WO2025172374A1 - Microbiocidal pyrazole derivatives - Google Patents

Abstract

A compound of formula (I), wherein the substituents are as defined in claim 1, and the agrochemically acceptable salts, or N-oxides of those compounds, which can be used as fungicides.

Description

MICROBIOCIDAL PYRAZOLE DERIVATIVES

The present invention relates to microbiocidal pyrazole derivatives, e.g., as active ingredients, which have microbiocidal activity, in particular fungicidal activity. The invention also relates to preparation of these pyrazole derivatives, to intermediates useful in the preparation of these pyrazole derivatives, to the preparation of these intermediates, to agrochemical compositions which comprise at least one of the pyrazole derivatives, to preparation of these compositions and to the use of the pyrazole derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi.

According to a first aspect of the present invention, there is provided a compound of formula (I): wherein

R¹ is selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, or Cs-Ce-cycloalkyl;

R² is selected from hydrogen, halogen, cyano, hydroxy, amino, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3- Ce-cycloalkyl, Ci-C4-alkoxy, Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, Ci-C4-alkoxy-Ci-C2-alkyl, Ci-C4-haloalkyl, C1- C4-haloalkoxy, Cs-Ce-cycloalkyloxy, Ci-C4-alkylamino, di(Ci-C4-alkyl)amino, Ci-C4-alkylsulfanyl, C1-C4- alkylsu Ifinyl, Ci-C4-alkylsulfonyl, or Ci-C4-haloalkylsulfanyl;

R³ is selected from hydrogen, halogen, Ci-C4-alkyl, or Ci-C4-haloalkyl;

R⁴ is selected from hydrogen, halogen, Ci-C4-alkyl, or Ci-C4-haloalkyl;

R⁵ is selected from hydrogen, halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-haloalkoxy, Ci-C4-alkoxy, C3-C6- alkenyloxy, Cs-Ce-alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-haloalkylsulfanyl, Ci-C4-alkylsulfinyl, C1-C4- haloalkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-haloalkylsulfonyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxycarbonyl, Ci-C6-alkylaminocarbonyl, di(Ci-C4-alkyl)aminocarbonyl, cyano-Ci-C4-alkyl, N-Ci-C4-alkoxy-C-Ci-C4-alkyl- carbonimidoyl, N-hydroxy-C-Ci-C4-alkyl-carbonimidoyl, hydroxy, amino, Ci-C4-alkylamino, di(Ci-C4- alkyl)amino, cyano, carboxy, phenyl, a 5- to 6-membered saturated, partially saturated or aromatic heteroaryl, or Cs-Ce-cycloalkyl; wherein any of said phenyl, and 5- to 6-membered saturated, partially saturated or aromatic heteroaryl are unsubstituted or substituted with 1 , 2, or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy; and wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-alkoxy, or Ci-C4-haloalkyl; R⁶ is selected from hydrogen, halogen, cyano, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, C3- Ce-cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkylsulfonyl, or C1-C4- alkoxycarbonyl;

R⁷ is selected from hydrogen, halogen, Ci-C4-alkyl, or Ci-C4-haloalkyl;

Z¹ is selected from Ci-Ce-alkoxy, wherein any of said Ci-Ce-alkoxy is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Cs-Ce-cycloalkyl, C2-Cs-alkenyl, C2- Ce-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Cs-alkenyloxy, Cs-Ce-alkynyloxy, C1-C4- alkylsulfanyl, Ci-C4-haloalkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-haloalkylsulfinyl, Ci-C4-alkylsulfonyl, C1-C4- haloalkylsulfonyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxycarbonyl, Ci-C4-alkylcarbonyl, N-Ci-C4-alkoxy-C-Ci- C4-alkyl-carbonimidoyl, or N-hydroxy-C-Ci-C4-alkyl-carbonimidoyl; and

Z² is hydrogen, Ci-Cs-alkyl, or Cs-Ce-cycloalkyl; or an agrochemically acceptable salt, or N-oxide thereof.

Surprisingly, it has been found that the compounds of formula (I) have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.

According to a second aspect of the invention, there is provided an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) according to the invention. Such an agricultural composition may further comprise at least one additional active ingredient and/or an agrochemically-acceptable diluent or carrier.

According to a third aspect of the invention, there is provided a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I) according to the invention, or a composition comprising the compound of formula (I), is applied to the plants, to parts thereof or the locus thereof.

According to a fourth aspect of the invention, there is provided the use of a compound of formula (I) according to the invention as a fungicide. According to this particular aspect of the invention, the use may exclude methods for treatment of the human or animal body by surgery or therapy and diagnostic methods practiced on the human or animal body.

The compounds of formula (I) or the intermediate compounds of formula (III) according to the invention, which have at least one basic centre, can form, for example, acid addition salts, for example with strong inorganic acids such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as Ci-C4-alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as Ci-C4-alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid. The compounds of formula (I) or the intermediate compounds of formula (III) according to the invention, which have at least one acidic group, can form, for example, salts with bases, for example mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine.

The presence of one or more possible asymmetric carbon atoms in a compound of formula (I) according to the invention means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. Also, atropisomers may occur as a result of restricted rotation about a single bond. Formula (I) is intended to include all those possible isomeric forms and mixtures thereof. The present invention includes all those possible isomeric forms and mixtures thereof for a compound of formula (I) according to the invention. Likewise, a compound of formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism) where present. The present invention includes all possible tautomeric forms for a compound of formula (I) according to the invention.

In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form as an N-oxide, in covalently hydrated form, or in salt form, e.g., an agronomically usable or agrochemically acceptable salt form. N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen containing heteroaromatic compounds. They are described for instance in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra, CRC Press, Boca Raton 1991. N-oxides can be prepared by reacting a compound of formula (I) with a suitable oxidizing agent, for example the H2O2/urea adduct, in the presence of an acid anhydride, e.g., trifluoroacetic anhydride. Such oxidations are known from the literature, for example from J. Med. Chem. 1989, 32 (12), 2561- 73, or W02000/15615. The compounds of formula (I) according to the invention also include hydrates, which may be formed during salt formation.

As used herein, the term "halogen" or “halo” refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl, haloalkenyl, haloalkynyl, haloalkoxy, and halocycloalkyl.

As used herein, amino means a -NH2 group.

As used herein, cyano means a -CN group.

As used herein, the term “hydroxyl” or “hydroxy” means an -OH group.

As used herein, the term “carboxylic acid” means a -COOH group.

As used herein, the term "Ci-Cn-alkyl” refers to a saturated straight-chain or branched hydrocarbon radical attached via any of the carbon atoms having 1 to n carbon atoms, for example, any one of the radicals methyl, ethyl, n-propyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1 -ethylpropyl, n-hexyl, n- pentyl, 1 ,1-dimethylpropyl, 1 , 2-dimethylpropyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 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, or 1-ethyl-2- methylpropyl.

As used herein, the term “C2-Cn-alkenyl” refers to a straight or branched alkenyl chain moiety having from two to n carbon atoms and one or two double bonds, for example, ethenyl, prop-1 -enyl, but-2-enyl.

As used herein, the term “C2-Cn-alkynyl” refers to a straight or branched alkynyl chain moiety having from two to n carbon atoms and one triple bond, for example, ethynyl, prop-2-ynyl, but-3-ynyl,

As used herein, the term “Cs-Cn-cycloalkyl” refers to three (3) to n membered cycloalkyl radical such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

As used herein, the term “cyano-Ci-Cn-alkyl” refers to Ci-C_n-alkyl radical having 1 to n carbon atoms (as mentioned above), where one of the hydrogen atoms in the radical is be replaced by a cyano group: for example, cyano-methyl, 2-cyano-ethyl, 2-cyano-propyl, 3-cyano-propyl, 1-(cyano-methyl)-2-ethyl, 1-(methyl)-

2-cyano-ethyl, 4-cyanobutyl, and the like. Similarly, the term “cyano-Cs-Cn-cycloalkyl” refers to a Cs-Cn- cycloalkyl radical substituted with one of the hydrogen atoms by a cyano group.

As used herein, the term "Ci-Cn-alkoxy" refers to a straight-chain or branched saturated alkyl radical having one (1 ) to n carbon atoms (as mentioned above) which is attached via an oxygen atom, i.e., for example, any one of the radicals methoxy, ethoxy, n-propoxy, 1 -methylethoxy, n-butoxy, 1 -methylpropoxy, 2-methylpropoxy and 1 ,1 -dimethylethoxy. The term “C2-Cn-alkenyloxy” as used herein refers to a straight-chain or branched alkenyl chain having two (2) to n carbon atoms (as mentioned above) which is attached via an oxygen atom.

As used herein, the term "C2-Cn-alkynyloxy" refers to a radical of the formula -ORa where R_a is a C2-Cn-alkynyl radical as generally defined above.

As used herein, the term “Ci-Cn-alkoxy-Ci-C_n-alkyl” refers to an alkyl radical Ci-Cn-alkyl (as mentioned above) substituted with a Ci-Cn-alkoxy group. Examples are methoxymethyl, methoxyethyl, ethoxymethyl and propoxymethyl. This term can be used interchangeably with the term “Ci-C_n-alkyl-Ci-C_n-alkoxy” which refers to a radical of the formula -R_a-ORb, where R_a is a Ci-Cn-alkyl group as defined above, and b refers to an Ci- Cn-alkyl group as defined aboveAs used herein, the term “Ci-Cn-alkyl-Ci-Cn-alkoxy-Ci-C_n-alkoxy” refers to a radical of the formula -R_a-ORb-OR_c, where R_a is a Ci-Cn-alkyl group as defined above, and Rb and R_c refer to an Ci-Cn-alkyl group as defined above.

As used herein, the term “Cs-Cn-cycloalkyl-Ci-Cn-alkyl” refers to an alkyl radical (as mentioned above) substituted with a Cs-Cn-cycloalkyl group. Examples are cyclopropylmethyl, cyclopropylethyl.

As used herein, the term "Ci-Cn-haloalkyl" refers to a straight-chain or branched saturated alkyl radical attached via any of the carbon atoms having 1 to n carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these radicals may be replaced by fluorine, chlorine, bromine and/or iodine, i.e., for example, any one of chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2- iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro- 2-fluoroethyl, 2,2,2-trichloroethyl.

As used herein, the term “Ci-C_n-alkylthio“ or “Ci-C_n-alkylsulfanyl“refers to a Ci-C_n-alkyl group linked through a sulfur atom.

As used herein, the term “Ci-C_n-haloalkylthio“ or “Ci-C_n-haloalkylsulfanyl“refers to a Ci-Cn-haloalkyl group linked through a sulfur atom.

As used herein, the term “Ci-C_n-alkylsulfinyl“ refers to a Ci-Cn-alkyl group linked through the sulfur atom of a sulfinyl (or S(=O)-) group.

As used herein, the term “Ci-C_n-alkylsulfonyl“ refers to a Ci-Cn-alkyl group linked through the sulfur atom of a sulfonyl (or S(=O)2-) group.

As used herein, the term “Ci-Cn-alkylsulfonyl-Ci-C_n-alkyl” refers to an a Ci-Cn-alkyl radical substituted with a Ci-Cn-alkylsulfonyl group.

As used herein, the term “Ci-Cn-alkylcarbonyl” refers to a Ci-Cn-alkyl group linked through the carbon atom of a carbonyl (C=O) group.

As used herein, the term “Ci-Cn-alkoxycarbonyl” refers to a Ci-Cn-alkoxy moiety linked through a carbon atom of a carbonyl (or C=O) group.

As used herein, the term “Ci-Cn-alkylaminocarbonyl” refers to a Ci-Cn-alkylamino group (or R_aNHC(=O)-), wherein R_a is a Ci-Cn-alkyl group linked through the carbon atom of a carbonyl (C=O) group.

As used herein, the term “aminocarbonyl-Ci-C_n-alkyl” refers to a Ci-Cn-alkyl radical substituted by an aminocarbonyl (or NH2C(=O)-) group.

As used herein, the term “N-Ci-C_n alkylamino” refers to a radical of the formula -NH-R_a where R_a is a Ci-C_n- alkyl radical as defined above.

As used herein, the term "N,N-di(Ci-C_n-alkyl)amino" refers to a radical of the formula -N(R_a)R_a where each R_a is a Ci-Cn-alkyl radical, which may be the same or different, as defined above.

As used herein, the term “heteroaryl" refers to a 5- or 6-membered aromatic monocyclic ring radical which comprises 1 , 2, 3 or 4 heteroatoms independently selected from N, O or S. Examples of heteroaryl include, but are not limited to, furanyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl or pyridyl. The term “heteroaryl-Ci-C_n-alkyl” or “heteroaryl- Cs-Cn-cycloalkyl” refers to an Ci-Cn-alkyl or Cs-Cn-cycloalkyl radical respectively substituted by a heteroaryl group. The heteroaryl-Ci-Cn-alkyl or heteroaryl-Cs-Cn-cycloalkyl radical may be substituted on heteroaryl, alkyl and/or cycloalkyl group as appropriate.

As used herein, the term "controlling" refers to reducing the number of pests, eliminating pests and/or preventing further pest damage such that damage to a plant or to a plant derived product is reduced. As used herein, the term "pest" refers to insects, and molluscs that are found in agriculture, horticulture, forestry, the storage of products of vegetable origin (such as fruit, grain, and timber); and those pests associated with the damage of man-made structures. The term pest encompasses all stages in the life cycle of the pest.

As used herein, the term "effective amount" refers to the amount of the compound, or a salt thereof, which, upon single or multiple applications provides the desired effect.

An effective amount is readily determined by the skilled person in the art, using known techniques and by observing results obtained under analogous circumstances. In determining the effective amount, a number of factors are considered including, but not limited to the type of plant or derived product to be applied; the pest to be controlled and its lifecycle; the particular compound applied; the type of application; and other relevant circumstances.

As used herein, the term “room temperature” or “RT” or “rt” or “ambient temperature” refer to a temperature of about 15°C to about 35°C. For example, rt can refer to a temperature of about 20°C to about 30°C.

The following list provides definitions, including preferred definitions, for substituents R¹, R², R³, R⁴, R⁵, R⁶, R⁷, Z¹ and Z² with reference to the compounds of formula (I) of the present invention. For any one of these substituents, any of the definitions given below may be combined with any definition of any other substituent given below or elsewhere in this document.

In one embodiment of the invention, R¹ is selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, or Cs-Ce-cycloalkyl. Preferably, R¹ is hydrogen, Ci-Cs-alkyl, Ci-C2-haloalkyl, C2-C4-alkenyl, C2- C4-alkynyl, or cyclopropyl. More preferably R¹ is Ci-Cs-alkyl, C2-C3-alkenyl, C2-C3-alkynyl, or cyclopropyl. Even more preferably R¹ is Ci-Cs-alkyl, or cyclopropyl. Even more preferably R¹ is methyl; or cyclopropyl.

In another embodiment R¹ is Ci-C4-alkyl. Preferably R¹ is Ci-Cs-alkyl. More preferably R¹ is methyl.

In one embodiment of the invention, R² is selected from hydrogen, halogen, cyano, hydroxy, amino, C1-C4- alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Cs-Ce-cycloalkyl, Ci-C4-alkoxy, Cs-Cs-alkenyloxy, Cs-Ce-alkynyloxy, C1-C4- alkoxy-Ci-C2-alkyl, Ci-C4-haloalkyl, Ci-C4-haloalkoxy, Cs-Ce-cycloalkyloxy, Ci-C4-alkylamino, di(Ci-C4- alkyl)amino, Ci-C4-alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, or Ci-C4-haloalkylsulfanyl. Preferably, R² is hydrogen, halogen, cyano, hydroxy, Ci-Cs-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, cyclopropyl, Ci-Cs-alkoxy- Ci-C2-alkyl, Ci-Cs-alkoxy, Cs-Cs-alkenyloxy, Cs-Ce-alkynyloxy, Ci-C2-haloalkyl, Ci-C2-haloalkoxy, C1-C2- alkylsulfanyl, or Ci-C2-haloalkylsulfanyl. More preferably, R² is hydrogen, halogen, cyano, hydroxy, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-C2-haloalkoxy, Ci-C3-alkoxy-Ci-C2-alkyl, or Ci-C2-alkylsulfanyl. Even more preferably, R² is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, or Ci-C2-alkylsulfanyl. Still even more preferably, R² is hydrogen, chloro, cyano, hydroxy, methyl, methoxy, ethoxy, or methylsulfanyl.

In one embodiment of the invention, R³ is selected from hydrogen, halogen, Ci-C4-alkyl, or Ci-C4-haloalkyl. Preferably R³ is hydrogen, or Ci-Cs-alkyl. More preferably R³ is hydrogen, methyl, or ethyl. Still more preferably R³ is hydrogen, or methyl. In one embodiment R³ is methyl. In another embodiment R³ is hydrogen. In one embodiment of the invention, R⁴ is hydrogen, halogen, Ci-C4-alkyl, or C1-C4 haloalkyl. Preferably R⁴ is hydrogen, or C1-C4 alkyl. More preferably R⁴ is hydrogen, or C1-C3 alkyl. Even more preferably R⁴ is hydrogen, or methyl. In one embodiment R⁴ is methyl. In another embodiment R⁴ is hydrogen.

In one one embodiment of the invention, R⁵ is selected from hydrogen, halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-haloalkoxy, Ci-C4-alkoxy, or Cs-Ce-alkenyloxy, Cs-Ce-alkynyloxy, Ci-C4-alkylsulfanyl, C1-C4- haloalkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-haloalkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-haloalkylsulfonyl, C1- C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxycarbonyl, Ci-Ce-alkylaminocarbonyl, di(Ci-C4-alkyl)aminocarbonyl, cyano- Ci-C4-alkyl, N-Ci-C4-alkoxy-C-Ci-C4-alkyl-carbonimidoyl, N-hydroxy-C-Ci-C4-alkyl-carbonimidoyl, hydroxy, amino, Ci-C4-alkylamino, di(Ci-C4-alkyl)amino, cyano, carboxy, phenyl, a 5- to 6-membered saturated, partially saturated or aromatic heteroaryl, or Cs-Ce-cycloalkyl; wherein any of said phenyl, and 5- to 6-membered saturated, partially saturated or aromatic heteroaryl are unsubstituted or substituted with 1 , 2, or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or Ci-C4-alkoxy; and wherein said Cs-Ce-cycloalkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-alkoxy, or Ci-C4-haloalkyl. Preferably, R⁵ is hydrogen, halogen, cyano, Ci-C4-alkyl, Ci-C4-alkoxy, or Ci-C4-alkylsulfanyl. More preferably, R⁵ is hydrogen, halogen, cyano, Ci-Cs-alkyl, C1-C3- alkoxy, or Ci-Cs-alkylsulfanyl. Even more preferably, R⁵ is hydrogen, chlorine, bromine, fluorine, cyano, or methyl.

In one embodiment of the invention, R⁶ is hydrogen, halogen, cyano, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, Cs-Ce-cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, C1-C4- alkylsulfonyl, or Ci-C4-alkoxycarbonyl. Preferably, R⁶ is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-C2-haloalkyl, or Ci-C2-alkoxy. More preferably, R⁶ is hydrogen, halogen, cyano, or Ci-Cs-alkyl. Still even more preferably, R⁶ is hydrogen, chlorine, bromine, cyano, methyl or ethyl. Most preferably, R⁶ is hydrogen.

In one embodiment of the invention, R⁷ is hydrogen, halogen, Ci-C4-alkyl, or Ci-C4-haloalkyl. Preferably, R⁷ is hydrogen, halogen, Ci-Cs-alkyl, or Ci-C2-haloalkyl. Even more preferably R⁷ is hydrogen, chlorine, bromine, methyl, or ethyl. Still even more preferably R⁷ is hydrogen.

In one embodiment of the invention, Z¹ is selected from Ci-Ce-alkoxy, wherein said Ci-Ce-alkoxy is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, C1-C4- alkyl, Cs-Ce-cycloalkyl, Cs-Ce-alkenyl, Cs-Ce-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Ce- alkenyloxy, Cs-Ce-alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-haloalkylsulfanyl, Ci-C4-alkylsulfinyl, C1-C4- haloalkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-haloalkylsulfonyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxycarbonyl, Ci-C4-alkylcarbonyl, N-Ci-C4-alkoxy-C-Ci-C4-alkyl-carbonimidoyl, or N-hydroxy-C-Ci-C4-alkyl-carbonimidoyl. Preferably, Z¹ is Ci-Ce-alkoxy, wherein said Ci-Ce-alkoxy is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Cs-Ce-cycloalkyl, Cs-Ce-alkenyl, C2-C6- alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, or Ci-C4-haloalkoxy. More preferably, Z¹ is C-i-Ce-alkoxy, wherein said C-i-Ce-alkoxy is unsubstituted or substituted with 1 , or 2 substituents independently selected from chloro, fluoro, cyano, cyclopropyl, Ci-Cs-alkyl, Cs-Ce-alkenyl, Cs-Ce-alkynyl, Ci-C2-haloalkyl, Ci-C2-alkoxy, or C1-C2- haloalkoxy. Even more preferably, Z¹ is Ci-Cs-alkoxy, wherein said Ci-Cs-alkoxy is unsubstituted or substituted with 1 , or 2 substituents independently selected from chloro, fluoro, or cylopropyl.

In one embodiment of the invention, Z² is hydrogen, Ci-Cs-alkyl, or Cs-Cs-cycloalkyl. Preferably, Z² is hydrogen, methyl, ethyl, isopropyl, or cyclopropyl. More preferably, Z² is hydrogen or Ci-Cs-alkyl. Even more preferably, Z² is hydrogen or methyl. Still even more preferably Z² is hydrogen.

The present invention, accordingly, makes available a compound of formula (I) having R¹, R², R³, R⁴, R⁵, R⁶, R⁷, Z¹ and Z² as defined above in all combinations / each permutation.

Embodiments according to the invention are provided as set out below.

In one embodiment of the invention, there is provided a compound of formula (I), wherein R¹ is Ci-Cs-alkyl, or cyclopropyl;R³ is hydrogen or Ci-Cs-alkyl; R⁴ is hydrogen or Ci-Cs-alkyl; R⁵ is hydrogen, halogen, cyano, Ci- Cs-alkyl, Ci-Cs-alkoxy, or Ci-Cs-alkylsulfanyl; and R², R⁶, R⁷, Z¹ and Z² are defined as for compounds of formula (I) according to the present invention.

In one embodiment of the invention, there is provided a compound of formula (I), wherein R¹ is Ci-Cs-alkyl, or cyclopropyl; R³ is hydrogen or Ci-Cs-alkyl; R⁴ is hydrogen or Ci-Cs-alkyl; R⁵ is hydrogen, halogen, cyano, Ci- Cs-alkyl, Ci-Cs-alkoxy, or Ci-Cs-alkylsulfanyl; R⁶ and R⁷ are hydrogen; and R², Z¹ and Z² are defined as for compounds of formula (I) according to the present invention.

In one embodiment of the invention, there is provided a compound of formula (I), wherein R¹ is Ci-Cs-alkyl, or cyclopropyl; R³ is hydrogen or Ci-Cs-alkyl; R⁴ is hydrogen or Ci-Cs-alkyl; R⁵ is hydrogen, halogen, cyano, Ci- Cs-alkyl, Ci-Cs-alkoxy, or Ci-Cs-alkylsulfanyl; R⁶ and R⁷ are hydrogen; Z² is hydrogen; and R² and Z¹ are defined as for compounds of formula (I) according to the present invention.

In one embodiment of the invention, there is provided a compound of formula (I), wherein R¹ is Ci-Cs-alkyl, or cyclopropyl; R² is hydrogen, halogen, cyano, hydroxy, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy, C1-C3- alkoxy-Ci-C2-alkyl , or Ci-C2-alkylsulfanyl; R³ is hydrogen or Ci-Cs-alkyl; R⁴ is hydrogen or Ci-Cs-alkyl; R⁵ is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, or Ci-Cs-alkylsulfanyl; R⁶ and R⁷ are hydrogen; Z² is hydrogen; and Z¹ is as defined as for compounds of formula (I) according to the present invention.

In one embodiment of the invention, there is provided a compound of formula (I), wherein R¹ is Ci-Cs-alkyl, or cyclopropyl; R² is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, or Ci-C2-alkylsulfanyl; R³ is hydrogen or Ci-Cs-alkyl; R⁴ is hydrogen or Ci-Cs-alkyl; R⁵ is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, or C1- Cs-alkylsulfanyl; R⁶ and R⁷ are hydrogen; Z² is hydrogen; and Z¹ is Ci-Cs-alkoxy, wherein said Ci-Cs-alkoxy is unsubstituted or substituted with 1 or 2 substituents independently selected from chloro, fluoro, cyano, cyclopropyl, Ci-Cs-alkyl, C2-Cs-alkenyl, C2-Cs-alkynyl, Ci-C2-haloalkyl, Ci-C2-alkoxy, or Ci-C2-haloalkoxy.

In one embodiment of the invention, there is provided a compound of formula (I), wherein R¹ is Ci-Cs-alkyl, or cyclopropyl; R² is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, or Ci-C2-alkylsulfanyl; R³ is hydrogen or Ci-Cs-alkyl; R⁴ is hydrogen or Ci-Cs-alkyl; R⁵ is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, or C1- Cs-alkylsulfanyl; R⁶ and R⁷ are hydrogen; Z² is hydrogen; and Z¹ is Ci-Cs-alkoxy, wherein said Ci-Cs-alkoxy is unsubstituted or substituted with 1 or 2 substituents independently selected from chloro, fluoro, cyano, or cyclopropyl.

The presence of one or more possible asymmetric carbon atoms in any of the compounds selected from compounds of formula (I), or compounds selected from compounds listed in Tables A1 to A24, or compounds listed in Table F (below), according to the invention means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms.

IN one embodiment of the invention, the compound of formula (I) according to the invention is selected from compounds listed in any one of Tables A1 to A24.

Even more preferably the compound of formula (I) according to the invention is selected from compounds as listed in Table F (below).

The compounds of formula (I) according to the present invention can be made as shown in the following Schemes below, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula (I).

Compounds of formula (I) can be prepared from amines of formula (III) and esters of formula (He), wherein R²³ is Ci-Ce-alkyl, by heating in an inert solvent such as xylene, in the presence of an optional promoter such as trimethyl aluminum or potassium terf-butoxide. Alternatively, compounds of formula (I) can be prepared from amines of formula (III) and activated carboxylic acids of formula (Ila), wherein R²¹ is halogen, 1-imidazolyl or N-hydroxysuccinimide, in the presence of an optional base such as triethyl amine or pyridine. The preparation of activated carboxylic acids of formula (Ila), wherein R²¹ is halogen, 1-imidazolyl or N-hydroxysuccinimide, from carboxylic acids of formula (II) is well known to a person skilled in the art. Alternatively, compounds of formula (I) can be prepared from amines of formula (III) and quinolines of formula (IV), wherein R²² is chloro, bromo, iodo or trifluoromethylsulfonyloxy, in the presence of carbon monoxide, a base such as triethylamine and a palladium catalyst such as bis(triphenylphosphin)palladium(ll)-dichlorid, a reaction known as amino carbonylation and well described in the scientific literature. This is shown in Scheme 1 .

Amines of formula (III) can be prepared from various types of precursors by methods well known to a person skilled in the art. Compounds of formula (lie), wherein R²³ is Ci-Ce-alkyl, can be prepared from compounds of formula (IV), wherein R²² is chloro, bromo, iodo or trifluoromethylsulfonyloxy, and a Ci-Ce-alkanol in the presence of carbon monoxide, a base such as triethylamine and a palladium catalyst such as bis(triphenylphosphin)palladium(ll)- dichlorid. Compounds for formula (IV), wherein R²² is chloro, bromo, iodo or trifluoromethylsulfonyloxy, can be prepared from quinoline oxides of formula (V), by treatment with an activating agent such as methane sulfonyl chloride and water to form a quinolone of formula (Va); which can then be treated with a reagent such phosphorus oxychloride or trifluoromethane sulfonic anhydride. This is demonstrated in Org. Lett. 2023, 1235- 1240 and Tetrahedron Lett. 2014, 7130-7132. Quinoline oxides of formula (V) can be prepared from quinolines of formula (VI) by treatment with an oxygenating agent such m-chloroperbenzoic acid (scheme 2).

Compounds of formula (VI) can be prepared from compounds of formula (VII), wherein R²² is chloro, bromo, iodo or trifluoromethylsulfonyloxy, and pyrazoles of formula (VIII), wherein R²⁴ is B(OH)2, B(pinacol), ZnCI, ZnBr, MgBr or hydrogen, in the presence of a transition metal catalyst such as Pd(ll)acetate, optionally supported by a phosphine ligand such as 1 ,T-dis(diphenylphosphino)ferrocene. Compounds of formula (VII), wherein R²² is chloro, bromo, iodo or trifluoromethylsulfonyloxy, can be prepared from quinolones of formula (IX) and an activating agent such phosphorus pentabromide or trifluoromethane sulfonic anhydride. This is shown in scheme 3.

Scheme 3

Pyrazoles of formula (VII), wherein R²⁴ is B(OH)2, B(pinacol), ZnBr or MgBr, can be prepared from pyrazoles of formula (Vila) by lithium bromo exchange using a reagent such as n-butyl lithium followed by trans-metalation using a suitable metal precursor such as ZnCl2 or 2-Methoxy-4,4,5,5-tetramethyl-1 ,3,2-dioxaborolane, in an inert solvent such as tetrahydrofurane (THF). Pyrazoles of formula (Vila) can be prepared from pyrazoles of formula (VI I b) by treatment with a brominating agent such as N-bromosuccinimide. This is shown in scheme 4.

(Vllb) (Vila) (VII)

Scheme 4

Pyrazoles of formula (VI lb) can be prepared from various precursors by methods well known to a person skilled in the art. Quinolones of formula (IX), wherein R⁴ is not hydrogen, can be prepared from quinolones of formula (X) by treatment with a halogenating agent, such as N-bromosuccinimide, optionally followed by transformation of the halogen to an alkyl or haloalkyl group. Quinolones of formula (X) can be prepared from anilines of formula (XI), trimethyl orthoformate and 2,2-dimethyl-1 ,3-dioxane-4, 6-dione in an inert solvent such diphenyl ether (Scheme 5).

Anilines of formula (XI) can be prepared from various precursors by methods well known to person skilled in the art.

Alternatively, certain compounds of formula (He), wherein is R⁴ is hydrogen and R²³ is Ci-Ce alkyl, can be prepared from pyrazoles of formula (XII), wherein is R⁴ is hydrogen, orformula (XI la), wherein is R⁴ is hydrogen and R²³ is Ci-Ce-alkyl, anilines of formula (XI) and carbonyl compounds of formula (XIII), wherein R²³ is Ci-Ce- alkyl, in the presence of a catalyst such as copper(ll)triflate. This is shown in scheme 6, similar reactions have been described in for example in Tetrahedron Lett. 2019, 60 (14), 965-970 and Org. Chem. Front. 2018, 5, 1713-1718.

Scheme 6

Pyrazoles of formula (XII), wherein R⁴ is hydrogen, or of formula (Xlla), wherein R⁴ is hydrogen and R²³ is Ci- Cs alkyl, can be prepared from the pyrazoles of formula (Vila) as shown in scheme 7.

Scheme 7

Alternatively, compounds of formula (I) can be obtained by transformation of another, closely related, compound of formula (I) (or analogue thereof) using standard synthesis techniques known to the person skilled in the art. Examples of such transformations are, but not limited to oxidations, oxygenations, reductions, reductive deoxygenations, hydrogenations, hydrolysis, coupling reactions, aromatic nucleophilic or electrophilic substitution reactions, nucleophilic substitutions, deoxyfluorination, alkylation, radical addition, nucleophilic addition, condensation and halogenation.

A compound of formula (I) as defined in any of the embodiments of the present invention can be converted in a manner known per se into another compound as defined in any of the embodiments of the present invention by replacing one or more substituents of the starting compound in the customary manner by (an)other substituent(s) according to the invention. Those skilled in the art will also appreciate that compounds of formula (I) can be further transformed to further derivatives of formula (I) by, for example, alkylation, nucleophilic substitution, elimination, C-C-bond forming reactions in the presence of metal catalysts, heteroatom-carbon bond formation in the presence of metal catalysts, oxidation, and reduction.

Depending on the choice of the reaction conditions and starting materials which are suitable in each case, it is possible, for example, in one reaction step only to replace one substituent by another substituent according to the invention, or a plurality of substituents can be replaced by other substituents according to the invention in the same reaction step. Salts of compounds of formula (I) may be prepared in a manner) known perse. Thus, for example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent. All other compounds mentioned in schemes 1 to 7 are readily prepared by those skilled in the art or are commercially available.

Salts of compounds of formula (I) can be converted in the customary manner into the free compounds (I), acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.

Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.

Depending on the procedure or the reaction conditions, the compounds of formula (I), which have salt-forming properties, can be obtained in free form or in the form of salts.

The compounds of formula (I) and, where appropriate, the tautomer’s thereof, in each case in free form or in salt form, can be present in the form of one of the isomers which are possible or as a mixture of these, for example in the form of pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, or diastereomer mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms which occur in the molecule and/or depending on the configuration of non-aromatic double bonds which occur in the molecule, the invention relates to the pure isomers and also to all isomer mixtures which are possible and is to be understood in each case in this sense hereinabove and herein below, even when stereochemical details are not mentioned specifically in each case.

Diastereomeric mixtures or racemic mixtures of compounds of formula (I), in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatography.

Enantiomeric mixtures, such as racemates, which can be obtained in a similar manner can be resolved into the optical antipodes by known methods, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-performance liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one enantiomer is complexed, or by conversion into diastereomeric salts, for example by reacting a basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphor, tartaric or malic acid, or sulfonic acid, for example camphorsulfonic acid, and separating the diastereomer mixture which can be obtained in this manner, for example by fractional crystallization based on their differing solubilities, to give the diastereomers, from which the desired enantiomer can be set free by the action of suitable agents, for example basic agents.

Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials of a suitable stereochemistry.

It is advantageous to isolate or synthesize in each case the biologically more effective isomer, for example enantiomer or diastereomer, or isomer mixture, for example enantiomer mixture or diastereomer mixture, if the individual components have a different biological activity.

As an example, compounds with more than one asymmetric carbon atoms may exist in diastereomeric forms which can be optionally separated using for example supercritical fluid chromatography (SFC) chromatography with chiral columns. Such diastereomers can show a different fungicidal activity profile, but all isomers and diastereomers form part of this invention.

The compounds of formula (I) and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.

As already indicated, surprisingly, it has now been found that the compounds of formula (I) of the present invention have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases that are caused by fungi.

The compounds of formula (I) according to the invention can be used in the agricultural sector and related fields of use, e.g., as active ingredients for controlling plant pests or on non-living materials for the control of spoilage microorganisms or organisms potentially harmful to man. The novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and can be used for protecting numerous cultivated plants. The compounds of formula (I) can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time also protecting those parts of the plants that grow later, e.g., from phytopathogenic microorganisms.

The present invention further relates to a method for controlling or preventing infestation of plants or plant propagation material and/or harvested food crops susceptible to microbial attack by treating plants or plant propagation material and/or harvested food crops wherein an effective amount a compound of formula (I) according to the invention is applied to the plants, to parts thereof or the locus thereof.

It is also possible to use a compound of formula (I) according to the invention as a fungicide. The term “fungicide” as used herein means a compound that controls, modifies, or prevents the growth of fungi. The term “fungicidally effective amount” where used means the quantity of such a compound or combination of such compounds that is capable of producing an effect on the growth of fungi. Controlling or modifying effects include all deviation from natural development, such as killing, retardation and the like, and prevention includes barrier or other defensive formation in or on a plant to prevent fungal infection.

It may also be possible to use compounds of formula (I) according to the invention as dressing agents for the treatment of plant propagation material, e.g., seed, such as fruits, tubers or grains, or plant cuttings, for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil. The propagation material can be treated with a composition comprising a compound of formula (I) before planting: seed, for example, can be dressed before being sown. The active compounds of formula (I) can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the planting site when the propagation material is being planted, for example, to the seed furrow during sowing. The invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.

Furthermore, the compounds of formula (I) according to the invention can be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management.

In addition, the invention could be used to protect non-living materials from fungal attack, e.g., lumber, wall boards, and paint.

The compounds of formula (I) according to the invention are for example, effective against fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses. These fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses are for example: Absidia corymbifera, Altemaria spp., Aphanomyces spp., Ascochyta spp., Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, Aureobasidium spp. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp. including B. dothidea, B. obtusa, Botrytis spp. inclusing B. cinerea, Candida spp. including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp., Cercospora spp. including C. arachidicola, Cercosporidium personatum, Cladosporium spp., Claviceps purpurea, Coccidioides immitis, Cochliobolus spp., Colletotrichum spp. including C. musae, Corynespora spp. including Corynespora cassiicola, Cryptococcus neoformans, Diaporthe spp. including Diaporthe miriciae (also known as Diaporthe ueckeri or Diaporthe ueckerae), Didymella spp., Drechslera spp., Elsinoe spp.,Epidermophyton spp., Erwinia amylovora, Erysiphe spp. including E. cichoracearum, Eutypa lata, Fusarium spp. including F. culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, F. solani, Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium spp., Hemileia spp., Histoplasma spp. including H. capsulatum, Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp., Monilinia spp., Mucor spp., Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp., Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp., Peronosclerospora spp. including P. maydis, P. philippinensis and P. sorghi, Peronospora spp., Phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp., Phoma spp., Phomopsis viticola, Phytophthora spp. including P. infestans, Plasmopara spp. including P. halstedii, P. viticola, Pleospora spp., Podosphaera spp. including P. leucotricha, Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp., Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila, Puccinia spp. including P. hordei, P. recondita, P. striiformis, P. triticina, Pyrenopeziza spp., Pyrenophora spp., Pyricularia spp. including P. oryzae, Pythium spp. including P. ultimum, Ramularia spp., Rhizoctonia spp., Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium spp., Scedosporium spp. including S. apiospermum and S. prolificans, Schizothyrium pomi, Sclerotinia spp., Sclerotium spp., Septoria spp., including S. nodorum, S. tritici, Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix spp., Stagonospora nodorum, Stemphylium spp., Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia spp., Trichoderma spp. including T. harzianum, T. pseudokoningii, T. viride, Trichophyton spp., Typhula spp., Uncinula necator, Urocystis spp., Ustilago spp., Venturia spp. including V. inaequalis, Verticillium spp., and Xanthomonas spp..

The compounds of formula (I) according to the invention may be used for example on turf, ornamentals, such as flowers, shrubs, broad-leaved trees, or evergreens, for example conifers, as well as for tree injection, pest management and the like.

Within the scope of present invention, target crops and/or useful plants to be protected typically comprise perennial and annual crops, such as berry plants for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals for example barley, maize (corn), millet, oats, rice, rye, sorghum triticale and wheat; fibre plants for example cotton, flax, hemp, jute and sisal; field crops for example sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St. Augustine grass and Zoysia grass; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes for example beans, lentils, peas and soya beans; nuts for example almond, cashew, ground nut, hazelnut, peanut, pecan, pistachio and walnut; palms for example oil palm; ornamentals for example flowers, shrubs and trees; other trees, for example cacao, coconut, olive and rubber; vegetables for example asparagus, aubergine, broccoli, cabbage, carrot, cucumber, garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines for example grapes.

The term "useful plants" is to be understood as also including useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate- synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPG (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g., imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®. The term "useful plants" is to be understood as also including useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesizing one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.

Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a Cryll IB(b1 ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CrylllA toxin); Nature-Gard® Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), Agrisure® RW (corn rootworm trait) and Protecta®.

The term "crops" is to be understood as including also crop plants which have been so transformed using recombinant DNA techniques that they are capable of synthesizing one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as delta-endotoxins, e.g., CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g., Vip1 , Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid- UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.

Further, in the context of the present invention there are to be understood by delta-endotoxins, for example CrylAb, CrylAc, Cry1 F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1 , Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins, and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WG02/15701 ). Truncated toxins, for example a truncated CrylAb, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into a Cry3A toxin (see WG2003/018810). Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-0374753, WO93/07278, WO95/34656, EP0427529, EP0451878 and W003/052073.

The processes for the preparation of such transgenic plants are generally known to a person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO95/34656, EP0367474, EP0401979 and WO90/13651 .

The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).

Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a Cry1 Ab toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGard Plus® (maize variety that expresses a Cry1 Ab and a Cry3Bb1 toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculex I® (maize variety that expresses a Cry1 Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a Cry1 Ac toxin); Bollgard II® (cotton variety that expresses a CrylAc and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a CrylAb toxin); NewLeaf® (potato variety that expresses a Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.

2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylAb toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.

3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WG2003/018810. 4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1 150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bb1 toxin and has resistance to certain Coleoptera insects.

5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry1 F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.

7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B 1 150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.

The compounds of formula (I) according to the invention may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi, especially phytopathogenic fungi on soybean plants. In one embodiment such soybean plants are genetically modified soybean plants.

In one embodiment the genetically modified plants are soybean plants. Examples of genetically modified plants of soybean are, but not limited to, Intacta®, lntacta®2, Intacta® Roundup Ready™ 2 Pro (lntacta®RR2 PRO), lntacta®2 Xtend™, Cultivance, Conkesta Soybean, Conkesta Enlist E3™ Soybean, Enlist™ Soybean, Enlist E3™ Soybean, Roundup Ready™ Soybean, Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready™ 2 Xtend™, Genuity® Roundup Ready 2 Yield™, Herbicide-tolerant Soybean line, Optimum GAT™, Liberty Link™ Soybean, Vistive Gold™, Verdeca HB4 Soybean, Treus™, Plenish™.

Transgenic soybean plants expressing toxins, for example insecticidal proteins such as delta-endotoxins, e.g., CrylAc (CrylAc Bt protein). Accordingly, this may include transgenic soybean plants comprising event MON87701 (disclosed in W02009/064652), event MON87701 x MON89788 (disclosed in WO2014/170327, e.g. commercially available as Intacta RR2 PRO® soybean), event MON87751 (disclosed in WO2014/201235), event DAS-44406-6 (e.g., commercially available as Enlist E3^TM, DAS-44406-6, disclosed in WO2012/075426), or event DAS-81419-2 (described in WO2013/016527, e.g., commercially available as Conkesta™ soybean); event DAS-81419-2 x DAS-44406-6 (e.g., commercially available as Conkesta™ Enlist E3™ Soybean).

Furthermore, such a list of transgenic events is provided by the United States Department of Agriculture's (USDA) Animal and Plant Health Inspection Service (APHIS) and can be found on their website on the World Wide Web at aphis.usda.gov.

The compounds of formula (I) according to the invention may be used in controlling or preventing phytopathogenic diseases, especially phytopathogenic fungi such as Altemaria spp. in fruits, vegetables and potatoes; Botrytis cinerea in strawberries, tomatoes, sunflower, pulse crops, vegetables and grapes; Rhizoctonia solan! in potatoes and vegetables; Uncinula necator in grapes; Cladosporium cucumerinum, Didymella bryoniae, Sphaerotheca fuliginea and Glomerella lagenarium in cucurbits; Leveillula taurica in cucurbits and solanaceous crops; Fusarium spp. in cereals; Leptosphaeria spp. in cereals; and Zymoseptoria spp. in cereals.

The compounds of formula (I) and compositions comprising said compounds, are suitable for controlling the following fungal diseases on soybeans and genetically modified soybeans, for example Bt soybeans: Altemaria spp. (Altemaria leaf spot); Cercospora spp. (Cercospora leaf spots), e.g., C. sojina or C. kikuchii Colletotrichum (teleomorph: Glomerella) spp. (anthracnose), e.g., C. truncatum orC. gloeosporioides) Corynespora cassiicola (leaf spots); Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot); Diaporthe spp., e.g., Diaporthe miriciae (also known as Diaporthe ueckeri or Diaporthe ueckerae), (damping off); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot), e.g. F. tucumaniae and F. brasiliense each causing sudden death syndrome on soybeans; Macrophomina phaseolina (syn. phaseoli) (root and stem rot); Microsphaera diffusa (powdery mildew); Peronospora spp. (downy mildew), e.g., P. manshurica Phakopsora pachyrhizi and P. meibomiae (soybean rust); Phialophora spp., e.g., P. gregata (stem rot); Phomopsis spp., e.g., P. phaseoli (stem rot) (teleomorph: Diaporthe phaseolorum); Pythium spp. (damping-off); Phytophthora spp. (wilt, root, leaf, fruit and stem root), e.g., P. megasperma, syn. P. sojae); Rhizoctonia spp., e.g., R. solani (root and stem rot); Sclerotinia spp. (stem rot or white mold); Septoria spp., e.g., S. glycines (brown spot); S. rolfsii (syn. Athelia rolfsii); Thielaviopsis spp. (black root rot).

The term “locus” as used herein means fields in or on which plants are growing, or where seeds of cultivated plants are sown, or where seed will be placed into the soil. It includes soil, seeds, and seedlings, as well as established vegetation.

The term “plants” refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.

The term “plant propagation material” is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There can be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes, and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants can be protected before transplantation by a total or partial treatment by immersion. Preferably “plant propagation material” is understood to denote seeds.

The compounds of formula (I) according to the invention may be used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they may be conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g., in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating, or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.

Suitable carriers and adjuvants, e.g., for agricultural use, can be solid or liquid and are substances useful in formulation technology, e.g., natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO1997/33890.

Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations include anti-settling agents and dispersing agents and may further include a wetting agent to enhance activity as well an anti-foam and a crystal growth inhibitor. In use, these concentrates are diluted in water and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers. The particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller’s earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain from 5% to 95% of the active ingredient plus a small amount of wetting, dispersing or emulsifying agent.

Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

Granular formulations include both extrudates and relatively coarse particles and are usually applied without dilution to the area in which treatment is required. Typical carriers for granular formulations include sand, fuller’s earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate and other organic or inorganic materials which absorb or which can be coated with the active compound. Granular formulations normally contain 5% to 25% of active ingredients which may include surface-active agents such as heavy aromatic naphthas, kerosene and other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.

Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.

Microcapsules are typically droplets or granules of the active ingredient enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates. Encapsulated droplets are typically 1 to 50 microns in diameter. The enclosed liquid typically constitutes 50 to 95% of the weight of the capsule and may include solvent in addition to the active compound. Encapsulated granules are generally porous granules with porous membranes sealing the granule pore openings, retaining the active species in liquid form inside the granule pores. Granules typically range from 1 millimetre to 1 centimetre and preferably 1 to 2 millimetres in diameter. Granules are formed by extrusion, agglomeration or prilling, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust, and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

Other useful formulations for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprayers, wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low boiling dispersant solvent carrier, may also be used.

Suitable agricultural adjuvants and carriers that are useful in formulating the compositions of the invention in the formulation types described above are well known to a person skilled in the art.

Liquid carriers that can be employed include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2- butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetonalcohol, 1 ,2-dichloropropane, diethanolamine, p diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl formamide, dimethyl sulfoxide, 1 ,4- dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethyl acetate, 2-ethyl hexanol, ethylene carbonate, 1 ,1 ,1 -trichloroethane, 2-heptanone, alpha pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gammabutyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octyl amine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerine and N- methyl-2-pyrrolidinone. Water is generally the carrier of choice for the dilution of concentrates.

Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller’s earth, cotton seed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.

A broad range of surface-active agents are advantageously employed in both said liquid and solid compositions, especially those designed to be diluted with carrier before application. These agents, when used, normally comprise from 0.1 % to 15% by weight of the formulation. They can be anionic, cationic, non-ionic, or polymeric in character and can be employed as emulsifying agents, wetting agents, suspending agents or for other purposes. Typical surface-active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C.sub. 18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecyl alcohol-C.sub. 16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalenesulfonate salts, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2 ethylhexyl) sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryl trimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.

Other adjuvants commonly utilized in agricultural compositions include crystallisation inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, anti-foaming agents, light-blocking agents, compatibilizing agents, antifoam agents, sequestering agents, neutralising agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants, and sticking agents.

In addition, further, other biocidal active ingredients or compositions may be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention. When applied simultaneously, these further active ingredients may be formulated together with the compositions of the invention or mixed in, for example, the spray tank. These further biocidal active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and/or plant growth regulators.

Pesticidal agents are referred to herein using their common name are known, for example, from "The Pesticide Manual", 15th Ed., British Crop Protection Council 2009.

In addition, the compositions of the invention may also be applied with one or more systemically acquired resistance inducers (“SAR” inducer). SAR inducers are known and described in, for example, United States Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar- S-methyl.

The compounds of formula (I) according to the invention are normally used in the form of agrochemical compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g., fertilizers or micronutrient donors or other preparations, which influence the growth of plants. They can also be selective herbicides or non-selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.

The compounds of formula (I) according to the invention may be used in the form of (fungicidal) compositions for controlling or protecting against phytopathogenic microorganisms, comprising as active ingredient at least one compound of formula (I) or of at least one preferred individual compound as defined herein, in free form or in agrochemical usable salt form, and at least one of the above-mentioned adjuvants.

The invention therefore provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I) according to the invention, an agriculturally acceptable carrier and optionally an adjuvant. An agricultural acceptable carrier is for example a carrier that is suitable for agricultural use. Agricultural carriers are well known in the art. Preferably, said composition may comprise at least one or more pesticidal-active compounds, for example an additional fungicidal active ingredient in addition to the compound of formula (I).

The compound of formula (I) according to the invention may be the sole active ingredient of a composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide, or plant growth regulator where appropriate. An additional active ingredient may, in some cases, result in unexpected synergistic activities.

Examples of suitable additional active ingredients include the following: acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenical fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine fungicides, organophosphorous fungicides, organotin fungicides, oxathiin fungicides, oxazole fungicides, phenylsulfamide fungicides, polysulfide fungicides, pyrazole fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungicides, quinone fungicides, quinoxaline fungicides, strobilurin fungicides, sulfonanilide fungicides, thiadiazole fungicides, thiazole fungicides, thiazolidine fungicides, thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, valinamide fungicides, and zinc fungicides.

The following mixtures of the compounds of formula (I) with active ingredients are preferred. The abbreviation “TX” means one compound selected from compounds of formula (I), or compounds selected from compounds listed in Tables A1 to A24, or compounds listed in Table F (below), and a compound selected from the group of substances consisting of (4E,10Z)-tetradeca-4, 10-dienyl acetate + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol + TX, (E)-tridec-4-en- 1-yl acetate + TX, (S)-bioallethrin + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-l 1-en-1-yl acetate + TX, (Z)-hexadec-l l-enal + TX, (Z)-hexadec-13-en-1 1-yn-1-yl acetate + TX, (Z)-icos-13-en-10-one + TX, (Z)- tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, 1 ,1 -bis(4- chlorophenyl)-2-ethoxyethanol + TX, 1-(2-chlorophenyl)-3,3-dimethyl-2-(1 ,2,4-triazol-1-ylmethyl)butan-2-ol + TX, 1 -(5-bromo-2-pyridyl)-2-(2,4-difluorophenyl)-1 ,1-difluoro-3-(1 ,2,4-triazol-1-yl)propan-2-ol + TX, 1-hydroxy- 1 H-pyridine-2-thione + TX, 1 -methylcyclopropene + TX, 1 -naphthaleneacetamide + TX, 1 -naphthylacetic acid + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2,4-D + TX, 2,4-DB + TX, 2,6-dichloro-N- (4-trifluormethylbenzyl)benzamide + TX, 2-(1 ,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-(2- butoxyethoxy)ethyl piperonylate + TX, 2-(4,5-dimethyl-1 ,3-dioxolan-2-yl)phenyl methylcarbamate + TX, 2- (difluoromethyl)-N-((3R)-1 ,1 ,3-trimethylindan-4-yl) pyridine-3-carboxamide + TX, 2-(octylthio)-ethanol + TX, 2- bromo-2-bromomethyl-pentanedinitrile + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidone + TX, 2- methyl(prop-2-ynyl)aminophenyl methylcarbamate + TX, 2-thiocyanatoethyl laurate + TX, 3-(4-chlorophenyl)-

5-methylrhodanine + TX, 3-(difluoromethyl)-1-methyl-N-[1 ,1 ,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 3-(difluoromethyl)-N-(7-fluoro-1 ,1 ,3,3-tetramethyl-indan-4-yl)-1-methyl-pyrazole-4-carboxamide + TX, 3- (difluoromethyl)-N-(7-fluoro-1 ,1 ,3,3-tetramethyl-indan-4-yl)-1-methyl-pyrazole-4-carboxamide + TX, 3-chloro-

6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, 3-methyl-1-phenylpyrazol-5-yl dimethyl-carbamate + TX, 3-phenylphenol + TX, 4,5-dichlorodithiol-3-one + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl- pyridazine-3-carbonitrile + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol- 3-amine + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide + TX, 4-[[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2- hydroxy-3-(1 ,2,4-triazol-1 -y I )p ropy l]-3-pyridyl]oxy] benzo n itri le + TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5- [(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, 4-CPA + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methylcarbamate + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one + TX, 4-phenylphenol + TX, 5-(1 ,3- benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, 5-amino-1 ,3,4-thiadiazole-2-thiol + TX, 5-fluoro-2-(p- tolylmethoxy)pyrimidin-4-amine + TX, 5-hydroxy-6-methyl-4-(((E)-pyridin-3-ylmethylene)amino)-4,5-dihydro- 1 ,2,4-triazin-3(2H)-one + TX, 5-methyl-6-thioxo-1 ,3,5-thiadiazinan-3-ylacetic acid + TX, 8-hydroxyquinoline sulfate + TX, 1 1 -ethyl-10, 12-dioxo-2,5,8-trithia-4, 11-diazatricyclo[7.3.0.03,7]dodeca-1 (9),3,6-triene-6- carbonitrile + TX, 14-methyloctadec-1-ene + TX, [(9Z,11 E)-tetradeca-9, 11-dienyl] acetate + TX, [(Z)-dodec-9- enyl] acetate + TX, abamectin + TX, acephate + TX, acequinocyl + TX, acetamiprid + TX, acethion + TX, acetoprole + TX, acibenzolar + TX, acibenzolar-S-methyl + TX, acrinathrin + TX, Adoxophyes orana GV + TX, Agrobacterium radiobacter + TX, alanycarb + TX, albendazole + TX, aldicarb + TX, allethrin + TX, allosamidin + TX, allyl alcohol + TX, allyxycarb + TX, alpha-ecdysone + TX, alpha-multistriatin + TX, Amblyseius spp. + TX, ametoctradin + TX, amidithion + TX, amidoflumet + TX, amidothioate + TX, aminocarb + TX, amisulbrom + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, anabasine + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, ancymidol + TX, anilazine + TX, anisiflupurin + TX, anthraquinone + TX, antu + TX, Aphelinus abdominalis + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, athidathion + TX, aureofungin + TX, Autographa californica NPV + TX, avermectin B1a + TX, azaconazole + TX, azadirachtin A + TX, azafenidin + TX, azamethiphos + TX, azinphos-ethyl + TX, azinphos-methyl + TX, azithiram + TX, azoxystrobin + TX, Bacillus sphaericus (Neide) + TX, Bacillus thuringiensis + TX, Bacillus thuringiensis delta endotoxin + TX, Bacillus thuringiensis ssp. aizawai + TX, baculovirus + TX, barthrin + TX, Beauveria brongniartii + TX, benalaxyl + TX, benalaxyl-M + TX, benazepril + TX, benclothiaz + TX, benfuracarb + TX, benomyl + TX, bensultap + TX, benthiavalicarb + TX, benzalkonium chloride + TX, benzamorf + TX, benzothiostrobin + TX, benzovindiflupyr + TX, beta-cyfluthrin + TX, beta-cypermethrin + TX, bethoxazin + TX, bifemetstrobin + TX, bifenazate + TX, bifenthrin + TX, binapacryl + TX, bioallethrin + TX, bioethanomethrin + TX, biopermethrin + TX, bioresmethrin + TX, bisthiosemi + TX, bistrifluron + TX, bitertanol + TX, bixafen + TX, blasticidin-S + TX, borax + TX, bordeaux mixture + TX, boscalid + TX, brodifacoum + TX, brofenvalerate + TX, brofluthrinate + TX, bromadiolone + TX, bromfenvinfos + TX, bromophos + TX, bromophos-ethyl + TX, bromuconazole + TX, bufencarb + TX, bupirimate + TX, buprofezin + TX, buserelin + TX, busulfan + TX, but-3-ynyl N-[6-[[(Z)-[(1- methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, butacarb + TX, butathiofos + TX, butocarboxim + TX, butonate + TX, butopyronoxyl + TX, butoxy(polypropylene glycol) + TX, butoxycarboxi m + TX, butylamine + TX, cadusafos + TX, calciferol + TX, calcium phosphate + TX, calcium polysulfide + TX, cambendazole + TX, captafol + TX, captan + TX, carbanolate + TX, carbaryl + TX, carbendazim + TX, carbendazim hydrochloride + TX, carbofuran + TX, carbosulfan + TX, carboxin + TX, carprofen + TX, carpropamid + TX, cartap + TX, cartap hydrochloride + TX, cefalexin + TX, cefovecin + TX, cefquinome + TX, ceftiour + TX, cestex + TX, cevadine + TX, chinomethionat + TX, chitosan + TX, chlobenthiazone + TX, chloralose + TX, chlorantraniliprole + TX, chlorbenside + TX, chlordimeform + TX, chlorethephon + TX, chlorethoxyfos + TX, chlorfenapyr + TX, chlorfenazole + TX, chlorfentazine + TX, chlorfenvinphos + TX, chlorfluazuron + TX, chlormephos + TX, chlormequat + TX, chlorodimeform hydrochloride + TX, chloroinconazide + TX, chloromebuform + TX, chloromethiuron + TX, chloroneb + TX, chlorothalonil + TX, chlorphoxim + TX, chlorprazophos + TX, chlorpyrifos + TX, chlorpyrifos-methyl + TX, chlortetracycline + TX, chlorthiophos + TX, chlozolinate + TX, cholecalciferol + TX, chromafenozide + TX, Chrysoperla carnea + TX, cinerin + TX, cinerin I + TX, cinerin II + TX, cis-jasmone + TX, cis-resmethrin + TX, cismethrin + TX, clenbuterol + TX, climbazole + TX, cloethocarb + TX, clofencet + TX, clorsulon + TX, clothianidin + TX, clozylacon (acetamide) + TX, codlelure + TX, copper acetate + TX, copper hydroxide + TX, copper naphthenate + TX, copper octanoate + TX, copper oleate + TX, copper oxide + TX, copper oxychloride + TX, copper silicate + TX, copper sulfate + TX, copper(ll) carbonate + TX, coumachlor + TX, coumafene + TX, coumafuryl + TX, Coumatetralyl + TX, coumethoxystrobin (jiaxiangjunzhi) + TX, coumithoate + TX, coumoxystrobin + TX, cryolite + TX, Cryptolaemus montrouzieri + TX, cuelure + TX, cufraneb + TX, cuprous(l) oxide + TX, cyanofenphos + TX, cyanthoate + TX, cyazofamid + TX, cybutryne + TX, cyclafuramid + TX, cyclethrin + TX, cyclobutrifluram + TX, Cydia pomonella GV + TX, cyenopyrafen + TX, cyflufenamid + TX, cyflumetofen + TX, cyfluthrin + TX, cyhalothrin + TX, cymiazole + TX, cymoxanil + TX, cypermethrin (alphametrin) + TX, cyphenothrin + TX, cyproconazole + TX, cyprodinil + TX, cyprodinil + TX, cyromazine + TX, cytokinins + TX, D-tetramethrin + TX, Dacnusa sibirica + TX, DAEP + TX, dazomet + TX, DCPM + TX, debacarb + TX, decarbofuran + TX, deltamethrin + TX, demephion-0 + TX, demephion-S + TX, demeton-0 + TX, demeton-S + TX, demeton-S-methyl + TX, demeton-S-methylsulphon + TX, diafenthiuron + TX, dialifos + TX, diazinon + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, dicapthon + TX, dichlobentiazox + TX, dichlofluanid + TX, dichlone + TX, dichlorprop + TX, dichlorvos + TX, dichlozoline + TX, diclocymet + TX, diclomezine + TX, dicloran + TX, dicofol + TX, dicresyl + TX, dicrotophos + TX, dicyclanil + TX, dicyclopentadiene + TX, diethofencarb + TX, diethyltoluamide + TX, difenacoum + TX, difenoconazole + TX, difenzoquat + TX, difethialone + TX, diflovidazin + TX, diflubenzuron + TX, diflumetorim + TX, Diglyphus isaea + TX, dimatif + TX, dimefluthrin + TX, dimetan + TX, dimethachlon + TX, dimethipin + TX, dimethirimol + TX, dimethoate + TX, dimethomorph + TX, dimethrin + TX, dimethyl disulfide + TX, dimethyl phthalate + TX, dimetilan + TX, dimoxystrobin + TX, dinactin + TX, diniconazole + TX, diniconazole-M + TX, dinobuton + TX, dinocap + TX, dinocton + TX, dinoseb + TX, dinotefuran + TX, diofenolan + TX, dioxabenzofos + TX, diphenylamine + TX, dipyrithione + TX, disparlure + TX, disulfiram + TX, disulfoton + TX, ditalimfos + TX, dithianon + TX, dithicrofos + TX, dithiocarbamate + TX, dodec-8-en-1-yl acetate + TX, dodemorph + TX, dodicin + TX, dodine + TX, dofenapyn + TX, dominicalure + TX, doramectin + TX, drazoxolon + TX, DSP + TX, ecdysterone + TX, edifenphos + TX, emamectin benzoate + TX, EMPC + TX, empenthrin + TX, Encarsia formosa + TX, endosulfan + TX, endothal + TX, endothion + TX, enestroburin (enoxastrobin) + TX, enrofloxacin + TX, entomopathogenic bacteria + TX, entomopathogenic fungi + TX, entomopathogenic virus + TX, EPBP + TX, epoxiconazole + TX, eprinomectin + TX, Eretmocerus eremicus + TX, esfenvalerate + TX, etaconazole + TX, ethaboxam + TX, ethiofencarb + TX, ethion + TX, ethiprole + TX, ethirimol + TX, ethoate-methyl + TX, ethoprophos + TX, ethoxyquin + TX, ethyl 4-methyloctanoate + TX, ethyl formate + TX, ethyl hexanediol + TX, etofenprox + TX, etoxazole + TX, etridiazole + TX, etrimfos + TX, eugenol + TX, eurax + TX, EXD + TX, exo- brevicomin + TX, famoxadone + TX, famphur + TX, farnesol with nerolidol + TX, febantel + TX, fenamidone + TX, fenaminstrobin + TX, fenamiphos + TX, fenarimol + TX, fenazaquin + TX, fenbendazole + TX, fenbuconazole + TX, fenbutatin oxide + TX, feneptamidoquin + TX, fenethacarb + TX, fenfluthrin + TX, fenfuram + TX, fenhexamid + TX, fenitrothion + TX, fenobucarb + TX, fenopyramid + TX, fenothiocarb + TX, fenoxacrim + TX, fenoxanil + TX, fenoxycarb + TX, fenpiclonil + TX, fenpicoxamid + TX, fenpirithrin + TX, fenpropathrin + TX, fenpropidin + TX, fenpropimorph + TX, fenpyrazamine + TX, fenpyroximate + TX, fensulfothion + TX, fenthion + TX, fenthion-ethyl + TX, fentin + TX, fentin acetate + TX, fentin chloride + TX, fentin hydroxide + TX, fenvalerate + TX, ferbam + TX, ferimzone + TX, ferric phosphate + TX, fipronil + TX, flocoumafen + TX, flonicamid + TX, florfenicol + TX, florylpicoxamid + TX, fluacrypyrim + TX, fluazinam + TX, fluazuron + TX, flubendazole + TX, flubendiamide + TX, flubeneteram + TX, flubenzimin + TX, flucycloxuron + TX, flucycloxuron + TX, flucythrinate + TX, fludioxonil + TX, fluenetil + TX, flufenerim + TX, flufenoxuron + TX, flufenoxystrobin + TX, flufenprox + TX, fluindapyr + TX, flumetralin + TX, flumetylsulforim + TX, flumorph + TX, fluopicolide + TX, fluopimomide + TX, fluopyram + TX, fluoroimide + TX, fluoxapiprolin + TX, fluoxastrobin + TX, fluoxytioconazole + TX, flupyrazofos + TX, fluquinconazole + TX, flusilazole + TX, flusulfamide + TX, flutianil + TX, flutolanil + TX, flutriafol + TX, fluxapyroxad + TX, folpet + TX, fonofos + TX, forchlorfenuron + TX, formaldehyde + TX, formetanate + TX, formetanate hydrochloride + TX, formothion + TX, formparanate + TX, fosetyl + TX, fosetyl- aluminium + TX, fosmethilan + TX, fosthiazate + TX, fosthietan + TX, frontalin + TX, fuberidazole + TX, furalaxyl + TX, furametpyr + TX, furathiocarb + TX, furethrin + TX, furfural + TX, gibberellic acid + TX, glyodin + TX, glyphosate + TX, grandlure I + TX, grandlure II + TX, grandlure III + TX, grandlure IV + TX, guazatine triacetate + TX, halfenprox + TX, halofenozide + TX, hemel + TX, heptenophos + TX, Heterorhabditis bacteriophora and H. megidis + TX, hexaconazole + TX, hexadecyl cyclopropanecarboxylate + TX, hexaflumuron + TX, hexalure + TX, hexamide + TX, hexythiazox + TX, Hippodamia convergens + TX, huanjunzuo ((rac-(1S,2S)-1-(4- chlorophenyl)-2-(1 ,2,4-triazol-1-yl)cycloheptanol)) + TX, hydramethylnon + TX, hydrated lime (calcium hydroxide) + TX, hymexazol + TX, hyquincarb + TX, icaridin + TX, imanin (hypericin) + TX, imazalil + TX, imazalil sulfate + TX, imibenconazole + TX, imidacloprid + TX, iminoctadine + TX, indoxacarb + TX, inpyrfluxam + TX, iodocarb + TX, ipconazole + TX, ipfentrifluconazole + TX, ipflufenoquin + TX, iprobenfos (IBP) + TX, iprodione + TX, iprovalicarb + TX, ipsdienol + TX, ipsenol + TX, IPSP + TX, isamidofos + TX, isazofos + TX, isocarbophos + TX, isofetamid + TX, isoflucypram + TX, isolan + TX, isoprocarb + TX, isoprothiolane + TX, isopyrazam + TX, isothioate + TX, isotianil + TX, isoxathion + TX, ivermectin + TX, japonilure + TX, jasmolin I + TX, jasmolin II + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, kadethrin + TX, kanamycin + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, kinetin + TX, kinoprene + TX, kresoxim-methyl + TX, kurstaki + TX, lambda-cyhalothrin + TX, Leptomastix dactylopii + TX, leptophos + TX, levamisole + TX, lineatin + TX, lirimfos + TX, looplure + TX, lufenuron + TX, Ivbenmixianan + TX, lythidathion + TX, m-cumenyl methylcarbamate + TX, Macrolophus caliginosus + TX, magnesium phosphide + TX, malathion + TX, maleic hydrazide + TX, malonoben + TX, Mamestra brassicae NPV + TX, mancopper + TX, mancozeb + TX, mandestrobin + TX, mandipropamid + TX, maneb + TX, mazidox + TX, mebendazole + TX, mecarbam + TX, mecarphon + TX, medlure + TX, mefentrifluconazole + TX, megatomoic acid + TX, meloxicam + TX, menazon + TX, mepanipyrim + TX, meperfluthrin + TX, mephosfolan + TX, mepiquat + TX, mepronil + TX, meptyldinocap + TX, mesulfenfos + TX, metaflumizone + TX, metalaxyl + TX, metalaxyl-M + TX, metaldehyde + TX, metam + TX, metam-potassium + TX, metam-sodium + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae + TX, metarylpicoxamid + TX, metconazole + TX, methacrifos + TX, methamidophos + TX, methasulfocarb + TX, methidathion + TX, methiocarb + TX, methiotepa + TX, methocrotophos + TX, methomyl + TX, methoprene + TX, methoquin-butyl + TX, methothrin + TX, methoxyfenozide + TX, methyl apholate + TX, methyl eugenol + TX, methyl iodide + TX, methyl neodecanamide + TX, metiram + TX, metofluthrin + TX, metolcarb + TX, metominostrobin + TX, metoxadiazone + TX, metrafenone + TX, metyltetraprole + TX, mevinphos + TX, mexacarbate + TX, MGK 264 + TX, milbemycin + TX, milbemycin oxime + TX, monocrotophos + TX, morantel tartrate + TX, morzid + TX, moxidectin + TX, muscalure + TX, myclobutanil + TX, myclozolin + TX, Myrothecium verrucaria composition + TX, N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, N- cyclopropyl-3-(difluoromethyl)-5-fluoro-N-[(2-isopropylphenyl)methyl]-1-methyl-pyrazole-4-carboxamide + TX, nabam + TX, naled + TX, NC-170 + TX, nemadectin + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, niclosamide-olamine + TX, nicotine + TX, nicotine sulfate + TX, nikkomycins + TX, nitenpyram + TX, nithiazine + TX, nitrapyrin + TX, nitrilacarb + TX, nitrothal-isopropyl + TX, norbormide + TX, nornicotine + TX, novaluron + TX, noviflumuron + TX, nuarimol + TX, O,O,O',O'-tetrapropyl dithiopyrophosphate + TX, octadeca-2,13-dien- 1-yl acetate + TX, octadeca-2,13-dien-1-yl acetate + TX, octhilinone + TX, ofurace + TX, oleic acid + TX, omethoate + TX, orfralure + TX, Orius spp. + TX, orysastrobin + TX, osthol + TX, ostramone + TX, oxadixyl + TX, oxamate + TX, oxamyl + TX, oxantel pamoate + TX, oxasulfuron + TX, oxathiapiprolin + TX, oxfendazole + TX, oxibendazole + TX, oxine copper + TX, oxolinic acid + TX, oxpoconazole + TX, oxycarboxin + TX, oxydemeton-methyl + TX, oxydeprofos + TX, oxydisulfoton + TX, oxytetracycline + TX, oxytetracycline dihydrate + TX, paclobutrazol + TX, Paecilomyces fumosoroseus + TX, paraoxon + TX, parathion + TX, parathion-methyl + TX, parbendazole + TX, pefurazoate + TX, penconazole + TX, pencycuron + TX, penethamate + TX, penflufen + TX, penthiopyrad + TX, permethrin + TX, petroleum oils + TX, PH 60-38 + TX, phenamacril + TX, phenthoate + TX, phorate + TX, phosacetim + TX, phosalone + TX, phosfolan + TX, phosglycin + TX, phosmet + TX, phosnichlor + TX, phosphamidon + TX, phosphocarb + TX, phosphonic acid + TX, phosphorus + TX, phoxim + TX, phoxim-methyl + TX, phthalide + TX, Phytoseiulus persimilis + TX, picarbutrazox + TX, picoxystrobin + TX, pimobendan + TX, pindone + TX, piperalin + TX, piperonyl butoxide + TX, piprotal + TX, pirimetaphos + TX, pirimicarb + TX, pirimiphos-methyl + TX, polycar + TX, polyoxin B + TX, polyoxin d + TX, potassium ethylxanthate + TX, potassium hy TX, praziquantel + TX, precocene I + TX, precocene II + TX, precocene III + TX, primido + TX, prochloraz + TX, procymidone + TX, profenofos + TX, profluthrin + TX, prohexadi calcium + TX, promacyl + TX, promecarb + TX, propamidine + TX, propamocarb propargite + TX, propetamphos + TX, propiconazole + TX, propineb + TX, propionic a propyl isomer + TX, proquinazid + TX, prothidathion + TX, prothioconazole + TX, prot TX, protrifenbute + TX, pydiflumetofen + TX, pymetrozine + TX, pyraclofos + T pyrafluprole + TX, pyrametostrobin + TX, pyrantel pamoate + TX, pyraoxystrobin + pyraziflumid + TX, pyrazophos + TX, pyrazoxone + TX, pyresmethrin + TX, pyrethrin pyrethrins (natural products) + TX, pyrethroids (natural products) + TX, pyribencarb + TX, pyridaben + TX, pyridachlometyl + TX, pyridalyl + TX, pyridaphenthion + TX, pyridin-4-amine + TX, pyrifenox + TX, pyrifluquinazon + TX, pyrimethanil + TX, pyrimidifen + TX, pyrimorph + TX, pyriofenone + TX, pyriprole + TX, pyriproxyfen + TX, pyrisoxazole + TX, pyroquilon + TX, quassia + TX, quinalphos + TX, quinalphos-methyl + TX, quinoclamine + TX, quinofumelin + TX, quinonamid + TX, quinothion + TX, quinoxyfen + TX, quintozene + TX, R-1492 + TX, R-metalaxyl + TX, Reynoutria sachalinensis extract + TX, ribavirin + TX, rotenone + TX, ryanodine (ryania) + TX, sabadilla + TX, schradan + TX, scilliroside + TX, seboctylamine + TX, sedaxane + TX, selamectin + TX, sesamex + TX, sesamolin + TX, siglure + TX, silafluofen + TX, silthiofam + TX, simeconazole + TX, sodium tetrathiocarbonate + TX, sophamide + TX, sordidin + TX, spinetoram + TX, spinosad + TX, spirodiclofen + TX, spiromesifen + TX, spirotetramat + TX, spiroxamine + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, streptomycin + TX, streptomycin sesquisulfate + TX, sulcatol + TX, sulcofuron + TX, sulfiram + TX, sulfur + TX, sulprofos + TX, tar oils + TX, tau-fluvalinate + TX, TCMTB + TX, TDE + TX, tebuconazole + TX, tebufenozide + TX, tebufenpyrad + TX, tebufloquin + TX, tebupirimfos + TX, tecnazene + TX, teflubenzuron + TX, tefluthrin + TX, temephos + TX, terallethrin + TX, terbam + TX, terbufos + TX, tetrachlorvinphos + TX, tetraconazole + TX, tetradec-11-en- 1-yl acetate + TX, tetradifon + TX, tetramethrin + TX, tetramethylfluthrin + TX, tetranactin + TX, thiabendazole + TX, thiacloprid + TX, thiadiazole copper + TX, thiamethoxam + TX, thiapronil + TX, thicrofos + TX, thicyofen + TX, thidiazuron + TX, thifluzamide + TX, thiocarboxime + TX, thiocyclam + TX, thiocyclam hydrogen oxalate + TX, thiodicarb + TX, thiofanox + TX, thiometon + TX, thiophanate + TX, thiophanate-methyl + TX, thioquinox + TX, thiosultap + TX, thiosultap-disodium + TX, thiram + TX, thuringiensin + TX, tiadinil + TX, tiamulin + TX, tioxymid + TX, tolclofos-methyl + TX, tolfenpyrad + TX, tolprocarb + TX, tolylfluanid + TX, tralomethrin + TX, transpermethrin + TX, tretamine + TX, triadimefon + TX, triadimenol + TX, triarathene + TX, triazamate + TX, triazophos + TX, triazoxide + TX, tribufos + TX, trichlorfon + TX, trichlormetaphos-3 + TX, trichloronat + TX, Trichogramma spp. + TX, triclabendazole + TX, triclopyricarb + TX, tricyclazole + TX, tridemorph + TX, trifenmorph + TX, trifloxystrobin + TX, triflumizole + TX, triflumuron + TX, triforine + TX, trimedlure + TX, trimedlure A + TX, trimedlure B1 + TX, trimedlure B2 + TX, trimedlure C + TX, trimethacarb + TX, trinactin + TX, trinexapac + TX, trinexapac-ethyl + TX, trioxyflanilide + TX, triprene + TX, triticonazole + TX, trunc-call + TX, tulathromycin + TX, Typhlodromus occidentalis + TX, uniconazole + TX, uredepa + TX, validamycin + TX, valifenalate + TX, vamidothion + TX, vaniliprole + TX, veratridine + TX, veratrine + TX, verbutin + TX, Verticillium lecanii + TX, vinclozolin + TX, XMC + TX, xylenols + TX, zeatin + TX, zeta-cypermethrin + TX, zhongshengmycin + TX, zinc naphthenate + TX, zinc thiazole + TX, zineb + TX, ziram + TX, zolaprofos + TX, zoxamide + TX, 2-(difluoromethyl)-N-[(3S)-3-ethyl-1 ,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (this compound may be prepared from the methods described in WO 2014/095675) + TX, methyl 3-[(4- chlorophenyl)methyl]-2-hydroxy-1 -methyl-2-(1 ,2,4-triazol-1 -ylmethyl)cyclopentanecarboxylate (this compound may be prepared from the methods described in WO 2019/093522) + TX, methyl (2R)-2-[2-chloro-4-(4- chlorophenoxy)phenyl]-2-hydroxy-3-(1 ,2,4-triazol-1-yl)propanoate (this compound may be prepared from the methods described in WO 2019/093522) + TX, 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(2,6- difluorophenyl)cyclopropyl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX, aminopyrifen (this compound may be prepared from the methods described in WO 2014/006945) + TX, dipymetitrone (this compound may be prepared from the methods described in WO 2011/138281 ) + TX, 1 -[6-(difluoromethyl)-5-methyl-3-pyridyl]-4,4-difluoro-3,3-dimethyl-isoquinoline (this compound may be prepared from the methods described in WO 2017/016915) + TX, 1 -[4-(difluoromethoxy)-2- methyl-phenyl]-2-(1 ,2,4-triazol-1-yl)-1-[1-(trifluoromethyl)cyclopropyl]ethanol (this compound may be prepared from the methods described in WO 2021 /249800) + TX, 1 -[2-chloro-4-(difluoromethoxy)phenyl]-2-(1 ,2,4-triazol- 1-yl)-1-[1-(trifluoromethyl)cyclopropyl]ethanol (this compound may be prepared from the methods described in WO 2021/249800) + TX, 1 -(5,6-dimethyl-3-pyridyl)-4,4-difluoro-3,3-dimethyl-isoquinoline (this compound may be prepared from the methods described in WO 2017/016915) + TX, N-methyl-4-[5-(trifluoromethyl)-1 ,2,4- oxadiazol-3-yl]benzenecarbothioamide (this compound may be prepared from the methods described in WO 2015/185485) + TX, 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]acetamide (this compound may be prepared from the methods described in WO 2017/178245) + TX, flufenoxadiazam + TX, N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide (this compound may be prepared from the methods described in WO 2015/185485) + TX, (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2- methoxyimino-N,3-dimethyl-pent-3-enamide (this compound may be prepared from the methods described in WO 2018/153707) + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3- enamide (this compound may be prepared from the methods described in WO 2013/092224) + TX, methyl (2E)-2-methoxyimino-2-[3-methyl-2-[[(E)-1-[4-(trifluoromethyl)-2-pyridyl]ethylideneamino]oxymethyl]phenyl] acetate (this compound may be prepared from the methods described in WO 2022/033906) + TX, (2E)-2- methoxyimino-N-methyl-2-[3-methyl-2-[[(E)-1-[4-(trifluoromethyl)-2-pyridyl]ethylideneamino]oxymethyl]phenyl] acetamide (this compound may be prepared from the methods described in WO 2022/033906) + TX, (2E)-2- [2-[[(E)-[3-(4-fluorophenyl)-1-methyl-prop-2-ynylidene]amino]oxymethyl]-3-methyl-phenyl]-2-methoxyimino-N- methyl-acetamide (this compound may be prepared from the methods described in WO 2021/249928) + TX, methyl (2E)-2-[2-[[(E)-[3-(4-fluorophenyl)-1-methyl-prop-2-ynylidene]amino]oxymethyl]-3-methyl-phenyl]-2- methoxyimino-acetate (this compound may be prepared from the methods described in WO 2021/249928) + TX, 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO 2016/156290) + TX, 3-[2-(1 -chlorocyclopropyl)- 3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound may be prepared from the methods described in WO 2016/156290) + TX, 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1 ,2,4- triazol-1-yl)propan-2-ol (this compound may be prepared from the methods described in WO 2017/029179) + TX, 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol (this compound may be prepared from the methods described in WO 2017/029179) + TX, 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2- yl]-N-[1-(2-fluorophenyl)ethyl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX, 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(3,5-difluorophenyl)ethyl]pyrimidin- 2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX, N-[1-(2- fluorophenyl)cyclopropyl]-5-[5-(trifluoromethyl)-1 ,3,4-oxadiazol-2-yl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX, 5-[5-(difluoromethyl)-1 ,3,4-oxadiazol-2-yl]- N-[1-(2,6-difluorophenyl)ethyl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX, 2-(difluoromethyl)-5-[2-[1-(2,6-difluorophenyl)cyclopropoxy]pyrimidin-5-yl]-1 ,3,4- oxadiazole (this compound may be prepared from the methods described in WO 2021/255093) + TX, 5-[5- (difluoromethyl)-1 ,3,4-oxadiazol-2-yl]-N-[1-(2-fluorophenyl)cyclopropyl]pyrimidin-2-amine (this compound may be prepared from the methods described in WO 2021/255093) + TX, 5-[(4-bromo-2-methyl-phenyl)methyl]-3- [3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2021/255070) + TX, 3-[3-(3-cyclopropyl-2-fluoro-phenoxy)-6- methyl-pyridazin-4-yl]-5-[(2,4-dimethylphenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2021/255070) + TX, N-(2,2,2-trifluoroethyl)-2-[[4-[5- (trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]oxazole-4-carboxamide (this compound may be prepared from the methods described in WO 2022/1331 14) + TX, ethyl 1 -[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3- yl]phenoxy]methyl]pyrazole-4-carboxylate (this compound may be prepared from the methods described in WO 2022/133114) + TX, ethyl 1 -[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enoxy]phenyl]methyl]pyrazole-4- carboxylate (this compound may be prepared from the methods described in WO 2020/056090 and WO 2021/183707) + TX, ethyl 1 -[[4-[[2-(trifluoromethyl)-1 ,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-4- carboxylate (this compound may be prepared from the methods described in WO 2020/056090 and WO 2021/183707) + TX, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate (this compound may be prepared from the methods described in WO 2020/097012) + TX, methyl N-[[5-[1-(2,6- difluoro-4-isopropyl-phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (this compound may be prepared from the methods described in WO 2020/097012) + TX, methyl N-[[5-[1-(4-cyclopropyl-2,6-difluoro- phenyl)pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate (this compound may be prepared from the methods described in WO 2020/097012) + TX, methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1 ,2,4- triazol-1-yl)propanoate (this compound may be prepared from the methods described in WO 2019/093522) + TX, 4,4,5-trifluoro-3,3-dimethyl-1-(3-quinolyl)isoquinoline + TX, 5-fluoro-3,3,4,4-tetramethyl-1-(3-quinolyl)- isoquinoline + TX, 2-methoxy-N-[methoxy-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2-thienyl]methyl]- acetamide (this compound may be prepared from the methods described in WO 2020/256113) + TX, N- [methoxy-[5-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]-2-thienyl]methyl]-2-methyl-propanamide (this compound may be prepared from the methods described in WO 2020/256113) + TX, N-[methoxy-[5-[5-(trifluoromethyl)- 1 ,2,4-oxadiazol-3-yl]-2-thienyl]methyl]butanamide (this compound may be prepared from the methods described in WO 2020/256113) + TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1 ,1-dimethyl-indan-4-yl]pyridine-3- carboxamide (this compound may be prepared from the methods described in WO 2014/095675) + TX, 2- (difluoromethyl)-N-(3-ethyl-1 ,1-dimethyl-indan-4-yl)pyridine-3-carboxamide (this compound may be prepared from the methods described in WO 2014/095675) + TX, 2-(difluoromethyl)-N-(1 ,1 ,3-trimethylindan-4- yl)pyridine-3-carboxamide + TX, (5R)-3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4- methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2020/127780 + TX, WO 2021/255070) + TX, (5S)-3-[3-(3-chloro-2-fluoro-phenoxy)-6-methyl- pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4-oxadiazine (this compound may be prepared from the methods described in WO 2020/127780 + TX, WO 2021/255070) + TX, 3-[3-(3-chloro-2- fluoro-phenoxy)-6-methyl-pyridazin-4-yl]-5-[(2-chloro-4-methyl-phenyl)methyl]-5,6-dihydro-4H-1 ,2,4- oxadiazine (this compound may be prepared from the methods described in WO 2020/127780 + TX, WO 2021/255070) + TX, methyl (Z)-3-methoxy-2-(2-methyl-5-phenyl-phenoxy)prop-2-enoate (this compound may be prepared from methods as described in JP2023078251) + TX, 2-[(2,6-difluoro-4-pyridyl)-(2- methylpropanoyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide + TX, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO2017207362A1 + TX, WO2019105933A1 + TX, W02020109511 A1 + TX, WO2021244952A1 ); 2-[(2,6- difluoro-4-pyridyl)-(tetrahydropyran-4-carbonyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4- carboxamide + TX, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO2017207362A1 + TX, WO2019105933A1 + TX, W02020109511A1 + TX, WO2021244952A1 ); 2-[cyano-(2,6-difluoro-4-pyridyl)amino]-5-methyl-N-spiro[3.4]octan-3-yl-thiazole-4- carboxamide + TX, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO2017207362A1 + TX, WO2019105933A1 + TX, W02020109509A1 ); 2-[cyano-(2,6- difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide + TX, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO2017207362A1 + TX, WO2019105933A1 + TX, W02020109509A1 ); 2-[(2,6-difluoro-4-pyridyl)-(2- methoxyacetyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide + TX, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO2017207362A1 + TX, WO2019105933A1 + TX, W02020109511 A1 + TX, WO2021244952A1 ); 2-[acetyl- (2,6-difluoro-4-pyridyl)amino]-5-methyl-N-spiro[3.4]octan-3-yl-thiazole-4-carboxamide + TX, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO2017207362A1 + TX, WO2019105933A1 + TX, W02020109511 A1 + TX, WO2021244952A1 ); N-methoxy- N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide (this compound may be prepared from the methods described in WO 2017/055473); methyl (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)- 3-methoxy-prop-2-enoate (this compound may be prepared from the methods described in W02020/193387); methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate (this compound may be prepared from the methods described in W02020/193387); N-[(1 R)-1-benzyl-1 ,3-dimethylbutyl]-8-fluoroquinoline-3- carboxamide (this compound may be prepared from the methods described in WO2017/153380); N-[(1 S)-1- benzyl-1 ,3-dimethylbutyl]-8-fluoroquinoline-3-carboxamide (this compound may be prepared from the methods described in WO2017/153380); 2-[(2,6-difluoro-4-pyridyl)-(oxetane-3-carbonyl)amino]-N-(2,2- dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide + TX, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO2017207362A1 + TX, WO2019105933A1 + TX, W02020109511 A1 + TX, WO2021244952A1 ); 2-[acetyl-(2,6-difluoro-4-pyridyl)amino]-N-(2,2- dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide + TX, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO2017207362A1 + TX, WO2019105933A1 + TX, W02020109511A1 + TX, WO2021244952A1 ); N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol- 3-yl]phenyl]methyl]propanamide + TX, or the (R) or (S) enantiomer or mixtures thereof (this compound may be prepared from the methods described in WO 2017/055473).

The references in brackets behind the active ingredients, e.g., [3878-19-1] refer to the Chemical Abstracts

Registry number. The above-described mixing partners are known. Where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: C. D. S.

TomLin; The British Crop Protection Council], they are described therein under the entry number given in round brackets hereinabove for the particular compound; for example, the compound "abamectin" is described under entry number (1 ). Where "[CCN]" is added hereinabove to the particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is accessible on the internet [A. Wood; ium of Pesticide Common Names Copyright © 1995-2004]; for example, the compound "acetoprole" is described under the internet address http://www.alanwood.net/pesticides/acetoprole.html.

Most of the active ingredients described above are referred to hereinabove by a so-called "common name", the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a "common name", the nature of the designation used instead is given in round brackets for the particular compound; in that case, the IUPAC name, the lUPAC/Chemical Abstracts name, a "chemical name", a "traditional name", a "compound name" or a "development code" is used or, if neither one of those designations nor a "common name" is used, an "alternative name" is employed. “CAS Reg. No” means the Chemical Abstracts Registry Number.

The active ingredient mixture of the compound selected from compounds of formula (I), or compounds selected from compounds listed in Tables A1 to A24, or compounds listed in Table F (below), is preferably in a mixing ratio of from 100:1 to 1 :100, especially from 50:1 to 1 :50, more especially in a ratio of from 20:1 to 1 :20, even more especially from 10:1 to 1 :10, and still more especially from 5:1 to 1 :5 Those mixing ratios are by weight.

The mixtures as described above can be used in a method for controlling pests, which comprises applying a composition comprising a mixture as described above to the pests or their environment, with the exception of a method for treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body. The mixtures comprising a compound selected from compounds of formula (I), or compounds selected from compounds listed in Tables A1 to A24, or compounds listed in Table F (below), and one or more active ingredients as described above can be applied, for example, in a single “ready-mix” form, in a combined spray mixture composed from separate formulations of the single active ingredient components, such as a “tank-mix”, and in a combined use of the single active ingredients when applied in a sequential manner, i.e. one after the other with a reasonably short period, such as a few hours or days. The order of applying a compound selected from compounds of formula (I), or compounds selected from compounds listed in Tables A1 to A24, or compounds listed in Table F (below), and the active ingredient(s) as described above, is not essential for working the present invention.

The compositions according to the invention can also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example bactericides, fungicides, nematocides, plant activators, molluscicides, or herbicides.

The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid active ingredient and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the active ingredient with the auxiliary (auxiliaries). These processes for the preparation of the compositions and the use of the compounds (I) for the preparation of these compositions are also a subject of the invention.

Another aspect of the invention is related to the use of a compound of formula (I) according to the invention or of a preferred individual compound as defined herein, of a composition comprising at least one compound of formula (I) or at least one preferred individual compound as defined herein, or of a fungicidal or insecticidal mixture comprising at least one compound of formula (I) or at least one preferred individual compound as defined herein, in admixture with other fungicides or insecticides as described above, for controlling or preventing infestation of plants, e.g., useful plants such as crop plants, propagation material thereof, e.g., seeds, harvested crops, e.g., harvested food crops, or non-living materials by insects, or by phytopathogenic microorganisms, preferably fungal organisms.

A further aspect of invention is related to a method of controlling or preventing an infestation of plants, e.g., useful plants such as crop plants, propagation material thereof, e.g., seeds, harvested crops, e.g., harvested food crops, or of non-living materials by phytopathogenic or spoilage microorganisms or organisms potentially harmful to man, especially fungal organisms, which comprises the application of a compound of formula (I) according to the invention or of a preferred individual compound as defined herein as active ingredient to the plants, to parts of the plants or to the locus thereof, to the propagation material thereof, or to any part of the non-living materials.

Controlling or preventing means reducing infestation by insects, or by phytopathogenic or spoilage microorganisms, or organisms potentially harmful to man, especially fungal organisms, to such a level that an improvement is demonstrated. A preferred method of controlling or preventing an infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, or insects which comprises the application of a compound of formula (I) according to the invention, or an agrochemical composition which contains at least one compound of formula (I), is foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen or insect. However, the compounds of formula (I) according to the invention can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g., in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field. The compounds of formula (I) may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.

A formulation, e.g., a composition containing the compound of formula (I) according to the invention and, if desired, a solid or liquid adjuvant or monomers for encapsulating the compound of formula (I), may be prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface active compounds (surfactants).

Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 10g to I kg a.i./ha, most preferably from 20g to 600g a.i./ha. When used as seed drenching agent, convenient dosages are from 10mg to 1g of active substance per kg of seeds.

The term “g a.i./ha” as used herein refer to the application rate given in gram [g] of active ingredient [a.i.] per unit of surface [ha]. The unit hectare (symbol ha) is the metric unit of area that equals a square with 100 m side (1 hm²) or 10,000 square meters. Hectare is a commonly used unit of area in the metric system.

When the combinations of the present invention are used for treating seed, rates of 0.001 to 50 g of a compound of formula (I) per kg of seed, preferably from 0.01 to 10g per kg of seed are generally sufficient.

Suitably, a composition comprising a compound of formula (I) according to the present invention is applied either preventative, meaning prior to disease development or curative, meaning after disease development.

The compositions of the invention may be employed in any conventional form, for example in the form of a twin pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EG), an emulsion, oil in water (EW), a microemulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

Such compositions may be produced in conventional manner, e.g., by mixing the active ingredients with appropriate formulation inerts (diluents, solvents, fillers, and optionally other formulating ingredients such as surfactants, biocides, anti-freeze, stickers, thickeners, and compounds that provide adjuvancy effects). Also, conventional slow-release formulations may be employed where long lasting efficacy is intended. Particularly formulations to be applied in spraying forms, such as water dispersible concentrates (e.g., EC, SC, DC, OD, SE, EW, EO and the like), wettable powders and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvancy effects, e.g., the condensation product of formaldehyde with naphthalene sulfonate, an alkyl aryl sulfonate, a lignin sulfonate, a fatty alkyl sulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.

A seed dressing formulation is applied in a manner known per se to the seeds employing the combination of the invention and a diluent in suitable seed dressing formulation form, e.g., as an aqueous suspension or in a dry powder form having good adherence to the seeds. Such seed dressing formulations are known in the art. Seed dressing formulations may contain the single active ingredients or the combination of active ingredients in encapsulated form, e.g., as slow-release capsules or microcapsules.

In general, the formulations include from 0.01 to 90% by weight of active agent, from 0 to 20% agriculturally acceptable surfactant and 10 to 99.99% solid or liquid formulation inerts, and adjuvant(s), the active agent consisting of at least the compound of formula (I) according to the invention optionally together with other active agents, particularly microbiocides or conservatives or the like. Concentrated forms of compositions generally contain in between about 2 to 80%, preferably between about 5 to 70% by weight of active agent. Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ diluted formulations.

Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.

The rates of application vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. As a general guideline, compounds may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.

Preferred formulations can have the following compositions (weight %)

Emulsifiable concentrates: active ingredient: 1 to 95 %, preferably 60 to 90 % surface-active agent: 1 to 30 %, preferably 5 to 20 % liquid carrier: 1 to 80 %, preferably 1 to 35 %

Dusts: active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %

Suspension concentrates: active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 %

Wettable powders: active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %

Granules: active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %

The disclosure in the present application makes available each and every combination of embodiments disclosed herein.

The compounds according to the following Tables A1 to A24 may be prepared according to the methods described above. The examples which follow are intended to illustrate the invention and show preferred compounds of formula (I). In any of Tables A1 to A24 below, the presence of one or more possible asymmetric carbon atoms in a compound of formula (I) according to the invention means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms.

Table A1 : This table discloses 30 compounds of formula (I), according to the present invention, wherein R¹ and R² are methyl; R³, R⁴, R⁵, R⁶ and R⁷are hydrogen; and wherein Z¹ and Z² are as define in table E below:

Table E: Definition of Z¹ and Z²

Table A2: This table provides 30 compounds of formula (I), wherein R¹ and R² are methyl; R³, R⁴, R⁶ and R⁷ are hydrogen; R⁵ is fluoro; and wherein Z¹ and Z² are as defined in Table E above;

Table A3: This table provides 30 compounds of formula (I), wherein R¹ and R² are methyl; R³, R⁴, R⁶ and R⁷ are hydrogen; R⁵ is chloro; and wherein Z¹ and Z² are as defined in Table E above;

Table A4: This table provides 30 compounds of formula (I), wherein R¹ and R² are methyl; R³, R⁴, R⁶ and R⁷ are hydrogen; R⁵ is bromo; and wherein Z¹ and Z² are as defined in Table E above;

Table A5: This table provides 30 compounds of formula (I), wherein R¹ and R² are methyl; R³, R⁴, R⁶ and R⁷ are hydrogen; R⁵ is cyano; and wherein Z¹ and Z² are as defined in Table E above;

Table A6: This table provides 30 compounds of formula (I), wherein R¹ and R² are methyl; R³, R⁴, R⁶ and R⁷ are hydrogen; R⁵ is methoxy; and wherein Z¹ and Z² are as defined in Table E above;

Table A7: This table provides 30 compounds of formula (I), wherein R¹ and R² are methyl; R³, R⁴, R⁶ and R⁷ are hydrogen; R⁵ is methylsulfanyl; and wherein Z¹ and Z² are as defined in Table E above;

Table A8: This table provides 30 compounds of formula (I), wherein R¹ and R² are methyl; R³, R⁴, R⁶ and R⁷ are hydrogen; R⁵ is methyl; and wherein Z¹ and Z² are as defined in Table E above;

Table A9: This table provides 30 compounds of formula (I), wherein R¹ is methyl; R² is chloro; R³, R⁴, R⁵, R⁶ and R⁷are hydrogen; and wherein Z¹ and Z² are as defined in Table E above;

Table A10: This table provides 30 compounds of formula (I), wherein R¹ is methyl; R² is chloro; R³, R⁴, R⁶ and R⁷are hydrogen; R⁵ is fluoro; and wherein Z¹ and Z² are as defined in Table E above

Table A11 : This table provides 30 compounds of formula (I), wherein R¹ is methyl; R² is chloro; R³, R⁴, R⁶ and R⁷are hydrogen; R⁵ is chloro; and wherein Z¹ and Z² are as defined in Table E above;

Table A12: This table provides 30 compounds of formula (I), wherein R¹ is methyl; R² is chloro; R³, R⁴, R⁶ and R⁷are hydrogen; R⁵ is bromo; and wherein Z¹ and Z² are as defined in Table E above;

Table A13: This table provides 30 compounds of formula (I), wherein R¹ is methyl; R² is chloro; R³, R⁴, R⁶ and R⁷are hydrogen; R⁵ is cyano; and wherein Z¹ and Z² are as defined in Table E above;

Table A14: This table provides 30 compounds of formula (I), wherein R¹ is methyl; R² is chloro; R³, R⁴, R⁶ and R⁷are hydrogen; R⁵ is methoxy; and wherein Z¹ and Z² are as defined in Table E above; Table A15 This table provides 30 compounds of formula (I), wherein R¹ is methyl R² is chloro; R³, R⁴, R⁶ and

R⁷are hydrogen; R⁵ is methylsulfanyl; and wherein Z¹ and Z² are as defined in Table E above;

Table A16 This table provides 30 compounds of formula (I), wherein R¹ is methyl R² is chloro; R³, R⁴, R⁶ and

R⁷are hydrogen; R⁵ is methyl; and wherein Z¹ and Z² are as defined in Table E above;

Table A17 This table provides 30 compounds of formula (I), wherein R¹ is methyl R² is methoxy; R³, R⁴, R⁵,

R⁶ and R⁷ are hydrogen; and wherein Z¹ and Z² are as defined in Table E above;

Table A18 This table provides 30 compounds of formula (I), wherein R¹ is methyl R² is methoxy; R³, R⁴, R⁶ and R⁷are hydrogen; R⁵ is fluoro; and wherein Z¹ and Z² are as defined in Table E above

Table A19 This table provides 30 compounds of formula (I), wherein R¹ is methyl R² is methoxy; R³, R⁴, R⁶ and R⁷are hydrogen; R⁵ is chloro; and wherein Z¹ and Z² are as defined in Table E above;

Table A20 This table provides 30 compounds of formula (I), wherein R¹ is methyl R² is methoxy; R³, R⁴, R⁶ and R⁷are hydrogen; R⁵ is bromo; and wherein Z¹ and Z² are as defined in Table E above;

Table A21 This table provides 30 compounds of formula (I), wherein R¹ is methyl; R² is methoxy; R³, R⁴, R⁶ and R⁷are hydrogen; R⁵ is cyano; and wherein Z¹ and Z² are as defined in Table E above;

Table A22 This table provides 30 compounds of formula (I), wherein R¹ is methyl R² is methoxy; R³, R⁴, R⁶ and R⁷are hydrogen; R⁵ is methoxy; and wherein Z¹ and Z² are as defined in Table E above;

Table A23 This table provides 30 compounds of formula (I), wherein R¹ is methyl R² is methoxy; R³, R⁴, R⁶ and R⁷are hydrogen; R⁵ is methylsulfanyl; and wherein Z¹ and Z² are as defined in Table E above;

Table A24 This table provides 30 compounds of formula (I), wherein R¹ is methyl R² is methoxy; R³, R⁴, R⁶ and R⁷are hydrogen; R⁵ is methyl; and wherein Z¹ and Z² are as defined in Table E above;

EXAMPLES

The Examples which follow serve to illustrate the invention and are not meant in any way to limit the invention.

The compounds of the invention can be distinguished from known compounds by virtue of greater efficacy at low application rates, which can be verified by a person skilled in the art using the experimental procedures outlined in the Examples, using lower application rates if necessary, for example 60 ppm, 20 ppm or 2 ppm.

Compounds of formula (I) may possess any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against diseases that are caused by fungi or superior properties for use as agrochemical active ingredients (for example, greater biological activity, an advantageous spectrum of activity, an increased safety profile (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).

FORMULATION EXAMPLES

Wettable powders a) b) c) active ingredients 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % - sodium lauryl sulfate 3 % - 5 % sodium diisobutylnaphthalenesulfonate 6 % 10 % phenol polyethylene glycol ether (7-8 mol of ethylene oxide) 2 % highly dispersed silicic acid 5 % 10 % 10 %

Kaolin 62 % 27 % -

The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.

Powders for dry seed treatment a) b) c) active ingredients 25 % 50 % 75 % light mineral oil 5 % 5 % 5 % highly dispersed silicic acid 5 % 5 % Kaolin 65 % 40 % -

Talcum 20 %

The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.

Emulsifiable concentrate active ingredients 10 % octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3 % calcium dodecylbenzene sulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 %

Cyclohexanone 30 % xylene mixture 50 %

Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.

Dusts a) b) c)

Active ingredients 5 % 6 % 4 %

Talcum 95 % -

Kaolin 94 % - mineral filler 96 %

Ready-for-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill. Such dusts can also be used for dry dressings for seed.

Extruder granules

Active ingredients 15 % sodium lignosulfonate 2 % carboxymethylcellulose 1 % Kaolin 82 %

The combination is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

Coated granules

Active ingredients 8% polyethylene glycol (mol. wt. 200) 3 %

Kaolin 89 %

The finely ground combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol.

Non-dusty coated granules are obtained in this manner.

Suspension concentrates active ingredients 40 % propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 %

Sodium lignosulfonate 10 % carboxymethylcellulose 1 % silicone oil (in the form of a 75 % emulsion in water) 1 %

Water 32 %

The finely ground combination is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Flowable concentrate for seed treatment active ingredients 40 % propylene glycol 5 % copolymer butanol PO/EO 2 %

Tristyrenephenole with 10-20 moles EO 2 %

1 ,2-benzisothiazolin-3-one (in the form of a 20% solution in water) 0.5 % monoazo-pigment calcium salt 5 %

Silicone oil (in the form of a 75 % emulsion in water) 0.2 %

Water 45.3 %

The finely ground combination is intimately mixed with the adjuvants, giving a flowable concentrate from which solutions of any desired dilution can be obtained by dilution with water, that can be used directly for seed treatment. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Slow Release Capsule Suspension 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1 .2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1 ,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.

Formulation types include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EG), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), a soluble granule (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

ABBREVIATIONS aq. aqueous

CDCI3 deuterated chloroform

DCC dicyclohexyl carbodiimide

DCM dichloromethane

DIPEA N,N-Diisopropylethylamine (or Hunig's base, also abbreviated as DIEA or /-Pr2Net)

DMF dimethylformamide

DMSO dimethyl sulfoxide

DMSO-d6 deuterated Dimethyl sulfoxide

EtOAc ethyl acetate

GCMS Gas Chromatography Mass Spectrometry (GCMS, GC-MS or GC/MS)

HCI hydrochloric acid h/hrs hour/hours

LC-MS Liquid Chromatography Mass Spectrometry (LC-MS, LCMS or LC/MS)

MgSO4 magnesium sulphate

Na2SO4 sodium sulphate rh relative humidity rt room temperature

Rt retention time sat. saturated ssp. subspecies

TLC thin layer chromatography

THF tetrahydrofuran PREPARATION EXAMPLES

The compounds of formula (I) according to the invention may be prepared using the synthetic techniques described both above and below.

Throughout this description, temperatures are given in degrees Celsius and “m.p.” means melting point.

¹H NMR and ¹⁹F NMR measurements were recorded on a Bruker 400MHz spectrometer (or 600MHz as indicated), chemical shifts are given in ppm relevant to a TMS (¹H) and CFCI3 (¹⁹F) standard. Spectra measured in deuterated solvents as indicated. The characteristic LC-MS values obtained for each compound were the retention time (“Rt”, recorded in minutes) and the measured molecular ion (M+H)⁺ or (M-H)-. The following LC- MS methods were used for the analysis of the compounds:

LC-MS Method B Spectra were recorded on a ACQUITY Mass Spectrometer from Waters Corporations (SQD or SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive or negative ions, Capillary: 3.0 kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150°C, Desolvation Temperature: 400°C, Cone Gas Flow: 60 L/hr, Desolvation Gas Flow: 700 L/hr, Mass range: 140 to 800 Da) and an ACQUITY UPLC from Waters Corporations with solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 pm, 30 x 2.1 mm, Temp: 60 °C, DAD Wavelength range (nm): 210 to 400, Solvent Gradient: A = Water/Methanol 9:1 + 0.1 % formic acid, B= Acetonitrile + 0.1 % formic acid, gradient: 0-100% B in 2.5 min; Flow (ml/min) 0.75.

LC-MS Method C Spectra were recorded on a Mass Spectrometer from Waters (SQD2 or QDA Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: Positive and Negative Polarity Switch), Capillary: 0.8-3.00 kV, Cone range: 25 Source Temperature: 120-150°C, Desolvation Temperature: 500-600°C, Cone Gas Flow: 50 L/h, Desolvation Gas Flow: 1000 L/h, Mass range: 110 to 850 Da) and an Acquity UPLC from Waters: Quaternary solvent manager, heated column compartment, diode-array detector. Column: Acquity UPLC HSS T3 C18, 1 .8 pm, 30 x 2.1 mm, Temp: 40 °C, DAD Wavelength range (nm): 200 to 400, Solvent Gradient: A = water + 5% Acetonitrile + 0.1 % HCOOH, B= Acetonitrile + 0.05 % HCOOH: gradient: 0 min 10% B; 0.-0.2 min 10-50% B; 0.2-0.6 min 50-100% B; 0.6-1 .3 min 100% B; 1.3-1 .4 min 100-10% B; 1.4-

1.6 min 10% B; Flow (mL/min) 0.6.

LC-MS Method G Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDII Single quadrupole mass spectrometer) equipped with an electrospray source (Polarity: positive and negative ions), Capillary: 0.8 kV, Cone range: 25 V, Source Temperature: 120°C, Desolvation Temperature: 600°C, Cone Gas Flow: 50 l/h, Desolvation Gas Flow: 1000 l/h, Mass range: 110 to 850 Da) and an Acquity UPLC from Waters: Binary pump, heated column compartment , diode-array detector and ELSD detector. Column: Waters UPLC HSS T3 C18 , 1 .8 pm, 30 x 2.1 mm, Temp: 40 °C, DAD Wavelength range (nm): 230 to 400, Solvent Gradient: A = water + 0.05 % HCOOH, B = Acetonitrile + 0.05 % HCOOH, gradient: 10-100% B in 1 .3 min; Flow (mL/min)

0.60. compound F.06, table F

Step 1 : Preparation of methyl 1-oxidoquinolin-1-ium-2-carboxylate

To a solution of methyl quinoline-2-carboxylate (CAS 19575-07-6) (0.670 g, 3.58 mmol, [CAS 19575-07-6]) in trifluoromethylbenzene (10 mL) at 0°C, was added 3-chlorobenzenecarboperoxoic acid (2.37 g, 8.95 mmol, 65 mass%) at 0°C. The reaction mixture was stirred at rt for 12 hr. The reaction mixture was quenched with 2N aq. NaOH solution and water and extracted with EtOAc. Combined organic layers were washed with brine, dried over Na2SO4, and concentrated under reduced pressure to afford methyl 1 -oxidoquinolin-1-ium-2- carboxylate.

LC-MS: 204 [M+H], Rt: 0.46 min (Method B)

Step 2: Preparation of methyl 4-chloroquinoline-2-carboxylate

A sample of methyl-1-oxidoquinolin-1-ium-2-carboxylate (900 mg, 3.10 mmol) was dissolved in phosphorus(V) oxychloride (18 mL). The resulting reaction mixture was heated to 80°C and stirred at this temperature for 3 hr. The reaction mixture was cooled to rt and was added dropwise over 20 minutes under stirring to water at rt, and quenched with an ice cooled solution of sat. NaHCOs. The reaction mixture was extracted with EtOAc and the combined organic layers dried over Na2SO4 and concentrated under reduced pressure. The crude product was purified by CombiFlash®, using 10-20% EtOAc in cyclohexane to afford methyl 4-chloroquinoline-2- carboxylate.

LC-MS: 222 [M+H], Rt: 1 .07 min (Method C); ¹H NMR (400 MHz, CDCI₃) 5 ppm 8.33 - 8.38 (m, 1 H) 8.28 - 8.32 (m, 2 H) 8.07 - 8.11 (m, 1 H) 7.97 - 8.02 (m, 1 H) 7.84 - 7.91 (m, 1 H) 7.76 -7.76 (m, 1 H) 7.75 - 7.81 (m, 1 H) 7.56 - 7.63 (m, 1 H) 7.40 - 7.48 (m, 1 H) 4.1 1 (s, 3 H).

Step 3: Preparation of methyl 4-(1 ,5-dimethylpyrazol-4-yl)quinoline-2-carboxylate

A solution of methyl 4-chloroquinoline-2-carboxylate (0.197 mg, 0.45 mmol) and 1 , 5-dimethyl-4-(4, 4,5,5- tetramethyl-1 ,3,2-dioxaborolan-2-yl)pyrazole (100 mg, 0.41 mmol) in 2-methyltetrahydrofuran (1.6 mL) was treated with potassium phosphate (0.263 g, 1.22 mmol) and the resulting reaction mixture was degassed with nitrogen. A sample of mesylate[(di(1 -adamantyl)-n-butylphosphine)-2-(2'-amino-1 ,T-biphenyl)]palladium(ll), [(Di(1-adamantyl)-butylphosphine)-2-(2'-amino-1 ,T-biphenyl)]palladium(ll) methanesulfonate (cataCXium® A Pd G3) (0.031 g, 0.041 mmol, [1651823-59-4]) was added (brown suspension) and the reaction mixture was stirred at 80°C for 1 hr. The reaction mixture was poured into water and extracted with EtOAc. The combined organic layers were washed with brine, dried over Na2SO4 and concentrated under reduced pressure. The crude product was purified by CombiFlash® to afford methyl 4-(1 ,5-dimethylpyrazol-4-yl)quinoline-2- carboxylate. LC-MS: 282 [M+H], Rt: 0.98 min (Method C); ¹H NMR (400 MHz, CDCI₃) 6 ppm 8.27 (d, J=8.68 Hz, 1 H) 7.96 (s, 1 H) 7.85 - 7.95 (m, 1 H) 7.66 - 7.76 (m, 1 H) 7.57 (s, 2H) 7.50 - 7.55 (m, 1 H) 7.20 (s, 1 H) 3.86 (s, 3 H) 3.65 - 3.71 (m, 3 H) 2.33 (s, 3 H).

Step 4: Preparation of 4-(1 ,5-dimethylpYrazol-4-Yl)quinoline-2-carboxylic acid

To a suspension of methyl 4-(1 ,5-dimethylpyrazol-4-yl)quinoline-2-carboxylate (0.50 g, 1.69 mmol) in THF (15 mL) and water (5 mL) was added LiOH-hydrate (0.15 g, 3.38 mmol) at 20°C. The reaction mixture was stirred for 3 hr at 20°C and then partially evaporated on the rotary evaporated at 50°C. Water was added and 2N HCI was added slowly to adjust the solution to pH 5. The resulting precipitate was collected by suction filtration and dried in vacuo to afford 4-(1 ,5-dimethylpyrazol-4-yl)quinoline-2-carboxylic acid.

LC-MS: 267 [M-H], Rt: 0.17 min (Method C)

Step 5: Preparation of N-butoxy-4-(1 ,5-dimethylpyrazol-4-yl)quinoline-2-carboxamide as light brown solid

A suspension of 4-(1 ,5-dimethylpyrazol-4-yl)quinoline-2-carboxylic acid (0.11 g, 0.32 mmol) and O- butylhydroxylamine hydrochloride (0.07 g, 0.56 mmol) in EtOAc (2 mL) was treated with diisopropyl ethyl amine (0.23 g, 0.18 mmol) and propylphosphonic anhydride (50%wt solution in EtOAc, 0.45 g, 0.64 mmol) at 20°C. The resulting reaction mixture was stirred for 2 h at 20°C, and then diluted with aqueous Na2COs solution and EtOAc. The organic phase was separated, dried over Na2SO4, filtrated, and concentrated in vacuo. The residue was purified by CombiFlash® to afford N-butoxy-4-(1 ,5-dimethylpyrazol-4-yl)quinoline-2-carboxamide as light brown solid.

LC-MS: 339 [M+H], Rt: 0.95 min (Method G); ¹H NMR (400 MHz, CDCI3) 5 ppm 10.67 (br s, 1 H) 8.22 (d, 1 H) 8.15 (s, 1 H) 7.02 - 8.09 (m, 1 H) 7.82 (ddd, 1 H) 7.56 - 7.72 (m, 2 H) 4.16 (t, 2 H) 3.96 (s, 3 H) 2.32 (s, 3 H) 1 .66 - 1 .92 (m, 2 H) 1 .45 - 1 .65 (m, 2 H) 1 .02 (t, 3 H).

Examples of synthesized compounds of formula (I) are shown in Table F.

Table F: Synthesized compounds and Spectral and Physical Chemical Data (melting point [mp] and/or LC/MS data (retention time (Rt))

BIOLOGICAL EXAMPLES

Example B1 : Altemaria solani / tomato / leaf disc (early blight)

Tomato leaf disks cv. Baby are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus

2 days after application. The inoculated leaf disks are incubated at 23°C / 21 °C (day/night) and 80% rh under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check disk leaf disks (5 to 7 days after application). The following compounds gave at least 80% control of Altemaria solani at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: F.01 , F.02

Example B2: Botryotinia fuckeliana (Botrytis cinerea) / liquid culture (Gray mould)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3 to 4 days after application. The following compounds gave at least 80% control of Botryotinia fuckeliana at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: F.01 , F.02

Example B3: Glomerella laqenarium (Colletotrichum laqenarium} / liquid culture (Anthracnose)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is measured photometrically 3 to 4 days after application. The following compounds gave at least 80% control of Glomerella lagenarium at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: F.02, F.03, F.05, F.06

Example B4: Fusarium culmorum / liquid culture (Head blight)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3 to 4 days after application. The following compounds gave at least 80% control of Fusarium culmorum at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: F.01 , F.02, F.03, F.04, F.05, F.06

Example B5: Phaeosphaeria nodorum (Septoria nodorum] / wheat / leaf disc preventative (Glume blotch) Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 2 days after application. The inoculated test leaf disks are incubated at 24°C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 to 7 days after application). The following compounds gave at least 80% control of Phaeosphaeria nodorum at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: F.01 , F.02, F.03, F.06

Example B6: Monoqraphella nivalis (Microdochium nivale] / liquid culture (foot rot cereals)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4 to 5 days after application. The following compounds gave at least 80% control of Monographella nivalis at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: F.01 , F.02, F.03, F.04, F.05, F.06

Example B7: Mycosphaerella arachidis (Cercospora arachidicola) I liquid culture (early leaf spot)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4 to 5 days after application. The following compounds gave at least 80% control of Mycosphaerella arachidis at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: F.01 , F.02, F.03, F.04, F.05, F.06

Example B8: Magnaporthe grisea (Pyricularia oryzae) I liquid culture (Rice Blast)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3 to 4 days after application. The following compounds gave at least 80% control of Magnaporthe grisea at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: F.01 , F.02, F.03, F.04, F.05, F.06

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4 to 5 days after application. The following compounds gave at least 80% control of Mycosphaerella graminicola at 20 ppm when compared to untreated control under the same conditions, which showed extensive disease development: F.01 , F.02, F.03, F.04, F.05, F.06

Example B10: Pyrenophora teres I barley / leaf disc preventative (Net blotch)

Barley leaf segments cv. Hasso are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf segments are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments are incubated at 20°C and 65% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 to 7 days after application). The following compounds gave at least 80% control of Pyrenophora teres at 200 ppm when compared to untreated control under the same conditions, which showed extensive disease development: F.01 , F.03, F.04

Claims

1. A compound of formula (I) wherein

R¹ is selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, or C3-C6- cycloalkyl;

R² is selected from hydrogen, halogen, cyano, hydroxy, amino, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4- alkynyl, Cs-Cs-cycloalkyl, Ci-C4-alkoxy, Cs-Cs-alkenyloxy, Cs-Cs-alkynyloxy, Ci-C4-alkoxy-Ci-C2-alkyl, Ci-C4-haloalkyl, Ci-C4-haloalkoxy, Cs-Cs-cycloalkyloxy, Ci-C4-alkylamino, di(Ci-C4-alkyl)amino, C1-C4- alkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-alkylsulfonyl, or Ci-C4-haloalkylsulfanyl;

R³ is selected from hydrogen, halogen, Ci-C4-alkyl, or Ci-C4-haloalkyl;

R⁴ is selected from hydrogen, halogen, Ci-C4-alkyl, or Ci-C4-haloalkyl;

R⁵ is selected from hydrogen, halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-haloalkoxy, Ci-C4-alkoxy, Cs-Cs-alkenyloxy, Cs-Cs-alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-haloalkylsulfanyl, Ci-C4-alkylsu Ifinyl, Ci-C4-haloalkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-haloalkylsulfonyl, Ci-C4-alkoxy-Ci-C4-alkyl, C1-C4- alkoxycarbonyl, Ci-Cs-alkylaminocarbonyl, di(Ci-C4-alkyl)aminocarbonyl, cyano-Ci-C4-alkyl, N-C1-C4- alkoxy-C-Ci-C4-alkyl-carbonimidoyl, N-hydroxy-C-Ci-C4-alkyl-carbonimidoyl, hydroxy, amino, C1-C4- alkylamino, di(Ci-C4-alkyl)amino, cyano, carboxy, phenyl, a 5- to 6-membered saturated, partially saturated or aromatic heteroaryl, or Cs-Cs-cycloalkyl; wherein any of said phenyl, and 5- to 6-membered saturated, partially saturated or aromatic heteroaryl are unsubstituted or substituted with 1 , 2, or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-haloalkyl, or C1-C4- alkoxy; and wherein said Cs-Cs-cycloalkyl is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Ci-C4-alkoxy, or Ci-C4-haloalkyl;

R⁶ is selected from hydrogen, halogen, cyano, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4- haloalkyl, Cs-Cs-cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, C1-C4- alkylsulfonyl, or Ci-C4-alkoxycarbonyl;

R⁷ is selected from hydrogen, halogen, Ci-C4-alkyl, or Ci-C4-haloalkyl;

Z¹ is selected from Ci-Cs-alkoxy, wherein said Ci-Cs-alkoxy is unsubstituted or substituted with 1 , 2 or 3 substituents independently selected from halogen, cyano, Ci-C4-alkyl, Cs-Cs-cycloalkyl, C2-C6- alkenyl, Cs-Cs-alkynyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Cs-alkenyloxy, C3-C6- alkynyloxy, Ci-C4-alkylsulfanyl, Ci-C4-haloalkylsulfanyl, Ci-C4-alkylsulfinyl, Ci-C4-haloalkylsulfinyl, C1- C4-alkylsulfonyl, Ci-C4-haloalkylsulfonyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxycarbonyl, C1-C4- alkylcarbonyl, N-Ci-C4-alkoxy-C-Ci-C4-alkyl-carbonimidoyl, or N-hydroxy-C-Ci-C4-alkyl-carbonimidoyl; and

Z² is hydrogen, Ci-Cs-alkyl, or Cs-Ce-cycloalkyl; or an agrochemically acceptable salt, or N-oxide thereof.

2. The compound of formula (I) according to claim 1 , wherein R¹ is Ci-Cs-alkyl.

3. The compound of formula (I) according to claim 1 or claim 2, wherein R³ and R⁴ are hydrogen or C1- Cs-alkyl.

4. The compound of formula (I) according to any one of claims 1 to 3, wherein R⁵ is hydrogen, halogen, cyano, Ci-Cs-alkyl, Ci-Cs-alkoxy, or Ci-Cs-alkylsulfanyl.

5. The compound of formula (I) according to any one of claims 1 to 4, wherein R⁵ is hydrogen, halogen, cyano, or Ci-Cs-alkyl; and R⁶ and R⁷ are hydrogen.

6. The compound of formula (I) according to any one of claims 1 to 5, wherein R² is hydrogen, halogen, cyano, hydroxy, Ci-Cs-alkyl, Ci-Cs-alkoxy, Ci-C2-haloalkoxy, Ci-C2-alkyl-Ci-C3-alkoxy, or C1-C2- alkylsulfanyl.

7. The compound of formula (I) according to claim 6, wherein R² is hydrogen, halogen, cyano, C1-C3- alkyl, Ci-Cs-alkoxy, or Ci-C2-alkylsulfanyl.

8. The compound of formula (I) according to any one of claims 1 to 7, wherein Z² is hydrogen or C1-C3- alkyl.

9. The compound of formula (I) according to claim 8, wherein Z² is hydrogen.

10. The compound of formula (I) according to any one of claims 1 to 8, wherein Z¹ is Ci-Cs-alkoxy, wherein said Ci-Cs-alkoxy is unsubstituted or substituted with 1 or 2 substituents independently selected from chloro, fluoro, cyano, cyclopropyl, Ci-Cs-alkyl, C2-Cs-alkenyl, C2-Ce-alkynyl, Ci-C2-haloalkyl, C1-C2- alkoxy, or Ci-C2-haloalkoxy.

11. The compound of formula (I) according to claim 10, wherein Z¹ is Ci-Ce-alkoxy, wherein said Ci-Ce- alkoxy is unsubstituted or substituted with 1 or 2 substituents independently selected from chloro, fluoro, cyano, or cyclopropyl

12. An agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 1 1 .

13. The agrochemical composition according to claim 12, further comprising at least one additional active ingredient and/or an agrochemically-acceptable diluent or carrier.

14. A method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 11 , or a composition comprising the compound of formula (I), is applied to the plants, to parts thereof or the locus thereof.

15. Use of a compound according to any one of claims 1 to 11 as a fungicide.