WO2015197458A1 - Substituted 1-[2-[[[2-alkoxyimino-alkenylidene]amino]oxymethyl]phenyl]-4-methyl-tetrazol-5-one compounds as phytopathogenic fungicides - Google Patents

Abstract

The present invention relates to the novel substituted 1-[2-[[[2-alkoxyimino-alkenylidene]amino]- oxymethyl]phenyl]-4-methyl-tetrazol-5-one compounds of formula (I) and the N-oxides and the salts thereof for combating phytopathogenic fungi, 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.

Description

SUBSTITUTED

-[2-[[[2-ALKOXYIMINO-ALKENYLIDENE]AMINO]OXYMETHYL]PHENYL]-4-METHYL-TETRAZOL-5-ONE

COMPOUNDS AS PHYTOPATHOGENIC FUNGICIDES

Description

The present invention relates to substituted 1 -[2-[[[2-alkoxyimino-alkenylidene]- amino]oxymethyl]phenyl]-4-methyl-tetrazol-5-one compounds, the N-oxides and the salts thereof, their use for combating phytopathogenic fungi, and to methods for combating such fungi. The invention also relates to processes for preparing these com- pounds, to compositions comprising at least one such compound, to plant health applications, and to seeds coated with at least one such compound.

The use of 4-methyl-tetrazol-5-one compounds for controlling phytopathogenic harmful fungi is inter alia known from WO 96/036229, DE 199 00 571 A1 ,

WO 13/092224, WO 13/162072 and WO 13/162077.

In WO 13/092224, certain substituted 4-methyl-tetrazol-5-one compounds have beed described as fungicides that are useful for combating phytopathogenic fungi which are resistant to Qo inhibitor fungicides, especially of fungi containing a G143A mutation in the mitochondrial cytochrome b gene conferring resitance to Qo inhibitors.

DE 199 00 571 A1 discloses certain 1 -[2-[[[2-alkoxyimino-alkylidene]- amino]oxymethyl]phenyl]-4-methyl-tetrazol-5-one of formula:

The compounds according to the present invention differ from those described in the abovementioned publications by bearing a specific unsaturated aliphatic hydrocarbon group R³ as defined herein.

WO 00/031023 discloses the synthesis of certain alkenyl-substituted bis(oximether) compounds that differ from those according to the present invention by bearing a branched residue (e. g. 2-methoxyimino-A/-methyl acetamide) instead of the specific cyclic 4-methyl tetrazolone residue connected to the phenyl ring.

In many cases, in particular at low application rates, the fungicidal activity of the known fungicidal compounds is unsatisfactory. Based on this, it was an object of the present invention to provide compounds having improved activity and/or a broader activity spectrum against phytopathogenic harmful fungi.

This object is achieved by the use of substituted 1 -[2-[[[2-alkoxyimino-alkenylidene]- amino]oxymethyl]phenyl]-4-methyl-tetrazol-5-one compounds having good fungicidal activity against phytopathogenic harmful fungi. Accordingly, the pres of formula I

wherein: n indicates the number of substituents Y on the phenyl ring and n is 0, 1 , 2, 3 or 4;

Y is halogen, OH, NH₂, NHCH₃, N(CH₃)₂ , CN, N0₂, Ci-C₄-alkyl, Ci-C₄-haloalkyl, Ci-C₄-alkoxy, Ci-C₄-haloalkoxy, C2-C₄-alkenyl, C2-C₄-haloalkenyl, C2-C₄-alkynyl, C2-C₄-haloalkynyl, Ci-C₄-alkylthio, Ci-C₄-haloalkylthio, C3-C6-cycloalkyl;

it being possible for n = 2, 3 or 4 that Y are identical or different;

R¹ is Ci-C2-alkyl, Ci-C2-alkoxy, Ci-C2-haloalkyl, Ci-C2-haloalkoxy, chloro, CN or cy- clopropyl; R² is hydrogen, d-Ce-alkyl, d-Ce-haloalkyl, Ci-C₄-alkoxy-Ci-C2-alkyl,

Ci-C₄-haloalkoxy-Ci-C₄-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, C3-C8-cycloalkyl-Ci-C₄-alkyl, phenyl, phenyl-Ci-C₄-alkyl, phenoxy-Ci-C₄-alkyl or a 5- or 6-membered heteroaryl, wherein the ring member atoms of the heteroaryl include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the aforementioned cyclic radicals are unsubstituted or carry 1 , 2, 3, 4 or 5 identical or different substituents R^a:

R^a is halogen, CN, Ci-C₄-alkyl, Ci-C₄-haloalkyl, Ci-C₄-alkoxy or

Ci-C₄-haloalkoxy; R³ is C2-Cio-alkenyl, C2-Cs-alkynyl, C2-C8-haloalkenyl or C2-C8-haloalkynyl, wherein the aforementioned radicals are unsubstituted or carry 1 , 2, 3 or 4 identical or different substituents R^b :

R^b is CN, Ci-C₄-alkoxy or Ci-C₄-haloalkoxy or C3-C6-cycloalkyl;

and wherein the R³ radicals may further carry one phenyl or one 5- or 6-mem- bered heteroaryl, wherein the ring member atoms of the heteroaryl include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from the group of N, O and S; wherein the aforementioned cyclic groups are unsubstituted or carry 1 , 2, 3 4 or 5 identical or different substituents R^c:

R^c is halogen, CN, Ci-C₄-alkyl, Ci-C₄-haloalkyl, Ci-C₄-alkoxy or Ci-C₄-haloalkoxy;

and the N-oxides and the agriculturally acceptable salts thereof. The compounds of the present invention are useful for combating harmful fungi. Therefore the present invention furthermore relates to a method for combating harmful fungi, which process comprises treating the fungi or the materials, plants, the soil or seeds to be protected against fungal attack, with an effective amount of at least one compound of formula I or of an N-oxide or an agriculturally acceptable salt thereof.

Furthermore, the present invention also relates to plant propagation material comprising a compound of formula I, or an N-oxide or an agriculturally acceptable salt thereof, in an amount of from 0.1 g to 10 kg per 100 kg of plant propagation material.

According to another embodiment of the invention, the invention also relates to a method for combating phytopathogenic fungi, comprising: treating the phytopathogenic fungi or the materials, plants, the soil or seeds that are at risk of being diseased from phytopathogenic fungi with an effective amount of at least one compound I, or a composition comprising it thereof.

According to a further embodiment of the invention, the invention also relates to a use and a method for combating phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, comprising: treating the phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors or the materials, plants, the soil or seeds that are at risk of being diseased from phytopathogenic fungi containing a muta- tion in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors with an effective amount of at least one compound I, or a composition comprising it thereof; more preferably wherein the mutation in the mitochondrial cytochrome b gene of the phytopathogenic fungi is G143A.

The term "phytopathogenic fungi containing a mutation in the mitochondrial cyto- chrome b gene conferring resistance to Qo inhibitors" ist be understood that at least 10% of the fungal isolates to be controlled contain a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors, more preferably at least 30%, even more preferably at least 50%, and most preferably at least 75% of the fungi, in particular between 90 and 100%.

According to further embodiment, the phytopathogenic fungi containing a mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors are selected from the group consisting of basidomycetes, ascomycetes, and Oomycetes; more preferably selected from the group consisting of Alternaria alternata, Blumeria graminis, Pyriculania oryzae (also known as Magnaporthe grisea), Septoria tritici (also known as Mycosphaerella graminicola), Mycosphaerella fijiensis, Venturia inaequalis, Pyrenophora teres, Pyrenophona tritici-repentis and Plasmopara viticola, in particular Septoria tritici.

In repect of the variables, the embodiments of the intermediates correspond to the embodiments of the compounds of formula I. The term "compounds I" refers to compounds of formula I. Likewise, this terminology applies to all sub-formulae, e. g. "compounds 1.1 " refers to compounds of the formula 1.1. The inventive compounds I can be prepared by various routes in analogy to prior art processes (e. g. DE 199 00 571 A1 , WO 00/0031023, WO 13/162072, and

WO 13/162077), advantageously, by the synthesis shown in the following scheme and in the experimental part of this application.

Compounds I may also be obtained by reacting compounds II with compounds III:

Generally, the reaction is carried out at temperatures of from 0°C to 200°C, preferably from 20°C to 120°C, in an inert organic solvent in presence of a base.

Suitable solvents are aromatic hydrocarbons such as toluene, o-, m- and p-xylene; halogenated hydrocarbons such as chlorobenzene; ethers such as diethyl ether, diiso- propyl ether, MTBE, dioxane, anisole and THF; nitriles such as acetonitrile and propi- onitrile; alcohols such as MeOH, EtOH, n-propanol, isopropanol, n-butanol and tert- butanol; and also DMSO, DMF, dimethyl acetamide, NMP, NEP and acetic acid ethyl ester, it being also possible to use mixtures of these solvents.

Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide; alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, potassium oxide and calcium oxide; alkali metal and alkaline earth metal phosphates such as lithium phosphate, sodium phosphate, potassium phosphate and calcium phosphate; alkali metal amides such as lithium amide, sodium amide and potassium amide; alkali metal and alkaline earth metal hydrides lithium hydride, sodium hydride, potassium ydride and calcium hydride; alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate; alkali metal alcoholates such as sodium or potassium methylate, sodium ethylate and potassium tert.-butylate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; moreover organic bases, for example tertiary amines such as trimethylamine, triethylamine, tributylamine, diisopropylethylamine and NMP, pyridine, substituted pyridines such as collidine, lutidine and 4 dimethylamino- pyridine, and also bicyclic amines. Particular preference is given to potassium car- bonate, sodium hydroxide, potassium hydroxide, sodium hydride, sodium methylate and potassium tert.-butylate. The bases are generally employed in equimolar amounts, in excess or, if appropriate, as solvent.

Known phase transfer catalysts can be added in catalytic amounts in order to improve yield and reaction speed if necessary.

The starting materials, are generally reacted with one another in equimolar amounts. Compounds I I are known from WO 95/021 153, WO 95/021 154, WO 96/016030, WO 97/003057 and WO 00/031023.

Compounds I I I are i. a. known from DE 199 00 571 A1 , WO 13/162072, and WO 13/162077.

If individual compounds I cannot be obtained by the routes described above, they can be prepared by derivatization of other compounds I .

If the synthesis yields mixtures of isomers in the case of oximes, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (e. g. under the action of light, acids or bases). Such conversions may also take place after use, e. g. in the treatment of plants in the treated plant, or in the harmful fungus to be controlled.

In the definitions of the variables given above, collective terms are used which are generally representative for the substituents in question. The term "C_n-C_m" indicates the number of carbon atoms possible in each case in the substituent or substituent moiety in question.

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

The term "Ci-C6-alkyl" refers to a straight-chained or branched saturated hydrocarbon group having 1 to 6 carbon atoms, e.g. methyl, ethyl, propyl, 1 -methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl (isobutyl), 1 , 1 -dimethylethyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, 1 , 1 -dimethylpropyl,

1 .2- dimethylpropyl, hexyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methyl- pentyl, 1 , 1 -dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl,

2.3- dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1 , 1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1 -ethyl-1 -methylpropyl and 1 -ethyl-2-methylpropyl. Likewise, the term "Ci-C4-alkyl" refers to a straight-chained or branched alkyl group having 1 to 4 carbon atoms.

The term "Ci-C4-haloalkyl" refers to a straight-chained or branched alkyl group having 1 to 4 carbon atoms (as defined above), 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, difluoro- methyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, 1 -bromoethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-tri- fluoroethyl, 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-difluoro- propyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromo- propyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, CH2-C2F5, CF2-C2F5, CF(CF3)2, 1 -(fluoromethyl)-2-fluoroethyl, 1 -(chloromethyl)-2-chloroethyl, 1 -(bromo- methyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl. Likewise, the term "Ci-C6-haloalkyl" refers to a straight-chained or branched alkyl group having 1 to 6 carbon atoms.

The term "Ci-C6-alkoxy" refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms which is bonded via an oxygen, at any position in the alkyl group, e.g. OCHs, OCH₂CH₃, 0(CH₂)2CH₃, 1 -methylethoxy, 0(CH₂)3CH₃, 1 -methyhpropoxy, 2-methylpropoxy or 1 ,1 -dimethylethoxy, 0(CH2)4CH3 or 0(CH2)5CH3. Likewise, the term "Ci-C4-alkoxy" 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.

The term "Ci-C4-haloalkoxy" refers to a Ci-C4-alkoxy group as defined above, wherein some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, for example, OCH₂F, OCHF₂, OCF₃, OCH₂CI, OCHCI₂, OCCI₃, chloro- fluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloro- ethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloro^-,ethoxy, OC₂F₅, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoro-"propoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy,

2-bromo^-,propoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH₂-C₂F₅, OCF₂-C₂F₅, 1 -(CH₂F)-2-fluoroethoxy, 1 -(CH₂CI)-2-chloroethoxy, 1 -(CH₂Br)- 2-bromo^-,ethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy.

The term "Ci-C4-alkoxy-Ci-C₂-alkyl" refers to alkyl having 1 to 2 carbon atoms, wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C4-alkoxy group.

The term "C₂-C4-alkenyl" refers to a straight-chain or branched unsaturated hydro- carbon radical having 2 to 4 carbon atoms and a double bond in any position, e.g. eth- enyl, 1 -propenyl, 2-propenyl (allyl), 1 -methylethenyl, 1 -butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1 -propenyl, 2-methyl-1 -propenyl, 1 -methyl-2-propenyl, 2-methyl-2-propenyl. Likewise, the term "C₂-C6-alkenyl" refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and a double bond in any position.

The term "C₂-C4-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, 1 -propynyl, 2-propynyl, 1 -butynyl, 2-butynyl, 3-butynyl, 1 -methyl-2-propynyl. Likewise, the term "C₂-C6-alkynyl" refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and at least one triple bond.

The term "C3-C6-cycloalkyl" refers to monocyclic, bicyclic, saturated hydrocarbon radicals having 3 to 6 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopen- tyl or cyclohexyl.

The term "C3-C6-cycloalkyl-Ci-C4-alkyl" 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.

The term "phenyl-Ci-C4-alkyl" refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a phenyl radical.

Agriculturally acceptable salts of compounds I encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the compounds I. Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potas- sium, of the alkaline earth metals, preferably calcium, magnesium and barium, of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry one to four Ci-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sul- fonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting a compound of formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

The compounds of formula I can be present in atropisomers arising from restricted rotation about a single bond of asymmetric groups. They also form part of the subject matter of the present invention.

epending on the substitution pattern, the compounds of formula I and their N-oxides may have one or more centers of chirality, in which case they are present as pure enantiomers or pure diastereomers or as enantiomer or diastereomer mixtures. Both, the pure enantiomers or diastereomers and their mixtures are subject matter of the present invention.

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

Preference is given to those compounds I and where applicable also to compounds of all sub-formulae provided herein, e. g. formulae 1.1 and 1.2, and to the intermediates such as compounds II and II I , wherein the substituents and variables (such as n, Y, R¹ , R², R³, R^a, R^b, R^A, R^B, R^c and R^D) 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 combi- nation (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 compounds I, wherein Y is halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy.

Another embodiment of the invention relates to compounds I , wherein Y is halogen, in particular CI. Another embodiment of the invention relates to compounds I, wherein Y is halogen, in particular F.

Another embodiment of the invention relates to compounds I, wherein Y is halogen, in particular Br.

According to a further embodiment, Y is OH, NH₂, NHCH₃ or N(CH₃)2.

According to a further embodiment, Y is Ci-C4-alkyl, more preferably Ci-C2-alkyl, in particular methyl.

According to a further embodiment, Y is Ci-C4-alkoxy, more preferably Ci-C2-alk- oxy, in particular methoxy.

According to a further embodiment, Y is Ci-C4-alkylthio, more preferably Ci-C2-al- kylthio, in particular methylthio (= methylsulfanyl).

According to a further embodiment, Y is Ci-C4-haloalkyl, more preferably Ci-C2-ha- loalkyl, even more preferably CHF2 or CF3.

According to a further embodiment, Y is Ci-C4-haloalkoxy, more preferably

Ci-C2-haloalkoxy, even more preferably OCHF2 or OCF3.

According to a further embodiment, Y is C3-C6-cycloalkyl, more preferably cyclopro- pyl or cyclopentyl , even more preferably cyclopropyl.

According to a further embodiment, Y is C2-C4-alkenyl, in particular ethenyl.

According to a further embodiment, Y is C2-C4-alkynyl, in particular ethynyl.

According to a further embodiment, n is 0, 1 or 2.

According to a further embodiment, n is 0.

According to a further embodiment, n is 1 or 2, in particular 1 .

According to a further embodiment, n is 2, wherein one Y preferably is at position 3.

A further embodiment

wherein Y is in position 3, 4 or 6 on the phenyl ring; more preferably position 3 or 6, in particular position 3. The numbering of the positions of Y is according to the sketch of formula I depicted above.

A further embodiment relates to compounds I wherein n is 1 and Y is in position 3 on the phenyl ring, which compounds are of formula 1.1 :

A further embodiment relates to compounds I wherein n is 1 and Y is in position 4 on the phenyl ring, which compounds are of formula 1.2:

A further embodiment relates to compounds I wherein n is 1 and Y is in position 5 on the phenyl ring, which compounds are of formula 1.3:

A further embodiment relates to compounds I wherein n is 1 and Y is in position 6 on the phenyl ring, which compounds are of formula 1.4:

A further embodiment relates to compounds I wherein Y is in position 3 and 4 on the phenyl ring, which compounds are of formula 1.5:

A further embodiment relates to compounds I wherein n is 2 and Y is in position 3 and 6 on the phenyl ring,

A further embodiment relates to compounds I wherein Y is in position 3 and 5 on the phenyl ring, which compounds are of formula 1.7:

According to a further embodiment, n is 1 and Y is in position 3 and selected from halogen, in particular CI.

According to a further embodiment, n is 1 and Y is in position 3 and selected from halogen, in particular F.

According to a further embodiment, n is 1 and Y is in position 3 and selected from halogen, in particular Br.

According to a further embodiment, n is 1 and Y is in position 3 and selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy.

According to a further embodiment, n is 1 and Y is in position 3 and selected from Ci-C4-alkyl, more preferably Ci-C2-alkyl, in particular methyl.

According to a further embodiment, n is 1 and Y is in position 3 and selected from Ci-C4-alkoxy, more preferably Ci-C2-alkoxy, in particular methoxy.

According to a further embodiment, n is 1 and Y is in position 3 and selected from Ci-C4-haloalkyl, more preferably Ci-C2-haloalkyl, even more preferably from CHF2 and CF₃. According to a further embodiment, n is 1 and Y is in position 3 and selected from Ci-C4-haloalkoxy, more preferably Ci-C2-haloalkoxy, even more preferably from

According to a further embodiment, n is 1 and Y is in position 3 and selected from Ci-C4-haloalkoxy, more preferably Ci-C2-haloalkoxy, even more preferably from

According to a further embodiment, n is 1 and Y is in position 3 and selected from C3-C6-cycloalkyl, more preferably cyclopropyl or cyclopentyl , even more preferably cyclopropyl.

According to a further embodiment, n is 2 and Y substituents are in position 3 and 4 and independently of each other selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy.

According to a further embodiment, n is 2 and Y substituents are in position 3 and 6 and independently of each other selected from halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy.

Further embodiments relate to compounds I in which Y_n are one of the following combinations Y-1 to Y-66 in Table Y:

Table Y:

No. Yn No. Yn No. Yn

Y-1 3-CI Y-21 3-CH3, 4-CI Y-41 4-cyclopropyl

Y-2 3-F Y-22 3-CI, 4-F Y-42 4-Br

Y-3 3-CHs Y-23 3-F, 4-CH3 Y-43 4-CHF2

Y-4 3-CH2CH3 Y-24 3-CI, 4-CH3 Y-44 4-OCF3

Y-5 3-OCH3 Y-25 3,-CH₃, 5-F Y-45 4-OCHF2

Y-6 3-CF3 Y-26 3,-CH₃, 5-CI Y-46 4-SCH3

Y-7 3-CHF2 Y-27 3-F, 5-CH3 Y-47 4-CH=CH₂

Y-8 3-OCHF2 Y-28 3-CI, 5-CH3 Y-48 4-C≡CH

Y-9 3-CN Y-29 3-OCH2CH3 Y-49 6-CI

Y-10 3-cyclopropyl Y-30 3-Br Y-50 6-CH3

Y-1 1 3,4-(CH₃)₂ Y-31 3-OCF3 Y-51 6-OCH3

Y-12 3,5-(CH₃)₂ Y-32 3-SCH3 Y-52 6-CH2CH3

Y-13 3,6-(CH₃)₂ Y-33 3-CH=CH₂ Y-53 6-OCH2CH3

Y-14 3,4-C Y-34 3-C≡CH Y-54 6-F

Y-15 3,5-CI₂ Y-35 4-CI Y-55 6-cyclopropyl

Y-16 3,6-CI₂ Y-36 4-CH3 Y-56 6-Br

Y-17 3,4-F₂ Y-37 4-OCH3 Y-57 6-CHF2

Y-18 3,5-F₂ Y-38 4-CH2CH3 Y-58 6-OCF3

Y-19 3,6-F₂ Y-39 4-OCH2CH3 Y-59 6-OCHF2

Y-20 3-CHs, 4-F Y-40 4-F Y-60 6-SCH3 No. Yn No. Yn No. Yn

Y-61 6-CH=CH₂ Y-63 3,4-(OCH₃)₂ Y-65 3-CI, 6-F

Y-62 6-C≡CH Y-64 3,6-(OCH₃)₂ Y-66 -

Even more preferred embodiments relate to compounds I in which Y_n are one of the abovementioned combinations Y-1 to Y-28 in Table Y.

According to a further embodiment, R¹ is Ci-C2-alkyl, Ci-C2-alkoxy, Ci-C2-haloalkyl, Ci-C2-haloalkoxy or chloro.

According to a further embodiment, R¹ is chloro or CN, in particular chloro.

According to a further embodiment, R¹ is Ci-C2-alkyl or Ci-C2-haloalkyl, more preferably methyl, ethyl, CF3 or CHF2, in particular methyl.

Further embodiments relate to compounds I in which R¹ is one of the following meanings R1 -1 to R1 -1 1 in Table A:

Table A:

According to a further embodiment, R² is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl or phenyl.

According to a further embodiment, R² is Ci-C6-alkyl or Ci-C6-haloalkyl; more preferably Ci-C4-alkyl or Ci-C4-haloalkyl; even more preferably methyl or ethyl, in particular methyl.

According to a further embodiment, R² is Cs-Cs-cycloalkyl, Cs-Cs-cycloalkyl- Ci-C4-alkyl, phenyl, phenyl-Ci-C4-alkyl, phenoxy-Ci-C4-alkyl; more preferably cyclopro- pyl, cycloprpoylmethyl, phenyl or benzyl, in particular benzyl; and wherein the aforementioned cyclic radicals are unsubstituted or carry 1 , 2, 3 or 4 identical or different substituents R^a as defined herein.

According to a further embodiment, R² is 5- or 6-membered heteroaryl, wherein the ring member atoms of the heteroaryl include besides carbon atoms 1 , 2, 3 or 4 het- eroatoms selected from the group of N, O and S, and wherein the aforementioned heteroaryl radicals are unsubstituted or carry 1 , 2, 3 or 4 identical or different substituents R^a: as defined herein.

According to a further embodiment, R² is pyridinyl, which is unsubstituted or carries 1 , 2, 3 or 4 identical or different substituents R^a as defined herein.

According to a further embodiment, R² is pyrazolyl, which is unsubstituted or carry 1 , 2 or 3 identical or different substituents R^a as defined herein.

According to a further embodiment, wherein R² is a cyclic radicyl, R^a is selected from halogen, CN, Ci-C2-alkyl, Ci-C2-haloalkyl, Ci-C2-alkoxy and Ci-C2-haloalkoxy; more preferably from halogen, CN, methyl, methoxy, CF3 and CHF2. According to a further embodiment, wherein R² is a cyclic radicyl, the cyclic radical R² is unsubstituted or carries 1 substituent R^a, which is selected from halogen, CN, Ci-C2-alkyl, Ci-C2-haloalkyl, Ci-C2-alkoxy and Ci-C2-haloalkoxy; more preferably from halogen, CN, methyl, methoxy, CF3 and CHF2.

5 According to a further embodiment, wherein R² is benzyl, which is unsubstituted or carries 1 substituent R^a selected from halogen, CN, Ci-C2-alkyl, Ci-C2-haloalkyl,

Ci-C2-alkoxy and Ci-C2-haloalkoxy; more preferably from halogen, CN, methyl, methoxy, CF₃ and CHF₂.

10 Further embodiments relate to compounds I in which R² is one of the following

meanings R2-1 to R2-24 in Table B:

A further embvodiment relates to compounds I wherein R¹ and R² are both methyl, which compounds are of formula 1.

According to a further embodiment, R³ is C2-Cio-alkenyl, more preferably -CH=CR^AR^B, wherein R^A and R^B are independently of each selected from hydrogen and Ci-C₄-alkyl; more preferably from hydrogen, methyl and ethyl.

According to a further embodiment, R³ is C2-Cio-alkenyl, more preferably -CR^C=CR^AR^B, wherein R^A, R^B and R^c are independently of each selected from hydrogen and Ci-C₄-alkyl; more preferably from hydrogen, methyl and ethyl.

According to a further embodiment, R³ is C2-C6-alkenyl, more preferably -CH=CR^AR^B, wherein R^A and R^B are independently of each other selected from hydrogen and Ci-C₄-alkyl; more preferably from hydrogen, methyl and ethyl.

According to a further embodiment, R³ is C2-C6-alkynyl, more preferably -CH≡CR^C, wherein R^c is hydrogen, Ci-C₄-alkyl or phenyl. According to a further embodiment, R³ is -CH≡C-phenyl, wherein phenyl is unsubstituted or carries 1 or 2 R^b substituents selected from halogen, CN, Ci-C2-alkyl, and Ci-C2-haloalkyl, more preferably selected from fluoro, chloro, methyl, CF3 and CHF2.

According to a further embodiment, R³ is -CH≡CR^D, wherein R^D is Ci-C4-alkyl, more prefera- bly methyl, ethyl, isopropyl or tert. -butyl.

According to a further embodiment, R³ is -CH≡CR^D, wherein R^D is Ci-C4-haloalkyl, more preferably CF3 or CHF2.

Further embodiments relate to compounds I n which R³ is one of the following meanings R3-1 to R3-76 in Table C:

Table A:

No. R³ No. R³

R3-1 -CH=CH₂ R3-31 -CH=CH-CH(CH₃)₂

R3-2 -CH=CHCH₃ R3-32 -CH=C(OCH₃)₂

R3-3 -C(CH₃)=CH₂ R3-33 -CH=C(OCH₂CH₃)₂

R3-4 -C(CH₃)=CHCH₃ R3-34 -CH=C(CH₃)OCH₃

R3-5 -CH=CHCH₂CH₃ R3-35 -CH=C(CH₃)OCH₂CH₃

R3-6 -CH=CHCH(CH₃)₂ R3-36 -CH=C(CH₂CH₃)OCH₃

R3-7 -CH=C(CH₃)₂ R3-37 -CH=C(CH₂CH₃)OCH₂CH₃

R3-8 -CH=C(CH₂CH₃)₂ R3-38 -C(CH₃)=CHCF₃

R3-9 -CH=C(CH₂CH₂CH₃)₂ R3-39 -CH=CHCF₃

R3-10 -CH=CCH₃(CH₂CH₃)₂ R3-40 -CH=C(CF₃)₂

R3-1 1 -C(CH₃)=CHCH₃ R3-41 -CH=CHCH₂CF₃

R3-12 -C(CH₃)=C(CH₃)₂ R3-42 -CCH₃=CHCH₂CF₃

R3-13 -C(CH₃)=C(CH₂CH₃)₂ R3-43 -CCH₃=C(CF₃)₂

R3-14 -CH=CH-cyclopropyl R3-44 -CH=CHCN

R3-15 -CH=CH-cyclopentyl R3-45 -CH=C(CH₃)CN

R3-16 -CH=CH-cyclohexyl R3-46 -C≡CH

R3-17 -C(CH₃)=CH-cyclopropyl R3-47 -C≡CCH₃

R3-18 -C(CH₃)=CH-cyclopentyl R3-48 -C≡CCH₂CH₃

R3-19 -C(CH₃)=CH-cyclohexyl R3-49 -C≡CCH₂CH₂CH₃

R3-20 -CH=C(CH₃)-cyclopropyl R3-50 -C≡CH(CH₃)₂

R3-21 -CH=C(CH₃)-cyclopentyl R3-51 -C≡CC(CH₃)₃

R3-22 -CH=C(CH₃)-cyclohexyl R3-52 -C≡CCH(CH₂CH₃)CH₃

R3-23 -CH=CH-phenyl R3-53 -C≡C-cyclopropyl

R3-24 -C(CH₃)=CH-phenyl R3-54 -C≡C-cyclopentyl

R3-25 -CH=C(CH₃)-phenyl R3-55 -C≡C-cyclohexyl

R3-26 -C(CH₃)=C(CH₃)-phenyl R3-56 -C≡C-phenyl

R3-27 -CH=CH-4-F-phenyl R3-57 -C≡C-(4-F-phenyl)

R3-28 -CH=CH-4-CI-phenyl R3-58 -C≡C-(4-CI-phenyl)

R3-29 -CH=CH-OCH₃ R3-59 -C≡C-(2,4-F₂-phenyl)

R3-30 -CH=CH-(CH₃)₃ R3-60 -C≡C-(2,4-CI₂-phenyl) No. R³ No. R³

R3-61 -C≡C-(2,6-F₂-phenyl) R3-69 -C≡C-pyridin-3-yl)

R3-62 -C≡C-(2,6-CI₂-phenyl) R3-70 -C≡C-pyridin-4-yl

R3-63 -C≡C-(3,5-F₂-phenyl) R3-71 -C≡C-pyrimidin-2-yl

R3-64 -C≡C-(3,5-CI₂-phenyl) R3-72 -C≡C-pyrimidin-5-yl

R3-65 -C≡C-(2-F-4-CI-phenyl) R3-73 -C≡C-(3-CF₃-pyridin-2-yl)

R3-66 -C≡C-(2-CI-4-F-phenyl) R3-74 -C≡C-(5-CF₃-pyridin-2-yl)

R3-67 -C≡C-(4-Br-phenyl) R3-75 -C≡C-(6-CF₃-pyridin-3-yl)

R3-68 -C≡C-(pyridin-2-yl) R3-76 -C≡C-(2-CF₃-pyridin-4-yl)

A skilled person will readily understand that the preferences given in connection with compounds I apply also for formulae 1.1 to 1.8 as defined above. A further embvodiment relates to compounds of formula I

wherein:

n indicates the number of substituents Y on the phenyl ring and n is 0 or 1 ;

Y is halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C₂-C₄-alkenyl or C₂-C₄-alkynyl;

R¹ is methyl;

R² is d-Ce-alkyl, Ci-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl;

R³ is C₂-Cio-alkenyl or C₂-C8-haloalkenyl;

and the N-oxides and the agriculturally acceptable salts thereof.

Especially preferred compounds I are described in Tables 1 to 28 below.

Table 1 : Compounds of formula 1.8, wherein Y_n is defined as in line Y-1 of table Y, and the meaning of R³ for each compound corresponds to one line of table A.

Table 2: Compounds of formula 1.8, wherein Y_n is defined as in line Y-2 of table Y, and the meaning of R³ for each compound corresponds to one line of table A.

Table 3: Compounds of formula 1.8, wherein Y_n is defined as in line Y-3 of table Y, and the meaning of R³ for each compound corresponds to one line of table A.

Table 4: Compounds of formula 1.8, wherein Y_n is defined as in line Y-4 of table Y, and the meaning of R³ for each compound corresponds to one line of table A.

Table 5: Compounds of formula 1.8, wherein Y_n is defined as in line Y-5 of table Y, and the meaning of R³ for each compound corresponds to one line of table A.

Table 6: Compounds of formula 1.8, wherein Y_n is defined as in line Y-6 of table Y, and the meaning of R³ for each compound corresponds to one line of table A.

Table 7: Compounds of formula 1.8, wherein Y_n is defined as in line Y-7 of table Y, and the meaning of R³ for each compound corresponds to one line of table A.

Table 8: Compounds of formula 1.8, wherein Y_n is defined as in line Y-8 of table Y, and the meaning of R³ for each compound corresponds to one line of table A.

Table 9: Compounds of formula 1.8, wherein Y_n is defined as in line Y-9 of table Y, and the meaning of R³ for each compound corresponds to one line of table A.

Table 10: Compounds of formula 1.8, wherein Y_n is defined as in line Y-10 of table Y, and the meaning of R³ for each compound corresponds to one line of table A. Table 1 1 : Compounds of formula I .8, wherein Y_n is defined as in line Y-^■1 1 of table Y, and the meaning of R³ for each compound corresponds to one line of tab le A.

Table 12: Compounds of formula I .8, wherein Y_n is defined as in line Y- ^■12 of table Y, and the meaning of R³ for each compound corresponds to one line of tab le A.

Table 13: Compounds of formula I .8, wherein Y_n is defined as in line Y- ^■13 of table Y, and the meaning of R³ for each compound corresponds to one line of tab le A.

Table 14: Compounds of formula I .8, wherein Y_n is defined as in line Y- ^■14 of table Y, and the meaning of R³ for each compound corresponds to one line of tab le A.

Table 15: Compounds of formula I .8, wherein Y_n is defined as in line Y- ^■15 of table Y, and the meaning of R³ for each compound corresponds to one line of tab le A.

Table 16: Compounds of formula I .8, wherein Y_n is defined as in line Y- ^■16 of table Y, and the meaning of R³ for each compound corresponds to one line of tab le A.

Table 17: Compounds of formula I .8, wherein Y_n is defined as in line Y- ^■17 of table Y, and the meaning of R³ for each compound corresponds to one line of tab le A.

Table 18: Compounds of formula I .8, wherein Y_n is defined as in line Y- ^■18 of table Y, and the meaning of R³ for each compound corresponds to one line of tab le A.

Table 19: Compounds of formula I .8, wherein Y_n is defined as in line Y- ^■19 of table Y, and the meaning of R³ for each compound corresponds to one line of tab le A.

Table 20: Compounds of formula I .8, wherein Y_n is defined as in line Y- ^■20 of table Y, and the meaning of R³ for each compound corresponds to one line of tab le A.

Table 21 : Compounds of formula I .8, wherein Y_n is defined as in line Y- ^■21 of table Y, and the meaning of R³ for each compound corresponds to one line of tab le A.

Table 22: Compounds of formula I .8, wherein Y_n is defined as in line Y- ^■22 of table Y, and the meaning of R³ for each compound corresponds to one line of tab le A.

Table 23: Compounds of formula I .8, wherein Y_n is defined as in line Y- ^■23 of table Y, and the meaning of R³ for each compound corresponds to one line of tab le A.

Table 24: Compounds of formula I .8, wherein Y_n is defined as in line Y- ^■24 of table Y, and the meaning of R³ for each compound corresponds to one line of tab le A.

Table 25: Compounds of formula I .8, wherein Y_n is defined as in line Y- ^■25 of table Y, and the meaning of R³ for each compound corresponds to one line of tab le A.

Table 26: Compounds of formula I .8, wherein Y_n is defined as in line Y- ^■26 of table Y, and the meaning of R³ for each compound corresponds to one line of tab le A.

Table 27: Compounds of formula I .8, wherein Y_n is defined as in line Y- ^■27 of table Y, and the meaning of R³ for each compound corresponds to one line of tab le A.

Table 28: Compounds of formula I .8, wherein Y_n is defined as in line Y- ^■28 of table Y, and the meaning of R³ for each compound corresponds to one line of tab le A.

Table 29: Compounds of formula I .8, wherein Y_n is defined as in line Y- ^■66 of table Y (n = 0), and the meaning of R³ for each compound corresponds to one line of table A. The compounds I and the compositions according to the invention, respectively, are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zy- gomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.

The compounds I and the compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e. g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.

Preferably, compounds I and compositions thereof, respectively are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.

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

These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.

Preferably, treatment of plant propagation materials with compounds I and compositions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.

The term "cultivated plants" is to be understood as including plants which have been modi- fied by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://cera-gmc.org/, see GM crop database therein). Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by gly- cosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.

The compounds I and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases:

Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A. tragopogonis); Altemaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassi- cae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A. alternata), tomatoes (e. g. A. solani or A. alternata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A. hordei on barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e. g. B. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad- leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cer- cospora leaf spots) on corn (e. g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvum: leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helmin- thosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. miyabeanus, anamorph: H. oryzae); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. gramini- co/a; Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatum or C. gloeosporioides); Corticium spp., e. g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C. liriodendri, teleomorph: Neonectria liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (£. pyri), soft fruits (£. veneta: anthracnose) and vines (£. ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (£. betae), vegetables (e. g. E. pisi), such as cucurbits (e. g. E. cichoracearum), cabbages, rape (e. g. E. cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e. g. E. turci- cum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. solani (f. sp. glycines now syn. F. virguliforme ) and F. tucumani- ae and F. brasiliense each causing sudden death syndrome on soybeans, and F. verticillioides on corn; Gaeumannomyces graminis (take-all) on cereals (e. g. wheat or barley) and corn; Gib- berella spp. on cereals (e. g. G. zeae) and rice (e. g. G. fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P. manshurica);

Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Phy- soderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P.

megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans: late blight) and broad- leaved trees (e. g. P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmopara spp., e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g. P. leucotricha on apples; Polymyxa spp., e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph: Tapesia yal- lundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila (red fire disease or .rotbrenner', anamorph: Phialophora) on vines; Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P. asparagi on asparagus; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. feres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum); Ramularia spp., e. g. R. collo-cygni (Ram ularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on barley, rye and triticale; Sa- rocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e. g. S. rolfsii or S. sclerotiorum); Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) no- dorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Lepto- sphaeria [syn. Phaeosphaeria] nodorum) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e. g. U. appendiculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae); Ustilago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes.

The compounds I and compositions thereof, respectively, may be used for improving the health of a plant. The invention also relates to a method for improving plant health by treating a plant, its propagation material and/or the locus where the plant is growing or is to grow with an effective amount of compounds I and compositions thereof, respectively.

The term "plant health" is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves ("greening effect")), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress. The above identified indicators for the health condition of a plant may be interdependent or may result from each other.

The compounds of formula I can be present in different crystal modifications whose biological activity may differ. They are likewise subject matter of the present invention.

The compounds I are employed as such or in form of compositions by treating the fungi or 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.

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.

The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I according to the invention.

An agrochemical composition comprises a fungicidally effective amount of a compound I. The term "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 materials and which does not result in a substantial damage to the treated plants. 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 or material, the climatic conditions and the specific compound I used.

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, gran- ules, pressings, capsules, and mixtures thereof. Examples for composition types 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). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6^th Ed. May 2008, CropLife International.

The compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New develop- ments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.

Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, disper- sants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibil- izers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.

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

Suitable solid carriers or fillers are mineral earths, e. g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magne- sium sulfate, magnesium oxide; polysaccharides, e. g. cellulose, starch; fertilizers, e. g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e. g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof. Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & De- tergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkyl naphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.

Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or al- kylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinyl pyrroli- done, vinyl alcohols, or vinyl acetate.

Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinyl amines or polyethylene amines.

Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target.

Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.

Suitable thickeners are polysaccharides (e. g. xanthan gum, carboxymethyl cellulose), inor- ganic clays (organically modified or unmodified), polycarboxylates, and silicates.

Suitable bactericides are bronopol and isothiazolinone derivatives such as alkyliso- thiazolinones and benzisothiazolinones.

Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin. Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.

Suitable colorants (e. g. in red, blue, or green) are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e. g. iron oxide, titan oxide, iron hexacy- anoferrate) and organic colorants (e. g. alizarin-, azo- and phthalocyanine colorants).

Suitable tackifiers or binders are polyvinyl pyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of active substance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).

For the purposes of treatment of plant propagation materials, particularly seeds, solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC), and gels (GF) are usually employed. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying compound I and compositions thereof, respectively, onto plant propagation material, especially seeds, include dressing, coat- ing, pelleting, dusting, and soaking as well as in-furrow application methods. Preferably, compound I or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting. 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.

In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of 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 kilogram of plant propagation material (preferably seeds) are generally required.

When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.

Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides (e. g. herbicides, insecticides, fungicides, growth regulators, safeners, biopesticides) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compo- sitions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.

The user applies the composition according to the invention 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.

According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.

Consequently, one embodiment of the invention is a kit for preparing a usable pesticidal composition, the kit comprising a) a composition comprising component 1 ) as defined herein and at least one auxiliary; and b) a composition comprising component 2) as defined herein and at least one auxiliary; and optionally c) a composition comprising at least one auxiliary and optionally a further active component 3) as defined herein.

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 being obtained or in a prevention of fungicide resistance development. Furthermore, in many cases, synergistic effects are obtained.

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 Q₀ site (e. g. strobilurins): azoxystrobin (A.1 .1 ), coumethoxy- strobin (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), kresox- im-methyl (A.1 .9), mandestrobin (A.1.10), metominostrobin (A.1.1 1 ), orysastrobin (A.1.12), picoxystrobin (A.1.13), pyraclostrobin (A.1.14), pyrametostrobin (A.1.15), pyraoxystrobin (A.1.16), trifloxystrobin (A.1 .17), 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylideneaminooxy- methyl)-phenyl)-2-methoxyimino-N-methyl-acetamide (A.1.18), pyribencarb (A.1.19), triclopyricarb/chlorodincarb (A.1.20), famoxadone (A.1.21 ), fenamidone (A.1 .21 ), methyl-A/- [2-[(1 ,4-dimethyl-5-phenyl-pyrazol-3-yl)oxylmethyl]phenyl]-N-methoxy-carbamate (A.1.22), 1 - [3-chloro-2-[[[1 -(4-chlorophenyl)-1 H-pyrazol-3-yl]oxy]methyl]phenyl]-1 ,4-dihydro-4-methyl- 5H-tetrazol-5-one (A.1.23), (Z,2£)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]-oxy-2- methoxyimino-/V,3-dimethyl-pent-3-enamide (A.1.24), (Z,2£)-5-[1 -(4-chlorophenyl)pyrazol-3- yl]oxy-2-methoxyimino-/V,3-dimethyl-pent-3-enamide (A.1.25), (Z,2£)-5-[1 -(4-chloro-2-fluoro- phenyl)pyrazol-3-yl]oxy-2-methoxyimino-/V,3-dimethyl-pent-3-enamide (A.1.26);

- inhibitors of complex III at Qi site: cyazofamid (A.2.1 ), amisulbrom (A.2.2), [(3S,6S,7R,8R)-8- benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-di- oxonan-7-yl] 2-methylpropanoate (A.2.3), [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)- 4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl]

2-methylpropanoate (A.2.4), [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-meth- oxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate (A.2.5), [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1 ,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2- carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate (A.2.6);

(3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6-methyl-4,9-dioxo-8- (phenylmethyl)-1 ,5-dioxonan-7-yl 2-methylpropanoate (A.2.7);

- inhibitors of complex II (e. g. carboxamides): 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.3.1 1 ), isopyrazam (A.3.12), mepronil (A.3.13), oxycarboxin (A.3.14), penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), tecloftalam (A.3.17), thifluzamide (A.3.18), N-(4'- trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxamide (A.3.19), N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole- 4-carboxamide (A.3.20), 3-(difluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4- carboxamide (A.3.21 ), 3-(trifluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4- carboxamide (A.3.22), 1 ,3-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.23), 3-(trifluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4- carboxamide (A.3.24), 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.25), N-(7-fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-1 ,3-dimethyl-pyrazole-4-carboxamide (A.3.26), N-[2-(2,4-dichlorophenyl)-2-methoxy-1 -methyl-ethyl]-3-(difluoromethyl)-1 -methyl- pyrazole-4-carboxamide (A.3.27);

- other respiration inhibitors (e. g. complex I, uncouplers): diflumetorim (A.4.1 ), (5,8-difluoro- quinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine (A.4.2); nitrophenyl derivates: binapacryl (A.4.3), dinobuton (A.4.4), dinocap (A.4.5), fluazinam (A.4.6); ferimzone (A.4.7); organometal compounds: fentin salts, such as fentin-acetate

(A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.1 1 ); and silthi- ofam (A.4.12);

B) Sterol biosynthesis inhibitors (SBI fungicides)

- C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole (B.1.1 ), bitertanol (B.1.2), bromuconazole (B.1.3), cyproconazole (B.1 .4), difenoconazole (B.1 .5), diniconazole (B.1.6), diniconazole-M (B.1 .7), epoxiconazole (B.1.8), fenbuconazole (B.1 .9), fluquin- conazole (B.1.10), flusilazole (B.1 .1 1 ), flutriafol (B.1.12), hexaconazole (B.1 .13), imiben- conazole (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), prothioconazole (B.1.23), simeconazole (B.1.24), tebuconazole (B.1.25), tetracon- azole (B.1.26), triadimefon (B.1.27), triadimenol (B.1 .28), triticonazole (B.1 .29), uniconazole (B.1.30), 1 -[re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thio- cyanato-1 H-[1 ,2,4]triazolo (B.1.31 ), 2-[re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)- oxiranylmethyl]-2H-[1 ,2,4]triazole-3-thiol (B.1 .32), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]- 1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol (B.1.33), 1 -[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]- 1 -cyclopropyl-2-(1 ,2,4-triazol-1 -yl)ethanol (B.1.34), 2-[4-(4-chlorophenoxy)-2-(trifluorometh- yl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1.35), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 - (1 ,2,4-triazol-1 -yl)butan-2-ol (B.1.36), 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3- methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1.37), 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)- phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol (B.1.38), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-3- methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1.39), 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)- phenyl]-1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol (B.1.40), 2-[4-(4-fluorophenoxy)-2-(trifluoromethyl)- phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol (B.1.41 ), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 - (1 ,2,4-triazol-1 -yl)pent-3-yn-2-ol (B.1 .51 ); imidazoles: imazalil (B.1 .42), pefurazoate (B.1.43), prochloraz (B.1 .44), triflumizol (B.1 .45); pyrimidines, pyridines and piperazines: fenarimol (B.1.46), nuarimol (B.1 .47), pyrifenox (B.1.48), triforine (B.1 .49), [3-(4-chloro-2-fluoro- phenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(3-pyridyl)methanol (B.1 .50);

- 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), spi- roxamine (B.2.8);

- Inhibitors of 3-keto reductase: fenhexamid (B.3.1 );

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 (mefenoxam, C.1 .5), ofurace (C.1 .6), oxadixyl (C.1.7);

- others: 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);

D) Inhibitors of cell division and cytoskeleton

- tubulin inhibitors, such as benzimidazoles, thiophanates: benomyl (D1 .1 ), carbendazim

(D1 .2), fuberidazole (D1.3), thiabendazole (D1 .4), thiophanate-methyl (D1.5); triazolopyrim- idines: 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine (D1 .6);

- other cell division inhibitors: diethofencarb (D2.1 ), ethaboxam (D2.2), pencycuron (D2.3), fluopicolide (D2.4), zoxamide (D2.5), metrafenone (D2.6), pyriofenone (D2.7);

E) Inhibitors of amino acid and protein synthesis

- methionine synthesis inhibitors (anilino-pyrimidines): 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 hydro- chloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6), polyoxine (E.2.7), validamycin A (E.2.8);

F) Signal transduction inhibitors

- MAP / histidine kinase inhibitors: fluoroimid (F.1 .1 ), iprodione (F.1 .2), procymidone (F.1 .3), vinclozolin (F.1 .4), fenpiclonil (F.1 .5), fludioxonil (F.1.6);

- 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);

- 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) and N-(1 -(1 -(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4- fluorophenyl) ester (G.3.8);

- compounds affecting cell membrane permeability and fatty acides: propamocarb (G.4.1 );

- fatty acid amide hydrolase inhibitors: oxathiapiprolin (G.5.1 ), 2-{3-[2-(1 -{[3,5-bis(di- fluoromethyl-1 H-pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5- yl}phenyl methanesulfonate (G.5.2), 2-{3-[2-(1 -{[3, 5-bis(difluoromethyl)-1 H-pyrazol-1 - yl]acetyl}piperidin-4-yl) 1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate (G.5.3);

H) Inhibitors with Multi Site Action

- inorganic active substances: Bordeaux mixture (H.1 .1 ), copper acetate (H.1.2), copper hydroxide (H.1 .3), copper oxychloride (H.1.4), basic copper sulfate (H.1.5), sulfur (H.1.6);

- 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 (e. g. phthalimides, sulfamides, chloronitriles): 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.3.1 1 ), N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl- benzenesulfonamide (H.3.12);

- 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-1 H,5H- [1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone (H.4.10);

I) Cell wall synthesis inhibitors

- inhibitors of glucan synthesis: validamycin (1.1.1 ), polyoxin B (1.1 .2);

- melanin synthesis inhibitors: pyroquilon (1.2.1 ), tricyclazole (1.2.2), carpropamid (1.2.3), dicy- clomet (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), prohexadi- one-calcium (J.1 .5); phosphonates: fosetyl (J.1 .6), fosetyl-aluminum (J.1 .7), phosphorous acid and its salts (J.1 .8), potassium or sodium bicarbonate (J.1.9);

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), diclomezine (K.1 .7), difenzoquat (K.1 .8), difenzoquat- methylsulfate (K.1 .9), diphenylamin (K.1 .10), fenpyrazamine (K.1 .1 1 ), flumetover (K.1.12), flusulfamide (K.1 .13), flutianil (K.1 .14), methasulfocarb (K.1 .15), nitrapyrin (K.1 .16), nitrothal- isopropyl (K.1.18), oxathiapiprolin (K.1 .19), tolprocarb (K.1.20), oxin-copper (K.1.21 ), pro- quinazid (K.1 .22), tebufloquin (K.1 .23), tecloftalam (K.1.24), triazoxide (K.1 .25), 2-butoxy-6- iodo-3-propylchromen-4-one (K.1.26), 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5- [2-(prop-2-yn-1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yljetha- none (K.1 .27), 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-fluoro-6-(prop-2-yn-1 - yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone (K.1.28), 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-chloro-6-(prop-2-yn-1 -yloxy)phenyl]- 4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone (K.1.29), N-(cyclo- propylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide (K.1.30), N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine (K.1.31 ), N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N- ethyl-N-methyl formamidine (K.1 .32), N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl- propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.33), N'-(5-difluoromethyl-2-methyl-4-(3- trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.34), methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester (K.1 .35), 3-[5-(4-methylphenyl)-2,3- dimethyl-isoxazolidin-3-yl]-pyridine (K.1 .36), 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin- 3-yl]-pyridine (pyrisoxazole) (K.1 .37), N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide (K.1.38), 5-chloro-1 -(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole (K.1.39), 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy- acetamide, 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), 2-[2-[(7,8-difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro- phenyl]propan-2-ol (K.1 .43), 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phen-yl]propan- 2-ol (K.1 .44), 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1 -yl)quinoline (K.1 .45), 3- (4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline (K.1.46), 3-(4,4,5-trifluoro- 3,3-dimethyl-3,4-dihydroisoquinolin-1 -yl)quinoline (K.1 .47), 9-fluoro-2,2-dimethyl-5-(3- quinolyl)-3H-1 ,4-benzoxazepine (K.1 .48);

M) Growth regulators

abscisic acid (M.1 .1 ), amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat, chlormequat chloride, choline chloride, cyclanilide, daminozide, dikegulac, dime- thipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gib- berellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat, mepiquat chloride, naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione, prohexadi- one-calcium, prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate,

2,3,5-tri-iodobenzoic acid , trinexapac-ethyl and uniconazole;

N) Herbicides

- acetamides: acetochlor (N.1.1 ), alachlor, butachlor, dimethachlor, dimethenamid (N.1 .2), flufenacet (N.1.3), mefenacet (N.1.4), metolachlor (N.1 .5), metazachlor (N.1 .6), napropa- mide, naproanilide, pethoxamid, pretilachlor, propachlor, thenylchlor;

- amino acid derivatives: bilanafos, glyphosate (N.2.1 ), glufosinate (N.2.2), sulfosate (N.2.3);

- aryloxyphenoxypropionates: clodinafop (N.3.1 ), cyhalofop-butyl, fenoxaprop (N.3.2), fluazi- fop (N.3.3), haloxyfop (N.3.4), metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;

- Bipyridyls: diquat, paraquat (N.4.1 );

- (thio)carbamates: asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam

(EPTC), esprocarb, molinate, orbencarb, phenmedipham (N.5.1 ), prosulfocarb, pyributicarb, thiobencarb, triallate;

- cyclohexanediones: butroxydim, clethodim (N.6.1 ), cycloxydim (N.6.2), profoxydim (N.6.3), sethoxydim (N.6.4), tepraloxydim (N.6.5), tralkoxydim;

- dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin (N.7.1 ), prodiamine (N.7.2), trifluralin (N.7.3);

- diphenyl ethers: acifluorfen (N.8.1 ), aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lac- tofen, oxyfluorfen;

- hydroxybenzonitriles: bomoxynil (N.9.1 ), dichlobenil, ioxynil;

- imidazolinones: imazamethabenz, imazamox (N.10.1 ), imazapic (N.10.2), imazapyr (N.10.3), imazaquin (N.10.4), imazethapyr (N.10.5); - phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D) (N.1 1.1 ), 2,4-DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop;

- pyrazines: chloridazon (N.1 1.1 ), flufenpyr-ethyl, fluthiacet, norflurazon, pyridate;

- pyridines: aminopyralid, clopyralid (N.12.1 ), diflufenican, dithiopyr, fluridone, fluroxypyr

(N.12.2), picloram (N.12.3), picolinafen (N.12.4), thiazopyr;

- sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron (N.13.1 ), chlorimuron-ethyl

(N.13.2), chlorsulfuron, cinosulfuron, cyclosulfamuron (N.13.3), ethoxysulfuron, flazasulfu- ron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron (N.13.4), mesosulfuron (N.13.5), metazosulfuron, metsulfuron-methyl (N.13.6), nicosulfuron (N.13.7), oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron (N.13.8), sul- fometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron (N.13.9), tritosulfuron, 1 -((2-chloro-6-propyl-imidazo[1 ,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6- d i methoxy-pyri m id i n-2-yl) u rea ;

- triazines: ametryn, atrazine (N.14.1 ), cyanazine, dimethametryn, ethiozin, hexazinone

(N.14.2), metamitron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam, trifludimoxazin (N14.3);

- ureas: chlorotoluron, daimuron, diuron (N.15.1 ), fluometuron, isoproturon, linuron, metha- benzthiazuron, tebuthiuron;

- other acetolactate synthase inhibitors: bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam (N.16.1 ), flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrim- isulfan, pyrithiobac, pyroxasulfone (N.16.2), pyroxsulam;

- others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarba- zone,benfluresate, benzofenap, bentazone (N.17.1 ), benzobicyclon, bicyclopyrone, broma- cil, bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-ethyl (N.17.2), chlorthal, cinmethylin (N.17.3), clomazone (N.17.4), cumyluron, cyprosulfamide, dicamba (N.17.5), difenzoquat, diflufenzopyr (N.17.6), Drechslera monoceras, endothal,

ethofumesate, etobenzanid, fenoxasulfone, fentrazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac (N.17.7), quinmerac (N.17.8), mesotrione (N.17.9), methyl arsonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotole, pyrazoxyfen, pyrazolynate, quinoclamine, saflufenacil (N.17.10), sulcotrione (N.17.1 1 ), sulfentrazone, terbacil, tefuryltrione, tembotrione, thien- carbazone, topramezone (N.17.12), (3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4- trifluoromethyl-3,6-dihydro-2H-pyrimidin-1 -yl)-phenoxy]-pyridin-2-yloxy)-acetic acid ethyl ester, 6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid methyl ester, 6-chloro-3-(2- cyclopropyl-6-methyl-phenoxy)-pyridazin-4-ol, 4-amino-3-chloro-6-(4-chloro-phenyl)-5-fluoro- pyridine-2-carboxylic acid, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxy-phenyl)- pyridine-2-carboxylic acid methyl ester, and 4-amino-3-chloro-6-(4-chloro-3-dimethylamino- 2-fluoro-phenyl)-pyridine-2-carboxylic acid methyl ester;

O) Insecticides

- organo(thio)phosphates: acephate (0.1.1 ), azamethiphos (0.1.2), azinphos-methyl (0.1 .3), chlorpyrifos (0.1 .4), chlorpyrifos-methyl (0.1 .5), chlorfenvinphos (0.1.6), diazinon (0.1 .7), dichlorvos (0.1 .8), dicrotophos (0.1 .9), dimethoate (0.1 .10), disulfoton (0.1 .1 1 ), ethion (0.1 .12), fenitrothion (0.1 .13), fenthion (0.1 .14), isoxathion (0.1 .15), malathion (0.1 .16), methamidophos (0.1 .17), methidathion (0.1 .18), methyl-parathion (0.1 .19), mevinphos (0.1 .20), monocrotophos (0.1 .21 ), oxydemeton-methyl (0.1 .22), paraoxon (0.1 .23), para- thion (0.1 .24), phenthoate (0.1 .25), phosalone (0.1 .26), phosmet (0.1 .27), phosphamidon (0.1 .28), phorate (0.1 .29), phoxim (0.1 .30), pirimiphos-methyl (0.1 .31 ), profenofos

(0.1 .32), prothiofos (0.1 .33), sulprophos (0.1 .34), tetrachlorvinphos (0.1 .35), terbufos (0.1 .36), triazophos (0.1 .37), trichlorfon (0.1 .38);

- carbamates: alanycarb (0.2.1 ), aldicarb (0.2.2), bendiocarb (0.2.3), benfuracarb (0.2.4), carbaryl (0.2.5), carbofuran (0.2.6), carbosulfan (0.2.7), fenoxycarb (0.2.8), furathiocarb

(0.2.9), methiocarb (0.2.10), methomyl (0.2.1 1 ), oxamyl (0.2.12), pirimicarb (0.2.13), propoxur (0.2.14), thiodicarb (0.2.15), triazamate (0.2.16);

- pyrethroids: allethrin (0.3.1 ), bifenthrin (0.3.2), cyfluthrin (0.3.3), cyhalothrin (0.3.4), cyphe- nothrin (0.3.5), cypermethrin (0.3.6), alpha-cypermethrin (0.3.7), beta-cypermethrin (0.3.8), zeta-cypermethrin (0.3.9), deltamethrin (0.3.10), esfenvalerate (0.3.1 1 ), etofenprox

(0.3.1 1 ), fenpropathrin (0.3.12), fenvalerate (0.3.13), imiprothrin (0.3.14), lambda- cyhalothrin (0.3.15), permethrin (0.3.16), prallethrin (0.3.17), pyrethrin I and II (0.3.18), resmethrin (0.3.19), silafluofen (O.3.20), tau-fluvalinate (0.3.21 ), tefluthrin (0.3.22), tetrame- thrin (0.3.23), tralomethrin (0.3.24), transfluthrin (0.3.25), profluthrin (0.3.26), dimefluthrin (0.3.27);

- insect growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron (0.4.1 ), cyramazin (0.4.2), diflubenzuron (0.4.3), flucycloxuron (0.4.4), flufenoxuron (0.4.5), hex- aflumuron (0.4.6), lufenuron (0.4.7), novaluron (0.4.8), teflubenzuron (0.4.9), triflumuron (0.4.10); buprofezin (0.4.1 1 ), diofenolan (0.4.12), hexythiazox (0.4.13), etoxazole (0.4.14), clofentazine (0.4.15); b) ecdysone antagonists: halofenozide (0.4.16), methoxyfenozide (0.4.17), tebufenozide (0.4.18), azadirachtin (0.4.19); c) juvenoids: pyriproxyfen (O.4.20), methoprene (0.4.21 ), fenoxycarb (0.4.22); d) lipid biosynthesis inhibitors: spirodiclofen (0.4.23), spiromesifen (0.4.24), spirotetramat (0.4.24);

- nicotinic receptor agonists/antagonists compounds: clothianidin (0.5.1 ), dinotefuran (0.5.2), flupyradifurone (0.5.3), imidacloprid (0.5.4), thiamethoxam (0.5.5), nitenpyram (0.5.6), ac- etamiprid (0.5.7), thiacloprid (0.5.8), 1 -2-chloro-thiazol-5-ylmethyl)-2-nitrimino-3,5-dimethyl- [1 ,3,5]triazinane (0.5.9);

- GABA antagonist compounds: endosulfan (0.6.19, ethiprole (0.6.2), fipronil (0.6.3),

vaniliprole (0.6.4), pyrafluprole (0.6.5), pyriprole (0.6.6), 5-amino-1 -(2,6-dichloro-4-methyl- phenyl)-4-sulfinamoyl-1 H-pyrazole-3-carbothioic acid amide (0.6.7);

- macrocyclic lactone insecticides: abamectin (0.7.1 ), emamectin (0.7.2), milbemectin

(0.7.3), lepimectin (0.7.4), spinosad (0.7.5), spinetoram (0.7.6);

- mitochondrial electron transport inhibitor (METI) I acaricides: fenazaquin (0.8.1 ), pyridaben (0.8.2), tebufenpyrad (0.8.3), tolfenpyrad (0.8.4), flufenerim (0.8.5);

- METI II and II I compounds: acequinocyl (0.9.1 ), fluacyprim (0.9.2), hydramethylnon (0.9.3);

- Uncouplers: chlorfenapyr (0.10.1 );

- oxidative phosphorylation inhibitors: cyhexatin (0.1 1 .1 ), diafenthiuron (0.1 1 .2), fenbutatin oxide (0.1 1 .3), propargite (0.1 1 .4); - moulting disruptor compounds: cryomazine (0.12.1 );

- mixed function oxidase inhibitors: piperonyl butoxide (0.13.1 );

- sodium channel blockers: indoxacarb (0.14.1 ), metaflumizone (0.14.2);

- ryanodine receptor inhibitors: chlorantraniliprole (0.15.1 ), cyantraniliprole (0.15.2), flu- bendiamide (0.15.3), N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]- 2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide (0.15.4); N-[4-chloro-2-[(di- ethyl-lambda-4-sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(triflu- oromethyl)pyrazole-3-carboxamide (0.15.5); N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanyli- dene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-car- boxamide (0.15.6); N-[4,6-dichloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]- phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide (0.15.7); N-[4,6-di- chloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(di- fluoromethyl)pyrazole-3-carboxamide (0.15.8); N-[4,6-dibromo-2-[(di-2-propyl-lambda-4-sul- fanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carbox- amide (0.15.9); N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-6-cyano- phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide (0.15.10); N-[4,6- dibromo-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(tri- fluoromethyl)pyrazole-3-carboxamide (0.15.1 1 );

- others: benclothiaz (0.16.1 ), bifenazate (0.16.2), artap (0.16.3), flonicamid (0.16.4),

pyridalyl (0.16.5), pymetrozine (0.16.6), sulfur (0.16.7), thiocyclam (0.16.8), cyenopyrafen (0.16.9), flupyrazofos (O.16.10), cyflumetofen (0.16.1 1 ), amidoflumet (0.16.12), imicyafos (0.16.13), bistrifluron (0.16.14), pyrifluquinazon (0.16.15) and

1 , 1 '-[(3S,4R,4aR,6S,6aS, 12R, 12aS, 12bS)-4-[[(2-cyclopropylacetyl)oxy]methyl]- 1 ,3,4,4a,5,6,6a,12,12a,12b-decahydro-12-hydroxy-4,6a,12b-trimethyl-1 1 -oxo-9-(3-pyridinyl)- 21-1,1 1 H-naphtho[2,1 -b]pyrano[3,4-e]pyran-3,6-diyl] cyclopropaneacetic acid ester (0.16.16).

The present invention furthermore relates to agrochemical compositions comprising a mixture of at least one compound I (component 1 ) and at least one further active substance useful for plant protection, e. g. selected from the groups A) to O) (component 2), in particular one fur- ther fungicide, e. g. one or more fungicide from the groups A) to K), as described above, and if desired one suitable solvent or solid carrier. Those mixtures are of particular interest, since many of them at the same application rate show higher efficiencies against harmful fungi. Furthermore, combating harmful fungi with a mixture of compounds I and at least one fungicide from groups A) to K), as described above, is more efficient than combating those fungi with indi- vidual compounds I or individual fungicides from groups A) to K).

By applying compounds I together with at least one active substance from groups A) to O) a synergistic effect can be obtained, i.e. more then simple addition of the individual effects is obtained (synergistic mixtures).

This can be obtained by applying the compounds I and at least one further active substance simultaneously, either jointly (e. g. as tank-mix) or seperately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance applied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s). The order of application is not essential for working of the invention. In the binary mixtures and compositions according to the invention the weight ratio of the component 1 ) and the component 2) generally depends from the properties of the active components used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 , even more preferably in the range of from 1 :4 to 4:1 and in particular in the range of from 1 :2 to 2:1. These ratios are also suitable for inventive mixtures applied by seed treatment.

The mixtures of active substances can be prepared as compositions comprising besides the active ingredients at least one inert ingredient (auxiliary) by usual means, e. g. by the means given for the compositions of compounds I. Concerning usual ingredients of such compositions reference is made to the explanations given for the compositions containing compounds I.

Synthesis examples

With due modification of the starting compounds, the procedures shown in the synthesis examples below were used to obtain further compounds I. The resulting compounds, together with physical data, are listed in Table I below.

I. Preparation of tetrazol-5-one compounds I

Example 1 : Preparation of 1 -[3-chloro-2-[[(E)-[(2E)-2-methoxyimino-1 ,4-dimethyl-pent-3- enylidene]amino]oxymethyl]phenyl]-4-methyl-tetrazol-5-one

A suspension of 126.1 mg (3E)-3-methoxyimino-5-methyl-hex-4-en-2-one oxime and 122.9 mg potassium carbonate was stirred for 30 min at 80 °C. To the reaction mixture 250 mg 1 -[3- chloro-2-(chloromethyl)phenyl]-4-methyl-tetrazol-5-one was added, heated to reflux, maintained for 8 h, cooled to 23°C and filtered. After removal of the solvent in vacuo the residue chromato- graphed an silica gel using cyclohexane-ethyl acetate to yield 1 10 mg colorless oil that cystal- lised upon standing (mp: 87°C).

Example 1.1 : Preparation of (3E)-3-methoxyimino-5-methyl-hex-4-en-2-one oxime

550 mg sodium methylate was added to 430 mg (3E)-3-methoxyimino-5-methyl-hex-5-en-2- one oxime (for preparation see WO 2000/031024) in DMF and stirred for 72 h at 20-25 °C. For workup, water was added and product was extracted in MtBE. The organic layer was washed with water, concentrated under vacuum and flash chromatographed an silica gel using cyclo- hexane-ethyl acetate to give the titled product as an off-white solid. 1 H-NMR (δ, ppm): 1 .85 (s, 3H); 2.1 (s, 3H); 3.95 (s, 3H); 5.7 (s, 1 H); 8.8 (s, 1 H). Table I: Compounds of formula I

ex. no Y n R¹ R2 R³ m. p. [°C]

1 3-CI 1 CHs CHs -CH=C(CHs)₂ 78

2 - 0 CHs CH₂C≡CH -CH=CH₂ 1 1 1

3 - 0 CHs CHs -CH=C(CHs)₂ 96

4 - 0 CHs CHs -CH₂C(CHs)=CH₂ 45

5 3-CHs 1 CHs CH2CH3 -CH=CCI₂ 1 1 1

6 3-CHs 1 CHs CH2CH3 -CH₂C(CH₂CHs)=CH₂ 387.1

7 3-CHs 1 CHs CH2CH3 -CH₂C(CHs)=CHCH3 407.1

8 - CHs CH₂C≡CH -CH₂C(CHs)=CH₂ 383.1

9 3-CI 1 CHs CHs -CH=C(CH₃)CH₂CHs 417.1

10 3-CI 1 CHs CH(CHs)₂ -CH=C(CH₃)₂ 421 .1

1 1 3-CI 1 CHs CH₂CH=CH₂ -CH=C(CHs)₂ 419.1

12 3-CI 1 CHs CH₂CHs -CH=C(CH₃)₂ 407.1

13 - CHs CH₂CH=CH₂ -CH=C(CHs)₂ 70°C

14 - CHs CH(CHs)₂ -CH=C(CH₃)₂ 387.1

15 3-CHs 1 CHs CH(CHs)₂ -CH=C(CHs)₂ 401 .1

16 3-CHs 1 CHs CH₂CH=CH₂ -CH=C(CH₃)₂ 399.1

17 3-CHs 1 CHs CH₂C≡CH -CH₂C(CHs)=CH₂ 82

18 3-CHs 1 CHs CH₂CHs -CH=C(CH₃)₂ 387.1

19 - CHs CH₂C≡CH -CH=CH₂ 1 1 1 °C

20 3-CHs 1 CHs CHs -CH=CCI₂ 63°C

21 3-CHs 1 CHs CHs -CH=C(CH₂CHs)₂ 401 .1

22 3-CHs 1 CHs CHs -CH=C(CH₃)CH₂CHs 387.1

23 - CHs CH₂CHs -CH=C(CH₃)₂ 88

24 3-CHs 1 CHs CHs -CH₂C(CHs)=CH₂ 373.2

25 3-CI 1 CHs CHs -CH₂C(CH₃)=CH₂ 393.1

26 *

3-CH=CH₂ 1 CHs CHs -CH=C(CHs)₂

27 3-F 1 CHs CHs -CH=C(CH₃)₂ 377

28 3-CH≡CH 1 CHs CHs -CH=C(CHs)₂ 383.1 m.p. = melting point.

^* 1 H-NMR: 1 ,4 (s,3H); 1.82 (s,3H); 1.95 (s,3H); 3.7 (s,3H); 3.9 (s, 3H); 5.2 (s, 2H); 5.41 (m,1 H); 5.6-5.78 (m,2H).

II. Examples of the action against harmful fungi

The fungicidal action of the compounds I was demonstrated by the following experiments: The active substances were formulated separately as a stock solution in dimethyl sulfoxide

(DMSO) at a concentration of 10 000 ppm.

Use example 1 : Activity against the wheat leaf blotch pathogen Septoria tritici

The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Septoria tritici in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The 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 and active compound-free blank value to determine the relative growth in % of the pathogens in the respective active compounds. These percentages were converted into efficacies using Abbot's formula. a) Comparative data obtained using a wild-type isolate of Septoria tritici

Compound Structure Efficacy (%) at 16 ppm

Compound I-240

of WO 13/092224 =-° 12

(p. 78)

Comp. 2 acc. to

32

the invention

Comparative data obtained using a Qol resistant isolate^* of Septoria tritici

^* isolate containing a G143A mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitor fungicides

Claims

Claims . Compounds of formula I

indicates the number of substituents Y on the phenyl ring and n is 0, 1 , 2, 3 or 4; is halogen, OH, NH₂, NHCH₃, N(CH₃)₂ , CN, N0₂, Ci-C₄-alkyl, Ci-C₄-haloalkyl, Ci-C₄-alkoxy, Ci-C₄-haloalkoxy, C2-C₄-alkenyl, C2-C₄-haloalkenyl, C2-C₄-alkynyl, C2-C₄-haloalkynyl, Ci-C₄-alkylthio, Ci-C₄-haloalkylthio, C3-C6-cycloalkyl; it being possible for n = 2, 3 or 4 that Y are identical or different; is Ci-C2-alkyl, Ci-C2-alkoxy, Ci-C2-haloalkyl, Ci-C2-haloalkoxy, chloro, CN or cyclopropyl; is hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C₄-alkoxy-Ci-C2-alkyl, Ci-C₄-haloalkoxy- Ci-C₄-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, Cs-Cs-cycloalkyl- Ci-C₄-alkyl, phenyl, phenyl-Ci-C₄-alkyl, phenoxy-Ci-C₄-alkyl or a 5- or 6-membered heteroaryl, wherein the ring member atoms of the heteroaryl include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from the group of N, O and S, and wherein the aforementioned cyclic radicals are unsubstituted or carry 1 , 2, 3, 4 or 5 identical or different substituents R^a:

R^a is halogen, CN, Ci-C₄-alkyl, Ci-C₄-haloalkyl, Ci-C₄-alkoxy or Ci-C₄-haloalkoxy; is C2-Cio-alkenyl, C2-Cs-alkynyl, C2-C8-haloalkenyl or C2-C8-haloalkynyl, wherein the aforementioned radicals are unsubstituted or carry 1 , 2, 3 or 4 identical or different substituents R^b :

R^b is CN, Ci-C₄-alkoxy or Ci-C₄-haloalkoxy or C3-C6-cycloalkyl;

and wherein the R³ radicals may further carry one phenyl or one 5- or 6-membered heteroaryl, wherein the ring member atoms of the heteroaryl include besides carbon atoms 1 , 2, 3 or 4 heteroatoms selected from the group of N, O and S; wherein the aforementioned cyclic groups are unsubstituted or carry 1 , 2, 3 4 or 5 identical or different substituents R^c:

R^c is halogen, CN, Ci-C₄-alkyl, Ci-C₄-haloalkyl, Ci-C₄-alkoxy or Ci-C4-haloalkoxy;

and the N-oxides and the agriculturally acceptable salts thereof.

2. The compounds according to claim 1 , wherein Y is halogen.

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

4. The compounds according to any of the claims 1 to 3, wherein R¹ is CrC₂-alkyl or CrC₂- haloalkyl.

5. The compounds according to any of the claims 1 to 4, wherein R² is CrC₄-alkyl or

CrC₄-haloalkyl.

6. The compounds according to claim 5, wherein R¹ and R² are both methyl.

7. The compounds according to any of the claims 1 to 6, wherein R³ is C2-Cio-alkenyl.

8. The compounds according to any of the claims 1 to 5, wherein R³ is -CH≡C-phenyl,

wherein phenyl is unsubstituted or carries 1 or 2 R^b substituents selected from halogen,

CN, Ci-C₂-alkyl, and Ci-C₂-haloalkyl.

9. Agrochemical compositions wherein said compositions comprise an auxiliary and at least one compound of formula I, as defined in any of the claims 1 to 8, an N-oxide or an agriculturally acceptable salt thereof.

10. The compositions according to claim 9 comprising at least one further active substance.

1 1 . Use of compounds of the formula I and the N-oxides and the agriculturally acceptable salts thereof as defined in any of the claims 1 to 8 for combating phytopathogenic fungi.

12. The use as according to claim 1 1 , wherein the phytopathogenic fungi contain a G143A mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors.

13. A method for combating phytopathogenic fungi, comprising:

treating the phytopathogenic fungi or the materials, plants, the soil or seeds that are at risk of being diseased from phytopathogenic fungi with an effective amount of at least one compound of formula I as defined in any of the claims 1 to 8, or with an effective amount of a composition as defined in any of claims 9 and 10.

14. The method according to claim 13, wherein the phytopathogenic fungi contain a G143A mutation in the mitochondrial cytochrome b gene conferring resistance to Qo inhibitors. Plant propagation material, comprising at least one compound of formula I as defined any of the claims 1 to 8, or a composition as defined in any of claims 9 and 10, in an amount of from 0.01 g to 10 kg per 100 kg of plant propagation material.