof.

[0017] The term "phytopathogenic fungi an amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors" is to be understood that at least 10% of the fungal isolates to be controlled contain a such F129L substitution in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors, preferably at least 30%, more preferably at least 50%, even more preferably at at least 75% of the fungi, most preferably between 90 and 100%; in particular between 95 and 100%.

[0018] Although the present invention will be described with respect to particular embodiments, this description is not to be construed in a limiting sense. The present invention is limited by the claims.

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

[0020] Unless otherwise indicated, 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 the appended claims. These definitions should not be interpreted in the literal sense as they are not intended to be general definitions and are relevant only for this application.

[0021] The term "compounds I" refers to compounds of formula I. Likewise, this terminology applies to all sub-formulae, e. g. "compounds I.2" refers to compounds of formula I.2 or "compounds V" refers to compounds of formula V, etc..

[0022] The term "independently" when used in the context of selection of substituents for a variable, it means that where more than one substituent is selected from a number of possible substituents, those substituents may be the same or different.

[0023] The organic moieties or groups mentioned in the above definitions of the variables are collective terms for individual listings of the individual group members. The term "C v -C w " indicates the number of carbon atom possible in each case.

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

[0025] The term "C 1 -C 4 -alkyl" refers to a straight-chained or branched saturated hydrocarbon group having 1 to 4 carbon atoms, for example, methyl (CH 3 ), ethyl (C 2 H 5 ), propyl, 1-methylethyl (isopropyl), butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl.

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

[0027] The term "C 2 -C 4 -alkynyl" refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 4 carbon atoms and containing at least one triple bond such as ethynyl, prop-1-ynyl, prop-2-ynyl, but-1-ynyl, but-2-ynyl, but-3-ynyl, 1-methyl-prop-2-ynyl.

[0028] The term "C 1 -C 4 -haloalkyl" refers to a straight-chained or branched alkyl group having 1 to 4 carbon atoms wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example 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.

[0029] The term "monohalo-ethenyl" refers to an ethenyl wherein one hydrogen atom is replaced by a halogen atom, e.g. 1-chloroethenyl, 1-bromoethenyl, 1-fluoroethenyl, 2-fluoroethenyl. Likewise, dihalo-ethenyl" refers to an ethenyl wherein two hydrogen atoms are replaced by halogen atoms.

[0030] The term "-O-C 1 -C 4 -alkyl" refers to a straight-chain or branched alkyl group having 1 to 4 carbon atoms which is bonded via an oxygen, at any position in the alkyl group, e.g. OCH 3 , OCH 2 CH 3 , O(CH 2 ) 2 CH 3 , 1-methylethoxy, O(CH 2 ) 3 CH 3 , 1-methyl¬propoxy, 2-methylpropoxy or 1,1-dimethylethoxy.

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

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

[0033] The term "-C 1 -C 4 -alkyl-C 3 -C 6 -cycloalkyl" refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a cycloalkyl radical having 3 to 6 carbon atoms.

[0034] The term "phenyl" refers to C 6 H 5 .

[0035] The term "5- or 6-membered heteroaryl" which contains 1, 2, 3 or 4 heteroatoms from the group consisting of O, N and S, is to be understood as meaning aromatic heterocycles having 5 or 6 ring atoms. Examples include: 5-membered heteroaryl which in addition to carbon atoms, e.g. contain 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; 6-membered heteroaryl which, in addition to carbon atoms, e.g. contain 1, 2, 3 or 4 N atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl.

[0036] The term "C 1 -C 2 -alkylene linker" means a divalent alkyl group such as -CH 2 - or -CH 2 -CH 2 -that is bound at one end to the core structure of formula I and at the other end to the particular substituent.

[0037] As used herein, the "compounds", in particular "compounds I" include all the stereoisomeric and tautomeric forms and mixtures thereof in all ratios, prodrugs, isotopic forms, their agriculturally acceptable salts, N-oxides and S-oxides thereof.

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

[0039] In respect of the variables, the embodiments of the intermediates correspond to the embodiments of the compounds I.

[0040] Preference is given to those compounds I and where applicable also to compounds of all sub-formulae provided herein, e. g. formulae I.1 and I.2, and to the intermediates such as compounds II, III, IV and V, wherein the substituents and variables (such as n, R 1< , R 2< , R 3< , R 4< , R 5< , R 6< , R a< , and R b< ) have independently of each other or more preferably in combination (any possible combination of 2 or more substituents as defined herein) the following meanings: Preference is also given to the uses, methods, mixtures and compositions, wherein the definitions (such as phytopathogenic fungi, treatments, crops, compounds II, further active ingredients, solvents, solid carriers) have independently of each other or more preferably in combination the following meanings and even more preferably in combination (any possible combination of 2 or more definitions as provided herein) with the preferred meanings of compounds I herein: One embodiment of the invention relates to the abovementioned use and or method of application (herein collectively referred to as "use") of compounds I, wherein R 1< is selected from O and NH; and R 2< is selected from CH and N, provided that R 2< is N in case R 1< is NH. In particular, R 1< is NH and R 2< is N.

[0041] According to another embodiment, R 3< is selected from halogen, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 1 -C 2 -monohaloalkyl, C 1 -C 2 -dihaloalkyl, monohalo-ethenyl, dihalo-ethenyl, C 3 -C 5 -cycloalkyl and -O-C 1 -C 4 -alkyl; preferably from halogen, C 1 -C 2 -alkyl, C 1 -C 2 -monohaloalkyl, C 1 -C 2 -dihaloalkyl, C 3 -C 4 -cycloalkyl and -O-C 1 -C 2 -alkyl; more preferably from C 1 -C 2 -alkyl, C 1 -C 2 -monohaloalkyl, C 1 -C 2 -dihaloalkyl, C 3 -C 4 -cycloalkyl and -O-C 1 -C 2 -alkyl; even more preferably from halogen, C 1 -C 2 -alkyl, C 2 -C 3 -alkenyl, CHF 2 , CFH 2 , -O-C 1 -C 2 -alkyl and cyclopropyl; even more preferably from C 1 -C 2 -alkyl, ethenyl, CHF 2 , CFH 2 , OCH 3 and cyclopropyl; particularly preferred from methyl, ethenyl, CHF 2 and CFH 2 ; in particular methyl.

[0042] R 4< is selected from C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, -C(=O)-C 1 -C 2 -alkyl, C 1 -C 4 -haloalkyl, C 2 -C 4 -haloalkenyl, -(C 1 -C 2 -alkyl)-O-(C 1 -C 2 -alkyl) and -CH 2 -cyclopropyl; more preferably from C 1 -C 4 -alkyl and C 1 -C 4 -haloalkyl, particularly preferably from methyl and C 1 -haloalkyl; in particular methyl.

[0043] According to a further embodiment, n is 1, 2, 3, 4 or 5; more preferably n is 1, 2 or 3, even more preferably n is 1 or 2; in particular n is 1.

[0044] According to a further embodiment, n is 0, 1, 2 or 3, more preferably 0, 1 or 2, in particular 0.

[0045] According to a further embodiment, n is 2 and the two substituents R a< are preferably in positions 2,3 (meaning one substituent in position 2, the other in position 3); 2,4; 2,5; 3,4 or 3,5; even more preferably in positions 2,3 or 2,4.

[0046] According to a further embodiment, n is 3 and the three substituents R a< are preferably in positions 2, 3 and 4.

[0047] According to a further embodiment, R a< is selected from CN, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, -O-C 1 -C 4 -alkyl, -C(=O)-C 1 -C 4 -alkyl,-C(=N-O-C 1 -C 4 -alkyl)-C 1 -C 4 -alkyl, -O-CH 2 -(=N-O-C 1 -C 4 -alkyl)-C 1 -C 4 -alkyl, -C(=N-O-C 1 -C 4 -alkyl)-C(=O-NH-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, 3- to 5-membered heterocycloalkyl, 3- to 5-membered heterocycloalkenyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl, hetercycloalkenyl and heteroaryl besides carbon atoms contain 1, 2 or 3 heteroatoms selected from N, O and S, wherein said phenyl, heterocycloalkyl, hetercycloalkenyl and heteroaryl are bound directly or via an oxygen atom or via a C 1 -C 2 -alkylene linker, and wherein the aliphatic and cyclic moieties of R a< are unsubstituted or carry 1, 2, or 3 of identical or different groups R b< which independently of one another are selected from halogen, CN, NH 2 , NO 2 , C 1 -C 2 -alkyl and C 1 -C 2 -haloalkyl.

[0048] More preferably, R a< is selected from CN, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, -O-C 1 -C 4 -alkyl, -C(=O)-C 1 -C 2 -alkyl,-C(=N-O-C 1 -C 2 -alkyl)-C 1 -C 2 -alkyl, -O-CH 2 -C(=N-O-C 1 -C 2 -alkyl)-C 1 -C 2 -alkyl, -C(=N-O-C 1 -C 2 -alkyl)-C(=O-NH-C 1 -C 2 -alkyl), C 3 -C 4 -cycloalkyl, C 3 -C 4 -cycloalkenyl, -C 1 -C 2 -alkyl-C 3 -C 4 -cycloalkyl, -O-C 3 -C 4 -cycloalkyl, phenyl, 3- to 5-membered heterocycloalkyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl and heterocycloalkyl and heteroaryl besides carbon atoms contain 1 or 2 heteroatoms selected from N, O and S, wherein said phenyl, heterocycloalkyl and heteroaryl are bound directly or via an oxygen atom or via a methylene linker, and wherein the aliphatic or cyclic moieties of R a< are unsubstituted or carry 1, 2, or 3 of identical or different groups R b< which independently of one another are selected from halogen, CN, C 1 -C 2 -alkyl and C 1 -C 2 -haloalkyl.

[0049] Even more preferably R a< is selected from C 1 -C 3 -alkyl, C 2 -C 3 -alkenyl, C 2 -C 3 -alkynyl, -O-C 1 -C 3 -alkyl, -C(=O)-C 1 -C 2 -alkyl,-C(=N-O-C 1 -C 2 -alkyl)-C 1 -C 2 -alkyl, C 3 -C 4 -cycloalkyl, -C 1 -C 2 -alkyl-C 3 -C 4 -cycloalkyl, -O-C 3 -C 4 -cycloalkyl, phenyl, 3- to 5-membered heterocycloalkyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl and heteroaryl besides carbon atoms contain 1 or 2 heteroatoms selected from N, O and S, wherein said phenyl and heteroaryl are bound directly or via an oxygen atom or via a methylene linker, and wherein the aliphatic and cyclic moieties of R a< are unsubstituted or carry 1, 2 or 3 of identical or different groups R b< which independently of one another are selected from halogen, CN, methyl and C 1 -haloalkyl.

[0050] Particularly preferred R a< are selected from halogen, C 1 -C 4 -alkyl, C 2 -C 3 -alkenyl, C 2 -C 3 -alkynyl, -O-C 1 -C 4 -alkyl, -C(=N-O-C 1 -C 2 -alkyl)-C 1 -C 2 -alkyl and phenyl, wherein the aliphatic or cyclic moieties of R a< are unsubstituted or carry 1, 2 or 3 of identical or different groups R b< which independently of one another are selected from halogen, CN, methyl and C 1 -haloalkyl.

[0051] According to a further embodiment, R 5< , R 6< are independently of each other preferably selected from the group consisting of H, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl and C 2 -C 4 -alkynyl, more preferably from H and C 1 -C 4 -alkyl.

[0052] According to a further preferred embodiment, the present invention relates to the use of compounds of formula I wherein: R 1< is selected from O and NH; and R 2< is selected from CH and N, provided that R 2< is N in case R 1< is NH; R 3< is selected from halogen, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 1 -C 2 -monohaloalkyl, C 1 -C 2 -dihaloalkyl, C 3 -C 4 -cycloalkyl and -O-C 1 -C 4 -alkyl; R 4< is selected from C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, -C(=O)-C 1 -C 2 -alkyl, C 1 -C 4 -haloalkyl, C 2 -C 4 -haloalkenyl, -(C 1 -C 2 -alkyl)-O-(C 1 -C 2 -alkyl) and -CH 2 -cyclopropyl ; R a< is selected from halogen, CN, -NR 5< R 6< , 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, 3- to 6-membered heterocycloalkyl, 3- to 6-membered heterocycloalkenyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl, heterocycloalkenyl and heteroaryl besides carbon atoms contain 1, 2 or 3 heteroatoms selected from N, O and S, wherein said phenyl, heterocycloalkyl, heterocycloalkenyl and heteroaryl are bound directly or via an oxygen atom or via a C 1 -C 2 -alkylene linker, and wherein the aliphatic and cyclic moieties of R a< are unsubstituted or carry 1, 2, 3, 4 or up to the maximum number of identical or different groups R b< : 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; R 5< , R 6< are independently of each other selected from the group consisting of H, C 1 -C 6 -alkyl and C 2 -C 4 -alkynyl; nis an integer selected from 0, 1, 2 and 3; and in form or stereoisomers and tautomers thereof, and the N-oxides and the agriculturally acceptable salts thereof, for combating phytopathogenic fungi containing an amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors.

[0053] Certain strobilurin type compounds of formula I have been described in EP 370629 and WO 98 / 23156.

[0054] However, it is not mentioned that these compounds inhibit fungal pathogens containing a F129L substitution in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors.

[0055] The compounds according to the present invention differ from those described in the abovementioned publications that R 3< is an aliphatic or cyclic substituent and the specific amide pharmacophore as defined herein.

[0056] Therefore, according to a second aspect, the invention provides novel compounds of formula I which are represented by formula I wherein R 2< is selected from CH and N; R 3< is selected from halogen, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 1 -C 2 -monohaloalkyl, C 1 -C 2 -dihaloalkyl, monohalo-ethenyl, dihalo-ethenyl, C 3 -C 6 -cycloalkyl and -O-C 1 -C 4 -alkyl; R 4< is selected from C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 1 -C 4 -haloalkyl, C 2 -C 4 -haloalkenyl, -(C 1 -C 2 -alkyl)-O-(C 1 -C 2 -alkyl) and -(C 1 -C 2 -alkyl)-O-(C 1 -C 2 -haloalkyl); R a< is selected from halogen, CN, NH-C 1 -C 4 -alkyl, N(C 1 -C 4 -alkyl) 2 , 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, 3- to 5-membered heterocycloalkyl, 3- to 5-membered heterocycloalkenyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl, heterocycloalkenyl and heteroaryl besides carbon atoms contain 1, 2 or 3 heteroatoms selected from N, O and S, wherein said phenyl, heterocycloalkyl, heterocycloalkenyl and heteroaryl are bound directly or via an oxygen atom or via a C 1 -C 2 -alkylene linker, and wherein the aliphatic and cyclic moieties of R a< are unsubstituted or carry 1, 2, 3, 4 or up to the maximum number of identical or different groups R b< : 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; nis an integer selected from 0, 1, 2, 3, 4 and 5; and in form or stereoisomers and tautomers thereof, and the N-oxides and the agriculturally acceptable salts thereof.

[0057] One embodiment of the invention relates to preferred compounds I, wherein R 2< is N. Another embodiment of the invention relates to preferred compounds I, wherein R 2< is CH.

[0058] According to another embodiment, R 3< is selected from halogen, C 1 -C 4 -alkyl, C 2 -C 3 -alkenyl, C 1 -C 2 -monohaloalkyl, C 1 -C 2 -dihaloalkyl, monohalo-ethenyl, dihalo-ethenyl, C 3 -C 6 -cycloalkyl and -O-C 1 -C 4 -alkyl; preferably from halogen, C 1 -C 2 -alkyl, C 1 -C 2 -monohaloalkyl, C 1 -C 2 -dihaloalkyl, C 3 -C 4 -cycloalkyl and -O-C 1 -C 2 -alkyl; preferably selected from C 1 -C 4 -alkyl, C 2 -C 3 -alkenyl, monohalo-methyl, dihalo-methyl, C 3 -C 4 -cycloalkyl and -O-C 1 -C 4 -alkyl; further more preferably selected from C 1 -C 2 -alkyl, CHF 2 , CFH 2 , cyclopropyl and OCH 3 ; particularly preferred from methyl, CHF 2 and CFH 2 ; in particular R 3< is methyl.

[0059] R 4< is selected from is selected from C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 1 -C 4 -haloalkyl, C 2 -C 4 -haloalkenyl and -(C 1 -C 2 -alkyl)-O-(C 1 -C 2 -alkyl; more preferably from C 1 -C 4 -alkyl, and C 1 -C 4 -haloalkyl, even more preferably from methyl and C 1 -haloalkyl; in particular methyl.

[0060] According to a further embodiment, n is 1, 2, 3, 4 or 5; more preferably n is 1, 2 or 3, even more preferably n is 1 or 2; in particular n is 1.

[0061] According to a further embodiment, n is 0, 1, 2 or 3, more preferably 0, 1 or 2, in particular 0.

[0062] According to a further embodiment, n is 2 and the two substituents R a< are preferably in positions 2,3 (meaning one substituent in position 2, the other in position 3); 2,4; 2,5; 3,4 or 3,5; even more preferably in positions 2,3 or 2,4.

[0063] According to a further embodiment, n is 3 and the three substituents R a< are preferably in positions 2, 3 and 4.

[0064] R a< is selected from halogen, CN, NH-C 1 -C 4 -alkyl, N(C 1 -C 4 -alkyl) 2 , 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, 3- to 5-membered heterocycloalkyl, 3- to 5-membered heterocycloalkenyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl, heterocycloalkenyl and heteroaryl besides carbon atoms contain 1, 2 or 3 heteroatoms selected from N, O and S, wherein said phenyl, heterocycloalkyl, heterocycloalkenyl and heteroaryl are bound directly or via an oxygen atom or via a C 1 -C 2 -alkylene linker.

[0065] Preferably, R a< is selected from halogen, CN, NH-C 1 -C 2 -alkyl, N(C 1 -C 2 -alkyl) 2 , C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, -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, 3- to 5-membered heterocycloalkyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl and heteroaryl besides carbon atoms contain 1 or 2 heteroatoms selected from N, O and S, wherein said phenyl, heterocycloalkyl and heteroaryl are bound 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, 3- to 5-membered heterocycloalkyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl and heteroaryl besides carbon atoms contain 1 or 2 heteroatoms selected from N, O and S, wherein said phenyl, heterocycloalkyl and heteroaryl are bound 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, ethenyl, ethynyl and -C(=N-O-CH 3 )-CH 3 .

[0068] According to the abovementioned embodiments for R a< , the abovementioned heterocycloalkyl is more preferably a 4-membered heterocycloalkyl, wherein said heterocycloalkyl besides carbon atoms contains 1 heteroatom selected from N, O and S, preferably N.

[0069] According to the abovementioned embodiments for R a< , the abovementioned heteroaryl is more preferably a 5-membered heteroaryl, wherein said heteroaryl besides carbon atoms contains 1 or 2 heteroatoms selected from N, O and S, preferably N or O.

[0070] According to the abovementioned embodiments for R a< , the aliphatic and cyclic moieties of R a< are unsubstituted or carry 1, 2, 3, 4 or up to the maximum number of identical or different groups 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; more preferably only the cyclic moieties of R a< are unsubstituted or carry 1, 2, 3, 4 or up to the maximum number of identical or different groups 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; even more preferably only the phenyl moiety of R a< is unsubstituted or carries 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 -C 4 -haloalkyl; in particular said phenyl is unsubstituted or carries 1, 2 or 3 identical or different groups R b< 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 preferred embodiment, the present invention relates to compounds of formula I wherein: R 2< is selected from CH and N; R 3< is selected from halogen, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 1 -C 2 -monohaloalkyl, C 1 -C 2 -dihaloalkyl, C 3 -C 4 -cycloalkyl and -O-C 1 -C 4 -alkyl; R 4< is selected from C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 1 -C 4 -haloalkyl, C 2 -C 4 -haloalkenyl, -(C 1 -C 2 -alkyl)-O-(C 1 -C 2 -alkyl) and -(C 1 -C 2 -alkyl)-O-(C 1 -C 2 -haloalkyl); R a< is selected from halogen, CN, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkyl, -O-C 1 -C 4 -alkyl, -O-C 1 -C 4 -haloalkyl, -C(=N-O-C 1 -C 4 -alkyl)-C 1 -C 4 -alkyl, -C(=O)-C 1 -C 4 -alkyl, C 3 -C 4 -cycloalkyl, -C 1 -C 2 -alkyl-C 3 -C 4 -cycloalkyl, -O-C 3 -C 4 -cycloalkyl, phenyl, 3- to 5-membered heterocycloalkyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl and heteroaryl besides carbon atoms contain 1 or 2 heteroatoms selected from N, O and S, wherein said phenyl, heterocycloalkyl and heteroaryl are bound directly or via an oxygen atom or via a methylene linker, and wherein the abovementioned cyclic moieties of R a< are unsubstituted or carry 1, 2 or 3 identical or different groups R b< 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; nis an integer selected from 0, 1, 2 and 3; and in form or stereoisomers and tautomers thereof, and the N-oxides and the agriculturally acceptable salts thereof.

[0072] According to a further embodiment, R 1< is O and R 2< is N, which compounds are of formula I.1:

[0073] According to a further embodiment, R 2< is CH, which compounds are of formula I.2:

[0074] Preferably, R 3< of compounds I is one of the following radicals 3-1 to 3-5: No. R 3< 3-1CH 3 3-2OCH 3 3-3CHF 2 3-4C 3 H 5 3-5CH=CH 2 Even more preferably R3 is CH3, OCH3, CHF2 or C3H5, in particular CH3.

[0075] Particularly preferred embodiments of the invention relate to compounds I, wherein the R 4< is one of the following radicals 4-1 to 4-5: No. R 4< 4-1CH 3 4-2C 2 H 5 4-3CH 2 OCH 3 4-4CH 2 CF 3 4-5CHF 2

[0076] Particularly preferred embodiments of the invention relate to compounds I, wherein the R a< is selected of one of the following radicals a-1 to a-17: No. R a< a-1Fa-2Cla-3Bra-4CH 3 a-5CHF 2 a-6CF 3 a-7OCH 3 a-8OCHF 2 a-9OCF 3 a-10C 2 H 5 a-11CH 2 CF 3 a-12CH=CH 2 a-13C 6 H 5 a-14C≡CHa-15C≡CCH 3 a-16C 3 H 5 a-17C(=NOCH 3 )CH 3

[0077] According to a further embodiment, n is 1. More preferably, R a< is in ortho-position (2-R a< ), which compounds are of formula I.A: wherein even more preferably R 2< is N. According to a further embodiment, R a< is in meta-position (3-R a< ), which compounds are of formula I.B: wherein even more preferably R 2< is N.

[0078] According to a further embodiment, n is 2. More preferably, n is 2 and the two R a< substituents are both in meta -position (3,5-R a< ), which compounds are of formula I.C: wherein even more preferably R 2< is N. According to a further embodiment, n is 2 and the two R a< substituents are both in ortho-position (2,6-R a< ), which compounds are of formula I.D: wherein even more preferably R 2< is N. According to a further embodiment, n is 2 and the two R a< substituents are in ortho- and meta-position, which compounds are of formula I.E: wherein even more preferably R 2< is N. According to a further embodiment, n is 2 and the two R a< substituents are in ortho- and para-position, which compounds are of formula I.F: wherein even more preferably R 2< is N.

[0079] In an embodiment, compounds I are of formula I.1 and n, R a< , R 3< and R 4< are as per any row of Table A below, which compounds are named I.1-A-1 to I.1-A-330.

[0080] In another embodiment, compounds I are of formula I.2 and n, R a< , R 3< and R 4< are as per any row of Table A below, which compounds are named I.2-A-1 to I.2-A-330. Table A:No. n R a< R 3< R 4< A-10-CH 3 CH 3 A-212-FCH 3 CH 3 A-312-CICH 3 CH 3 A-412-BrCH 3 CH 3 A-512-CH 3 CH 3 CH 3 A-612-CHF 2 CH 3 CH 3 A-712-CF 3 CH 3 CH 3 A-812-OCH 3 CH 3 CH 3 A-912-OCHF 2 CH 3 CH 3 A-1012-OCF 3 CH 3 CH 3 A-1112-C 2 H 5 CH 3 CH 3 A-1212-CH 2 CF 3 CH 3 CH 3 A-1312-CH=CH 2 CH 3 CH 3 A-1412-C 6 H 5 CH 3 CH 3 A-1512-C≡CHCH 3 CH 3 A-1612-C≡CCH 3 CH 3 CH 3 A-1712-C 3 H 5 CH 3 CH 3 A-1812-C(=NOCH 3 )CH 3 CH 3 CH 3 A-1912-CNCH 3 CH 3 A-2013-FCH 3 CH 3 A-2113-CICH 3 CH 3 A-2213-BrCH 3 CH 3 A-2313-CH 3 CH 3 CH 3 A-2413-CHF 2 CH 3 CH 3 A-2513-CF 3 CH 3 CH 3 A-2613-OCH 3 CH 3 CH 3 A-2713-OCHF 2 CH 3 CH 3 A-2813-OCF 3 CH 3 CH 3 A-2913-C 2 H 5 CH 3 CH 3 A-3013-CH 2 CF 3 CH 3 CH 3 A-3113-CH=CH 2 CH 3 CH 3 A-3213-C 6 H 5 CH 3 CH 3 A-3313-C≡CHCH 3 CH 3 A-3413-C≡CCH 3 CH 3 CH 3 A-3513-C 3 H 5 CH 3 CH 3 A-3613-C(=NOCH 3 )CH 3 CH 3 CH 3 A-3713-CNCH 3 CH 3 A-3814-FCH 3 CH 3 A-3914-CICH 3 CH 3 A-4014-BrCH 3 CH 3 A-4114-CH 3 CH 3 CH 3 A-4214-CHF 2 CH 3 CH 3 A-4314-CF 3 CH 3 CH 3 A-4414-OCH 3 CH 3 CH 3 A-4514-OCHF 2 CH 3 CH 3 A-4614-OCF 3 CH 3 CH 3 A-4714-C 2 H 5 CH 3 CH 3 A-4814-CH 2 CF 3 CH 3 CH 3 A-4914-CH=CH 2 CH 3 CH 3 A-5014-C 6 H 5 CH 3 CH 3 A-5114-C≡CHCH 3 CH 3 A-5214-C≡CCH 3 CH 3 CH 3 A-5314-C 3 H 5 CH 3 CH 3 A-5414-C(=NOCH 3 )CH 3 CH 3 CH 3 A-5514-CNCH 3 CH 3 A-560-CH 3 C 2 H 5 A-5712-FCH 3 C 2 H 5 A-5812-CICH 3 C 2 H 5 A-5912-BrCH 3 C 2 H 5 A-6012-CH 3 CH 3 C 2 H 5 A-6112-CHF 2 CH 3 C 2 H 5 A-6212-CF 3 CH 3 C 2 H 5 A-6312-OCH 3 CH 3 C 2 H 5 A-6412-OCHF 2 CH 3 C 2 H 5 A-6512-OCF 3 CH 3 C 2 H 5 A-6612-C 2 H 5 CH 3 C 2 H 5 A-6712-CH 2 CF 3 CH 3 C 2 H 5 A-6812-CH=CH 2 CH 3 C 2 H 5 A-6912-C 6 H 5 CH 3 C 2 H 5 A-7012-C≡CHCH 3 C 2 H 5 A-7112-C≡CCH 3 CH 3 C 2 H 5 A-7212-C 3 H 5 CH 3 C 2 H 5 A-7312-C(=NOCH 3 )CH 3 CH 3 C 2 H 5 A-7412-CNCH 3 C 2 H 5 A-7513-FCH 3 C 2 H 5 A-7613-CICH 3 C 2 H 5 A-7713-BrCH 3 C 2 H 5 A-7813-CH 3 CH 3 C 2 H 5 A-7913-CHF 2 CH 3 C 2 H 5 A-8013-CF 3 CH 3 C 2 H 5 A-8113-OCH 3 CH 3 C 2 H 5 A-8213-OCHF 2 CH 3 C 2 H 5 A-8313-OCF 3 CH 3 C 2 H 5 A-8413-C 2 H 5 CH 3 C 2 H 5 A-8513-CH 2 CF 3 CH 3 C 2 H 5 A-8613-CH=CH 2 CH 3 C 2 H 5 A-8713-C 6 H 5 CH 3 C 2 H 5 A-8813-C≡CHCH 3 C 2 H 5 A-8913-C≡CCH 3 CH 3 C 2 H 5 A-9013-C 3 H 5 CH 3 C 2 H 5 A-9113-C(=NOCH 3 )CH 3 CH 3 C 2 H 5 A-9213-CNCH 3 C 2 H 5 A-9314-FCH 3 C 2 H 5 A-9414-CICH 3 C 2 H 5 A-9514-BrCH 3 C 2 H 5 A-9614-CH 3 CH 3 C 2 H 5 A-9714-CHF 2 CH 3 C 2 H 5 A-9814-CF 3 CH 3 C 2 H 5 A-9914-OCH 3 CH 3 C 2 H 5 A-10014-OCHF 2 CH 3 C 2 H 5 A-10114-OCF 3 CH 3 C 2 H 5 A-10214-C 2 H 5 CH 3 C 2 H 5 A-10314-CH 2 CF 3 CH 3 C 2 H 5 A-10414-CH=CH 2 CH 3 C 2 H 5 A-10514-C 6 H 5 CH 3 C 2 H 5 A-10614-C≡CHCH 3 C 2 H 5 A-10714-C≡CCH 3 CH 3 C 2 H 5 A-10814-C 3 H 5 CH 3 C 2 H 5 A-10914-C(=NOCH 3 )CH 3 CH 3 C 2 H 5 A-11014-CNCH 3 C 2 H 5 A-1110-CH 3 CH 2 CF 3 A-11212-FCH 3 CH 2 CF 3 A-11312-CICH 3 CH 2 CF 3 A-11412-BrCH 3 CH 2 CF 3 A-11512-CH 3 CH 3 CH 2 CF 3 A-11612-CHF 2 CH 3 CH 2 CF 3 A-11712-CF 3 CH 3 CH 2 CF 3 A-11812-OCH 3 CH 3 CH 2 CF 3 A-11912-OCHF 2 CH 3 CH 2 CF 3 A-12012-OCF 3 CH 3 CH 2 CF 3 A-12112-C 2 H 5 CH 3 CH 2 CF 3 A-12212-CH 2 CF 3 CH 3 CH 2 CF 3 A-12312-CH=CH 2 CH 3 CH 2 CF 3 A-12412-C 6 H 5 CH 3 CH 2 CF 3 A-12512-C≡CHCH 3 CH 2 CF 3 A-12612-C≡CCH 3 CH 3 CH 2 CF 3 A-12712-C 3 H 5 CH 3 CH 2 CF 3 A-12812-C(=NOCH 3 )CH 3 CH 3 CH 2 CF 3 A-12912-CNCH 3 CH 2 CF 3 A-13013-FCH 3 CH 2 CF 3 A-13113-CICH 3 CH 2 CF 3 A-13213-BrCH 3 CH 2 CF 3 A-13313-CH 3 CH 3 CH 2 CF 3 A-13413-CHF 2 CH 3 CH 2 CF 3 A-13513-CF 3 CH 3 CH 2 CF 3 A-13613-OCH 3 CH 3 CH 2 CF 3 A-13713-OCHF 2 CH 3 CH 2 CF 3 A-13813-OCF 3 CH 3 CH 2 CF 3 A-13913-C 2 H 5 CH 3 CH 2 CF 3 A-14013-CH 2 CF 3 CH 3 CH 2 CF 3 A-14113-CH=CH 2 CH 3 CH 2 CF 3 A-14213-C 6 H 5 CH 3 CH 2 CF 3 A-14313-C≡CHCH 3 CH 2 CF 3 A-14413-C≡CCH 3 CH 3 CH 2 CF 3 A-14513-C 3 H 5 CH 3 CH 2 CF 3 A-14613-C(=NOCH 3 )CH 3 CH 3 CH 2 CF 3 A-14713-CNCH 3 CH 2 CF 3 A-14814-FCH 3 CH 2 CF 3 A-14914-CICH 3 CH 2 CF 3 A-15014-BrCH 3 CH 2 CF 3 A-15114-CH 3 CH 3 CH 2 CF 3 A-15214-CHF 2 CH 3 CH 2 CF 3 A-15314-CF 3 CH 3 CH 2 CF 3 A-15414-OCH 3 CH 3 CH 2 CF 3 A-15514-OCHF 2 CH 3 CH 2 CF 3 A-15614-OCF 3 CH 3 CH 2 CF 3 A-15714-C 2 H 5 CH 3 CH 2 CF 3 A-15814-CH 2 CF 3 CH 3 CH 2 CF 3 A-15914-CH=CH 2 CH 3 CH 2 CF 3 A-16014-C 6 H 5 CH 3 CH 2 CF 3 A-16114-C≡CHCH 3 CH 2 CF 3 A-16214-C≡CCH 3 CH 3 CH 2 CF 3 A-16314-C 3 H 5 CH 3 CH 2 CF 3 A-16414-C(=NOCH 3 )CH 3 CH 3 CH 2 CF 3 A-16514-CNCH 3 CH 2 CF 3 A-1660-CH 3 CH 2 OCH 3 A-16712-FCH 3 CH 2 OCH 3 A-16812-CICH 3 CH 2 OCH 3 A-16912-BrCH 3 CH 2 OCH 3 A-17012-CH 3 CH 3 CH 2 OCH 3 A-17112-CHF 2 CH 3 CH 2 OCH 3 A-17212-CF 3 CH 3 CH 2 OCH 3 A-17312-OCH 3 CH 3 CH 2 OCH 3 A-17412-OCHF 2 CH 3 CH 2 OCH 3 A-17512-OCF 3 CH 3 CH 2 OCH 3 A-17612-C 2 H 5 CH 3 CH 2 OCH 3 A-17712-CH 2 CF 3 CH 3 CH 2 OCH 3 A-17812-CH=CH 2 CH 3 CH 2 OCH 3 A-17912-C 6 H 5 CH 3 CH 2 OCH 3 A-18012-C≡CHCH 3 CH 2 OCH 3 A-18112-C≡CCH 3 CH 3 CH 2 OCH 3 A-18212-C 3 H 5 CH 3 CH 2 OCH 3 A-18312-C(=NOCH 3 )CH 3 CH 3 CH 2 OCH 3 A-18412-CNCH 3 CH 2 OCH 3 A-18513-FCH 3 CH 2 OCH 3 A-18613-CICH 3 CH 2 OCH 3 A-18713-BrCH 3 CH 2 OCH 3 A-18813-CH 3 CH 3 CH 2 OCH 3 A-18913-CHF 2 CH 3 CH 2 OCH 3 A-19013-CF 3 CH 3 CH 2 OCH 3 A-19113-OCH 3 CH 3 CH 2 OCH 3 A-19213-OCHF 2 CH 3 CH 2 OCH 3 A-19313-OCF 3 CH 3 CH 2 OCH 3 A-19413-C 2 H 5 CH 3 CH 2 OCH 3 A-19513-CH 2 CF 3 CH 3 CH 2 OCH 3 A-19613-CH=CH 2 CH 3 CH 2 OCH 3 A-19713-C 6 H 5 CH 3 CH 2 OCH 3 A-19813-C=CHCH 3 CH 2 OCH 3 A-19913-C≡CCH 3 CH 3 CH 2 OCH 3 A-20013-C 3 H 5 CH 3 CH 2 OCH 3 A-20113-C(=NOCH 3 )CH 3 CH 3 CH 2 OCH 3 A-20213-CNCH 3 CH 2 OCH 3 A-20314-FCH 3 CH 2 OCH 3 A-20414-CICH 3 CH 2 OCH 3 A-20514-BrCH 3 CH 2 OCH 3 A-20614-CH 3 CH 3 CH 2 OCH 3 A-20714-CHF 2 CH 3 CH 2 OCH 3 A-20814-CF 3 CH 3 CH 2 OCH 3 A-20914-OCH 3 CH 3 CH 2 OCH 3 A-21014-OCHF 2 CH 3 CH 2 OCH 3 A-21114-OCF 3 CH 3 CH 2 OCH 3 A-21214-C 2 H 5 CH 3 CH 2 OCH 3 A-21314-CH 2 CF 3 CH 3 CH 2 OCH 3 A-21414-CH=CH 2 CH 3 CH 2 OCH 3 A-21514-C 6 H 5 CH 3 CH 2 OCH 3 A-21614-C≡CHCH 3 CH 2 OCH 3 A-21714-C≡CCH 3 CH 3 CH 2 OCH 3 A-21814-C 3 H 5 CH 3 CH 2 OCH 3 A-21914-C(=NOCH 3 )CH 3 CH 3 CH 2 OCH 3 A-22014-CNCH 3 CH 2 OCH 3 A-2210-CH 3 CHF 2 A-22212-FCH 3 CHF 2 A-22312-CICH 3 CHF 2 A-22412-BrCH 3 CHF 2 A-22512-CH 3 CH 3 CHF 2 A-22612-CHF 2 CH 3 CHF 2 A-22712-CF 3 CH 3 CHF 2 A-22812-OCH 3 CH 3 CHF 2 A-22912-OCHF 2 CH 3 CHF 2 A-23012-OCF 3 CH 3 CHF 2 A-23112-C 2 H 5 CH 3 CHF 2 A-23212-CH 2 CF 3 CH 3 CHF 2 A-23312-CH=CH 2 CH 3 CHF 2 A-23412-C 6 H 5 CH 3 CHF 2 A-23512-C≡CHCH 3 CHF 2 A-23612-C≡CCH 3 CH 3 CHF 2 A-23712-C 3 H 5 CH 3 CHF 2 A-23812-C(=NOCH 3 )CH 3 CH 3 CHF 2 A-23912-CNCH 3 CHF 2 A-24013-FCH 3 CHF 2 A-24113-CICH 3 CHF 2 A-24213-BrCH 3 CHF 2 A-24313-CH 3 CH 3 CHF 2 A-24413-CHF 2 CH 3 CHF 2 A-24513-CF 3 CH 3 CHF 2 A-24613-OCH 3 CH 3 CHF 2 A-24713-OCHF 2 CH 3 CHF 2 A-24813-OCF 3 CH 3 CHF 2 A-24913-C 2 H 5 CH 3 CHF 2 A-25013-CH 2 CF 3 CH 3 CHF 2 A-25113-CH=CH 2 CH 3 CHF 2 A-25213-C 6 H 5 CH 3 CHF 2 A-25313-C≡CHCH 3 CHF 2 A-25413-C≡CCH 3 CH 3 CHF 2 A-25513-C 3 H 5 CH 3 CHF 2 A-25613-C(=NOCH 3 )CH 3 CH 3 CHF 2 A-25713-CNCH 3 CHF 2 A-25814-FCH 3 CHF 2 A-25914-CICH 3 CHF 2 A-26014-BrCH 3 CHF 2 A-26114-CH 3 CH 3 CHF 2 A-26214-CHF 2 CH 3 CHF 2 A-26314-CF 3 CH 3 CHF 2 A-26414-OCH 3 CH 3 CHF 2 A-26514-OCHF 2 CH 3 CHF 2 A-26614-OCF 3 CH 3 CHF 2 A-26714-C 2 H 5 CH 3 CHF 2 A-26814-CH 2 CF 3 CH 3 CHF 2 A-26914-CH=CH 2 CH 3 CHF 2 A-27014-C 6 H 5 CH 3 CHF 2 A-27114-C≡CHCH 3 CHF 2 A-27214-C≡CCH 3 CH 3 CHF 2 A-27314-C 3 H 5 CH 3 CHF 2 A-27414-C(=NOCH 3 )CH 3 CH 3 CHF 2 A-27514-CNCH 3 CHF 2 A-2760-CH 3 CH 2 C 3 H 5 A-27712-FCH 3 CH 2 C 3 H 5 A-27812-CICH 3 CH 2 C 3 H 5 A-27912-BrCH 3 CH 2 C 3 H 5 A-28012-CH 3 CH 3 CH 2 C 3 H 5 A-28112-CHF 2 CH 3 CH 2 C 3 H 5 A-28212-CF 3 CH 3 CH 2 C 3 H 5 A-28312-OCH 3 CH 3 CH 2 C 3 H 5 A-28412-OCHF 2 CH 3 CH 2 C 3 H 5 A-28512-OCF 3 CH 3 CH 2 C 3 H 5 A-28612-C 2 H 5 CH 3 CH 2 C 3 H 5 A-28712-CH 2 CF 3 CH 3 CH 2 C 3 H 5 A-28812-CH=CH 2 CH 3 CH 2 C 3 H 5 A-28912-C 6 H 5 CH 3 CH 2 C 3 H 5 A-29012-C≡CHCH 3 CH 2 C 3 H 5 A-29112-C≡CCH 3 CH 3 CH 2 C 3 H 5 A-29212-C 3 H 5 CH 3 CH 2 C 3 H 5 A-29312-C(=NOCH 3 )CH 3 CH 3 CH 2 C 3 H 5 A-29412-CNCH 3 CH 2 C 3 H 5 A-29513-FCH 3 CH 2 C 3 H 5 A-29613-CICH 3 CH 2 C 3 H 5 A-29713-BrCH 3 CH 2 C 3 H 5 A-29813-CH 3 CH 3 CH 2 C 3 H 5 A-29913-CHF 2 CH 3 CH 2 C 3 H 5 A-30013-CF 3 CH 3 CH 2 C 3 H 5 A-30113-OCH 3 CH 3 CH 2 C 3 H 5 A-30213-OCHF 2 CH 3 CH 2 C 3 H 5 A-30313-OCF 3 CH 3 CH 2 C 3 H 5 A-30413-C 2 H 5 CH 3 CH 2 C 3 H 5 A-30513-CH 2 CF 3 CH 3 CH 2 C 3 H 5 A-30613-CH=CH 2 CH 3 CH 2 C 3 H 5 A-30713-C 6 H 5 CH 3 CH 2 C 3 H 5 A-30813-C≡CHCH 3 CH 2 C 3 H 5 A-30913-C≡CCH 3 CH 3 CH 2 C 3 H 5 A-31013-C 3 H 5 CH 3 CH 2 C 3 H 5 A-31113-C(=NOCH 3 )CH 3 CH 3 CH 2 C 3 H 5 A-31213-CNCH 3 CH 2 C 3 H 5 A-31314-FCH 3 CH 2 C 3 H 5 A-31414-CICH 3 CH 2 C 3 H 5 A-31514-BrCH 3 CH 2 C 3 H 5 A-31614-CH 3 CH 3 CH 2 C 3 H 5 A-31714-CHF 2 CH 3 CH 2 C 3 H 5 A-31814-CF 3 CH 3 CH 2 C 3 H 5 A-31914-OCH 3 CH 3 CH 2 C 3 H 5 A-32014-OCHF 2 CH 3 CH 2 C 3 H 5 A-32114-OCF 3 CH 3 CH 2 C 3 H 5 A-32214-C 2 H 5 CH 3 CH 2 C 3 H 5 A-32314-CH 2 CF 3 CH 3 CH 2 C 3 H 5 A-32414-CH=CH 2 CH 3 CH 2 C 3 H 5 A-32514-C 6 H 5 CH 3 CH 2 C 3 H 5 A-32614-C≡CHCH 3 CH 2 C 3 H 5 A-32714-C≡CCH 3 CH 3 CH 2 C 3 H 5 A-32814-C 3 H 5 CH 3 CH 2 C 3 H 5 A-32914-C(=NOCH 3 )CH 3 CH 3 CH 2 C 3 H 5 A-33014-CNCH 3 CH 2 C 3 H 5 Synthesis

[0081] The compounds can be obtained by various routes in analogy to prior art processes known (e.g EP 463488) and, advantageously, by the synthesis shown in the following schemes 1 to 4 and in the experimental part of this application.

[0082] A suitable method to prepare compounds I is illustrated in Scheme 1. It starts with the conversion of a ketone to the corresponding oxime using hydxroxylamine hydrochloride and a base such as pyridine, sodium hydroxide or sodium acetate in polar solvents such as methanol, methanol-water mixture, or ethanol at reaction temperatures of 60 to 100 °C, preferably at about 65 °C. In cases where a E / Z mixture was obtained, the isomers could be separated by purifycation techniques known in art (e.g. column chromatography, crystallization, distillation etc.). Then, coupling with the intermediate IV, wherein X is a leaving group such as halogen, toluene- and methanesulfonates, preferably X is Cl or Br, is carried out under basic conditions using e.g. sodium hydride, cesium carbonate or potassium carbonate as a base and using an organic solvent such as dimethyl formamide (DMF) or acetonitrile, preferably cesium carbonate as base and acetonitrile as solvent at room temperature (RT) of about 24 °C . The ester compound I wherein R' is O can be converted to the amide of formula I wherein R 1< is NH by reaction with methyl amine (preferably 40% aq. solution) using tetrahydrofuran (THF) as solvent at RT.

[0083] Another general method to prepare the compounds I is depicted in Scheme 2. Intermediate IV is reacted with N-hydroxysuccimide VI, using a base such as triethylamine in DMF. The reaction temperature is usually 50 to 70 °C preferably about 70 °C. Conversion to the correspondding O-benzylhydroxyl amine, intermediate VIII, was achieved through removal of the phthalimide group, preferably using hydrazine hydrate in methanol as solvent at 25 °C. Alternatively, removal of the phthalimide group using methyl amine in methanol as solvent at 25 °C can provide intermediate IX. Intermediate VIII and intermediate IX, respectively can be condensed with ketones using acetic acid or pyridine in methanol as solvent at temperature of 50 to 65 °C. Alternatively, the condensation could also carried out with titanium (IV) ethoxide (Ti(OEt) 4 ) using THF as solvent at about 70 °C. The desired product is usually accompanied by an undesired isomer, which can be removed e.g by column chromatography, crystallization.

[0084] A general method for preparation of intermediate IV is shown in Scheme 3. Compound XI could be obtained from X by lithium-halogen exchange or by generating Grignard reagent and further reaction with dimethyl oxalate or chloromethyl oxalate in presence of a solvent. The preferred solvent is THF, 2-methyl-THF and the temperature can be between -70 to - 78 °C. Conversion of intermediate XI to intermediate XII can be achieved using N-methylhydroxylamine hydrochloride and a base such as pyridine or sodium acetate in polar solvents such as methanol. The reaction temperature is preferably about 65 °C. An E / Z mixture is usually obtained, the isomers can be separated by purification techniques known in art (e.g. column chromatography, crystallization). Bromination of intermediate XII provides the desired intermediate compounds IV, wherein R 1< is O and R 2< = N. This reaction of intermediate XII with N-bromosuccinimide in solvents such as carbon tetrachloride, chlorobenzene, acetonitrile, using radical initiators such as 1,1'-azobis (cyclohexanecarbonitrile) or azobisisobutyronitrile and is carried out at temperatures of 70 to 100 °C. The preferred radical initiator is 1,1'-azobis (cyclohexanecarbonitrile), preferred solvent chlorobenzene and preferred temperature 80 °C.

[0085] The synthesis of compounds containing different substituents R 3< follows similar sequence as in Scheme 3, wherein R 3< is bromo. Coupling of intermediate III with intermediate IV, wherein R 3< is bromo, provides compounds I as described above. Using standard chemical reactions, such as Suzuki or Stille reaction, the bromo group can be converted e.g. to other R 3< substituents such as cycloalkyl, alkoxy and alkenyl. Additional transformations e.g. of ethenyl provide compounds I with other R 3< substituents such as ethyl, CN and haloalkyl.

[0086] Most of the ketones of general formula II were commercially available, however for the ones which were not commercially available, preparation of these was carried out in house using methods known in prior art. Scheme 4 depicts various methods known in literature for the synthesis of these ketones. The ketone II can be obtained from the corresponding halogen bearing precursors XIV, wherein X is preferably bromine or iodine. Lithium-halogen exchange (J Org Chem, 1998, 63 (21), 7399-7407) in compound XIII using n-butyllithium or synthesis of the corresponding Grignard reagent (Nature Comm, 2017, 8(1), 1-7) using THF as solvent, and subsequent reaction with N-methoxy-N-methylacetamide at about -70 to -78 °C can provide the ketone II. Alternatively, the coupling reaction of compound XIV and tributyl(1-ethoxyvinyl)stannane in presence of a transition metal catalyst, preferably palladium, with suitable ligands in a solvent such as dioxane and at a reaction temperature of about 100 °C, followed by treatment with 1N HCl can provide ketone II (Org Lett, 2016, 18(7), 1630-1633, WO 2018 / 115380). Reaction of XIV with 1,4-butanediol vinyl ether in the presence of transition metal catalyst, preferably palladium with suitable ligands and solvent such as 1,2-propane diol and base such as sodium carbonate and reaction temperature of about 120 °C followed by treatment with 1N HCl can provide ketone II (Chem A Eur J, 2008, 14(18), 5555-5566). Another method uses acid compounds XV, which can be converted to the corresponding Weinreb amide or carboxylic ester XVII and subsequent reaction with methylmagnesium bromide (MeMgBr) in solvent such as THF and temperatures of -78 to 0 °C, preferably 0 °C, to provide ketone II. Another method uses the reaction of nitrile XVI with MeMgBr which is carried out in solvent such as THF or toluene, preferably THF, and reaction temperature is 25 to 60 °C, preferably 60 °C, followed by treatment with 1N HCl (Eur J Med Chem, 2015, 102, 582-593).

[0087] The compounds I and the compositions thereof, respectively, are suitable as fungicides effective against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, in particular from the classes of Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes (syn. Fungi imperfecti). They can be used in crop protection as foliar fungicides, fungicides for seed dressing, and soil fungicides.

[0088] The compounds I and the compositions thereof are preferably useful in the control of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats, or rice; beet, fruits, leguminous plants such as soybean, oil plants, cucurbits, fiber plants, citrus fruits, vegetables, lauraceous plants, energy and raw material plants, corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); natural rubber plants; or ornamental and forestry plants; on the plant propagation material, such as seeds; and on the crop material of these plants.

[0089] According to the invention all of the above cultivated plants are understood to comprise all species, subspecies, variants, varieties and / or hybrids which belong to the respective cultivated plants, including but not limited to winter and spring varieties, in particular in cereals such as wheat and barley, as well as oilseed rape, e.g. winter wheat, spring wheat, winter barley etc.

[0090] Corn is also known as Indian corn or maize (Zea mays) which comprises all kinds of corn such as field corn and sweet corn. According to the invention all soybean cultivars or varieties are comprised, in particular indeterminate and determinate cultivars or varieties.

[0091] The term "cultivated plants" is to be understood as including plants which have been modified by mutagenesis or genetic engineering to provide a new trait to a plant or to modify an already present trait.

[0092] The compounds I and compositions thereof, respectively, are particularly suitable for controlling the following causal agents of plant diseases: rusts on soybean and cereals (e.g. Phakopsora pachyrhizi and P. meibomiae on soybean; Puccinia tritici and P. striiformis on wheat); molds on specialty crops, soybean, oil seed rape and sunflowers (e.g. Botrytis cinerea on strawberries and vines, Sclerotinia sclerotiorum, S. minor and S. rolfsii on oil seed rape, sunflowers and soybean); Fusarium diseases on cereals (e.g. Fusarium culmorum and F. graminearum on wheat); downy mildews on specialty crops (e.g. Plasmopara viticola on vines, Phytophthora infestans on potatoes); powdery mildews on specialty crops and cereals (e.g. Uncinula necator on vines, Erysiphe spp. on various specialty crops, Blumeria graminis on cereals); and leaf spots on cereals, soybean and corn (e.g. Septoria tritici and S. nodorum on cereals, S. glycines on soybean, Cercospora spp. on corn and soybean).

[0093] The compounds I and compositions thereof, respectively, are also suitable for controlling harmful microorganisms in the protection of stored products or harvest, and in the protection of materials.

[0094] The compounds I are employed as such or in form of compositions by treating the fungi, the plants, plant propagation materials, such as seeds; soil, surfaces, materials, or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds; soil, surfaces, materials or rooms by the fungi.

[0095] An agrochemical composition comprises a fungicidally effective amount of a compound I. The term "fungicidally effective amount" denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of stored products or harvest or of materials and which does not result in a substantial damage to the treated plants, the treated stored products or harvest, or to the treated materials. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant, stored product, harvest or material, the climatic conditions and the specific compound I used.

[0096] Plant propagation materials may be treated with compounds I as such or a composition comprising at least one compound I prophylactically either at or before planting or transplanting.

[0097] The user applies the agrochemical composition usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and / or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.

[0098] The compounds I, their N-oxides and salts can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types (see "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International) are suspensions (e. g. SC, OD, FS), emulsifiable concentrates (e. g. EC), emulsions (e. g. EW, EO, ES, ME), capsules (e. g. CS, ZC), pastes, pastilles, wettable powders or dusts (e. g. WP, SP, WS, DP, DS), pressings (e. g. BR, TB, DT), granules (e. g. WG, SG, GR, FG, GG, MG), insecticidal articles (e. g. LN), as well as gel formulations for the treatment of plant propagation materials, such as seeds (e. g. GF). The compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or by Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005. The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I. Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.

[0099] The agrochemical compositions generally comprise between 0.01 and 95 %, preferably between 0.1 and 90%, more preferably between 1 and 70 %, and in particular between 10 and 60 %, by weight of active substance (e.g. at least one compound I). Further, the agrochemical compositions generally comprise between 5 and 99.9 %, preferably between 10 and 99.9 %, more preferably between 30 and 99 %, and in particular between 40 and 90 %, by weight of at least one auxiliary.

[0100] When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.

[0101] In treatment of plant propagation materials, such as seeds, e. g. by dusting, coating, or drenching, amounts of active substance of generally from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kg of plant propagation material (preferably seeds) are required.

[0102] Various types of oils, wetters, adjuvants, fertilizers, or micronutrients, and further pesticides (e. g. fungicides, growth regulators, herbicides, insecticides, safeners) may be added to the compounds I or the compositions thereof as premix, or, not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

[0103] Mixing the compounds I or the compositions comprising them in the use form as fungicides with other fungicides results in many cases in an expansion of the fungicidal spectrum of activity or in a prevention of fungicide resistance development. Furthermore, in many cases, synergistic effects are obtained (synergistic mixtures).

[0104] The following list of pesticides II, in conjunction with which the compounds I can be used, is intended to illustrate the possible combinations but does not limit them: A) Respiration inhibitors Inhibitors of complex III at Q o site: azoxystrobin (A.1.1), coumethoxystrobin (A.1.2), coumoxystrobin (A.1.3), dimoxystrobin (A.1.4), enestroburin (A.1.5), fenaminstrobin (A.1.6), fenoxystrobin / flufenoxystrobin (A.1.7), fluoxastrobin (A.1.8), kresoxim-methyl (A.1.9), mandestrobin (A.1.10), metominostrobin (A.1.11), orysastrobin (A.1.12), picoxystrobin (A.1.13), pyraclostrobin (A.1.14), pyrametostrobin (A.1.15), pyraoxystrobin (A.1.16), trifloxy-strobin (A.1.17), 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N-methyl-acetamide (A.1.18), pyribencarb (A.1.19), triclopyricarb / chloro-dincarb (A.1.20), famoxadone (A.1.21), fenamidone (A.1.21), methyl-N-[2-[(1,4-dimethyl-5-phenyl-pyrazol-3-yl)oxylmethyl]phenyl]-N-methoxy-carbamate (A.1.22), metyltetraprole (A.1.25), (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]-oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (A.1.34), (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (A.1.35), pyriminostrobin (A.1.36), bifujunzhi (A.1.37), 2-(ortho-((2,5-dimethylphenyl-oxymethylen)phenyl)-3-methoxy-acrylic acid methylester (A.1.38); inhibitors of complex III at Q i site: cyazofamid (A.2.1), amisulbrom (A.2.2), [(6S,7R,8R)-8-benzyl-3-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-di-oxo-1,5-dioxonan-7-yl] 2-methylpropanoate (A.2.3), fenpicoxamid (A.2.4), florylpicoxamid (A.2.5), metarylpicoxamid (A.2.6); inhibitors of complex II: benodanil (A.3.1), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.11), isopyrazam (A.3.12), mepronil (A.3.13), oxycarboxin (A.3.14), penflufen (A.3.15), penthiopyrad (A.3.16), pydiflumetofen (A.3.17), pyraziflumid (A.3.18), sedaxane (A.3.19), tecloftalam (A.3.20), thifluzamide (A.3.21), inpyrfluxam (A.3.22), pyrapropoyne (A.3.23), fluindapyr (A.3.28), N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-5-fluoro-1-methyl-pyrazole-4-carboxamide (A.3.29), methyl (E)-2-[2-[(5-cyano-2-methyl-phenoxy)methyl]phenyl]-3-methoxy-prop-2-enoate (A.3.30), isoflucypram (A.3.31), 2-(difluoromethyl)-N-(1,1,3-trimethyl-indan-4-yl)-pyridine-3-carboxamide (A.3.32), 2-(difluoromethyl)-N-[(3R)-1,1,3-trimethylindan-4-yl]-pyridine-3-carboxamide (A.3.33), 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)-pyridine-3-carboxamide (A.3.34), 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]-pyridine-3-carboxamide (A.3.35), 2-(difluoromethyl)-N-(1,1-dimethyl-3-propyl-indan-4-yl)pyridine-3-carboxamide (A.3.36), 2-(difluoromethyl)-N-[(3R)-1,1-dimethyl-3-propyl-indan-4-yl]-pyridine-3-carboxamide (A.3.37), 2-(difluoromethyl)-N-(3-isobutyl-1,1-dimethyl-indan-4-yl)-pyridine-3-carboxamide (A.3.38), 2-(difluoromethyl)-N-[(3R)-3-isobutyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (A.3.39) cyclobutrifluram (A.3.24); other respiration inhibitors: diflumetorim (A.4.1); nitrophenyl derivates: binapacryl (A.4.2), dinobuton (A.4.3), dinocap (A.4.4), fluazinam (A.4.5), meptyldinocap (A.4.6), ferimzone (A.4.7); organometal compounds: fentin salts, e. g. fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.11); silthiofam (A.4.12); B) Sterol biosynthesis inhibitors (SBI fungicides) C14 demethylase inhibitors: triazoles: azaconazole (B.1.1), bitertanol (B.1.2), bromu-conazole (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), ipconazole (B.1.15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), paclobutrazole (B.1.20), penconazole (B.1.21), propiconazole (B.1.22), prothio-conazole (B.1.23), simeconazole (B.1.24), tebuconazole (B.1.25), tetraconazole (B.1.26), triadimefon (B.1.27), triadimenol (B.1.28), triticonazole (B.1.29), uniconazole (B.1.30), 2-(2,4-difluorophenyl)-1,1-difluoro-3-(tetrazol-1-yl)-1-[5-[4-(2,2,2-trifluoroethoxy)phenyl]-2-pyridyl]propan-2-ol (B.1.31), 2-(2,4-difluorophenyl)-1,1-difluoro-3-(tetrazol-1-yl)-1-[5-[4-(tri-fluoromethoxy)phenyl]-2-pyridyl]propan-2-ol (B.1.32), fluooxytioconazole (B.1.33), ipfentri-fluconazole (B.1.37), mefentrifluconazole (B.1.38), (2R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, (2S)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, 2-(chloromethyl)-2-methyl-5-(p-tolylmethyl)-1-(1,2,4-triazol-1-ylmethyl)cyclopentanol (B.1.43); imidazoles: imazalil (B.1.44), pefurazoate (B.1.45), prochloraz (B.1.46), triflumizol (B.1.47); pyrimidines, pyridines, piperazines: fena-rimol (B.1.49), pyrifenox (B.1.50), triforine (B.1.51), [3-(4-chloro-2-fluoro-phenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(3-pyridyl)methanol (B.1.52), 4-[[6-[2-(2,4-difluorophenyl)-1,1-diflu-oro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile (B.1.53), 2-[6-(4-bromo-phenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (B.1.54), 2-[6-(4-chlo-rophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (B.1.55); Delta14-reductase inhibitors: aldimorph (B.2.1), dodemorph (B.2.2), dodemorph-acetate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spiroxamine (B.2.8); Inhibitors of 3-keto reductase: fenhexamid (B.3.1); Other Sterol biosynthesis inhibitors: chlorphenomizole (B.4.1); C) Nucleic acid synthesis inhibitors phenylamides or acyl amino acid fungicides: benalaxyl (C.1.1), benalaxyl-M (C.1.2), kiralaxyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (C.1.5), ofurace (C.1.6), oxadixyl (C.1.7); other nucleic acid synthesis inhibitors: hymexazole (C.2.1), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine (C.2.6), 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine (C.2.7), 5-fluoro-2-(4-chlorophenylmethoxy)pyrimidin-4 amine (C.2.8); D) Inhibitors of cell division and cytoskeleton tubulin inhibitors: 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-quinolyl)oxy]butanamide (D.1.8), N-ethyl-2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methyl-sulfanyl-acetamide (D.1.9), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-(2-fluoroethyl)butanamide (D.1.10), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-(2-fluoroethyl)-2-methoxy-acetamide (D.1.11), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-propyl-butanamide (D.1.12), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methoxy-N-propyl-acetamide (D.1.13), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methylsulfanyl-N-propyl-acetamide (D.1.14), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-(2-fluoroethyl)-2-methylsulfanyl-acetamide (D.1.15), 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine (D.1.16); other cell division inhibitors: diethofencarb (D.2.1), ethaboxam (D.2.2), pencycuron (D.2.3), fluopicolide (D.2.4), zoxamide (D.2.5), metrafenone (D.2.6), pyriofenone (D.2.7), phenamacril (D.2.8); E) Inhibitors of amino acid and protein synthesis methionine synthesis inhibitors: cyprodinil (E.1.1), mepanipyrim (E.1.2), pyrimethanil (E.1.3); protein synthesis inhibitors: blasticidin-S (E.2.1), kasugamycin (E.2.2), kasugamycin hydrochloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6); F) Signal transduction inhibitors MAP / histidine kinase inhibitors: fluoroimid (F.1.1), iprodione (F.1.2), procymidone (F.1.3), vinclozolin (F.1.4), fludioxonil (F.1.5); G protein inhibitors: quinoxyfen (F.2.1); G) Lipid and membrane synthesis inhibitors Phospholipid biosynthesis inhibitors: edifenphos (G.1.1), iprobenfos (G.1.2), pyrazophos (G.1.3), isoprothiolane (G.1.4); lipid peroxidation: dicloran (G.2.1), quintozene (G.2.2), tecnazene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7), zinc thiazole (G.2.8); phospholipid biosynthesis and cell wall deposition: dimethomorph (G.3.1), flumorph (G.3.2), mandipropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7); compounds affecting cell membrane permeability and fatty acides: propamocarb (G.4.1); inhibitors of oxysterol binding protein: oxathiapiprolin (G.5.1), fluoxapiprolin (G.5.3), 4-[1-[2-[3-(difluoromethyl)-5-methyl-pyrazol-1-yl]acetyl]-4-piperidyl]- N-tetralin-1-yl-pyridine-2-carboxamide (G.5.4), 4-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.5), 4-[1-[2-[3-(difluoromethyl)-5-(trifluoromethyl)pyr-azol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.6), 4-[1-[2-[5-cyclopropyl-3-(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.7), 4-[1-[2-[5-methyl-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.8), 4-[1-[2-[5-(difluoromethyl)-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.9), 4-[1-[2-[3,5-bis(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.10), (4-[1-[2-[5-cyclopropyl-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.11); H) Inhibitors with Multi Site Action inorganic active substances: Bordeaux mixture (H.1.1), copper (H.1.2), copper acetate (H.1.3), copper hydroxide (H.1.4), copper oxychloride (H.1.5), basic copper sulfate (H.1.6), sulfur (H.1.7); thio- and dithiocarbamates: ferbam (H.2.1), mancozeb (H.2.2), maneb (H.2.3), metam (H.2.4), metiram (H.2.5), propineb (H.2.6), thiram (H.2.7), zineb (H.2.8), ziram (H.2.9); organochlorine compounds: anilazine (H.3.1), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.11); guanidines and others: guanidine (H.4.1), dodine (H.4.2), dodine free base (H.4.3), guazatine (H.4.4), guazatine-acetate (H.4.5), iminoctadine (H.4.6), iminoctadine-triacetate (H.4.7), iminoctadine-tris(albesilate) (H.4.8), dithianon (H.4.9), 2,6-dimethyl-1H,5H-[1,4]di-thiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetraone (H.4.10); I) Cell wall synthesis inhibitors inhibitors of glucan synthesis: validamycin (I.1.1), polyoxin B (I.1.2); melanin synthesis inhibitors: pyroquilon (I.2.1), tricyclazole (I.2.2), carpropamid (I.2.3), dicyclomet (I.2.4), fenoxanil (I.2.5); J) Plant defence inducers acibenzolar-S-methyl (J.1.1), probenazole (J.1.2), isotianil (J.1.3), tiadinil (J.1.4), prohexa-dione-calcium (J.1.5); phosphonates: fosetyl (J.1.6), fosetyl-aluminum (J.1.7), phosphorous acid and its salts (J.1.8), calcium phosphonate (J.1.11), potassium phosphonate (J.1.12), potassium or sodium bicarbonate (J.1.9), 4-cyclopropyl-N-(2,4-dimethoxyphenyl)thiadiazole-5-carboxamide (J.1.10); K) Unknown mode of action bronopol (K.1.1), chinomethionat (K.1.2), cyflufenamid (K.1.3), cymoxanil (K.1.4), dazomet (K.1.5), debacarb (K.1.6), diclocymet (K.1.7), diclomezine (K.1.8), difenzoquat (K.1.9), difenzoquat-methylsulfate (K.1.10), diphenylamin (K.1.11), fenitropan (K.1.12), fenpyrazamine (K.1.13), flumetover (K.1.14), flumetylsulforim (K.1.60), flusulfamide (K.1.15), flutianil (K.1.16), harpin (K.1.17), methasulfocarb (K.1.18), nitrapyrin (K.1.19), nitrothal-isopropyl (K.1.20), tolprocarb (K.1.21), oxin-copper (K.1.22), proquinazid (K.1.23), seboctylamine (K.1.61), tebufloquin (K.1.24), tecloftalam (K.1.25), triazoxide (K.1.26), N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine (K.1.27), N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine (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-isopro-pylcyclohexoxy)-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-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.34), N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-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 (pyrisoxazole) (K.1.37), 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (K.1.38), 5-chloro-1-(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1H-benzoimidazole (K.1.39), ethyl (Z)-3-amino-2-cyano-3-phenyl-prop-2-enoate (K.1.40), picarbutrazox (K.1.41), pentyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate (K.1.42), but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate (K.1.43), ipflufenoquin (K.1.44), quinofumelin (K.1.47), benzothiazolinone (K.1.48), bromothalonil (K.1.49), 2-(6-benzyl-2-pyridyl)quinazoline (K.1.50), 2-[6-(3-fluoro-4-methoxy-phenyl)-5-methyl-2-pyridyl]quinazoline (K.1.51), dichlobentiazox (K.1.52), N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine (K.1.53), aminopyrifen (K.1.54), fluopimomide (K.1.55), N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.56), N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine (K.1.57), flufenoxadiazam (K.1.58), N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide (K.1.59), N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide (WO2018 / 177894, WO 2020 / 212513);

[0105] In the binary mixtures the weight ratio of the component 1) and the component 2) generally depends from the properties of the components used, usually it is in the range of from 1:10,000 to 10,000:1, often from 1:100 to 100:1, regularly from 1:50 to 50:1, preferably from 1:20 to 20:1, more preferably from 1:10 to 10:1, even more preferably from 1:4 to 4:1 and in particular from 1:2 to 2:1. According to further embodiments, the weight ratio of the component 1) and the component 2) usually is in the range of from 1000:1 to 1:1, often from 100: 1 to 1:1, regularly from 50:1 to 1:1, preferably from 20:1 to 1:1, more preferably from 10:1 to 1:1, even more preferably from 4:1 to 1:1 and in particular from 2:1 to 1:1. According to further embodiments, the weight ratio of the component 1) and the component 2) usually is in the range of from 20,000:1 to 1:10, often from 10,000:1 to 1:1, regularly from 5,000:1 to 5:1, preferably from 5,000:1 to 10:1, more preferably from 2,000:1 to 30:1, even more preferably from 2,000:1 to 100:1 and in particular from 1,000:1 to 100:1. According to further embodiments, the weight ratio of the component 1) and the component 2) usually is in the range of from 1:1 to 1:1000, often from 1:1 to 1:100, regularly from 1:1 to 1:50, preferably from 1:1 to 1:20, more preferably from 1:1 to 1:10, even more preferably from 1:1 to 1:4 and in particular from 1:1 to 1:2. According to further embodiments, the weight ratio of the component 1) and the component 2) usually is in the range of from 10:1 to 1:20,000, often from 1:1 to 1:10,000, regularly from 1:5 to 1:5,000, preferably from 1:10 to 1:5,000, more preferably from 1:30 to 1:2,000, even more preferably from 1:100 to 1:2,000 to and in particular from 1:100 to 1:1,000.

[0106] In the ternary mixtures, i.e. compositions comprising the component 1) and component 2) and a compound III (component 3), the weight ratio of component 1) and component 2) depends from the properties of the active substances used, usually it is in the range of from 1:100 to 100:1, regularly from 1:50 to 50:1, preferably from 1:20 to 20:1, more preferably from 1:10 to 10:1 and in particular from 1:4 to 4:1, and the weight ratio of component 1) and component 3) usually it is in the range of from 1:100 to 100:1, regularly from 1:50 to 50:1, preferably from 1:20 to 20:1, more preferably from 1:10 to 10:1 and in particular from 1:4 to 4:1. Any further active components are, if desired, added in a ratio of from 20:1 to 1:20 to the component 1). These ratios are also suitable for mixtures applied by seed treatment.

[0107] Preference is given to mixtures comprising as component 2) at least one active substance selected from inhibitors of complex III at Q o site in group A), 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).

[0108] Preference is also given to mixtures comprising as component 2) at least one active substance selected from inhibitors of complex III at Q i site in group A), 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).

[0109] Preference is also given to mixtures comprising as component 2) at least one active substance selected from inhibitors of complex II 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).

[0110] Preference is also given to mixtures comprising as component 2) at least one active substance selected from other respiration inhibitors in group A), more preferably selected from compounds (A.4.5) and (A.4.11); in particular (A.4.11).

[0111] Preference is also given to mixtures comprising as component 2) at least one active substance 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); particularly 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).

[0112] Preference is also given to mixtures comprising as component 2) at least one active substance selected from Delta14-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).

[0113] Preference is also given to mixtures comprising as component 2) at least one active substance selected from phenylamides 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); particularly selected from (C.1.1) and (C.1.4).

[0114] Preference is also given to mixtures comprising as component 2) at least one active substance selected from other nucleic acid synthesis inhibitors in group C), more preferably selected from compounds (C.2.6), (C.2.7) and (C.2.8).

[0115] Preference is also given to mixtures comprising as component 2) at least one active substance selected from group D), more preferably selected from compounds (D.1.1), (D.1.2), (D.1.5), (D.2.4) and (D.2.6); particularly selected from (D.1.2), (D.1.5) and (D.2.6).

[0116] Preference is also given to mixtures comprising as component 2) at least one active substance selected from group E), more preferably selected from compounds (E.1.1), (E.1.3), (E.2.2) and (E.2.3); in particular (E.1.3).

[0117] Preference is also given to mixtures comprising as component 2) at least one active substance selected from group F), more preferably selected from compounds (F.1.2), (F.1.4) and (F.1.5).

[0118] Preference is also given to mixtures comprising as component 2) at least one active substance selected from group G), more preferably selected from compounds (G.3.1), (G.3.3), (G.3.6), (G.5.1), (G.5.3), (G.5.4), (G.5.5), G.5.6), G.5.7), (G.5.8), (G.5.9), (G.5.10) and (G.5.11); particularly selected from (G.3.1), (G.5.1) and (G.5.3).

[0119] Preference is also given to mixtures comprising as component 2) at least one active substance 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).

[0120] Preference is also given to mixtures comprising as component 2) at least one active substance selected from group I), more preferably selected from compounds (I.2.2) and (I.2.5).

[0121] Preference is also given to mixtures comprising as component 2) at least one active substance 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); in particular (J.1.5).

[0122] Preference is also given to mixtures comprising as component 2) at least one active substance selected from group K), more preferably selected from compounds (K.1.41), (K.1.42), (K.1.44), (K.1.47), (K.1.57), (K.1.58) and (K.1.59); particularly selected from (K.1.41), (K.1.44), (K.1.47), (K.1.57), (K.1.58) and (K.1.59).

[0123] The compositions comprising mixtures of active ingredients can be prepared by usual means, e. g. by the means given for the compositions of compounds I.Examples:Synthetic processExample 1: Methyl (2E)-2-[2-[[(E)-3-(2-fluorophenyl)ethylideneamino]oxymethyl]-3-methylphenyl]-2-methoxyimino-acetate

[0124] Step 1: 1-(2-Fluorophenyl)ethanone oxime

[0125] 1-(2-fluorophenyl)ethenone (10 g, 1.0 eq) was taken in methanol (300 ml) and hydroxyl amine hydrochloride (7.54 g, 1.8 eq) was added. Pyridine (33.45 g, 2 eq) was added drop wise at 25 °C. Reaction mixture was stirred at 50 °C for 2 hr. Reaction was monitored using LCMS & TLC. Methanol was evaporated under vacuum. Crude mass was diluted with water (200 ml) and it was extracted with ethyl acetate (3 x 100 ml). Combined organic layer was again washed with water and brine. Organic layer was dried over sodium sulphate and concentrated under vacuum. Crude compound was purified by flash column chromatography. Pure compound was eluted with 0% to 20% ethyl acetate (EtOAc) in heptane. Evaporation of solvent afforded 8 g title compound as white solid (Yield 72%). 1< H NMR 300 MHz, DMSO-d6: δ 11.4 (s ,1 H), 7.46-7.41 (m, 2 H), 7.27-7.23 (m, 2H), 2.14 (s, 3H).Step 2: Ethyl (2E)-2-[2-[[(E)-1-(2-fluorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate (Ex. 2)

[0126] 1-(2-fluorophenyl)ethanone oxime (0.3 g, 3 eq) was taken in dimethyl formamide (DMF, 5 ml) and Cs 2 CO 3 (3.27 g, 2.0 eq) was added. The reaction mixture was stirred for 30 minutes at room temperature (RT; at about 25 °C) and then added methyl (2E)-2-[2-(bromomethyl)-3-methyl-phenyl]-2-methoxyimino-acetate (0.6 g, 3.02 eq). The reaction mixture was stirred at RT for 32 hr and monitored by TLC and LCMS. Reaction was quenched with water (45 ml) and the product was extracted in ethyl acetate (3 x 35 ml). The combined organic layer was washed with brine (50 ml), dried over sodium sulphate and concentrated under vacuum. Crude material was purified by flash chromatography. Pure compound was eluted by using 35-20% EtOAc in heptane. Evaporation of solvent afforded an off-white solid title compound (0.328 g, 45% yield). 1< H NMR (300 MHz, DMSO-d6): δ 7.56 - 7.36 (m, 2H), 7.33 - 7.32 (m, 4H), 7.03 (dd, J = 6.2, 2.8 Hz, 3H), 5.00 (s, 2H), 3.93 (s, 3H), 3.64 (s, 3H), 2.42 (s, 3H), 2.08 (d, J = 2.5 Hz, 3H).Example 2: (2E)-2-[2-[[(E)-1-(2-fluorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-N-methyl-acetamide

[0127]

[0128] Methyl (2E)-2-[2-[[(E)-1-(2-fluorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate (ex. 1; 8 g,1 eq) was taken in THF (80 ml) and methylamine (40% aqueous) solution (16 ml, 2 vol) was added. The reaction mixture was stirred at 25 °C for 5 hr and monitored by TLC and LCMS. Reaction was quenched with water (200 ml) and the product was extracted in ethyl acetate (3 x 150 ml). The combined organic layer was washed with brine (150 ml), dried over sodium sulphate and concentrated under vacuum. Crude material was purified by flash chromatography. Pure compound was eluted by using 30-40% EtOAc in heptane. Evaporation of solvent afforded white solid title compound (7 g, 87.7% yield). 1< H NMR (500 MHz, DMSO-d6): δ 8.20 (q, J = 4.7 Hz, 1H), 7.44 (ddt, J = 7.8, 5.6, 2.0 Hz, 2H), 7.37 - 7.14 (m, 4H), 6.95 (dd, J = 7.1, 2.0 Hz, 1H), 5.01 (s, 2H), 3.86 (s, 3H), 2.65 (d, J = 4.8 Hz, 3H), 2.42 (s, 3H), 2.09 (d, J = 2.6 Hz, 3H).Example 3: Methyl (2E)-2-[2-[[(E)-1-(3,5-dichlorophenyl)ethylideneamino]oxymethyl]-3-methylphenyl]-2-methoxyimino-acetate

[0129] Step 1: 1-(3,5-dichlorophenyl)ethanone oxime

[0130] 3-(3,5-Dichlorophenyl)ethanone (3.0 g, 3eq) was taken in methanol (30 ml) and NH 2 OH (0.735 g, 2 eq) followed by pyridine (3.04 g, 2.5 eq) were added. Reaction mixture was heated to 70 °C and stirred for 3 hr. Reaction was monitored using LCMS & TLC. Solvent was evaporated and the residue was diluted with water (50 ml). The product was extracted in with ethyl acetate (3 x 30 ml). The combined organic layer was washed with brine (50 ml), dried over sodium sulphate and concentrated under vacuum. Crude material was purified by flash chromatography. Pure compound was eluted by using 15-20% EtOAc in heptane. Evaporation of solvent afforded white solid compound 1-(3,5-dichlorophenyl)ethanone oxime (1 g, 92.6% yield).Step 2: Methyl (2E)-2-[2-[[(E)-1-(3,5-dichlorophenyl)ethylideneamino]oxymethyl]-3-methylphenyl]-2-methoxyimino-acetate

[0131] 3-(3,5-Dichlorophenyl)ethanone oxime (0.4 g, 1 eq) was taken in acetonitrile (10 ml) and Cs 2 CO 3 (1.8 g, 2.5 eq) was added. The reaction mixture was stirred for 30 min at RT and then added methyl (2E)-2-[2-(bromomethyl)-3-methyl-phenyl]-2-methoxyimino-acetate (0.65 g, 1.05 eq). The reaction mixture was stirred at RT for 3 hr and monitored by TLC and LCMS. Reaction was quenched with water (50 ml) and the product was extracted in ethyl acetate (3 x 30 ml). The combined organic layer was washed with brine (50 ml), dried over sodium sulphate and concentrated under vacuum. Crude material was purified by flash chromatography. Pure compound was eluted by using 20-25% EtOAc in heptane. Evaporation of solvent afforded an off-white solid title compound (0.6 g, 68% yield). 1< H NMR (500 MHz, DMSO-d6): δ 7.66 (t, J = 1.9 Hz, 1H), 7.61 (d, J = 1.9 Hz, 2H), 7.36 - 7.23 (m, 2H), 7.05 - 6.98 (m, 1H), 5.04 (s, 2H), 3.91 (s, 3H), 3.70 (s, 3H), 2.43 (s, 3H), 2.30 (s, 3H).Example 4: (2E)-2-[2-[[(E)-1-(3,5-dichlorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-N-methyl-acetamide

[0132]

[0133] Methyl (2E)-2-[2-[[(E)-3-(3,5-dichlorophenyl)ethylideneamino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-acetate (ex. 3; 0.6 g, 1 eq) was taken in THF (6 ml) and methyl amine (40% aq.) solution (1.2 ml, 2v) was added. The reaction mixture was stirred at RT for 3 hr and monitored by TLC and LCMS. Reaction was quenched with water (25 ml) and the product was extracted in ethyl acetate (3 x 20 ml). The combined organic layer was washed with brine (25 ml), dried over sodium sulphate and concentrated under vacuum. Crude material was purified by flash chromatography. Pure compound was eluted by using 40-45% EtOAc in heptane. Evaporation of solvent afforded white solid title compound (example 2, 0.53 g, 85% yield). 1< H NMR (500 MHz, DMSO-d6): δ 8.24 (d, J = 4.8 Hz, 1H), 7.69 - 7.58 (m, 3H), 7.37 - 7.15 (m, 2H), 6.95 (dd, J = 7.1, 1.9 Hz, 1H), 5.05 (s, 2H), 3.86 (s, 3H), 2.68 (d, J = 4.7 Hz, 3H), 2.42 (s, 3H), 2.11 (s, 3H).Example 5: Methyl (2E)-2-methoxyimino-2-[3-methyl-2-[[(E)-1-(p-tolyl)ethylideneamino] oxymethyl]phenyl]acetate

[0134] Step 1: 1-(p-tolyl)ethanone oxime

[0135] To a solution of 1-(p-tolyl)ethanone (1.0 g, 4.45 mmol, 3 eq.) in methanol (10 mL) was added hydroxylamine hydrochloride (0.77 g, 11.17 mmol, 1.5 eq) followed by addition of sodium acetate (1.82 g, 15 mmol, 2 eq.) at RT under nitrogen atmosphere. Reaction mixture was refluxed for 2 hrs. Reaction was monitored by TLC. Reaction mixture was concentrated on rotavapor. To this crude residue was added water (20 mL) and stirred for 0.5 hr. Solid material filtered and dried to obtain pure title compound (1.1 g, yield 98 %) as white solid. MS: [M + H] +< 150.Step 2: Methyl (2E)-2-methoxyimino-2-[3-methyl-1-[[(E)-3-(p-tolyl)ethylideneamino] oxymethyl]phenyl]acetate

[0136] To a stirred solution of 1-(p-tolyl)ethanone oxime (0.15g, 1.0 mmol, 1 eq) in acetonitrile (2mL) was added Cs 2 CO 3 (0.66 g, 2.0 mmol, 2 eq). The reaction mixture was stirred at 25 °C for 30 min. Then, methyl (2E)-2-[2-(bromomethyl)-3-methyl-phenyl]-2-methoxyimino-acetate (0.33 g, 1.1 mmol, 1.1 eq) was added. The mixture was stirred at 25 °C for 6 h. Reaction was monitored by TLC and LCMS. To this reaction mixture was added water (30 mL) and extracted with EtOAc (3 x 30 mL). Combined organic layer was washed with H 2 O (2 x 25 mL), followed by brine wash (2 x 20 mL). Organic layer was dried over Na 2 SO 4 and Concentrated to afford crude compound which was further purified by flash column chromatography using 0-20% EtOAc in heptane as the eluent to obtain pure title compound as white solid (0.37 g, Yield 96%). 1< H NMR (500 MHz, chloroform-d): δ 7.42 (d, J = 8.2 Hz, 2H), 7.26 - 7.19 (m, 3H), 7.07 (d, J = 8.0 Hz, 2H), 6.94 (dd, J = 7.2, 1.8 Hz, 2H), 5.03 (s, 2H), 3.94 (s, 3H), 3.70 (s, 3H), 2.41 (s, 3H), 2.27 (s, 3H), 2.06 (s, 3H). MS: [M + H] +< 369.Example 6: (2E)-2-Methoxyimino-N-methyl-2-[3-methyl-2-[[(E)-1-(p-tolyl)ethylidene-amino]oxymethyl]phenyl]acetamide

[0137]

[0138] To a stirred solution of methyl (2E)-2-methoxyimino-2-[3-methyl-1-[[(E)-3-(p-tolyl)-ethylideneamino]oxymethyl]phenyl]acetate in THF (5 mL), methyl amine solution in water (5.0 mL, 40 %) was added at RT. Reaction was continued for 1 hr. Reaction was monitored by TLC. Reaction mixture was evaporated on rotavapor, residue was diluted with EtOAc (20 mL) and washed with 1N HCl (3 x 20 mL), followed by brine wash (2 x 20 mL). Organic layer was dried over Na 2 SO 4 and Concentrated to afford crude compound which was further purified by flash column chromatography using 0-50% EtOAc in heptane as the eluent to afford pure title compound as white solid (0.200 g, Yield 88%). 1< H NMR (500 MHz, DMSO-d 6 ): δ 8.20 (d, J = 5.0 Hz, 1H), 7.54 - 7.48 (m, 2H), 7.31 - 7.22 (m, 2H), 7.19 (d, J = 8.0 Hz, 2H), 6.95 (dd, J = 6.9, 2.1 Hz, 1H), 4.99 (s, 2H), 3.86 (s, 3H), 2.69 (d, J = 4.7 Hz, 3H), 2.43 (s, 3H), 2.31 (s, 3H), 2.08 (s, 3H). MS: [M + H] +< 368.Example 7: (2E)-2-methoxyimino-N-methyl-2-[3-methyl-2-[[(E)-[3,3,3-trifluoro-1-[3-(trifluoromethyl)phenyl]propylidene]amino]oxymethyl]phenyl]acetamide

[0139]

[0140] 3,3,3-Trifluoro-1-[3-(trifluoromethyl)phenyl]propan-1-one (0.5 g, 1 eq), prepared in analogy to prior art process (Chem Commun, 2016, 52, 13668-13670), was taken in THF (10 ml) and (2E)-2-[2-(aminooxymethyl)-3-methyl-phenyl]-2-methoxyimino-N-methyl-acetamide (0.98 g, 2 eq) followed by Ti(OEt) 4 (1.33g, 3 eq) were added. The mixture was heated to 70°C and stirred for 12 hr. The reaction was monitored by TLC and LCMS. The reaction was quenched with water (25 ml) followed by EtOAc (25 ml). The emulsion formed was filtered through celite and washed with EtOAc (50 ml). The layers were separated and the aequous layer was extracted in EtOAc (2 x 25ml). The combined organic layer was washed with brine (25 ml), dried over sodium sulphate and concentrated under vacuum. Crude material was purified by flash chromatography. Pure compound was eluted by using 40-45% EtOAc in heptane. Evaporation of solvent followed by crystallization in heptane afforded an off-white solid (0.34g, 35% yield). 1< H NMR (500 MHz, DMSO-d6): δ 8.27 (q, J = 4.7 Hz, 1H), 8.07 - 8.00 (m, 2H), 7.85 - 7.79 (m, 1H), 7.68 (t, J = 7.8 Hz, 1H), 7.35 - 7.24 (m, 2H), 6.97 (dd, J = 7.3, 1.7 Hz, 1H), 5.12 (s, 2H), 4.03-3.96 (q, J = 10 Hz, 2H), 3.86 (s, 3H), 2.67 (d, J = 4.7 Hz, 3H), 2.43 (s, 3H).

[0141] The following examples in Table S were synthesized as per general Scheme 1 described above (except Ex. 7 and 212 which were synthesized as per scheme 2) and characterized by LCMS as described in Table L. Table L: LCMS MethodsLCMS Method A Method details Device details Column: Agilent Eclipse Plus C18 (50 mm × 4.6 mm × 3 µm particles)LCMS2020 (Shimadzu) Ionization source: ESIMobile Phase:Mass range: 100 - 800 amuA: 10 mM Ammonium formate in water.Polarity: Dual (positive and negative simultaneous scan)B: 0.1 % Formic acid in acetonitrileGradient: 10 % B to 100 % B in 1.5 min.Mode: ScanHold 1 min 100 % B. 1 min 10 % B. Run time: 3.50 or 3.75 min.LC System: Nexera High pressure gradient system, Binary pumpFlow: 1.2 ml / min;Detector: PDAColumn oven: 30°C / 40°CScanning wavelength: 220 nm / max plotLCMS Method B Method details Device details Column: Luna-C18 (30 mm × 2.0 mm × 3 µm particles)LCMS DELIVER-220 (Shimadzu) Ionization source: ESIMobile Phase:Mass range: 100 - 1000 amuA: 0.037% Trifluoroacetic acid in water.Polarity: PositiveB: 0.018% Trifluoroacetic acid in HPLC grade acetonitrileMode: ScanLC System: Nexera High pressure gradient system, Binary pumpGradient: 5-95% B in 3.00 min .5% B in 0.01 min, 5-95% B (0.01-1.60 min), 95-100% B (1.60 - 2.50 min), 100 -5% (2.50 - 2.52 min) with a hold at 5% B for 0.48 min.Detector: DADScanning wavelength: 220 nm / max plotFlow: 0.8 mL / min;Column oven: 40°C LCMS Method C Method details Device details Column: Xbridge Shield RP18 (50 mm x 2.1 mm, 5 µm particles)Agilent Ionization source: ESIMobile Phase:Mass range: 100 - 1000 amuA: H 2 O+10 mM NH 4 HCO 3 Polarity: PositiveB: AcetonitrileMode: ScanGradient: 5% B in 0.40 min and 5-95% B at 0.40-3.40 min, hold on 95% B for 0.45 min, and then 95-5%B in 0.01 min.LC System: Nexera High pressure gradient system, Binary pumpDetector: DADFlow: 0.8 ml / min;Scanning wavelength: 220 nm / max plotColumn oven: 40°C LCMS Method D Method details Device details Column: Agilent Eclipse Plus C18 (50 mm × 4.6 mm × 3 µm particles)LCMS 2020 (Shimadzu) Ionization source: ESIMobile Phase:Mass range: 100 - 800 amuA: 10 mM NH 4 (HCOO) in waterPolarity: Dual (positive and negative simultaneous scan)B: AcetonitrileGradient: 10 % B to 100 % B in 5 min, hold on 100 % B for 3 min, 2 min 10 % B.Mode: ScanLC System: Nexera High pressure gradient system, Binary pumpRun time: 10 min.Flow: 1.2 ml / min;Detector: PDAColumn oven: 40°CScanning wavelength: 220 nm / max plot

[0142] Used LCMS Method in Table S to be found in Column LCMS. Table S:No. Structure R t [min] Mass LCMS 1 2.08373.7A2 1.941372A3 2.252422.9A4 2.15421.9A5 2.144369A6 2.027368A7 2.123490A8 2.15422.5A9 2.19423.5A10 2.22449.2 3A11 2.13448.4A12 1.95404A13 2.18435.3A14 2.11434.4A15 2.05425.2A16 2.17426.2A17 1.99447.1A18 2.09448.2A19 2.06404A20 2.155425A21 2.06408.5A22 2.08424A23 2.04458.3A24 2.07458.9A25 2.07441.0 5A26 1.984440A27 1.97408A28 2.17439A29 2.09438A30 2.058355A31 1.963354A32 2.17490A33 2.25456.9A34 2.25491A35 2.1446.8A36 2.101423A37 2.155422.9A38 1.999422A39 2.059422A40 2.271423.7A41 2.15422A42 1.94435.9A43 2.09436A44 1.99445.9A45 2.13397A46 2.01447A47 2.08440A48 2.11448A49 2.18441A50 2.11440.8A51 2.2441A52 2.274447.8A53 2.094379.8A54 1.984378A55 2.02396A56 2.197435.6A57 2.208446.1A58 2.091432.8A59 2.26457A60 2.15456A61 2.22437A62 2.146436A63 2.099436A64 1.97435A65 2.24437A66 2.24491A67 2.15490A68 2.14436A69 2.059440A70 2.197480A71 2.091479A72 1.337391A73 1.256390A74 2.208463A75 2.101462A76 2.22369A77 2.1368A78 2.133385A79 2.005384A80 2.13421A81 2.037420A82 2.08425A83 1.92424A84 2.08390A85 2.03372A86 2.17373A87 2.08391A88 2.24448A89 2.15449A90 2.261459A91 2.155458A92 2.21451A93 2.11450A94 2.187383A95 2.22397A96 2.283411A97 2.208431A98 5.01430D99 2.08382A100 2.187410A101 2.22403A102 2.21403A103 2.08373A104 1.995380A105 2.144396A106 2.112402A107 2.123402A108 1.952372A109 2.123402A110 2.25441A111 2.2431A112 1.87379A113 2.11430A114 2.17435A115 2.113369A116 2.101389A117 2.197423A118 2.091391A119 2.12434A120 2.005433A121 2.2431A122 2.05379A123 2.04385A124 2.11430A125 1.93378A126 1.931384A127 1.984368A128 1.984388A129 2.112391A130 2.08422A131 1.984390A132 1.984390A133 2.187439A134 2.155453A135 2.29513A136 2.08438A137 2.18383A138 2.261453A139 2.155382A140 2.144450A141 2.069452A142 2.208512A143 2.197447A144 2.304499A145 2.261463A146 2.261451A147 2.24449A148 2.187446A149 2.347498A150 2.272462A151 2.261450A152 2.229448A153 2.155389A154 2.144389A155 1.995380A156 2.133459A157 2.132388A158 2.133388A159 1.941379A160 2.08425A161 162 2.091458A163 2.229403A164 1.995384A165 2.187382A166 2.048397A167 2.219440A168 2.133434A169 2.112409A170 1.984408A171 2.29423A172 2.165379A173 2.069422A174 2.24383A175 2.261383A176 2.145382A177 2.165391A178 2.037390A179 1.888396A180 2.273459A181 2.261426A182 2.144425A183 2.251383A184 2.123438A185 2.23462A186 2.112452A187 2.027426A188 2.24437A189 2.144436A190 2.187456A191 2.229453A192 2.24439A193 2.101402A194 2.421465A195 2.144382A196 1.931378A197 2.176458A198 2.204441A199 2.144440A200 2.315457A201 2.133439A202 2.016438A203 2.283383A204 2.315437A205 2.15490A206 2.336451A207 2.229450A208 2.219452A209 2.187450A210 2.219381A211 2.091380A212 1.952425A213 2.123391A214 1.947391A215 2.357463A216 2.048385A217 2.208395A218 2.261397A219 2.101394A220 2.155396A221 2.251410A222 2.165437A223 2.048436A224 1.963380A225 1.853379A226 2.069455A227 2.187456A228 2.25456A229 2.24437A230 2.155436.3A231 2.16422A232 2.165421A233 2.21469A234 2.251462A235 2.251465A236 2.24439A237 2.325463A238 2.165469A239 2.315437A240 2.315469A241 2.208468A242 2.219415A243 2.112414A244 2.18422A245 2.176456A246 2.4441A247 2.283440A248 2.048452A249 2.133441A250 2.251491A251 2.197457A252 1.963420A253 208421A254 2.176453A255 2.229490A256 2.155407A257 2.251503A258 2.155502A259 2.251453A260 2.059440A261 2.165452A262 2.034406A263 2.144441A264 2.144513A265 2.229514A266 2.069391A267 3902.005A268 2.283473A269 2.229457A270 2.144456A271 2.176472A272 2.123490A273 2.123436A274 2.219491A275 2.165491A276 2.219437A277 1.952398A278 2.155382A279 2.347411A280 2.06399A281 2.176431A282 1.99445.9A283 2.12407A284 2.0406A285 2.16387A286 2.02396A287 2.14397A288 2.02430A289 2.20457A290 2.1456A291 1.95394A292 2.25395A293 2.02386A294 2.05369A295 1.94384A296 2.18408A297 2.20395A298 1.98404A299 2.14394A300 2.22469A301 2.1468A302 2.16419A303 2.04418A304 1.416456.8A305 1.95447B306 1.96465B307 1.99427B308 1.64412B309 1.9413B310 1.9426B311 1.74413B312 1.76398B313 1.88411B314 1.69414B315 1.82412B316 4641.86B317 1.86399B318 1.83412B319 1.93413B320 1.86453B321 1.87446B322 1.8415B323 1.386456.7A324 1.79452B325 1.64456B326 1.77440B327 1.83436B328 1.88453B329 1.78410B330 1.86441B331 1.77452B332 1.93437B333 2.25503A334 1.9457B335 1.53549A336 1.458548.1A337 1.67468B338 2473B339 1.85426B340 1.7452B341 1.65437B342 1.88505B343 1.95506B344 1.68474B345 1.6440B346 1.82474B347 1.92355B348 1.97453B349 3.04522C350 1.99507B351 1.92457B352 1.84488B353 1.86419B354 1.82456B355 2.97535C356 3.13536C357 1.62458B358 2.93519C359 1.95459B360 1.73459B361 1.76475B362 1.93455B363 1.89506B364 1.74438A365 1.7441B366 1.9475B367 1.84354B368 3.09520C369 1.87458B370 1.94489B371 3.79523C372 1.76418B373 374 1.94427B375 1.91472B376 2.07403A377 1.95402A378 1.67456B379 2.2457A380 2.04422A381 2.13423A382 2.2417A383 2.07416A384 1.67472B385 1.78473B386 2.24383A387 2.25383A388 2.14382A389 2.11382A390 2.18440A391 2.15437A392 2.16437A393 2.03436A394 2.08454A395 2.19421A396 2.05420A397 2.23381A398 2.18367A399 2.03380A400 1.99366A401 2.03396A402 2.197455A403 1.25436A404 2.167473A405 2.22472A406 2.12472A407 2.26512A408 2.29513A409 2.21459A410 2.04458A411 2.24489A412 2.13488A413 2.25498A414 2.34499A415 2.18509A416 2.27529A417 2.24494A418 2.28510A419 2.106528A420 2.02493A421 2.18457A422 2.12456A423 2.03448A424 1.898447A425 2.26517A426 2.15516A427 1.86507B428 1.75506B429 2.27491A430 2.3490A431 2.17490A432 2.33516A433 2.4514A434 2.33515A435 2.15514A436 1.86506B437 1.71436B438 1.77491B439 1.82507B440 1.66490B441 1.71506B442 1.77490B443 1.72489B444 1.83506B445 2.23500A446 2.12436A447 1.87475B448 1.75488B449 1.8490B450 1.89474B451 1.78474B452 1.91490B453 1.85488B454 1.83489B455 1.9491B456 1.81488B457 1.72488B458 2.04408A459 2.16409A460 2.64465A461 2.00438A462 2.21438A463 2.31472A464 2.10452A Biological studiesGreen House and detached leaf tests

[0143] The compound was dissolved in a mixture of acetone and / or dimethylsulfoxide and the wetting agent / emulsifier Wettol, which is based on ethoxylated alkylphenoles, in a ratio (volume) solvent-emulsifier of 99 to 1 to give a total volume of 5 ml. Subsequently, water was added to total volume of 100 ml. This stock solution was then diluted with the described solvent-emulsifier-water mixture to the final concentration given in the table below.Use example 1. Curative control of soybean rust on soybeans caused by Phakopsora pachyrhizi (PHAKPA K4)

[0144] Leaves of potted soybean seedlings were inoculated with spores of Phakopsora pachyrhizi. The strain used contains the amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors. To ensure the success of the artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95% and 20 to 24 °C for 24 hr. The next day the plants were cultivated for 3 days in a greenhouse chamber at 23 to 27 °C and a relative humidity between 60 and 80 %. Then the plants were sprayed to run-off with the previously described spray solution, containing the concentration of active ingredient or their mixture as described below. The plants were allowed to air-dry. Then the trial plants were cultivated for up to 14 days in a greenhouse chamber at 23 to 27 °C and a relative humidity between 60 and 80 %. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area, the disease level of untreated controls was usually higher than 85 %.Use example 2. Protective control of soybean rust on soybeans caused by Phakopsora pachyrhizi (PHAKPA P2)

[0145] Leaves of potted soybean seedlings were sprayed to run-off with the previously described spray solution, containing the concentration of active ingredient or their mixture as described below. The plants were allowed to air-dry. The trial plants were cultivated for 2 days in a greenhouse chamber at 23-27 °C and a relative humidity between 60 and 80 %. Then the plants were inoculated with spores of Phakopsora pachyrhizi. The strain used contains the amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95 % and 20 to 24 °C for 24 hr. The trial plants were cultivated for up to 14 days in a greenhouse chamber at 23 to 27 °C and a relative humidity between 60 and 80 %. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area, the disease level of untreated controls was usually higher than 85 %.Use example 3. Protective control of soybean rust on soybeans caused by Phakopsora pachyrhizi (PHAKPA P6)

[0146] Leaves of potted soybean seedlings were sprayed to run-off with the previously described spray solution, containing the concentration of active ingredient as described below. The plants were allowed to air-dry. The trial plants were cultivated for six days in a greenhouse chamber at 23-27 °C and a relative humidity between 60 and 80 %. Then the plants were inoculated with spores of Phakopsora pachyrhizi. The strain used contains the amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors. To ensure the success the artificial inoculation, the plants were transferred to a humid chamber with a relative humidity of about 95 % and 23 to 27 °C for 24 hr. The trial plants were cultivated for up to 14 days in a greenhouse chamber at 23 to 27 °C and a relative humidity between 60 and 80 %. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area, the disease level of untreated controls was usually higher than 85 %.Use example 4. Protective control of soybean rust on detached soybean leaves caused by Phakopsora pachyrhizi (PHAKPA P1 DL)

[0147] Leaves of potted soybean seedlings were sprayed to run-off with the previously described spray solution, containing the concentration of active ingredient as described below. The plants were left for drying in a green house chamber at 20 °C and 14 hours lightning over night. The next day, leaves were harvested and placed on water agar plates. Subsequently, the leaves were inoculated with spores of Phakopsora pachyrhizi. Two different isolates were used: one being sensitive to Qo inhibitors (wt); and one which contains the amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors (F129L). Inoculated leaves were incubated for 16 to 24 h at room temperature in a dark dust chamber, followed by incubation for 2 to 3 weeks in an incubator at 20 °C and 12 hours light / day. The extent of fungal attack on the leaves was visually assessed as % diseased leaf area.Micro titer plate tests

[0148] The active compounds were formulated separately as a stock solution having a concentration of 10,000 ppm in dimethyl sulfoxide. The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations.

[0149] After addition of the respective spore suspension as indicated in the different use examples below, plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free blank value to determine the relative growth in % of the pathogens in the respective active compounds.Use example 5. Activity against Pyricularia oryzae causing rice blast (PYRIOR)

[0150] A spore suspension of Pyricularia oryzae in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was used.Use example 6. Activity against Septoria tritici causing leaf blotch on wheat (SEPTTR)

[0151] A spore suspension of Septoria tritici in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was used.Use example 7. Activity against Colletotrichum orbiculare causing anthracnose (COLLLA)

[0152] A spore suspension of Colletotrichum orbiculare in an aqueous 2% malt solution was used.Use example 8. Activity against Leptosphaeria nodorum causing wheat leaf spots (LEPTNO)

[0153] A spore suspension of Leptosphaeria nodorum in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was used.Use example 9. Activity against Alternaria solani causing early blight (ALTESO, wt and F129L)

[0154] Two different spore suspensions of Alternaria solani in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution were used: a sensitive wild-type isolate (wt) and a Qo inhibitor-resistant isolate containing the amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors (F129L).Use example 10. Activity against Pyrenophora teres causing net blotch on barley (PYRNTE, wt and F129L)

[0155] Two different spore suspensions of Pyrenophora teres in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution were used: a sensitive wild-type isolate (wt) and a Qo inhibitor-resistant isolate containing the amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors (F129L).Use example 11. Activity against Cercospora sojina causing frogeye leaf spot of soybeans (CERCSO)

[0156] A spore suspension of Cercospora sojina in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was then added.Use example 12. Activity against Microdochium nivale causing snow mould (MONGNI)

[0157] A spore suspension of Microdochium nivale in an aqueous biomalt or yeast-bactopeptone-glycerine or DOB solution was used.

[0158] The results of the abovementioned use examples are given in the following Tables.

[0159] The test results in Tables 1 and C1 to C4 below are given for the control of phytopathogenic fungi containing the amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors. Table 1:Treatment with compound % PHAKPA (F129L) Disease level No. Structure P2 at 4 ppm P2 at 16 ppm P6 at 4 ppm P6 at 16 ppm 1 802790562 502613 3034064 201315 2815046 101918 40509 352341410 22245311 23120012 25137913 28025014 6011115 4024117 7050635719 87087120 7329971821 10077978822 100901009323 12120124 366042825 16350226 12019127 5032028 0029 0030 53177231 004032 8050734333 5033607534 10090908336 100421004337 40340238 37447139 30415240 4018632241 159361442 6023602043 100100978744 7717772146 6350905747 13012048 100801006749 601860750 216051 28215052 6328904353 63171004754 0120055 3113556 4324671957 258431558 204059 6720631160 23153261 7015901862 43060363 9077937764 8773804365 93771008766 10070938767 672803069 2013070 30010171 206072 10087938073 01974 27616375 8013176 3039077 67440378 40130179 21244480 501030381 602082 875783 977384 000085 100086 12323387 807093 8332433794 22535295 11033496 613097 411098 301099 43128733100 180254101 70376017102 60119043103 403354104 22151911105 1813913106 51329107 10151108 1010109 81120110 203301111 2884610112 133309113 25264125114 3855215115 83639275116 85578567117 85108812118 100320119 93639263120 434908121 100989892122 100739390123 100829078124 98879275125 7299044126 87349570127 90449362128 322772129 281242130 201401131 0020132 1060133 1020134 3710227135 151162136 1032137 192505138 472351139 4727224140 80134141 2020142 195265143 40150144 87809290145 2883716146 73127748147 73189518148 92137149 83458731150 5687029151 373536152 241387153 123221154 3013639155 97309320156 270473157 1010158 0020159 282281160 100978790161 10010010090162 0010163 201479164 50270165 00170166 100839043167 2090168 2050169 770770170 9040171 1001008050172 3518312173 100539717174 1001008070175 1009710093176 10010010090177 100218747178 6020179 100479028180 40750181 2211335182 60130183 160382184 424161185 100679077186 1020187 1001009090188 10110189 82289737190 200453191 7728322193 150140196 10115197 0020198 4100199 0000200 937310077202 902210047203 87329332204 504805206 1006710090207 4011835211 1004310077213 5034011214 140284215 87378733216 77138029217 975393100218 10087100100219 6088743220 903010077221 10063100100222 1005710093223 40280224 97100100100225 832710097226 283577227 1004710057228 50222229 272776230 221734231 0020232 1007310083233 100578727234 53185315235 100738777236 977797100238 1005310077240 708733241 303312242 87108720243 40371244 140152245 288132246 4015777247 162338248 332302249 87379043250 90909080251 80808080252 5038732253 1008710057254 10077100100255 978310087256 50187020257 933510057258 327738259 80179340260 220220261 7098732262 631474263 80157322266 67189043267 20104268 6366017269 50180270 3001271 51272 608273 603277 10060100100278 90609093282 1518283 83308722284 63446234285 87509035286 67159727288 87309720290 92148321294 1120295 20110296 1004010083297 90378737298 6379737299 53135322302 474473303 20120304 532810037312 10053314 10040315 10060321 10040324 21120325 244221326 250301327 233484328 338235329 1005310073330 83249317335 77538025336 63205017337 90131340 234427344 60160345 221321346 4050349 97509735354 172214355 347484357 131180358 77178318359 1003710043360 539805361 80188831363 291252365 77159743366 53138312367 6399330368 83479073372 85268516373 772710038375 478406378 181171380 5356012387 60308047388 1030389 284433390 220182393 93559342394 93122395 4346718396 3040399 6789015400 2080401 175324405 97277027406 97306723407 126174408 30123313409 77408373410 90351412 476406413 40153315414 5395315415 4756711416 57276725417 35186322418 70337357419 40186012420 80121421 100338757422 300322423 100579353424 100279750425 27285340426 712710427 100906047428 70118320429 83506743430 2263717431 3274012432 120133433 83678057435 93578760436 70157327437 2080440 93237323441 100439750442 100938077444 100478353445 151302446 2060447 70331449 3310579450 3141451 1020452 6067014458 93578350461 262526462 3765510463 6030464 1080 Comparative trials

[0160] Table C1:PHAKPA (F129L) Disease level (%) Compound Structure P2 at 4 ppm P2 at 16 ppm P6 at 4 ppm P6 at 16 ppm Trifloxystrobin as comparative example 71177933Ex. 9 35 23 41 4 Table C2: PHAKPA (F129L) Disease level (%) Compound Structure P2 at 4 ppm P6 at 4 ppm Comparative example 630Ex. 231 0 2 Comparative example 2770Ex. 58 0 4 Comparative example 100100Ex. 6 0 23 Comparative example 4080Ex. 158 1 4 Comparative example 4380Ex. 157 02Comparative example 10097Ex. 4 2 17 Comparative example 87100Ex. 31 0 12 Comparative example 1238Ex. 8 1 13 Comparative example 4377Ex. 41 4 35 Comparative example 3583Ex. 165 0 27 Comparative example 8797Ex. 130 33 67 Comparative example 6070Ex. 188 2 30 Comparative example 4390Ex. 73 1 37 Untreated10099 Table C3: PHAKPA (F129L) Disease level (%) Compound Structure P2 at 16 ppm P6 at 16 ppm Comparative example 2328Ex. 120 6 15 Comparative example 8780Ex. 126 32 60 Comparative example 3728Ex. 113 17 6 Comparative example 3763Ex. 159 0 0 Comparative example 114Ex. 60 0 0 Comparative example 1635Ex. 12 3 9 Comparative example 1515Ex. 27 0 0 Comparative example 7053Ex. 282 15 18 Comparative example 2332Ex. 205 1 1 Untreated10087 Table C4: PHAKPA (F129L) Disease level (%) Compound Structure P2 at 16 ppm P6 at 16 ppm Comparative example 2717Ex. 3 2 1 Comparative example 8087Ex. 56 32 15 Comparative example 8790Ex. 36 47 57 Comparative example 2510Ex. 5 1 4 Comparative example 6733Ex. 216 20 15 Comparative example 8377Ex. 1 28 47 Comparative example 4313Ex. 37 0 0 Comparative example 8743Ex. 30 2 1 Comparative example 5760Ex. 181 12 5 Comparative example 8753Ex. 155 23 18 Comparative example 10090Ex. 20 30 18 Comparative example 6343Ex. 154 25 17 Comparative example 9383Ex. 76 1 0 Comparative example 9080Ex. 86 6 7 Comparative example 7370Ex. 153 5 1 Comparative example 8043Ex. 104 37 28 Comparative example 119Ex. 244 0 2 Comparative example 122Ex. 131 0 0 Untreated>90>85

[0161] The results in Tables C1 to C4 show that the specific substituent at position R 3< improves the fungicidal activity against phytopathogenic fungi containing the amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors compared to compounds where the position R 3< is unsubstituted. Table C5:Fungal growth (%) Concentration applied (ppm) 0.016 0.016 0.016 0.016 Compound Structure PYRIOR ALTESO wt ALTESO F129L MONGNI Comparative example from WO 2017 / 157923 879810097Ex. 158 38 66 79 71 Table C6a: PHAKPA P1 DL Disease level (%) Qo I-sensitive wt isolate (0 % F129L) Test concentration (ppm) Compound Structure 0 0.3 1 3 10 30 100 300 Comparative example from WO 17 / 157923 937880774830185Ex. 158 38 7 2 1 4 5 4 Table C6b: PHAKPA P1 DL Disease level (%) Qo I-resistant F129L isolate (100 % F129L) Test concentration (ppm) Compound Structure 0 0.3 1 3 10 30 100 300 Comparative example from WO 17 / 157923 9388909592906552Ex. 158 87 57 8 2 4 4 5

[0162] The results in Tables C5 to C6b show that the compounds to the present invention significantly improve the fungicidal activity against phytopathogenic fungi containing the amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors compared to the use of a compound disclosed in WO 2017 / 157923. Table C7a:Fungal growth (%) Concentration applied (ppm) 0.016 0.016 0.025 4 Compound Structure PYRIOR ALTESO wt PYRNTE wt CERCSO Comparative example from WO 98 / 23156 100948433Ex. 9 38 73 44 11 Table C7b: PHAKPA (F129L) Disease level (%) Compound Structure P2 at 4 ppm Comparative example from WO 98 / 23156 17Ex. 9 6Untreated92 Table C8a: Fungal growth (%) Concentration applied (ppm) 0.016 0.063 0.016 4 Compound Structure PYRIOR COLLLA ALTESO wt ALTESO F129L Comparative example from WO 98 / 23156 100779487Ex. 84 48 33 43 39 Table C8b: Fungal growth (%) Concentration applied (ppm) 0.25 0.25 0.063 0.016 Compound Structure PYRNTE wt PYRNTE F129L LEPTNO MONGNI Comparative example from WO 98 / 23156 87847986Ex. 84 39 49 60 32

[0163] The results in Table C7a to C8b show that the specific substituent R a< of the terminal phenyl improves the fungicidal activity against phytopathogenic fungi compared to compounds from the prior art. Table C9:Fungal growth (%) Concentration applied (ppm) 0.016 0.063 4 Compound Structure PYRIOR LEPTNO CERCSO Comparative example from WO 98 / 23156 5810056Ex. 9 38 67 11 Table C10: Fungal growth (%) Concentration applied (ppm) 0.016 0.063 0.016 4 0.016 Compound Structure PYRIOR LEPTNO ALTESO F129L CERCSO MONGNI Comparative example from WO 98 / 23156 4993856684Ex. 8 13 70 55 27 54 Table C11a: Fungal growth (%) Concentration applied (ppm) 0.016 0.25 0.063 0.016 0.016 Compound Structure PYRIOR SEPTTR LEPTNO ALTESO wt ALTESO F129L Comparative example from WO 98 / 23156 39779510087Ex. 8 13 57 70 56 52 Table C11b: Fungal growth (%) Concentration applied (ppm) 4 0.016 Compound Structure CERCSO MONGNI Comparative example from WO 98 / 23156 6080Ex. 8 27 54 Table C12: Fungal growth (%) Concentration applied (ppm) 0.016 0.25 0.063 0.016 0.25 Compound Structure PYRIOR SEPTTR COLLLA MONGNI PYRTNE F129L Comparative example from WO 98 / 23156 87618169Comparative example from WO 98 / 23156 8289938487Ex. 76 43 0 39 35 66 Table C13: Fungal growth (%) Concentration applied (ppm) 0.063 0.016 0.016 0.25 4 Compound Structure LEPTNO ALTESO wt ALTESO F129L PYRNTE wt CERCSO Comparative example from WO 98 / 23156 8567665971Comparative example from WO 98 / 23156 6593815367Comparative example from WO 98 / 23156 100100877887Ex. 76 39 55 37 39 28 Table C14: Fungal growth (%) Concentration applied (ppm) 0.016 0.25 0.063 0.016 0.016 Compound Structure PYRIOR SEPTTR COLLLA ALTESO wt ALTESO F129L Comparative example from WO 98 / 23156 80100819395Comparative example from WO 98 / 23156 8187938993Ex. 77 20 49 39 73 69 Table C15a: Fungal growth (%) Concentration applied (ppm) 0.016 0.25 0.063 0.016 0.016 Compound Structure PYRIOR SEPTTR COLLLA ALTESO wt ALTESO F129L Comparative example from WO 98 / 23156 88398294100Comparative example from WO 98 / 23156 8339898189Ex. 153 50 0 55 71 68 Table C15b: Fungal growth (%) Concentration applied (ppm) 0.063 0.25 4 0.016 Compound Structure LEPTNO PYRNTE wt CERCSO MONGNI Comparative example from WO 98 / 23156 88576295Comparative example from WO 98 / 23156 6961Ex. 153 55 31 26 75 Table C16a: Fungal growth (%) Concentration applied (ppm) 0.016 0.25 0.063 0.25 0.016 Compound Structure PYRIOR SEPTTR COLLLA ALTESO wt ALTESO F129L Comparative example from WO 98 / 23156 10059824390Ex. 157 15 20 63 27 57 Table C16b: Fungal growth (%) Concentration applied (ppm) 0.25 0.25 4 0.016 Compound Structure PYRNTE wt PYRNTE F129L CERCSO MONGNI Comparative example from WO 98 / 23156 768078100Ex. 157 54 58 36 56 Table C17: PHAKPA (F129L) Disease level (%) Compound Structure P2 at 4 ppm P6 at 16 ppm Comparative example from WO 98 / 23156 8357Comparative example from WO 98 / 23156 8037Comparative example from WO 98 / 23156 6030Ex. 76 35 4 Comparative example from WO 98 / 23156 45Comparative example from WO 98 / 23156 6767Ex. 77 3720Comparative example from WO 98 / 23156 23Ex. 9 1Comparative example from WO 98 / 23156 209Ex. 157 11Comparative example from WO 98 / 23156 8387Comparative example from WO 98 / 23156 4718Ex. 153 19 5 Untreated9275 Table C18: PHAKPA (F129L) Disease level (%) Compound Structure P2 at 1 ppm P6 at 4 ppm Comparative example from WO 98 / 23156 3243Ex. 8 6 1 Untreated9275

[0164] The results in Tables C9 to C18 show that the specific substituent R 4< improves the fungicidal activity against phytopathogenic fungi compared to compounds from the prior art.

Claims

1. Non-therapeutic use of compounds of formula I wherein R1 is selected from O and NH; R2 is selected from CH and N, provided that R2 is N in case R1 is NH; R3 is selected from halogen, C1-C4-alkyl, C2-C4-alkenyl, C1-C2-monohaloalkyl, C1-C2-dihaloalkyl, monohalo-ethenyl, dihalo-ethenyl, C3-C6-cycloalkyl and -O-C1-C4-alkyl; R4 is selected from C1-C4-alkyl, C2-C4-alkenyl, -C(=O)-C1-C2-alkyl, C1-C4-haloalkyl, C2-C4-haloalkenyl, -(C1-C2-alkyl)-O-(C1-C2-alkyl) and -CH2-cyclopropyl; Ra is selected from halogen, CN, -NR5R6, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, -O-C1-C4-alkyl, -C(=N-O-C1-C4-alkyl)-C1-C4-alkyl, -C(=O)-C1-C4-alkyl, -O-CH2-C(=N-O-C1-C4-alkyl)-C1-C4-alkyl, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, -C1-C2-alkyl-C3-C6-cycloalkyl, -O-C3-C6-cycloalkyl, phenyl, 3- to 6-membered heterocycloalkyl, 3- to 6-membered heterocycloalkenyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl, heterocycloalkenyl and heteroaryl besides carbon atoms contain 1, 2 or 3 heteroatoms selected from N, O and S, wherein said phenyl, heterocycloalkyl, heterocycloalkenyl and heteroaryl are bound directly or via an oxygen atom or via a C1-C2-alkylene linker, and wherein the aliphatic and cyclic moieties of Ra are unsubstituted or carry 1, 2, 3, 4 or up to the maximum number of identical or different groups Rb: Rb is selected from halogen, CN, NH2, NO2, C1-C4-alkyl, C1-C4-haloalkyl, -O-C1-C4-alkyl, and -O-C1-C4-haloalkyl; R5, R6 are independently of each other selected from the group consisting of H, C1-C6-alkyl, C1-C6-haloalkyl and C2-C4-alkynyl; n is an integer selected from 0, 1, 2, 3, 4 and 5; and in form or stereoisomers and tautomers thereof, and the N-oxides and the agriculturally acceptable salts thereof, for combating phytopathogenic fungi containing an amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors.

2. The use according to claim 1, wherein in formula I R1 is NH; and R2 is N.

3. The use according to claim 1 or claim 2, wherein in formula I R3 is selected from C1-C2-alkyl, C1-C2-monohaloalkyl, C1-C2-dihaloalkyl, C3-C4-cycloalkyl and -O-C1-C2-alkyl.

4. The use according to any of claims 1 to 3, wherein in formula I R4 is selected from C1-C4-alkyl, -C(=O)-C1-C2-alkyl, C1-C4-haloalkyl and -(C1-C2-alkyl)-O-(C1-C2-alkyl).

5. The use according to any one of claims 1 to 4, wherein in formula I Ra is selected from C1-C3-alkyl, C2-C3-alkenyl, C2-C3-alkynyl, -O-C1-C3-alkyl, -C(=N-O-C1-C2-alkyl)-C1-C2-alkyl, -O-CH2-C(=N-O-C1-C2-alkyl)-C1-C2-alkyl, C3-C4-cycloalkyl, -C1-C2-alkyl-C3-C4-cycloalkyl, - O-C3-C4-cycloalkyl, phenyl, 3- to 5-membered heterocycloalkyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl and heteroaryl besides carbon atoms contain 1 or 2 heteroatoms selected from N, O and S, wherein said phenyl and heteroaryl are bound directly or via an oxygen atom or via a methylene linker, and wherein the aliphatic and cyclic moieties of Ra are unsubstituted or carry 1, 2 or 3 of identical or different groups Rb which independently of one another are selected from halogen, CN, methyl and C1-haloalkyl.

6. The use according to any one of claims 1 to 5, wherein the phytopathogenic fungi are soybean rust (Phakopsora pachyrhizi and / or P. meibomiae).

7. A method for combating phytopathogenic fungi containing an amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors, comprising: treating curatively and / or preventively the plants or the plant propagation material of said plants that are at risk of being diseased from the said phytopathogenic fungi with an effective amount of at least one compound of formula I as defined in any of claims 1 to 5 or a composition comprising such compound; and / or a non-therapeutic method for combating phytopathogenic fungi containing an amino acid substitution F129L in the mitochondrial cytochrome b protein conferring resistance to Qo inhibitors, comprising: applying to the said phytopathogenic fungi with an effective amount of at least one compound of formula I as defined in any of claims 1 to 5 or a composition comprising such compound.

8. Compounds of formula I wherein R2 is selected from CH and N; R3 is selected from halogen, C1-C4-alkyl, C2-C4-alkenyl, C1-C2-monohaloalkyl, C1-C2-dihaloalkyl, monohalo-ethenyl, dihalo-ethenyl, C3-C6-cycloalkyl and -O-C1-C4-alkyl; R4 is selected from C1-C4-alkyl, C2-C4-alkenyl, C1-C4-haloalkyl, C2-C4-haloalkenyl, -(C1-C2-alkyl)-O-(C1-C2-alkyl) and -(C1-C2-alkyl)-O-(C1-C2-haloalkyl); Ra is selected from halogen, CN, NH-C1-C4-alkyl, N(C1-C4-alkyl)2, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, -O-C1-C4-alkyl, -C(=N-O-C1-C4-alkyl)-C1-C4-alkyl, -C(=O)-C1-C4-alkyl, -O-CH2-C(=N-O-C1-C4-alkyl)-C1-C4-alkyl, C5-C4-cycloalkyl, -C1-C2-alkyl-C3-C4-cycloalkyl, -O-C3-C4-cycloalkyl, phenyl, 3- to 5-membered heterocycloalkyl, 3- to 5-membered heterocycloalkenyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl, heterocycloalkenyl and heteroaryl besides carbon atoms contain 1, 2 or 3 heteroatoms selected from N, O and S, wherein said phenyl, heterocycloalkyl, heterocycloalkenyl and heteroaryl are bound directly or via an oxygen atom or via a C1-C2-alkylene linker, and wherein the aliphatic and cyclic moieties of Ra are unsubstituted or carry 1, 2, 3, 4 or up to the maximum number of identical or different groups Rb: Rb is selected from halogen, CN, NH2, NO2, C1-C4-alkyl, C1-C4-haloalkyl, -O-C1-C4-alkyl and -O-C1-C4-haloalkyl; n is an integer selected from 0, 1, 2, 3, 4 and 5; and in form or stereoisomers and tautomers thereof, and the N-oxides and the agriculturally acceptable salts thereof.

9. The compounds according to claim 8, wherein R2 is N.

10. The compound according to any one of the claims 8 to 9, wherein R3 is selected from C1-C2-alkyl, C1-C2-monohaloalkyl, C1-C2-dihaloalkyl, C3-C4-cycloalkyl and -O-C1-C2-alkyl.

11. The compound according to any one of the claims 8 to 10, wherein R4 is selected from C1-C4-alkyl, C1-C4-haloalkyl and -(C1-C2-alkyl)-O-(C1-C2-alkyl).

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

13. The compounds according to any one of the claims 8 to 12, wherein Ra is selected from halogen, CN, C1-C4-haloalkyl, C1-C4-alkyl, -O-C1-C4-alkyl, -O-C1-C4-haloalkyl, -C(=N-O-C1-C4-alkyl)-C1-C4-alkyl, -C(=O)-C1-C4-alkyl, C3-C4-cycloalkyl, -C1-C2-alkyl-C3-C4-cycloalkyl, -O-C3-C4-cycloalkyl, phenyl, 3- to 5-membered heterocycloalkyl and 5- or 6-membered heteroaryl, wherein said heterocycloalkyl and heteroaryl besides carbon atoms contain 1, 2 or 3 heteroatoms selected from N, O and S, wherein said phenyl, heterocycloalkyl and heteroaryl are bound directly or via an oxygen atom or via a C1-C2-alkylene linker, and wherein the cyclic moieties of Ra are unsubstituted or carry 1, 2 or 3 identical or different groups Rb selected from halogen, CN, C1-C2-alkyl, C1-C2-haloalkyl, -O-C1-C2-alkyl and -O-C1-C2-haloalkyl.

14. Agrochemical compositions comprising an auxiliary and at least one compound of formula I, as defined in any of claims 8 to 13 or in the form of a stereoisomer or an agriculturally acceptable salt or a tautomer or N-oxide thereof.

15. A method for combating phytopathogenic fungi comprising: treating curatively and / or preventively the plants or the plant propagation material of said plants that are at risk of being diseased from the said phytopathogenic fungi at least one compound of formula I as defined in any of the claims 8 to 13 or an agrochemical composition as defined in claim 14; and / or a non-therapeutic method for combating phytopathogenic fungi comprising: applying to the said phytopathogenic fungi at least one compound of formula I as defined in any of the claims 8 to 13 or an agrochemical composition as defined in claim 14.