TW202430031A - Microbiocidal pyrazole derivatives - Google Patents

Abstract

A compound of formula (I):

Description

Microbicidal pyrazole derivatives

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

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According to a first aspect of the present invention, there is provided a compound having formula (I): (I) wherein R ¹ is selected from hydrogen, C ₁ -C _4- alkyl, C ₂ -C _4- alkenyl, C ₂ -C ₄ -alkynyl, or C ₃ -C ₆ cycloalkyl; R ² is selected from hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₂ -C ₄ -alkenyl, C ₂ -C ₄ -alkynyl, C ₁ -C ₄ -halogenated alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C _4- alkylcarbonyl, N-C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl-carboimido, N-hydroxy-C ₁ -C ₄ alkyl-carboimido, or C ₁ -C _4- alkoxycarbonyl; R ³ and R ⁴ are independently selected from hydrogen, halogen, or C ₁ -C ₄ -alkyl; R ⁵ and R R ⁶ is independently selected from hydrogen, or C ₁ -C ₄ alkyl; R ⁷ is selected from hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylcarbonyl, N-C ₁ -C ₄ alkoxy-C C ₁ -C ₄ alkyl-carboimido, N-hydroxy-C C ₁ -C ₄ alkyl-carboimido, C ₁ -C ₄ alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C ₁ -C ₄ alkylaminocarbonyl, di(C ₁ -C ₆ alkylamino)carbonyl, phenyl, 5 to 6 membered heteroaryl, or C ₃ -C ₆ -cycloalkyl; wherein the 5- or 6-membered heteroaryl includes 1, 2, 3, or 4 heteroatoms independently selected from N, O, or S and wherein the phenyl and the 5- to 6-membered heteroaryl are unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C ₁ -C ₄ haloalkyl, cyano, carboxyl, C ₁ -C ₄ alkyl, or C ₁ -C ₄ alkoxy; and wherein the C ₃ -C ₆ -cycloalkyl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C ₁ -C ₄ haloalkyl, cyano, C ₁ -C ₄ alkyl, or C ₁ -C ₄ alkoxy; B ¹ is selected from CR ¹⁰ , or N; B ² is selected from CR ¹¹ , or N; R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are independently selected from hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ halogenated alkyl, C ₁ -C 4 alkoxy, C ₁ -C ₄ halogenated alkoxy, C ₂ -C ₄ alkenyloxy, C ₂ -C ₄ alkynyloxy, C ₁ -C ₄ alkylthio, C 1 -C ₄ alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl, N-C _1-4 alkylamino, N,N-diC _1-4 alkylamino, C _{1 -C 6} alkoxycarbonyl _, C ₁ -C ₄ alkylcarbonyl, N-C _{1 -C 4 alkoxy-C 1 -C 4 alkyl} -carboimido, N-hydroxy-C ₁ -C wherein the phenyl, the 5- to 6-membered heteroaryl and the C ₃ -C ₆ -cycloalkyl are unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C 1 -C 4 alkyl, C ₁ -C ₄ halogenated alkyl, or C _{1 -C 4} alkoxy; A ¹ is selected from CR ^12a , or N; A ² is selected _from CR ^13a , or N; A ³ is selected from CR ^14a , or _N ; R ^12a _{, R} R ^13a and R ^14a are independently selected from hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ halogenated alkyl, C ₂ -C ₄ alkenyl, or C ₂ -C ₄ alkynyl; and Z ¹ is selected from C ₁ -C ₄ alkyl, phenyl, 5- or 6-membered heteroaryl, or C ₃ -C ₆ cycloalkyl, wherein the 5- or 6-membered heteroaryl includes 1, 2, 3, or 4 heteroatoms independently selected from N, O, or S, and wherein any of the phenyl, 5- or 6-membered heteroaryl is unsubstituted or substituted by 1, 2, or 3 halogenated, cyano, C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₁ -C ₄ halogenated alkyl, C 1 -C ₄ alkoxy, C ₁ -C ₄ halogenated alkoxy, C ₃ -C 6 cycloalkyl, The present invention relates _{to an} agrochemically acceptable salt, stereoisomer _or N-oxide _{thereof wherein the C3-C6 cycloalkyl group is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl , C1 - C4 halogenated alkyl or C1 - C4 alkoxy} .

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

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

According to a third aspect of the present invention, there is provided a method for controlling or preventing useful plants from being infected by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I) according to the present invention, or a composition comprising the compound of formula (I), is applied to the plant, its part or its location.

According to a fourth aspect of the present invention, there is provided the use of a compound of formula (I) according to the present invention as a fungicide. According to this particular aspect of the present invention, the use may not include a method of treating a human or animal body by surgery or therapy and a method of diagnosing a human or animal body.

According to a fifth aspect of the present invention, there is provided a compound of formula (IIb), a compound of formula (III) and a compound of formula (IV), as respectively described in the present invention.

Compounds of the formula I which have at least one basic center can form acid addition salts, for example, with strong inorganic acids, such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrohalogen acids, strong organic carboxylic acids, such as unsubstituted or, for example, halogen-substituted _C1 - _C4 -alkanecarboxylic acids, for example acetic acid, saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or benzoic acid, or organic sulfonic acids, such as unsubstituted or, for example, halogen-substituted _C1 - _C4 -alkanesulfonic acids or arylsulfonic acids, for example methanesulfonic acid or p-toluenesulfonic acid. Compounds of formula (I) having at least one acidic group can form salts, for example with bases, for example mineral salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts; or with ammonia or organic amines (such as The invention can be used to form a salt with 1, 2 or 3 lower alkylamines such as ethylamine, diethylamine, triethylamine or dimethylpropylamine, or a mono-, di- or tri-hydroxy lower alkylamine such as monoethanolamine, diethanolamine or triethanolamine.

In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form (such as N-oxides), or in salt form (e.g., in agronomically usable salt form).

N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen-containing heteroaromatic compounds. They are described, for example, in the book " Heterocyclic N-oxides " by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.

The compounds of formula (I) according to the present invention also include hydrates which may be formed during salt formation.

When substituents are indicated as "optionally substituted", this means that they may or may not carry one or more identical or different substituents, for example, one, two or three R ^x substituents. For example, C ₁ -C ₆ alkyl substituted with 1, 2 or 3 halogens may include, but are not limited to, -CH ₂ Cl, -CHCl ₂ , -CCl ₃ , -CH ₂ F, -CHF ₂ , -CF ₃ , -CH ₂ CF ₃ or -CF ₂ CH ₃ groups. As another example, C ₁ -C ₆ alkoxy substituted with 1, 2 or 3 halogens may include, but are not limited to, CH ₂ ClO-, CHCl ₂ O-, CCl ₃ O-, CH ₂ FO-, CHF ₂ O-, CF ₃ O-, CF ₃ CH ₂ O- or CH ₃ CF ₂ O- groups. As used herein, the term "optionally substituted" may be used interchangeably with "unsubstituted or substituted."

As used herein, the term "halogen" or "halogenated" refers to fluorine (fluorine, fluoro), chlorine (chlorine, chloro), bromine (bromo) or iodine (iodine, iodo), preferably fluorine, chlorine or bromine. This also applies to halogens in combination with other meanings, such as halogenated alkyl, halogenated alkenyl, halogenated alkynyl, halogenated alkoxy, and halogenated cycloalkyl.

As used herein, an amine group refers to a -NH ₂ group.

As used herein, cyano refers to a -CN group.

As used herein, the term "hydroxyl" or "hydroxy" refers to an -OH group.

As used herein, the term "carboxylic acid" refers to a -COOH group.

As used herein, the term "C ₁ -C _n alkyl" refers to a saturated straight or branched chain alkyl group having 1 to n carbon atoms, attached via any carbon atom, such as any of the following groups: 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 "C ₂ -C _n -alkenyl" refers to a straight or branched alkenyl chain having from two to n carbon atoms and one or two double bonds, for example vinyl, prop-1-enyl, but-2-enyl.

As used herein, the term "C ₂ -C _n -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 "C ₃ -C _n -cycloalkyl" refers to tri(3) to n-membered cycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

As used herein, the term "C ₁ -C _n alkoxy" refers to a straight or branched saturated alkyl group (as mentioned above) having one (1) to n carbon atoms, which is attached via an oxygen atom, i.e., for example, any of the following groups: methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy. As used herein, the term "C ₂ -C _n alkenyloxy" refers to a straight or branched alkenyl chain (as mentioned above) having two (2) to n carbon atoms, which is attached via an oxygen atom.

As used herein, the term "C ₁ -C _n -alkoxy-C ₁ -C _n -alkyl" refers to an alkyl group (as mentioned above) substituted by a C ₁ -C _n -alkoxy group. Examples are methoxymethyl, methoxyethyl, ethoxymethyl and propoxymethyl.

As used herein, the term " _Ci - _Cn haloalkyl" refers to a straight or branched saturated alkyl group (as mentioned above) having 1 to n carbon atoms, attached via any carbon atom, wherein some or all of the hydrogen atoms in the groups may be replaced by fluorine, chlorine, bromine and/or iodine, i.e., for example, any of the following: 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, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl, or nonafluorobutyl. Correspondingly, the term "C ₁ -C ₂ fluoroalkyl" will refer to a C ₁ -C ₂ alkyl group carrying 1, 2, 3, 4 or 5 fluorine atoms, such as any of the following: difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl or pentafluoroethyl. Similarly, as used herein, the term "C ₂ -C _n -haloalkenyl" or "C ₂ -C _n -haloalkynyl" refers to a C ₂ -C _n -alkenyl or C ₂ -C _n -alkynyl group, respectively, substituted by one or more halogen atoms which may be the same or different. Similarly, as used herein, the term "C ₃ -C _n -halocycloalkyl" or "C ₁ -C _n -haloalkoxy" refers to a C ₃ -C _n -cycloalkyl or C ₁ -C _n -alkoxy group, respectively, substituted with one or more halogen atoms which may be the same or different.

As used herein, the term "C ₁ -C _n -alkylthio" or "C ₁ -C _n -alkenylhydrothio" refers to a C ₁ -C _n -alkyl group attached via a sulfur atom.

As used herein, the term "C ₁ -C _n haloalkylthio" or "C ₁ -C _n haloalkylhydrothio" refers to a C ₁ -C _n haloalkyl group linked through a sulfur atom.

As used herein, the term "C ₁ -C _n -alkylsulfinyl" refers to a C ₁ -C _n alkyl group linked via a sulfur atom of a sulfinyl (or S(═O)—) group.

As used herein, the term "C ₁ -C _n -alkylsulfonyl" refers to a C ₁ -C _n alkyl group linked via the sulfur atom of a sulfonyl (or S(═O) ₂ —) group.

As used herein, the term "C ₁ -C _n -alkylsulfonyl-C ₁ -C _n -alkyl" refers to a C ₁ -C _n alkyl group substituted with a C ₁ -C _n alkylsulfonyl group.

As used herein, the term "C ₁ -C _n -alkylcarbonyl" refers to a C ₁ -C _n -alkyl group attached via the carbon atom of a carbonyl group (C=0).

As used herein, the term "C ₁ -C _n -alkoxycarbonyl" refers to a C ₁ -C _n -alkoxy moiety attached through the carbon atom of the carbonyl group (or C=0).

As used herein, the term "benzoyl" refers to a phenyl group attached through the carbon atom of a carbonyl group (C=O).

As used herein, the term "C ₁ -C _n -alkylaminocarbonyl" refers to a C ₁ -C _n -alkylamino group attached through the carbon atom of a carbonyl group (C═O) (or _RaNHC (═O)—, wherein _Ra is C ₁ -C _n -alkyl).

As used herein, the term "aminocarbonyl-C ₁ -C _n -alkyl" refers to a C ₁ -C _n -alkyl group substituted with an aminocarbonyl group (or NH ₂ C(═O)—).

As used herein, the term "NC ₁ -C ₄ alkoxy-CC ₁ -C ₄ alkyl-carboimido" refers to a group having the formula -C( _Ra )=NO( _Rb ), wherein _Ra is a C1-C4 alkyl group as generally defined above, and _Rb is a C1-C4 alkyl group as generally defined above.

As used herein, the term "N-hydroxy- _C1 - _C4alkyl -carboimido" refers to a group having the formula -C( _Ra )=NOH, wherein _Ra is a _C1 - _C4 alkyl group as generally defined above.

As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic group containing 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, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazolyl ... Base, Da The term "heteroaryl-C ₁ -C _n -alkyl" or "heteroaryl-C ₃ -C _n -cycloalkyl" refers to a C ₁ -C _n -alkyl or C 3 -C _n -cycloalkyl substituted with a heteroaryl group, respectively. The heteroaryl-C ₁ -C _n -alkyl or heteroaryl- _{C 3 -C n} -cycloalkyl group may be substituted on the heteroaryl group, alkyl group and/or cycloalkyl group as appropriate.

As used herein, the term "control" refers to reducing the number of pests, eliminating pests and/or preventing further pest damage, thus resulting in reduced damage to plants or to plant-derived products.

As used herein, the term "pests" refers to insects and molluscs present in agriculture, horticulture, forestry, storage of products of plant origin (such as fruits, grains and wood); and those pests associated with the damage of man-made structures. The term pest covers all stages of the life cycle of the pest in question.

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

The effective amount is readily determined by one skilled in the art using known techniques and by observing the results obtained under similar circumstances. In determining the effective amount, many 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 life cycle; the specific compound applied; the type of application; and other relevant circumstances.

As used herein, the term "room temperature" or "RT" or "rt" refers to a temperature of about 15° C. to about 35° C. For example, rt may refer to a temperature of about 20° C. to about 30° C.

The following list provides definitions, including preferred definitions, of substituents R ¹ , R ² , R ³ , R 4 , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , B ¹ , B ² , A ¹ , A ² , ^{A 3 and} Z for compounds of formula (I) of the present invention. For any of the substituents, any definition given below can be combined with any definition of any other substituent given below or elsewhere in this document.

In an embodiment of the present invention, R ¹ is selected from hydrogen, C ₁ -C _4- alkyl, C ₂ -C _4- alkenyl, C ₂ -C ₄ -alkynyl, or C ₃ -C ₆ cycloalkyl. In another embodiment of the present invention, R ¹ is selected from hydrogen, C ₁ -C _4- alkyl, C ₂ -C _4- alkenyl, C ₂ -C ₄ -alkynyl, or C ₃ -C ₆ cycloalkyl. Preferably, R ¹ is C ₁ -C ₄ alkyl. More preferably, R ¹ is methyl, ethyl, or isopropyl. Most preferably, R ¹ is methyl.

In an embodiment of the present invention, ^R2 is selected from hydrogen, halogen, _C1 - _C4- alkyl, C2- _C4 -alkenyl, _C2 - _C4 -alkynyl, _C1 - _C4 -halogenated alkyl, _C3 - _C6 cycloalkyl, _C1 -C4 _- alkylcarbonyl, _{N-C1-C4alkoxy-C1 - C4alkyl - carboimido} , N-hydroxy- _C1 - _C4alkyl -carboimido, or _C1 -C4 _- alkoxycarbonyl. In another embodiment of the present invention, ^R2 is selected from hydrogen, halogen, _C1 - _C4- alkyl, _C2 -C4-alkenyl _{, C2} - _C4 -alkynyl, _C1 - _C4 -halogenated alkyl, _C3 - _C6 cycloalkyl, C1-C4 _- alkylcarbonyl, N- _C1 - _C4 alkoxy _{-C1 - C4} alkyl-carboimido, N-hydroxy- _C1 - _C4 alkyl-carboimido, or _C1 - _C4- alkoxycarbonyl. In yet another embodiment, ^R is selected from hydrogen, halogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ alkylcarbonyl, N C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl-carboimido, or N-hydroxy-C ₁ -C ₄ alkyl-carboimido. Preferably, ^R is selected from hydrogen, halogen, methyl, ethyl, cyclopropyl, C ₁ -C ₂ alkylcarbonyl, N C ₁ -C ₂ alkoxy-C ₁ -C ₂ alkyl-carboimido, or N-hydroxy-C ₁ -C ₂ alkyl-carboimido. More preferably, R ² is selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, cyclopropyl, acetyl, -C(CH ₃ )=NOCH ₃ , -C(CH ₃ )=NOCH ₂ CH ₃ , or -C(CH ₃ )=NOH. In a preferred embodiment of the present invention, R ² is selected from hydrogen, halogen, or C ₁ -C ₄ alkyl. Preferably, R ² is hydrogen, chlorine, or methyl.

In one embodiment, R ³ is selected from hydrogen, halogen, or C ₁ -C ₄ alkyl. In another embodiment, R ³ is selected from hydrogen, halogen, or C ₁ -C ₄ alkyl. Preferably, R ³ is hydrogen or C ₁ -C ₄ alkyl. More preferably, R ³ is hydrogen or methyl. Most preferably, R ³ is hydrogen.

In one embodiment of the present invention, R ⁴ is selected from hydrogen, halogen, or C ₁ -C ₄ -alkyl. In another embodiment of the present invention, R ⁴ is hydrogen, halogen, or C ₁ -C ₄ -alkyl. Preferably, R ⁴ is hydrogen, chlorine, bromine, fluorine, methyl, or ethyl. More preferably, R ⁴ is hydrogen, chlorine, bromine, or methyl. Still more preferably, R ⁴ is hydrogen or methyl. In one embodiment of the present invention, R ⁴ is hydrogen. In another embodiment of the present invention, R ⁴ is methyl.

In one embodiment of the present invention, R ⁵ and R ⁶ are independently selected from hydrogen or C ₁ -C ₆ alkyl. In another embodiment of the present invention, R ⁵ and R ⁶ are independently selected from hydrogen or C ₁ -C ₄ -alkyl. Preferably, R ⁵ and R ⁶ are independently selected from hydrogen, methyl or ethyl. More preferably, R ⁵ and R ⁶ are independently selected from hydrogen or methyl. Even more preferably, R ⁵ and R ⁶ are hydrogen.

In an embodiment of the present invention, R ⁷ is selected from hydrogen, C ₁ -C ₄ alkyl, C ₁ -C _{4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl ,} N C ₁ -C ₄ alkoxy-C C ₁ -C ₄ alkyl-carboimido, N-hydroxy-C C ₁ -C ₄ alkyl-carboimido, N-methoxy-N-methyl-carbonyl, C ₁ -C ₄ alkylaminocarbonyl, di(C ₁ -C ₆ alkylamino)carbonyl, phenyl, 5 to 6 membered heteroaryl, or C ₃ -C ₆ -cycloalkyl, wherein the 5 to 6 membered heteroaryl includes 1 heteroatom selected from N and wherein the phenyl and the 5 to 6 membered heteroaryl are unsubstituted or substituted by 1 or 2 independently selected from halogen, C ₁ -C ₄ halogenated alkyl, cyano, or C ₁ -C 6 alkyl. ₄ -alkyl; and wherein the C ₃ -C ₆ -cycloalkyl is unsubstituted or substituted by a substituent selected from cyano. Preferably, R ⁷ is selected from hydrogen, methyl, acetyl, C(CH ₃ )=NOCH ₃ , -C(CH ₃ )=NOCH ₂ CH ₃ , -C(CH ₃ )=NOH, methoxycarbonyl, ethoxycarbonyl, N-methoxy-N-methyl-carbonyl, methylaminocarbonyl, dimethylaminocarbonyl, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, [4-(trifluoromethyl)pyrazol-1-yl], [3-(trifluoromethyl)pyrazol-1-yl], (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), (5-chloropyrazol-1-yl), (5-fluoropyrazol-1-yl), (3,5-dimethylpyrazol-1-yl), (5-methylpyrazol-1-yl), pyrazol-1-yl, cyclopropyl, or 1-cyanocyclopropyl. More preferably, R ⁷ is selected from hydrogen, methyl, acetyl, C(CH ₃ )=NOCH ₃ , -C(CH ₃ )=NOCH ₂ CH ₃ , -C(CH ₃ )=NOH, phenyl, 4-cyanophenyl, pyrazol-1-yl, cyclopropyl, or 1-cyanocyclopropyl. Even more preferably, R ⁷ is selected from hydrogen, methyl, cyclopropyl, or 1-cyanocyclopropyl.

In another embodiment, ^R is selected from hydrogen, C ₁ -C ₄ alkyl, or C ₃ -C ₆ -cycloalkyl. Preferably, ^R is hydrogen, methyl, cyclopropyl, or 1-cyanocyclopropyl. Even more preferably, ^R is hydrogen, methyl, or cyclopropyl. In one embodiment, ^R is hydrogen or methyl. In another embodiment, ^R is hydrogen. In yet another embodiment, R is ^methyl .

In an embodiment of the present invention, R ⁸ and R ⁹ are independently selected from hydrogen, halogen, cyano, C ₁ -C ₄ alkyl, or C ₁ -C ₄ alkoxy. Preferably, R ⁸ and R ⁹ are independently selected from hydrogen, halogen, methyl, methoxy, or cyano. More preferably, R ⁸ and R ⁹ are independently selected from hydrogen, methyl, chlorine, fluorine, bromine, or methoxy. Even more preferably, R ⁸ and R ⁹ are hydrogen or methoxy.

In another embodiment of the present invention, R ⁸ is selected from hydrogen, halogen, or cyano. More preferably, R ⁸ is hydrogen, cyano, or bromine. Even more preferably, R ⁸ is hydrogen.

In another embodiment, R ^is selected from hydrogen, halogen, C ₁ -C ₃ alkyl, C ₁ -C ₂ halogenated alkyl, C ₁ -C ₃ halogenated alkoxy, C ₁ -C _{4 alkoxy, C 1 -C 3 alkenyloxy, C 1} -C ₃ alkynyloxy, C ₁ -C ₂ alkylthio, C ₁ -C ₂ alkylsulfinyl, C ₁ -C ₂ alkylsulfonyl, C ₁ -C ₂ alkoxy-C ₁ -C ₂ alkyl, C _{1 -C 3 alkoxycarbonyl, C 1 -C 2 alkylcarbonyl, N C 1 -C 2 alkoxy-C C 1 -C 2 alkyl - carboimido , N - hydroxy -} C C ₁ -C ₂ alkyl-carboimidohydroxy, C ₁ -C ₂ alkylaminocarbonyl, di(C ₁ -C ₂ -alkylamino)carbonyl, trifluoromethylsulfonyloxy, cyano, carboxyl, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, [4-(trifluoromethyl)pyrazol-1-yl], [3-(trifluoromethyl)pyrazol-1-yl], (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), (5-chloropyrazol-1-yl), -yl), (4-chloropyrazol-1-yl), (3-chloropyrazol-1-yl), (5-fluoropyrazol-1-yl), (4-fluoropyrazol-1-yl), (3-fluoropyrazol-1-yl), (3,5-dimethylpyrazol-1-yl), (5-methylpyrazol-1-yl), (4-methylpyrazol-1-yl), (3-methylpyrazol-1-yl), pyrazol-1-yl, cyclopropyl, or 1-cyanocyclopropyl. Preferably, R ⁹ is selected from hydrogen, chlorine, fluorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, difluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, methoxy, ethoxy, propoxy, -allyloxy, prop-2-ynyloxy, methylthio _, methylsulfinyl, methylsulfonyl, methoxymethyl, ethoxymethyl, 2-methoxyethoxymethyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, acetyl, propionyl, -C(CH ₃ )=NOCH ₃ , -C(CH ₃ )=NOCH ₂ CH ₃ , -C(CH ₃ )=NOH, methylaminocarbonyl, di(methylamino)carbonyl, trifluoromethylsulfonyloxy, cyano, carboxyl, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, [4-(trifluoromethyl)pyrazol-1-yl], [3-(trifluoromethyl)pyrazol-1-yl], (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), ( 5-chloropyrazol-1-yl), (4-chloropyrazol-1-yl), (3-chloropyrazol-1-yl), (5-fluoropyrazol-1-yl), (4-fluoropyrazol-1-yl), (3-fluoropyrazol-1-yl), (3,5-dimethylpyrazol-1-yl), (5-methylpyrazol-1-yl), (4-methylpyrazol-1-yl), (3-methylpyrazol-1-yl), pyrazol-1-yl, cyclopropyl, or 1-cyanocyclopropyl. More preferably, R ⁹ is selected from hydrogen, chlorine, bromine, fluorine, methyl, methoxy, propoxy, allyloxy, methoxymethyl, 2-methoxyethoxymethyl, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, [4-(trifluoromethyl)pyrazol-1-yl], [3-(trifluoromethyl)pyrazol-1-yl], (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), (5-chloropyrazol-1-yl), R 9 is hydrogen, chloro, fluoro, methyl, or methoxy. Most preferably, R ⁹ is ^hydrogen or methoxy.

In an embodiment of the present invention, ^B1 is ^CR10 and ^B2 is ^CR11 , or ^B1 is N and ^B2 is ^CR11 , or ^B1 is ^CR10 and ^B2 is N. Preferably, ^B1 is ^CR10 and ^B2 is ^CR11 .

In one embodiment of the present invention, ^R10 and ^R11 are independently selected from hydrogen, halogen, hydroxyl, cyano, amine, _C1 - _C4 alkyl, _C1 - _C4 halogenated alkyl, _C1 - _C4 alkoxy, _C1 - _C4 halogenated alkoxy, _C2 - _C4 alkenyloxy, _C2 - _C4 alkynyloxy, _C1 - _C4 alkylthio, _C1 - _C4 alkylsulfinyl, C1- _C4 alkylsulfonyl, _C1 - _C4 alkoxy- _{C1 - C4} alkyl, N,N- _diC1-4 alkylamino, C1 _{- C6} alkoxycarbonyl, _{C1 - C4} alkylcarbonyl, N,N- _diC1-4 alkyloxy- _{C1 -} C The invention also includes but is not limited to _C 1 -C 4 alkyl-carboimido, N-hydroxy-C ₁ -C ₄ alkyl-carboimido, hydroxy, trifluoromethylsulfonyloxy, carboxyl, phenyl, 5- or 6-membered heteroaryl, or C ₃ -C ₆ cycloalkyl, wherein the 5- or 6-membered heteroaryl includes 1, 2, 3, or 4 heteroatoms independently selected from N, O, or S, and wherein any of the phenyl, 5- or 6-membered heteroaryl and C ₃ -C ₆ -cycloalkyl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ halogenated alkyl, or C ₁ -C ₄ alkoxy. Preferably, R ¹⁰ and R ¹¹ are independently selected from hydrogen, chlorine, fluorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, difluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, methoxy, ethoxy, propoxy, -allyloxy, prop-2-ynyloxy, methylthio, methylsulfinyl, methylsulfonyl, methoxymethyl, ethoxymethyl, 2-methoxyethoxymethyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, acetyl, propionyl, -C(CH ₃ )=NOCH ₃ , -C(CH ₃ )=NOCH ₂ CH ₃ , -C(CH ₃ )=NOH, methylaminocarbonyl, di(methylamino)carbonyl, trifluoromethylsulfonyloxy, cyano, carboxyl, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, [4-(trifluoromethyl)pyrazol-1-yl], [3-(trifluoromethyl)pyrazol-1-yl], (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), ( 5-chloropyrazol-1-yl), (4-chloropyrazol-1-yl), (3-chloropyrazol-1-yl), (5-fluoropyrazol-1-yl), (4-fluoropyrazol-1-yl), (3-fluoropyrazol-1-yl), (3,5-dimethylpyrazol-1-yl), (5-methylpyrazol-1-yl), (4-methylpyrazol-1-yl), (3-methylpyrazol-1-yl), pyrazol-1-yl, cyclopropyl, or 1-cyanocyclopropyl. More preferably, R ¹⁰ and R ¹¹ are independently selected from hydrogen, chlorine, bromine, fluorine, methyl, methoxy, propoxy, allyloxy, methoxymethyl, 2-methoxyethoxymethyl, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, [4-(trifluoromethyl)pyrazol-1-yl], [3-(trifluoromethyl)pyrazol-1-yl], (3-cyanopyrazol-1-yl), (4-cyanopyrazol-1-yl), (5-chloropyrazol-1-yl), (4-chloropyrazol-1-yl), (3-chloropyrazol-1-yl), (5-fluoropyrazol-1-yl), (4-fluoropyrazol-1-yl), (3-fluoropyrazol-1-yl), (3,5-dimethylpyrazol-1-yl), (5-methylpyrazol-1-yl), (4-methylpyrazol-1-yl), (3-methylpyrazol-1-yl), pyrazol-1-yl, C(CH ₃ )=NOCH ₃ , -C(CH ₃ )=NOCH ₂ CH ₃ , -C(CH ₃ )=NOH, cyclopropyl, or 1-cyanocyclopropyl.

In another embodiment, R ¹⁰ and R ¹¹ are independently selected from hydrogen, halogen, C ₁ -C ₃ alkyl, or C ₁ -C ₄ alkoxy. Preferably, R ¹⁰ and R ¹¹ are independently selected from hydrogen or halogen. More preferably, R ¹⁰ and R ¹¹ are hydrogen.

In an embodiment of the present invention, ^A1 is ^CR12a or N; ^A2 is ^CR13a or N; ^A3 is ^CR14a or N. Preferably, at least two of ^A1 , ^A2 and ^A3 are selected from N. More preferably, ^A1 , ^A2 and ^A3 are N.

In an embodiment of the present invention, R ^12a , R ^13a and R ^14a are independently selected from hydrogen, halogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ -cycloalkyl, or C ₁ -C ₄ halogenated alkyl. Preferably, R ^12a , R ^13a and R ^14a are independently selected from hydrogen, halogen, methyl, cyclopropyl, or trifluoromethyl. More preferably, R ^12a , R ^13a and R ^14a are hydrogen.

In another embodiment, ^A1 is selected from ^CR12a , or N; ^A2 is selected from ^CR13a , or N; ^A3 is selected from ^CR14a , or N; wherein at least two of ^A1 , ^A2 and ^A3 are selected from N; and wherein ^R12a , ^R13a , and ^R14a are hydrogen.

In an embodiment of the present invention, ^Z1 is selected from _C1 - _C4 alkyl, phenyl, 5- to 6-membered heteroaryl, or _C3 - _C6 -cycloalkyl; wherein the 5- or 6-membered heteroaryl includes 1, 2, 3, or 4 heteroatoms independently selected from N, O, or S, and wherein any of the phenyl and 5- to 6-membered heteroaryl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, _C1 - _C4 alkyl, _C1 - _C4 haloalkyl, _C1 - _C4 haloalkoxy, _C1 - _C4 alkoxy, _C2 - _C4 -alkynyl, _C1 - _C4 alkylthiothio, _C1 - _C4 alkylsulfinyl, or _C1 - _C4 alkylsulfonyl, and wherein the _C3 - _C6 -Cycloalkyl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, or C ₁ -C ₄ alkoxy.

In another embodiment, ^Z1 is selected from _C1 - _C3 alkyl, phenyl, 5- to 6-membered heteroaryl, or _C3 - _C6 -cycloalkyl; wherein the 5- or 6-membered heteroaryl includes 1, 2, or 3 heteroatoms independently selected from N, O, or S and wherein any of the phenyl and 5- to 6-membered heteroaryl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from fluorine, chlorine, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and wherein the _C3 - _C6 -cycloalkyl is unsubstituted or substituted with 1 or 2 substituents selected from methyl.

In another embodiment, ^Z1 is selected from _C1 - _C3 alkyl, phenyl, 5- to 6-membered heteroaryl, or _C3 - _C6 -cycloalkyl, wherein the 5- or 6-membered heteroaryl includes 1 heteroatom selected from N, O, or S and wherein any of the phenyl and 5- to 6-membered heteroaryl is unsubstituted or substituted with 1 or 2 substituents independently selected from fluorine, chlorine, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and wherein the _C3 - _C6 -cycloalkyl is unsubstituted or substituted with 1 or 2 substituents selected from methyl. Preferably, Z ¹ is selected from 1-methylpyrazol-4-yl, 2,3,4-trifluorophenyl, 2,3-difluorophenyl, 3,4-difluorophenyl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2-pyridyl, 2-fluoro-4-methoxy-phenyl, 2-fluoro-4-methylsulfonyl-phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3,5-difluoro-2-furan phenyl, 3-fluoro-2-thienyl, 5-fluoro-2-thienyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3-methoxyphenyl, 4-ethynyl-2-fluoro-phenyl, 4-fluoro-2-methoxy-phenyl, cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, n-propyl, or phenyl. More preferably, ^Z is selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2-chlorophenyl, 2-fluorophenyl, 3,5-difluoro-2-pyridyl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-fluorophenyl, 3-methylphenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, 4-methylphenyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, or phenyl. Even more preferably, ^Z is selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 3,5-difluoro-2-pyridyl, 2,4-difluorophenyl, 2-fluorophenyl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, cyclobutyl, cyclohexyl, cyclopentyl, or phenyl. Still even more preferably, ^Z is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, 4-fluorophenyl, or phenyl.

In another embodiment of the present invention, ^Z1 is selected from _C1 - _C4 alkyl, phenyl, 5- to 6-membered heteroaryl, or _C3 - _C6 -cycloalkyl; wherein the 5- or 6-membered heteroaryl includes 1, 2 or 3 heteroatoms independently selected from N, O, or S, and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, _C1 - _C4 alkyl, _C1 - _C4 haloalkyl, _C1 - _C4 haloalkoxy, or _C1 - _C4 alkoxy and wherein the _C3 - _C6 -cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen or _C1 - _C4 alkyl. Preferably, ^Z1 is selected from phenyl or 5- to 6-membered heteroaryl; wherein the 5- or 6-membered heteroaryl includes 1 heteroatom selected from N or S, and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from fluorine, chlorine, _C1 - _C4 alkyl, or _C1 - _C4 alkoxy. More preferably, ^Z is selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2-pyridyl, 2-fluorophenyl, 3,5-difluoro-2-furyl, 3-fluoro-2-furyl, 5-fluoro-2-furyl, 3,5-difluoro-2-thienyl, 3-fluoro-2-thienyl, 5-fluoro-2-thienyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, cyclobutyl, cyclohexyl, cyclopentyl, or methyl. Still more preferably, ^Z is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2-pyridyl, 3,5-difluoro-2-furyl, 3-fluoro-2-furyl, 5-fluoro-2-furyl, 3,5-difluoro-2-thienyl, 3-fluoro-2-thienyl, 5-fluoro-2-thienyl, 2-fluorophenyl, 4-fluorophenyl, or phenyl.

In another embodiment of the present invention, ^Z1 is selected from phenyl, 5- to 6-membered heteroaryl, or _C3 - _C6 -cycloalkyl; wherein the 5- or 6-membered heteroaryl includes 1 heteroatom selected from N or S, and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, _C1 - _C4 alkyl, _C1 - _C4 halogenated alkyl, _C1 - _C4 halogenated alkoxy, or _C1 - _C4 alkoxy and wherein the _C3 - _C6 -cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen or _C1 - _C4 alkyl. Preferably, ^Z1 is selected from phenyl, or 5- to 6-membered heteroaryl; wherein the 5- or 6-membered heteroaryl includes 1 heteroatom selected from N or S, and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from fluorine, chlorine, _C1 - _C4 alkyl, or _C1 - _C4 alkoxy.

Accordingly, the present invention makes it possible to provide compounds of formula (I) with ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^B1 , ^B2 , ^A1 , ^A2 , ^A3 and ^Z1 being as defined above in all combinations/permutations.

Implementation methods according to the present invention are provided as listed below.

In one embodiment of the present invention, a compound of formula (I) is provided, wherein R ¹ is selected from hydrogen, C ₁ -C _6- alkyl, C ₂ -C _6- alkenyl, C ₂ -C ₆ -alkynyl, or C ₃ -C ₆ -cycloalkyl; R ² is selected from hydrogen, halogen, C ₁ -C 6-alkyl, C 2 -C ₆ -alkenyl, C 2 -C 6 -alkynyl, C ₁ -C ₆ -halogenated alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₄ -alkylcarbonyl, N-C 1 -C 4 alkoxy-C ₁ -C ₄ alkyl-carboimido, N-hydroxy-C ₁ -C ₄ alkyl-carboimido, or C ₁ -C ₆ -alkoxycarbonyl; R 3 and R 4 are independently selected from hydrogen, halogen, or C ₂ -C ₆ -alkenyl, C 2 -C 6 -alkynyl, C _{1 -C 6 -halogenated alkyl, C 3 -C 6 cycloalkyl, C 1 -C 4-alkylcarbonyl, N-C 1 -C 4 alkoxy-C 1 -C 4 alkyl-carboimido, or C 1} ^-C _{6 -} ^{alkoxycarbonyl} _; ^R5 and ^R6 are independently selected from hydrogen, or _C1 - _C6 alkyl; ^R7 is selected from hydrogen, _C1 - _C6 alkyl, C1- _C6 alkylcarbonyl, N _-C1 - _C4 alkoxy- _{C1 - C4} alkyl-carboimido, N-hydroxy _{- C1 -C4 alkyl} -carboimido, C1- _C6 alkoxycarbonyl, N-methoxy-N _- methyl-carbonyl, _C1 - _C6 alkylaminocarbonyl, di( _C1 - _C6 alkylamino)carbonyl, phenyl, 5 to 6 membered heteroaryl and _C3 - _C6 -cycloalkyl; wherein the 5- or 6-membered heteroaryl includes 1, 2, 3, or 4 heteroatoms independently selected from N, O, or S and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C ₁ -C ₄ haloalkyl, cyano, carboxyl, C ₁ -C ₄ alkyl, and C ₁ -C ₄ alkoxy; and wherein the C ₃ -C ₆ -cycloalkyl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C ₁ -C ₄ haloalkyl, cyano, C ₁ -C ₄ alkyl, and C ₁ -C ₄ alkoxy; B ¹ is selected from CR ¹⁰ , and N; B ² is selected from CR ¹¹ , and N; R ⁸ , R ⁹ , R R ¹⁰ and R ¹¹ are independently selected from hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ halogenated alkyl, C _{1 -C 4 alkoxy, C 1 -C 4 halogenated} alkoxy, C ₂ -C ₄ alkenyloxy, C 2 -C 4 alkynyloxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ alkoxy- _{C 1 -C 4 alkyl, N-C 1-4 alkylamino, N,N-diC 1-4 alkylamino , C 1 -C 6 alkoxycarbonyl} , C ₁ -C ₄ alkylcarbonyl, N-C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl-carboimido, N-hydroxy-C ₁ -C wherein the phenyl, the 5- or 6-membered heteroaryl group and the C ₃ -C ₆ -cycloalkyl group are unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C 1 -C 4 alkyl, C ₁ -C ₄ halogenated alkyl, or C ₁ -C ₄ alkoxy; A ¹ is selected from CR ^12a , or N; A ² is selected _from CR ^13a , or N; A ³ is selected ^from CR ^14a _, or _N ; R _{12a ,} R R ^13a and R ^14a are independently selected from hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ halogenated alkyl, C ₂ -C ₄ alkenyl, or C ₂ -C ₄ alkynyl; and Z ¹ is selected from C ₁ -C ₄ alkyl, phenyl, 5- or 6-membered heteroaryl, or C ₃ -C ₆ cycloalkyl, wherein the 5- or 6-membered heteroaryl includes 1, 2, 3, or 4 heteroatoms independently selected from N, O, or S, and wherein any of the phenyl, 5- or 6-membered heteroaryl is unsubstituted or substituted by 1, 2, or 3 halogenated, cyano, C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₁ -C ₄ halogenated alkyl, C 1 -C ₄ alkoxy, C ₁ -C ₄ halogenated alkoxy, C ₃ -C 6 cycloalkyl. The invention relates to _{a C3 -} C6 cycloalkyl group, wherein the _C3 - _C6 cycloalkyl group is unsubstituted _{or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl , C1 - C4 halogenated} alkyl, _{C1 - C4 alkoxy} ; or an agrochemically acceptable salt, stereoisomer or N-oxide thereof.

In one embodiment, in the compounds of formula (I) according to the present invention, ^R1 is hydrogen, _C1 - _C4 alkyl, _C2 - _C4 alkenyl, _C2 - _C4 alkynyl, or _C3 - _C6 cycloalkyl; ^R2 is hydrogen, halogen, or _C1 - _C4 alkyl; ^R3 and ^R4 are independently selected from hydrogen, halogen, or _C1 - _C4 alkyl; ^R5 and ^R6 are independently selected from hydrogen and _C1 - _C4 alkyl; ^R7 is hydrogen, _C1 - _C4 alkyl, or _C3 - _C6 -cycloalkyl, wherein the _C3 - _C6 -cycloalkyl is unsubstituted or substituted by 1 selected from halogen, _C1 - _C4 haloalkyl, cyano, _C1 - _C4 alkyl, or _C1 -C wherein ^B1 is selected from ^CR10 , and N; ^B2 is selected from ^CR11 , and N; ^R8 and ^R9 are independently selected from hydrogen, halogen, cyano, _C1 - _C4 alkyl ^, or _C1 - _C4 alkoxy; _R10 and ^R11 are independently selected from hydrogen, halogen, _C1 - _C3 alkyl, or C1- _C4 alkoxy; ^A1 is selected from ^CR12a , or N; ^A2 is selected from ^CR13a , or N; ^A3 is selected from ^CR14a , or N; ^R12a , ^R13a , and ^R14a are independently selected from hydrogen, halogen, _{C1 - C4} alkyl, _C3 - _C6 -cycloalkyl, or _C1 - _C4 halogenated alkyl; and Z ¹ is phenyl, 5- to 6-membered heteroaryl, or C ₃ -C ₆ -cycloalkyl, wherein the 5- or 6-membered heteroaryl includes 1 heteroatom selected from N and S, and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ halogenated alkyl, C ₁ -C ₄ halogenated alkoxy, or C ₁ -C ₄ alkoxy, and wherein the C ₃ -C ₆ -cycloalkyl is unsubstituted or substituted by 1 substituent selected from halogen or C ₁ -C ₄ alkyl.

In an embodiment of the present invention, the compound having formula (I) may be a compound having formula (II): (II) wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , B ¹ and B ² and Z ¹ are as defined for the compound of formula (I) according to the present invention, and A is selected from: in indicates a bond to a C(═O) group, and an asterisk (*) indicates a nitrogen having a bond to a Z ¹ group, and wherein R ^12a , R ^13a , and R ^14a are independently selected from hydrogen, halogen, C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, or C ₁ -C ₄ haloalkyl.

In one embodiment of the present invention, R ^12a , R ^13a and R ^14a are independently selected from hydrogen, halogen, methyl, cyclopropyl, or trifluoromethyl.

In another embodiment of the present invention, R ^12a , R ^13a and R ^14a are hydrogen.

Preferably, in the compound of formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and Z ¹ are as defined for the compound of formula (I) according to the present invention, A is selected from A1, A2, A3, A4, A5, A6, A7 or A8; R ¹² , R ¹³ and R ¹⁴ are hydrogen; B ¹ is CR ¹⁰ ; and B ² is CR ¹¹ ; wherein R ¹⁰ and R ¹¹ are as defined for the compound of formula (I) according to the present invention.

More preferably, in the compound of formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and Z ¹ are as defined for the compound of formula (I) according to the present invention, A is selected from A1, A2, A3, A4, A5, A6, A7 or A8; R ¹² , R ¹³ and R ¹⁴ are hydrogen; B ¹ is CH and B ² is CH.

In an embodiment of the present invention, in the compound having formula (II), A is selected from: in indicates a bond to a C(═O) group, and an asterisk (*) indicates a nitrogen with a bond to a Z ¹ group.

In a preferred embodiment of the present invention, in the compound having formula (II), A is selected from: in indicates a bond to a C(═O) group, and an asterisk (*) indicates a nitrogen with a bond to a Z ¹ group.

Preferably, in the compound of formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and Z ¹ are as defined for the compound of formula (I) according to the present invention, A is selected from A1, A2, or A3; B ¹ is CR ¹⁰ ; and B ² is CR ¹¹ ; wherein R ¹⁰ and R ¹¹ are as defined for the compound of formula (I) according to the present invention.

More preferably, in the compound of formula (II), ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 and ^Z1 are as defined for the compound of formula (I) according to the present invention, A is selected from A1, A2, or A3; ^B1 is CH; and ^B2 is CH.

Even more preferably, in the compound of formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and Z ¹ are as defined for the compound of formula (I) according to the invention, A is selected from A1, or A2; B ¹ is CH; and B ² is CH.

In an embodiment of the present invention, in the compound having formula (II), A is selected from: in indicates a bond to a C(═O) group, and an asterisk (*) indicates a nitrogen with a bond to a Z ¹ group.

In an embodiment of the present invention, the compound of formula (II) may be a compound of formula (II-A), wherein ^B1 and ^B2 are CH, and A is as defined for the compound of formula (II): (II-A) wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and Z ¹ are as defined for the compound of formula (I) according to the present invention.

In a variation of this embodiment of the invention, the compound of formula (II-A) may be a compound of formula (II-A1) wherein ^B1 and ^B2 are CH; ^R3 , ^R5 , ^R6 are hydrogen and A is as defined for compound (II): (II-A1) wherein R ¹ , R ² , R ⁴ , R ⁷ , R ⁸ , R ⁹ and Z ¹ are as defined for the compound of formula (I) according to the present invention.

Preferably, in the compounds of formula (II-A1) of the present invention, R ¹ is C ₁ -C ₄ alkyl, preferably methyl, ethyl or isopropyl; R ² is hydrogen, fluorine, chlorine or methyl; R ⁴ is hydrogen or methyl; R ⁷ is hydrogen, C ₁ -C ₄ alkyl or C ₃ -C ₆ -cycloalkyl; R ⁸ and R ⁹ are independently selected from hydrogen, halogen, cyano C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; A is as defined for compound (II), and Z ¹ is as defined for the compound of formula (I) according to the present invention.

Preferably, in the compounds of formula (II-A1) of the present invention, ^R1 is _C1 - _C4 alkyl, preferably methyl, ethyl or isopropyl; ^R2 is hydrogen, fluorine, chlorine or methyl; ^R4 is hydrogen or methyl; ^R7 is hydrogen, _C1 - _C4 alkyl or _C3 - _C6 -cycloalkyl; ^R8 and ^R9 are independently selected from hydrogen, halogen, cyano _C1 - _C4 alkyl or _C1 - _C4 alkoxy; A is selected from A1 or A2; and ^Z1 is as defined for the compounds of formula (I) according to the present invention.

Preferably, in the compound of formula (II-A1) of the present invention, ^R1 is _C1 - _C4 alkyl, preferably methyl, ethyl, or isopropyl; ^R2 is hydrogen, fluorine, chlorine, or methyl; ^R4 is hydrogen, or methyl; ^R7 is hydrogen, _C1 - _C4 alkyl, or _C3 - _C6 -cycloalkyl; ^R8 and ^R9 are independently selected from hydrogen, halogen, cyano _C1 - _C4 alkyl, or _C1 - _C4 alkoxy; A is selected from A1, or A2; and ^Z1 is phenyl, 5 to 6 membered heteroaryl, or _C3 - _C6 -cycloalkyl, wherein the 5- or 6-membered heteroaryl includes 1 heteroatom selected from N or S, and wherein the phenyl and the 5- to 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ halogenated alkyl, C ₁ -C ₄ halogenated alkoxy, or C ₁ -C ₄ alkoxy and wherein the C ₃ -C ₆ -cycloalkyl is unsubstituted or substituted by 1 substituent selected from halogen or C ₁ -C ₄ alkyl.

In an embodiment of the present invention, the compound having formula (II) may be a compound having formula (II-B), wherein ^B1 and ^B2 are CH, and wherein A is A1, (II-B) R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and Z ¹ are as defined for the compound of formula (I) according to the present invention.

In a variation of this embodiment of the invention, the compound of formula (II-B) may be a compound of formula (II-B1) wherein ^B1 and ^B2 are CH; ^R3 , ^R5 , ^R6 are hydrogen, and A is A1 (II-B1) wherein R ¹ , R ² , R ⁴ , R ⁷ , R ⁸ , R ⁹ and Z ¹ are as defined for the compound of formula (I) according to the present invention.

Preferably, in the compounds of formula (II-B1) of the present invention, ^R1 is _C1 - _C4 alkyl, preferably methyl, ethyl or isopropyl; ^R2 is hydrogen, fluorine, chlorine or methyl; ^R4 is hydrogen or methyl; ^R7 is hydrogen, _C1 - _C4 alkyl or _C3 - _C6 -cycloalkyl; ^R8 and ^R9 are independently selected from hydrogen, halogen, cyano _C1 - _C4 alkyl or _C1 - _C4 alkoxy; and ^Z1 is as defined for the compounds of formula (I) according to the present invention.

Preferably, in the compound of formula (II-B1) of the present invention, ^R1 is _C1 - _C4 alkyl, preferably methyl, ethyl, or isopropyl; ^R2 is hydrogen, fluorine, chlorine, or methyl; ^R4 is hydrogen or methyl; ^R7 is hydrogen, _C1 - _C4 alkyl, or _C3 - _C6 -cycloalkyl; ^R8 and ^R9 are independently selected from hydrogen, halogen, cyano _C1 - _C4 alkyl, or _C1 - _C4 alkoxy; and ^Z1 is phenyl, 5 to 6 membered heteroaryl, or _C3 - _C6 -cycloalkyl, wherein the 5- or 6-membered heteroaryl includes 1 heteroatom selected from N or S, and wherein the phenyl and the 5- to 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ halogenated alkyl, C ₁ -C ₄ halogenated alkoxy, or C ₁ -C ₄ alkoxy and wherein the C ₃ -C ₆ -cycloalkyl is unsubstituted or substituted by 1 substituent selected from halogen or C ₁ -C ₄ alkyl.

In an embodiment of the present invention, the compound having formula (II) may be a compound having formula (II-C), wherein ^B1 and ^B2 are CH; and wherein A is A2: (II-C) R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and Z ¹ are as defined for the compound of formula (I) according to the present invention.

In a variation of this embodiment of the invention, the compound of formula (II-C) may be a compound of formula (II-C1) wherein ^B1 and ^B2 are CH; ^R3 , ^R5 , ^R6 are hydrogen; and A is A2 (II-C1) wherein R ¹ , R ² , R ⁴ , R ⁷ , R ⁸ , R ⁹ and Z ¹ are as defined for the compound of formula (I) according to the present invention.

Preferably, in the compounds of formula (II-C1) of the present invention, R ¹ is C ₁ -C ₄ alkyl, preferably methyl, ethyl or isopropyl; R ² is hydrogen, fluorine, chlorine or methyl; R ⁴ is hydrogen or methyl; R ⁷ is hydrogen, C ₁ -C ₄ alkyl or C ₃ -C ₆ -cycloalkyl; R ⁸ and R ⁹ are independently selected from hydrogen, halogen, cyano C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; and Z ¹ is as defined for the compounds of formula (I) according to the present invention.

Preferably, in the compound of formula (II-C1) of the present invention, ^R1 is _C1 - _C4 alkyl, preferably methyl, ethyl, or isopropyl; ^R2 is hydrogen, fluorine, chlorine, or methyl; ^R4 is hydrogen or methyl; ^R7 is hydrogen, _C1 - _C4 alkyl, or _C3 - _C6 -cycloalkyl; ^R8 and ^R9 are independently selected from hydrogen, halogen, cyano _C1 - _C4 alkyl, or _C1 - _C4 alkoxy; and ^Z1 is phenyl, 5 to 6 membered heteroaryl, or _C3 - _C6 -cycloalkyl, wherein the 5- or 6-membered heteroaryl includes 1 heteroatom selected from N or S, and wherein the phenyl and the 5- to 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ halogenated alkyl, C ₁ -C ₄ halogenated alkoxy, or C ₁ -C ₄ alkoxy and wherein the C ₃ -C ₆ -cycloalkyl is unsubstituted or substituted by 1 substituent selected from halogen or C ₁ -C ₄ alkyl.

In an embodiment of the present invention, the compound having formula (II) may be a compound having formula (II-D), wherein ^B1 and ^B2 are CH, and wherein A is A3: (II-D) R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and Z ¹ are as defined for the compound of formula (I) according to the present invention.

In a variation of this embodiment of the invention, the compound of formula (II-D) may be a compound of formula (II-D1) wherein ^B1 and ^B2 are CH; ^R3 , ^R5 , ^R6 are hydrogen; and A is A3 (II-D1) wherein R ¹ , R ² , R ⁴ , R ⁷ , R ⁸ , R ⁹ and Z ¹ are as defined for the compound of formula (I) according to the present invention.

Preferably, in the compounds of formula (II-D1) of the present invention, R ¹ is C ₁ -C ₄ alkyl, preferably methyl, ethyl, or isopropyl; R ² is hydrogen, fluorine, chlorine, or methyl; R ⁴ is hydrogen or methyl; R ⁷ is hydrogen, C ₁ -C ₄ alkyl, or C ₃ -C ₆ -cycloalkyl; R ⁸ and R ⁹ are independently selected from hydrogen, halogen, cyano C ₁ -C ₄ alkyl, or C ₁ -C ₄ alkoxy; and Z ¹ is as defined for the compounds of formula (I) according to the present invention.

Preferably, in the compound of formula (II-D1) of the present invention, ^R1 is _C1 - _C4 alkyl, preferably methyl, ethyl, or isopropyl; ^R2 is hydrogen, fluorine, chlorine, or methyl; ^R4 is hydrogen or methyl; ^R7 is hydrogen, _C1 - _C4 alkyl, or _C3 - _C6 -cycloalkyl; ^R8 and ^R9 are independently selected from hydrogen, halogen, cyano _C1 - _C4 alkyl, or _C1 - _C4 alkoxy; and ^Z1 is phenyl, 5 to 6 membered heteroaryl, or _C3 - _C6 -cycloalkyl, wherein the 5- or 6-membered heteroaryl includes 1 heteroatom independently selected from N or S, and wherein the phenyl and the 5- to 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ halogenated alkyl, C ₁ -C ₄ halogenated alkoxy, or C ₁ -C ₄ alkoxy and wherein the C ₃ -C ₆ -cycloalkyl is unsubstituted or substituted by 1 substituent selected from halogen or C ₁ -C ₄ alkyl.

The following intermediates are novel and themselves constitute another aspect of the present invention.

According to the sixth aspect of the present invention, there is provided an intermediate compound having the formula (III) or a salt thereof: (III), wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , B ¹ and B ² are as defined for the compound of formula (I) according to the present invention.

The intermediate compounds of formula (III) have the same definitions of ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^B1 and ^B2 as for the compounds of formula (I) according to the present invention and their corresponding preferred cases.

The presence of one or more possible asymmetric carbon atoms in the compounds of formula (III) according to the present invention means that the compounds may exist in the form of chiral isomers, i.e. mirror isomers or non-mirror isomers.

According to a seventh aspect of the present invention, there is provided an intermediate compound having the formula (IV): (IV) wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , B ¹ and B ² are as defined for the compound of formula (I) according to the present invention.

The intermediate compounds of formula (IV) have the same definitions of ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^B1 and ^B2 as for the compounds of formula (I) according to the present invention and their corresponding preferred cases.

The presence of one or more possible asymmetric carbon atoms in the compounds of formula (IV) according to the present invention means that the compounds may exist in the form of chiral isomers, i.e. mirror isomers or non-mirror isomers.

According to an eighth aspect of the present invention, there is provided an intermediate compound having the formula (IIb) or a salt thereof: (IIb) wherein R ⁰ is C ₁ -C ₆ alkyl and wherein A ¹ , A ² , A ³ and Z ¹ are as defined for the compound of formula (I) according to the present invention.

The intermediate compounds of formula (IIb) have the same definitions of A ¹ , A ² , A ³ and Z ¹ as for the compounds of formula (I) according to the present invention and their corresponding preferred embodiments.

In one embodiment, R ⁰ is C ₁ -C ₄ alkyl, A ¹ , A ² , A ³ are N and Z ¹ is as defined for the compound of formula (I) according to the present invention.

In one embodiment, the compound having formula (IIb) may be a compound having formula (IIb-1): (IIb-1) wherein Z ¹ is as defined for the compound of formula (I) according to the present invention, R ⁰ is as defined for the compound of formula (IIb) and A is selected from A1, A2, A3, A4, A5, A6, A7, or A8 as defined for the compound of formula (II).

Preferably, in the compound having formula (IIb-1), A is selected from: in indicates a bond to a C(═O) group and an asterisk (*) indicates a nitrogen with a bond to a Z ¹ group, wherein Z ¹ is as defined for the compound of formula (I) according to the present invention and R ⁰ is as defined for the compound of formula (IIb).

More preferably, in compounds of formula (IIb-1), A is selected from A1 or A2, wherein ^Z1 is as defined for compounds of formula (I) according to the present invention and ^R0 is as defined for compounds of formula (IIb).

In another embodiment of the invention, in the compound of formula (IIb-1), A is A1, wherein ^Z1 is as defined for the compound of formula (I) according to the invention and ^R0 is as defined for the compound of formula (IIb).

The presence of one or more possible asymmetric carbon atoms in the compounds of formula (I), (II), (II-A), (II-A1), (II-B), (II-B1), (II-C), (II-C1), (II-D) or (II-D1) according to the present invention or in any of the compounds selected from Tables A-1 to A-24 or listed in Table P (below) means that the compounds may exist in the form of chiral isomers, i.e., mirror isomers or non-mirror isomers.

More preferably, the compound of formula (I) according to the present invention is selected from the compounds listed in any one of Tables A-1 to A-24.

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

In one embodiment of the present invention, the compound having formula (I) is selected from [1-(2-fluorophenyl)pyrazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(2,4-difluorophenyl)pyrazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(2-fluorophenyl)pyrazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2,5-dimethyl-1-(2,2,2-trifluoroethyl)pyrrol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, (1,5-dimethylpyrazol-3-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, (2-phenyltriazol-4-yl)-[4-(1,3,5-trimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, (1-phenyltriazol-4-yl)-[4-(1,3,5-trimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(2,4-difluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(4-fluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(1-phenylimidazol-4-yl)methanone, [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(1-phenyltriazol-4-yl)methanone, [2,5-dimethyl-1-(5-methylisoquinol-3-yl)pyrrol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, (1-benzyltriazol-4-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone, (1-isopropyltriazol-4-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(1-phenylpyrazol-3-yl)methanone, [1-(4-fluorophenyl)-5-methyl-triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2-(4-fluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(1-phenyl-1,2,4-triazol-3-yl)methanone, (1-tributylimidazol-4-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(4-fluorophenyl)pyrazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, (5-cyclopropyl-1-methyl-pyrazol-3-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(3-fluoro-2-pyridyl)-1,2,4-triazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(3-fluorophenyl)-3-methyl-pyrazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, (5-benzyl-1-methyl-pyrazol-3-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-[1-[5-(trifluoromethyl)-2-pyridyl]triazol-4-yl]methanone, [1-(2-methoxyphenyl)imidazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, (5-cyclopropyl-1-ethyl-pyrazol-3-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(2,6-difluorophenyl)pyrazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(3,4-difluorophenyl)pyrazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone, [1-(2,4-difluorophenyl)-1,2,4-triazol-3-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2-(2,4-difluorophenyl)tetrazol-5-yl]-[6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone, [(1R,4R)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone, [(1S,4S)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone, [2-(2,4-difluorophenyl)tetrazol-5-yl]-[(1S,4S)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2-(2,4-difluorophenyl)tetrazol-5-yl]-[(1R,4R)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2-(2,4-difluorophenyl)triazol-4-yl]-[rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(2,4-difluorophenyl)triazol-4-yl]-[rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone, or [2-(2,4-difluorophenyl)tetrazol-5-yl]-[rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone.

In a preferred embodiment of the present invention, the compound having formula (I) is selected from: [(1S,4S)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[1-(2,4-difluorophenyl)triazol-4-yl]methanone, [(1S,4S)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[1-(3,5-difluoro-2-pyridyl)triazol-4-yl]methanone, [1-(3,5-difluoro-2-pyridyl)triazol-4-yl]-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2-(2,4-difluorophenyl)tetrazol-5-yl]-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(3,5-difluoro-2-pyridyl)triazol-4-yl]-[rac-(1S,4S)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [1-(3,5-difluoro-2-pyridyl)triazol-4-yl]-[(1S,4S)-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [(1S,4S)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[2-(2,4-difluorophenyl)tetrazol-5-yl]methanone, [1-(2,4-difluorophenyl)triazol-4-yl]-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazolyl-5-yl)methanone, [2-(2,4-difluorophenyl)tetrazolyl-5-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazolyl-5-yl)methanone, [(1S,4S)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone, [1-(2,4-difluorophenyl)triazol-4-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2-(2,4-difluorophenyl)tetrazol-5-yl]-[6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2-(2,4-difluorophenyl)tetrazol-5-yl]-[(1S,4S)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [(1R,4R)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone, [1-(3,5-difluoro-2-pyridyl)triazol-4-yl]-[(1R,4R)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [(1R,4R)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[1-(2,4-difluorophenyl)triazol-4-yl]methanone, (1-phenyltriazol-4-yl)-[4-(1,3,5-trimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(1-phenyltriazol-4-yl)methanone, [2-(4-fluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [2-(2,4-difluorophenyl)triazol-4-yl]-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone, [(1S,4S)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[2-(2,4-difluorophenyl)triazol-4-yl]methanone, or [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone.

Compounds of formula (I) according to the present invention can be prepared as shown in the following schemes, wherein, unless otherwise stated, each variable is defined as above for compounds of formula (I).

Compounds of formula (I) according to the present invention can be prepared as shown in the following Schemes 1 to 19, wherein, unless otherwise stated, each variable is defined as above for compounds of formula (I).

In particular, compounds of formula (I) wherein R ⁴ and R ⁶ are hydrogen and R ⁵ is hydrogen or methyl can be prepared as shown in the following schemes, wherein, unless otherwise stated, each variable is defined as above for compounds of formula (I).

In any of the following Schemes 1 to 19, the presence of one or more possible asymmetric carbon atoms in the compounds of formula (I) according to the present invention means that these compounds can exist in the form of chiral isomers, i.e., mirror isomers or non-mirror isomers.

Compounds of formula (I) can be prepared by methods known to those skilled in the art. More specifically, compounds of formula (I) can be prepared by reacting a compound of formula (III) or a salt thereof (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , B ¹ and B ² are as defined above for compounds of formula (I)) with a compound of formula (II) (wherein A ¹ , A ² , A ³ and Z ¹ are as defined above for compounds of formula (I)). This reaction is shown in Scheme 1. Process 1

In Scheme 1 , a compound of formula (II) wherein ^A1 , ^A2 , A3 and Z1 are as defined above for the compound of formula (I) is activated to a compound of formula (IIa) by a method known to ^those skilled in the art and described, for example, in Tetrahedron, ^{2005, 61} (46), 10827-10852 . For example, a compound of formula (IIa) wherein ^X0 is a halogen is formed by treating the compound of formula (II) with, for example, oxalyl chloride or thionyl chloride in the presence of a catalytic amount of N,N-dimethylformamide (DMF) in an inert solvent such as dichloromethane or tetrahydrofuran (THF) at a temperature between 20°C and 100°C, preferably 25°C. A compound of formula (IIa) is treated with a compound of formula (III) (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , B ¹ and B ² are as defined above for the compound of formula (I)) in the presence of a base such as triethylamine or pyridine, optionally to produce a compound of formula (I). Alternatively, compounds of formula (I) can be prepared by treating compounds of formula ( _II ) with dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) or 1-[bis ₍ dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium-3-oxide hexafluorophosphate (HATU) in an inert solvent such as pyridine, DMF, acetonitrile, CH2Cl2 or THF, optionally in the presence of a base such as triethylamine at a temperature between 30°C and 180°C to give activated compounds of formula (IIa) (wherein ^X0 is ^G01 , ^G02 or ^G03 as described below). Finally, compounds of formula (II) can also be activated by reaction with a coupling agent such as propanephosphonic anhydride (T3P) to provide compounds of formula (IIa), wherein ^X0 is ^G04 as described below, as described, for example, in Synthesis 2013 , 45, 1569. Further reaction with an amine (or a salt thereof ) of a compound of formula (III) gives a compound of formula (I).

Compounds of formula (II) can be prepared from compounds of formula (IIb) (wherein ^A1 , ^A2 , ^A3 are N and ^Z1 is as described in formula (I) and ^R0 is _C1 - _C4 alkyl) by ester hydrolysis. A variety of conditions can be used, such as aqueous sodium hydroxide, or lithium hydroxide and an organic water-soluble solvent such as THF, or dimethoxyethane, or methanol, or ethanol. Such ester hydrolysis is well known to those skilled in the art. Compounds of formula (IIb) can also be directly converted to compounds of formula (I) by reacting compounds of formula (IIb) with compounds of formula (III) in the presence of trimethylaluminum or trimethylaluminum-DABCO complex in an inert solvent such as toluene or dichloromethane. Such reactions have been reported in the literature (see Tetrahedron Lett. 1977 , 4171-4174, and Tetrahedron Lett . 2006 , 5767-5769 , and references cited therein). Compounds of formula (II) and (IIb) are commercially available or can be synthesized as described below .

Compounds of formula (IIIa) wherein ^R4 and ^R6 are hydrogen, ^R5 is hydrogen or methyl and ^R1 , ^R2 , ^R3 , ^R7 , ^R8 , ^R9 , ^B1 and ^B2 are as defined above for compounds of formula (I) can be prepared by those skilled in the art according to known methods.

For example, a compound of formula (IIIa) wherein ^R4 and ^R6 are hydrogen, ^R5 is hydrogen or methyl and ^R1 , ^R2 , ^R3 , ^R7 , ^R8 , ^R9 , ^B1 and ^B2 are as defined above for the compound of formula (I) can be prepared from a compound of formula (IVa) wherein ^R4 and ^R6 are hydrogen, ^R5 is hydrogen or methyl and ^R1 , ^R2 , ^R3 , ^R7 , ^R8 , ^R9 , ^B1 and ^B2 are as defined above for the compound of formula (I) by treatment with a reducing agent (e.g. _NaBH3CN ) and an acid (e.g. hydrochloric acid or acetic acid) in a protic solvent (e.g. methanol or ethanol, etc.). Such reactions are well known in the literature and similar reactions have been described , for example, in Deng, Zeping et al., CN 103772278 and Synthesis ( 1979 ), 4 , 281-3. Alternatively, compounds of formula (IIIa) can be prepared from compounds of formula (IVa) by reduction with hydrogen and a suitable ligand (e.g., diphosphine [1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp) or 1,4-bis(diphenylphosphino)butane (dppb)]) in the presence of a suitable metal catalyst (e.g., Pd, Ir, Rh). Similar reactions have been reported in, for example , Reaction Kinetics and Catalysis Letters 2007 , 92 , 99-104. This reaction is shown in Scheme 2. Process 2

Alternatively, compounds of formula (IIIa) can be prepared as shown in Scheme 3.

As shown in Scheme 3, compounds of formula (IIIb) (wherein R4, R6 and R7 are hydrogen, ^R5 is hydrogen or methyl and R1, R2, R3, R8, R9, B1 _{and B2} are as defined above for compounds of formula (I)) can be converted to compounds of formula (V) (wherein ^R4 , ^R6 and ^R7 are hydrogen, ^R5 is hydrogen or methyl and ^R1 , ^R2 , _R3 , ^R8 , ^R9 , ^B1 and ^B2 are as defined above for compounds of formula (I)) by methods known ^to those skilled in the art and by those methods described in Scheme ^{1 by} treating the compound of formula ( ^IIIb ) with a compound of formula ( ^{VI) (wherein X0 is} a ^halogen , such as a halogen, and R0 is ^{a C1 - C6} alkyl). ¹ and ^B2 are as defined above for compounds of formula (I). Alternatively, compounds of formula (V) may be prepared by treatment with an anhydride of formula (R0CO)2O wherein R0 is ^C1 - _C6 alkyl in an inert solvent such as dichloromethane, THF or ₂ -methyl-THF, optionally in the presence of a base such as triethylamine or dimethylaminopyridine, at a temperature between ⁰ °C and ₆₀ °C. The compound of formula (V) is then metallated with a base (e.g., an alkyl metal base such as tertiary butyl lithium) and an additive (e.g., N , N , N ′, N′ -tetramethylethylenediamine (TMEDA)) in an inert polar solvent (e.g., THF or 2-methyl-THF) at low temperature (e.g., -78°C to room temperature). The anion of formula (V) formed under such conditions is subsequently treated with an electrophile of formula ^RX - ^X0 (wherein ^X0 is as previously defined and ^RX is _C1 - _C4 alkyl, _C1 - _C4 alkylcarbonyl, _C1 - _C4 alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, _C1 - _C4 alkylaminocarbonyl, di( _C1 - _C4 alkylamino)carbonyl or _C3 - _C6 cycloalkyl, wherein said _C3 - _C6 -cycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, _C1 - _C4 alkyl, _C1 - _C4 haloalkyl and _C1 - _C4 alkoxy) to afford a compound of formula (Va) (wherein ^R4 and ^R6 are hydrogen, R ^R5 is hydrogen or methyl, ^R0 is _C1 - _C6 alkyl and ^R1 , ^R2 , ^R3 , ^R7 , ^R8 , ^R9 , ^B1 and ^B2 are as defined above for the compound of formula (I). This reaction is shown in Scheme 3. Process 3

Compounds of formula (Va) can be converted to compounds of formula (IIIa) (wherein ^R4 and ^R6 are hydrogen, ^R5 is hydrogen or methyl and ^R1 , ^R2 , ^R3 , ^R7 , ^R8 , ^R9 , ^B1 and ^B2 are as defined above for compounds of formula (I)) by methods known to those skilled in the art. For example, compounds of formula (Va) (wherein ^R0 is tertiary butyl) can be treated with an organic or inorganic acid (such as trifluoroacetic acid or HCl) to obtain compounds of formula (IIIa). This reaction is shown in Scheme 4. Process 4

The compound of formula (IVa) (wherein ^R4 and ^R6 are hydrogen, ^R5 is hydrogen or methyl and ^R1 , ^R2 , ^R3 , ^R7 , ^R8 , ^R9 , ^B1 and ^B2 are as defined above for the compound of formula (I)) can be prepared by reacting a compound of formula (VIII) (wherein ^R1 , ^R2 and ^R3 are as defined above for the compound of formula (I) and ^X0 is a halogen, preferably chlorine, bromine or iodine) with a compound of formula (VII) (wherein ^R5 is hydrogen or methyl and ^R7 , ^R8 , ^R9 , ^B1 and ^B2 are as defined above for the compound of formula (I) The compounds defined by (defined by) are prepared by means of a C—C bond forming reaction typically reacting under palladium-catalyzed (alternatively nickel-catalyzed) cross-coupling conditions. This reaction is shown in Scheme 5. Process 5

The Suzuki-Miyaura cross-coupling reaction between a compound of formula (VIII) and a compound of formula (VII) is well known to those skilled in the art and is generally carried out in the presence of a palladium catalyst (e.g., tetrakis(triphenylphosphine)-palladium(0) or [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex) and a base (e.g., sodium carbonate or potassium carbonate) in a solvent (e.g., N,N-dimethylformamide, dioxane or a dioxane-water mixture) at a temperature between room temperature and 160° C., optionally under microwave heating conditions, and preferably under an inert atmosphere. Such reactions have been reviewed, for example, in the following literature: J. Organomet. Chem . , 1999 , 576, 147-168. Those skilled in the art will also recognize that the reaction can be reversed, i.e., by reacting a compound of formula (X) (wherein R ¹ , R ² and R ³ are as defined above for compounds of formula (I)) with a compound of formula (IX) (wherein R ⁵ is hydrogen or methyl, R ⁷ , R ⁸ , R ⁹ , B ¹ and B ² are as defined above for compounds of formula (I) and X ⁰ is a halogen, preferably chloro, bromo or iodo) to provide a compound of formula (IVa) (wherein R ⁴ and R ⁶ are hydrogen, R ⁵ is hydrogen or methyl and R ¹ , R ² , R ³ , R ⁷ , R ⁸ , R ⁹ , B ¹ and B ² are as defined above for compounds of formula (I)). This reaction is shown in Scheme 6. Process 6

Alternative cross-coupling chemistry, i.e., C—H activation, can also be used to prepare compounds of formula (IVa) (wherein R ⁴ and R ⁶ are hydrogen, R ⁵ is hydrogen or methyl and R ¹ , R ² , R ³ , R ⁷ , R ⁸ , R ⁹ , B ¹ and B ² are as defined above for compounds of formula (I)) (Scheme 7). Process 7

As shown in Scheme 7, a compound of formula (IX) (wherein R ⁵ is hydrogen or methyl, R ⁷ , R ⁸ , R ⁹ , B ¹ and B ² are as defined above for the compound of formula (I), and X ⁰ is a halogen, preferably chlorine, bromine or iodine) and a compound of formula (XI) (wherein R ¹ , R ² and R ³ are as defined above for the compound of formula (I)) are reacted in the presence of a palladium catalyst (typically palladium acetate Pd(OAc) ₂ ), in the presence of a suitable ligand (e.g. 1,10-phenanthroline), in the presence of a base (e.g. cesium carbonate or potassium carbonate), in an inert solvent (e.g. chlorobenzene, toluene or xylene), at a temperature between room temperature and 180°C, optionally under microwave heating conditions, preferably under an inert atmosphere. Similar reactions have been reported in the literature, for example in Chemical Science [ Chemical Science ] 2013 , 4 , 2374-2379.

Alternatively, compounds of formula (III) can be prepared from compounds of formula (XVI) (Scheme 8). Process 8

As shown in Scheme 8, compounds of formula (III) can be prepared by one skilled in the art by carbamate deprotection of compounds of formula (XVI) (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , B ¹ and B ² are as defined above for compounds of formula (I) and R ⁰¹ can be a member of a common carbamate protecting group substituent, such as methyl, tert-butyl, allyl, 2,2,2-trichloroethyl or benzyl). For example, when R ⁰¹ is methyl, a suitable solvent (such as dichloromethane) and a suitable reagent (such as iodotrimethylsilane) can be used to obtain the product by heating at a temperature between room temperature and 200° C., preferably between 20° C. and the boiling point of the reaction mixture, as described, for example, in J. Am. Chem. Soc. [ American Chemical Society Journal ] 1992 , 114, 5959. The compound of formula (III) thus obtained is converted into a compound of formula (I) (Scheme 1).

Compounds of formula (XVI) (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , B ¹ and B ² are as defined above for compounds of formula (I) and wherein R ⁰¹ is as described above) can be prepared by reacting an aldehyde (including formaldehyde in its various forms) of formula (XV) (wherein R ⁷ is as defined above for compounds of formula (I)) with a compound of formula (XIV) (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , B ¹ and B ² are as defined above for compounds of formula (I) and wherein R 01 is as described above ⁰¹ is as described above) by combination with an acid in a suitable solvent, for example as described in Tetrahedron 1987 , 43 , 439 (Scheme 9). Process 9

When a compound of formula (XIV) (wherein R ¹ , R ² , R ³ , R ⁸ , R ⁹ are as described in formula (I), B ¹ is CR ¹⁰ , B ² is CR ¹¹ , and wherein R ⁰¹ is as described above), i.e., a compound of formula (XIVa) is reacted with a compound of formula (XVa) (wherein R ⁷ is C ₁ -C ₄ alkyl) to give a racemic compound of formula rac - cis- ( XVIa) having a cis -relationship of the pyrazole ring and the R ⁷ substituent, the Pict-Spengler reaction is stereospecific (Scheme 10). Process 10

A further consequence of the stereospecific formation of compounds of formula racemic - cis- ( XVIa) in the Pict-Spengler reaction is that chiral compounds of formula (XVIa) can be obtained if the synthesis starts with chemically pure compounds of formula (XIVa). This is illustrated in Scheme 11 for compounds of formula (XIV) wherein R ¹ , R ² are methyl, R ⁸ , R ⁹ , R ¹¹ , and R11 are hydrogen, and R ⁰ is methyl, i.e. ( S )-(XIVb) and ( R )-(XIVb), which after Pict-Spengler reaction with (XV) wherein R ⁷ is methyl, give (S,S) -cis- (XVIb) and (R,R) -cis- (XVIb), respectively. Process 11

Compounds of formula (XIV) (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , B ¹ and B ² are as defined above for compounds of formula (I) and wherein R ⁰¹ is as described above) can be optionally reacted with an amine of formula (XIII) (wherein R ¹ , R ² , R ₃ , R ⁴ , R 5 , R 6 , R 8 , R ⁹ , B ¹ and B ² are as defined above for compounds of formula (I) in the presence of a base such as ^{triethylamine} or pyridine in a suitable solvent such as dichloromethane at a temperature between -20°C and the boiling point of the ^{mixture .} The compounds are prepared by reaction of a compound (defined in the formula (a)) with a suitable protecting agent (such as methyl chloroformate ) , as described, for example, in Org. Biomol. Chem. 2016 14, 6853 (Scheme 12). Process 12

Compounds of formula (XIII) or salts thereof (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , B ¹ and B ² are as defined above for compounds of formula (I)) can be prepared by one skilled in the art by reaction of a nitrile of formula (XII) (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁸ , R ⁹ , B ¹ and B ² are as defined above for compounds of formula (I)) with a suitable nucleophile (such as (dimethyl sulfide) dihydroborane (BMS)) in a suitable aprotic solvent (such as tetrahydrofuran), for example as described in J. Org. Chem. [ Journal of Organic Chemistry ] 1981 , 47, 3153. Nitriles with formula (XII) can also be reduced to primary amines with hydrogen in the presence of a catalyst (such as a platinum salt or nickel Raeder) in the presence of a hydrogen donor (such as ethanol or methanol). Many other conditions for reducing nitrile to primary amines are well known to those familiar with the art. Alternatively, Grignard reagents R ⁵ MgBr or R ⁶ MgBr (wherein R ⁵ and R ⁶ are as defined above for compounds with formula (I)) can be added sequentially or simultaneously as nucleophiles to compounds with formula (XII) to allow the preparation of more highly substituted amines with formula (XIII). Such Grignard additions to nitriles are carried out in the presence of a Lewis acid such as Ti(O- ^iPr ) ₄ in an inert solvent such as diethyl ether, tert-butyl methyl ether and cyclopentyl methyl ether (see Synlett [ Synthesis Letters ] ( 2007 ), (4), 652-654). This reaction is shown in Scheme 13. Process 13

Compounds of formula (XII) (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁸ , R ⁹ , B ¹ and B ² are as defined above for compounds of formula (I)) can be prepared by those skilled in the art according to known methods. More specifically, compounds of formula (XII) and intermediates thereof can be prepared from compounds of formula (XVII) as shown in Scheme 14. Process 14

For example, compounds of formula (XII) (wherein R ¹ , R ² , R ³ , R ⁸ , R ⁹ , B ¹ and B ² are as defined above for compounds of formula (I) and R ⁴ is not hydrogen) can be prepared by one skilled in the art by deprotonating compounds of formula (XIIa) (wherein R 1 , R ² , R ³ , R ⁸ , R 9 , B ₁ and B 2 are as defined above for compounds of formula (I)) using a strong base such as n-butyl lithium or sodium hydride in an inert solvent such as tetrahydrofuran ^at low temperature followed by addition of a suitable alkylating agent R ₄ ^—X (wherein R ⁴ is C ¹ -C ⁴ alkyl and ^X is a halogen) such as iodomethane.

Compounds of formula (XIIa) wherein R ⁴ is hydrogen and R ¹ , R ² , R ³ , R ⁸ , R ⁹ , B ¹ and B ² are as defined above for compounds of formula (I) can be prepared from alcohols of formula (XVII) by treatment with cyanotrimethylsilane (TMSCN) in the presence of a base such as lithium carbonate in a non-polar solvent such as dichloromethane at a temperature between 0° C. and the boiling point of the reaction mixture. Such transformations are well known in the literature under various conditions, for example as described in Org. Lett [ Organic Letters ] 2008 10 , 4570 and references therein. This reaction is shown in Scheme 14.

further synthesis of a compound of formula (III) (wherein ^{B1 is CR10, B2 is CR11, R1a is C1-C4 alkyl, R2a is hydrogen ,} _{halogen or} ^{C1 -C4 alkyl, R3 is hydrogen, R4a, R5a, R6a, R7a} _{are hydrogen} ^{or C1 - C4} _{alkyl and} ^R8 , ^R9 , ^R10 and ^R11 are as previously defined under formula (I)), i.e. a compound of formula (IIIc); (IIIc) can also be obtained by treating a compound having formula (XVIII) (XVIII) (wherein R ^1a is C ₁ -C ₄ alkyl, R ² is hydrogen, halogen, or C ₁ -C ₄ alkyl, R ^4a , R ^5a , R ^6a , R ^7a are hydrogen or C ₁ -C ₄ alkyl, and R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are as previously defined under formula (I)) is treated with a strong acid (e.g., sulfuric acid, hydrochloric acid, hydrobromic acid, trifluoroacetic acid, trifluoromethanesulfonic acid (trifllic), or methanesulfonic acid, etc.), or a Lewis acid (e.g., aluminum trichloride, or bismuth (III) trifluoromethanesulfonate), in an inert solvent (e.g., chlorobenzene, nitrobenzene) at a temperature between 0°C and 180°C to produce a compound of formula (IIIc). As described above, these compounds are converted to compounds of formula (I). Those skilled in the art will recognize that such cyclization can be accomplished via intermediates such as compounds of formula (XIX), (XIX) and (when R ^4a is methyl), a compound having the formula (XX) (XX) and wherein the substituents R ^1a , R ^2a , R ^3a , R ^4a , R ^5a , R ^6a , R ^7a , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ in the compounds are as previously defined). Depending on the reaction conditions, the intermediates can be isolated and/or further directly converted into compounds of formula (IIIc). Those skilled in the art will also recognize that when R ⁷ is C ₁ -C ₄ alkyl, a mixture of non-mirror isomers racemic- ( cis -IIIc) and racemic- ( trans -IIIc) can be obtained, the ratio of which can be controlled to direct the preferential formation of one isomer relative to the other isomer (Scheme 15). Process 15

Compounds (XVIII), (XIX), and (XX) can be prepared as shown in Scheme 16 below and as described in the Experimental Section. Process 16

As shown in Scheme 16, benzylamine of formula (XXI) is used to alkylate a compound of formula (XXII) in the presence of a base such as triethylamine ( _Et3N ) in an inert solvent such as DMF or DMA. The compound (XXIII) thus obtained can be isolated or directly treated in situ with BOC-anhydride to give a compound of formula (XXIV). The compound of formula XXIV can be reduced with a hydride source such as NaBH4 in MeOH/THF to give the target molecule (XVIIIb), which can then be cyclized with, for example, camphorsulfonic acid in EtOAc to give a compound of formula (XIXb). Alternatively, a compound of formula (XXIV) can be reacted with a Grignard reagent R ⁴ MgBr in an inert ethereal solvent such as THF to give a compound of formula (XVIIIa), which can be cyclized with camphorsulfonic acid in, for example, EtOAc to give a compound of formula (XIXa). In compounds (XIX) and (XVIII), R ^1a is C ₁ -C ₄ alkyl, R ^2a is hydrogen, halogen, or C ₁ -C ₄ alkyl, R ^4a is hydrogen or C ₁ -C ₄ alkyl, R ^5a , R ^6a and R ^7a are hydrogen or C ₁ -C ₄ alkyl, and R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are as previously defined under formula (I).

An additional aspect of the Friedel-Crafts chemistry should be noted. If the chemistry is carried out starting with a chiral amine (XXI), i.e. R ^7a is C ₁ -C ₄ alkyl, the stereochemistry is retained in the final compound having formula (I). This is shown in the following Scheme 17 for when R ^7a is methyl: Process 17

Compounds of formula (XVII) can be prepared by methods known to those skilled in the art. Compounds of formula (XXI) and (XXII) are easily prepared by those skilled in the art or can be purchased.

Compounds of formula II are commercially available or can be synthesized as described below .

Compounds of formula (IIb) (wherein ^A1 , ^A2 , ^A3 are N and ^Z1 is as defined for the compounds of formula (I) of the present invention, and wherein ^R0 is _C1 - _C6 alkyl) i.e. compounds of formula (IIba) (IIba) can be prepared by treating a diazonium salt of formula (XXV) (XXV) wherein Z ¹ is as defined for the compounds of formula (I) of the present invention and Y ^- is a relative ion depending on the conditions in which the diazotization step is carried out, for example Cl ^- or BF ₄ ^- , and a compound of formula (XXVI) (XXVI) wherein R ⁰ is C ₁ -C ₆ alkyl. The reaction can be catalyzed by various silver salts (preferably silver salts such as silver acetate) and carried out in various solvents (e.g. THF, DMF or toluene or mixtures thereof), usually at a temperature between 0°C and 25°C, in the presence of at least one equivalent of a base (e.g. sodium carbonate). Such dipolar [3 + 2] cycloadditions are highly site-selective and are described, for example , in Tetrahedron 2020 , 76(14), 131063. Compounds of formula (XXV) as defined above can be prepared from primary amines of formula (XXVII) by reaction with a diazotizing agent (e.g. a nitrite, e.g. sodium nitrite). The solvent may be an aqueous acid solution, for example dilute hydrochloric acid or tetrafluoroboric acid. The relative ion ^Y- is defined by the acid used. Diazotization reactions are commonly used in organic synthesis, even on an industrial scale, and are known to those skilled in the art.

In order to reduce the risk of decomposition of the intermediate of formula (XXV), the diazotization step and the cycloaddition step can be performed sequentially without isolating (XXV). This variant is also described in Tetrahedron 2020 , 76(14), 131063 (Scheme 18). Process 18

Compounds of formula (XXVII) are commercially available, as are compounds of formula (XXVI) (eg R ⁰ is methyl, CAS [6832-16-2]).

Very similarly, a compound of formula (IIba) wherein A ¹ , A ² , A ³ are N and Z ¹ is as described in formula (I) can be prepared by reacting a compound of formula (XXVIII): wherein R ⁰ is C ₁ -C ₆ alkyl and Ar ¹ is phenyl or p-tolyl, reacts with a compound of formula (XXV) in the presence of a base (e.g. pyridine) at a temperature of from -50°C to 50°C to obtain a compound of formula (IIba). Such reactions have a good precedence in the literature, for example, Chem. Comm. [ Chemical Communication ] 2017 , 53(69), 9620-9623, Ang. Chem. Int. Ed . [ German Journal of Applied Chemistry ] 2017 , 56(47), 15044-15048 and J. Am. Chem. Soc . [ American Journal of Chemical Society ] 2016 , 138(44), 14609-14615. Compounds of formula (XXVIII) are prepared as described in the literature cited above and as exemplified in the preparation embodiments of the present application.

Alternatively, a compound of formula (IIba) wherein A ¹ , A ² and A ³ are N and Z ¹ is as defined in formula (I) may be prepared by coupling a compound of formula (XXIX) (XXIX) (wherein A ¹ , A ² and A ³ are N, and R ⁰ is as described above), and a boronic acid derivative having the formula (XXX) (XXX) (wherein Z ¹ is as defined in formula I) to obtain. This Chan-Lam type coupling reaction is usually carried out in a solvent (such as dichloromethane), in the presence of a catalytic amount of a copper-based catalyst, at a mild reaction temperature, in the presence of a base (such as potassium carbonate), under atmospheric air or oxygen. It should be noted that compounds of formula (XXIX) (wherein A ¹ , A ² and A ³ are N) exist in tautomeric forms, namely; Those familiar with the art will envision that the coupling product of the reaction may be one of the positional isomers or a mixture thereof, but when the reaction conditions are selected as described in J. Org. Chem. [ Organic Chemistry ] 2014 , 79, 6703-6707, the reaction shows excellent position selectivity for compounds of formula (IIba). Those familiar with the art will recognize that this Chan-Lam coupling is a general method for preparing compounds of formula (IIb). Examples of the following compounds are shown in the literature: Compounds of formula (IIbb) (IIbb) wherein Z ¹ , R ^12a , and R ⁰ are as previously defined (see J. Med. Chem. 2018 , 61 , 8 , 3370-3388 and WO 14/041106, 2014 ), compounds of formula (IIbc) and (IIbd) wherein Z ¹ , R ^12a , R ^13a , R ^14a , and R ⁰ are as defined under formula (I) (see WO 15/155626, 2015 , EP 2390252 , 2011 ) and compounds having formula (IIbe) (IIbe) wherein Z ¹ , R ^12a , R ^13a , R ^14a , and R ⁰ are as defined under formula (I) (see J. Med. Chem . [ Journal of Medicinal Chemistry ] 2017 , 60(14), 6166-6190, Org. Lett . [ Organic Express ] 2008 , 10(8), 1653-1655 and Bio. Med. Chem. Lett. [ Biological Organic Chemistry and Pharmaceutical Chemistry Communications ] 2009 , 19(5), 1451-1456) as representative examples.

Another method for preparing compounds of formula (IIba) wherein A ¹ , A ² and A ³ are N and Z ¹ is as defined in formula (I) is shown in Scheme 19. Process 19

As shown in Scheme 19, the sequence begins with diazotization of a compound of formula (XXVII) as described above, and then treating the diazonium salt with a compound of formula (XXXI) (wherein R ^is C ₁ -C ₆ alkyl) in the presence of a weak base (e.g. sodium acetate) to give a compound of formula (XXXII). The compound of formula (XXXII) (wherein Z ¹ and R ⁰ are as previously defined) is then treated with aqueous ammonia at a temperature between 0°C and 30°C in a miscible organic solvent (e.g. tetrahydrofuran or 2-methyltetrahydrofuran) to give a compound of formula (XXXIII). Finally, the compound of formula (XXXIII) is diazotized with a nitrite (e.g. sodium nitrite) in an aqueous solution in a slightly acidic medium (e.g. acetic acid or hydrochloric acid) at a temperature between -20°C and 0°C resulting in the spontaneous cyclization of the formed diazonium salt to a tetrazole compound of formula (IIba). The reaction sequence has been previously described in WO 13/087805, 2013 .

The compound of formula (IIb) can also be prepared by mixing a compound of formula (XXIX) (XXIX) Using a compound having the formula (XXXIV) (XXIV) wherein Z ¹ is as previously described under formula I and X ⁰ is a halogen (preferably chlorine, bromine or iodine) in the presence of a base (e.g., an alkali earth metal base such as NaOH, KOH, LiOH, Cs ₂ CO ₃ , K ₂ CO ₃ , etc.) in an inert aprotic or protic solvent. Such alkylations are well known to those skilled in the art and have been used in this context to prepare compounds of formula (IIb), as described, for example, in WO 14/168221; WO 10/043000; and WO 14/32498. Those skilled in the art will recognize that this can result in mixtures of positionally isomeric compounds which can be separated by chromatographic techniques, or the pure isomers can be obtained by judicious choice of conditions and additives (e.g. palladium catalysts for the so-called Buchwald amination). For the case where Z ¹ is a heteroaryl or aryl group, the SnAr reaction (with or without copper catalysis) can be used to prepare compounds of formula (IIb) (see, for example, Polyhedron 2019 , 165 , 22-30 ; US 18/0170909; Org. Lett. 2022 , 24(20), 3620-3625, J.Org. Chem. 2017 , 82 ( 14), 7420-7427, Chem. Comm. 2021 , 57(57), 7047-7050, ACS Catalysis 2019 , 9 ( 12), 10674-10679, Synthesis 2017 , 49(23), 5120-5130, J.Org. Chem. 2019 , 84 (12), 8160-8167 and references cited therein ).

Salts of compounds of formula (I) can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchange reagent, and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchange reagent.

Salts of compounds of formula (I) can be converted in a conventional manner into free compounds (I), acid addition salts (e.g. by treatment with a suitable basic compound or with a suitable ion exchange reagent) and salts with bases (e.g. by treatment with a suitable acid or with a suitable ion exchange reagent).

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

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

The compounds of formula (I) and, where appropriate, their tautomeric isomers (in each case in free form or in salt form) can be in the form of one of the possible isomers or in the form of a mixture of such isomers, for example in the form of pure isomers (such as enantiomers and/or non-mirror image isomers) or in the form of isomer mixtures (such as mirror image isomer mixtures, for example racemates or non-mirror image isomer mixtures). The present invention relates to the pure isomers and also to all possible isomer mixtures and is to be understood in this sense in every case, even without specific reference to stereochemical details.

Mixtures of diastereoisomers or racemates of compounds of formula (I) in free form or in salt form, the acquisition of which may depend on the starting materials and procedures chosen, can be separated in a known manner into the pure diastereoisomers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and/or chromatographic methods.

Mixtures of mirror image isomers which can be obtained in an analogous manner (e.g. racemates) can be resolved into the optical mirror image isomers by known methods, for example by recrystallization from optically active solvents; by chromatography on chiral adsorbents, for example high performance liquid chromatography (HPLC) on acetylcellulose; by cleavage with specific immobilized enzymes with the aid of suitable microorganisms; by forming containing compounds, for example using chiral crown ethers, in which only one mirror image isomer is complexed; or by conversion The formation of non-mirror image isomer salts, for example by reacting the alkaline final product racemate with an optically active acid (e.g. a carboxylic acid, for example camphoric acid, tartaric acid or apple acid, or a sulfonic acid, for example camphorsulfonic acid), and separation of the non-mirror image isomer mixture obtainable in this way, for example by fractional crystallization on the basis of their different solubilities, thereby obtaining the non-mirror image isomers from which the desired mirror image isomer can be freed by the action of a suitable reagent, for example an alkaline reagent.

Pure non-mirror image isomers or mirror image isomers can be obtained according to the present invention not only by separation of the appropriate isomeric mixture, but also by generally known diastereoselective or enantioselective synthesis methods, for example by carrying out the method according to the present invention with starting materials having appropriate stereochemistry.

If the individual components have different biological activities, it is advantageous to isolate or synthesize the biologically more effective isomer in each case, such as an image-bearing isomer or a non-image-bearing isomer or a mixture of isomers, such as a mixture of image-bearing isomers or a mixture of non-image-bearing isomers.

As an example, compounds with more than one asymmetric carbon atom may exist as non-mirror image isomers which can be separated if desired using, for example, supercritical fluid chromatography (SFC) chromatography with a chiral column. Such non-mirror image isomers may show different fungicidal activity characteristics, but all isomers and non-mirror image isomers form part of the present invention.

The compound of formula (I) has three chiral carbon atoms (three stereocenters, where an asterisk (*) indicates a chiral carbon atom), so that there are eight available stereoisomers. These eight stereoisomers consist of four sets of mirror image isomers. For compounds of formula (I), the relationship between mirror image isomers and non-mirror image isomers is shown in Scheme 20.

Those skilled in the art will fully appreciate that such non-mirror isomers and mirror isomers of formula (I) (as shown in Scheme 20, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , B ¹ , B ² , A (A ¹ , A ² , A ³ ) and Z ¹ are as defined above for compounds of formula (I)) are within the scope of the present invention. Process 20

The compounds of formula (I) and, where appropriate, their tautomers (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, such as those which can be used for crystallization of compounds present in solid form.

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

The compounds of formula (I) according to the invention can be used in the agricultural sector and related fields of use as active ingredients, for example, for controlling plant pests, or on non-living materials for controlling spoilage microorganisms or organisms potentially harmful to humans. The novel compounds are characterized by excellent activity at low application rates, good plant tolerance and environmental safety. They have very useful therapeutic, preventive and systemic properties and can be used to protect a wide range of cultivated plants. The compounds of formula (I) can be used to inhibit or destroy pests that occur on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of different useful plant crops, while also protecting those plant parts that grow later from, for example, plant pathogenic microorganisms.

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

It is also possible to use the compounds of formula (I) according to the present invention as fungicides. As used herein, the term "fungicide" means a compound that controls, modifies, or prevents the growth of fungi. The term "fungicidal effective amount" when used means an amount 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 deviations from natural development, such as killing, retardation, etc., and prevention includes the formation of a barrier or other defense in or on a plant to prevent fungal infection.

It is also possible to use the compounds of formula (I) according to the invention as seed dressings for treating plant propagation material (e.g. seeds, such as fruits, tubers or grains) or plant cuttings for protection against fungal infections and against phytopathogenic fungi present in the soil. The propagation material can be treated with a composition comprising a compound of formula (I) before planting: for example, the seeds can be dressed before sowing. The active compound of formula (I) can also be applied to grains (coating) by immersing 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 planted, for example to the furrows of the seeds during sowing. The invention also relates to such methods for 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 fields, for example in the protection of industrial materials (including wood and wood-related technical products), in food storage, in hygiene management.

In addition, the invention can be used to protect non-living materials (such as wood, wallboard and paint) from fungal attack.

The compounds of formula (I) according to the invention are effective, for example, against fungi and fungal vectors of diseases and phytopathogenic bacteria and viruses. The fungi and fungal vectors of such diseases and phytopathogenic bacteria and viruses are, for example, Alternaria species, Mycosporium species, Aspergillus species, Aspergillus species (including Flavour mould, Tobacco mould, Nidulans mould, Black mould, A. terrestris), Brachypodium species (including A. pullulans), Blastomyces dermatitidis, Powdery mildew of wheat, Bremia lactucae, Botrytis species (including B. dothidea, B. obtusa), Botrytis species (including B. cinerea, B. cinerea), Candida species (including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis), Cephaloascus fragrans, Cercospora species, Cercospora species (including C. arachidicola), Cercosporidium personatum, Cladosporium species, Ergot, Coccidioides immitis, Coccidioidomyces species, Colletotrichum species (including C. musae), Cryptococcus neoformans, Diaporthe species, Subsporus species, Helminthosporium species, Entomophthora species, Epidermophyton species, Erwinia amylovora, Erysiphe species (including E. cichoracearum), Eutypa lata, F. langsethiae species (including F. langsethiae, F. moniliformis, F. gloeosporioides, F. solanacearum, F. oxysporum, F. laminaris), Gaeumannomyces graminis, Gibberella fujikuroi), Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium species, Camellia species, Histoplasma species (including H. capsulatum), Red Line Pathogen, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale), Microsporum species, Chain Sclerotinia species, Trichoderma species, Mycosphaeria species (including Mycosphaeria graminicola and M. pomi), Blight fungus, Spruce fungus, Paracoccidioides species, Penicillium species (including Penicillium digitatum and Penicillium italicum), Pseudomonas species, Frosomyces species (including Frosomyces maize, Frosomyces philippinica and Frosomyces sorghum), Frosomyces species, Phellinus glabrata, Phellinus igniarus, Phyllinus species, Phomopsis species, Phomopsis pseudostem spot of grapes, Phomopsis spp. viticola), Phytophthora species (including Phytophthora infestans), Monosporus species (including P. holmes, P. viticola), Grifola species, Pseudocercosporella species (including P. leucotricha), Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas species, Pseudocercosporella species (including Pseudocercosporella spp., Pseudocercosporella spp.), Pseudopeziza tracheiphila, Pseudocercosporella species (including P. leucotricha), Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas species, Pseudocercosporella species (including Pseudocercosporella spp., Pseudocercosporella spp.), Pseudopeziza tracheiphila, Pseudocercosporella species (including P. hordei), P. recondita, P. Striiformis, P. triticina), Pyricularia species, Pyricularia species, Pyricularia species (including P. oryzae), Pythium species (including P. ultimum), Pyricularia species, Rhizoctonia species, Rhizoctonia species, Rhizomucor pusillus, Rhizoctonia spp., Rhizosporium species, Mycosporium species (including Scedosporium apiosporum and Scedosporium prolificum), Schizosporium pomi, Pyricularia species, Sclerotium species, Septoria species (including Septoria spp. nodorum), S. tritici), Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix species, Stagonospora nodorum, Stemphylium species, Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola), Tilletia species, Trichoderma species (including T. harzianum, T. simconi, and T. viridis), Trichoderma species, Pseudomonas species, V. vinifera, Urocystis species, Ustilago species, Venturia species (including V. inaequalis), Verticillium species, and Xanthomonas species.

The compounds of formula (I) according to the present invention can be used, for example, in lawns, ornamental plants such as flowers, shrubs, broad-leaved trees or evergreen plants such as pines, as well as tree injection, pest management, etc.

In the context of the present invention, target crops and/or useful plants to be protected typically include 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; fiber plants, for example cotton, flax, hemp, jute and ramie; field crops, for example sugar beets and fodder beets, coffee beans, hops, mustard, rapeseed (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees, for example apples, apricots, avocados, bananas, cherries, citrus, nectarines, peaches, pears and plums; grasses, for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, rye, etc. Augustine grass, and knotweed; herbs such as basil, borage, chives, cilantro, lavender, lovage, mint, oregano, parsley, rosemary, sage, and thyme; legumes such as beans, lentils, peas, and beans; nuts such as almonds, cashews, peanuts, hazelnuts, peanuts, pecans, pistachios, and walnuts; palm plants such as such as oil palm; ornamental plants such as flowers, shrubs and trees; other trees such as cocoa trees, coconut trees, olive trees and rubber trees; vegetables such as asparagus, eggplant, broccoli, cabbage, carrots, cucumbers, garlic, lettuce, zucchini, melon, okra, onions, peppers, potatoes, pumpkins, rhubarb, spinach and tomatoes; and vines such as grapes.

The term "useful plants" is to be understood as also including useful plants which have been rendered tolerant to herbicides (such as bromoxynil) or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, such as primisulfuron, primisulfuron and trifloxysulfuron, EPSPS (5-enol-pyruvyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrin oxidase) inhibitors) as a result of conventional breeding methods or genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones (such as imazamox) by conventional breeding methods (induction) is Clearfield® summer rapeseed (Canora). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate-resistant and ammonium phosphine-resistant corn 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 transformed by the use of recombinant DNA techniques in such a way that they are able to synthesize one or more selectively acting toxins, as are known, for example, from toxigenic bacteria, in particular those of the genus Bacillus.

Examples of such plants are: YieldGard® (a corn variety expressing CryIA(b) toxin); YieldGard Rootworm® (a corn variety expressing CryIIIB(b1) toxin); YieldGard Plus® (a corn variety expressing CryIA(b) and CryIIIB(b1) toxins); Starlink® (a corn variety expressing Cry9(c) toxin); Herculex I® (a corn variety expressing CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) which confers tolerance to the herbicide ammonium phosphinothricin); NuCOTN 33B® (a cotton variety expressing CryIA(c) toxin); Bollgard I® (a cotton variety expressing CryIA(c) toxin); II® (cotton variety expressing CryIA(c) and CryIIA(b) toxins); VIPCOT® (cotton variety expressing VIP toxins); NewLeaf® (potato variety expressing CryIIIA toxins); Nature-Gard® Agrisure® GT Advantage (GA21 glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), Agrisure® RW (corn rootworm trait), and Protecta®.

The term "crops" should be understood as also including crop plants which have been transformed by the use of recombinant DNA technology in such a way that they are able to synthesize one or more selectively acting toxins, as are known, for example, from toxigenic bacteria, in particular those of the genus Bacillus.

Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus japonicus; or insecticidal proteins from Bacillus thuringiensis, such as delta-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or plant insecticidal proteins (Vips), for example Vip1, Vip2, Vip3, or Vip3A; or nematode parasitic bacteria (e.g., Photorhabdus spp.) or Xenorhabdus spp., such as Photorhabdus spp. luminescens), Xenorhabdus nematophilus); toxins produced by animals, such as scorpion toxins, spider toxins, bee toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptococcus toxins; plant lectins, such as pea lectin, barley lectin or snowdrop lectin; agglutinin; protease inhibitors, such as trypsin inhibitors, serine protease inhibitors, potato glycoproteins, cystatins, papain inhibitors; ribose steroid metabolic enzymes such as 3-hydroxysteroid oxidase, glycoside-UDP-transferase, cholesterol oxidase, corticosteroid inhibitor, HMG-COA-reductase, ion channel blockers such as sodium channel or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

Further, in the context of the present invention, delta-endotoxins (e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C) or plant insecticidal proteins (Vips) (e.g., Vip1, Vip2, Vip3 or Vip3A) are understood to obviously also include mixed toxins, truncated toxins and modified toxins. Mixed toxins are produced by recombining new combinations of different domains of those proteins (see, e.g., WO 02/15701). Truncated toxins, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid substitutions, it is preferred to insert a non-naturally occurring protease recognition sequence into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G recognition sequence was inserted into the Cry3A toxin (see WO 2003/018810).

Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed in, for example, EP-0374753, WO 93/07278, WO 95/34656, EP 0427529, EP 0451878 and WO 03/052073.

Methods for preparing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. CryI-type DNAs and their preparation are known, for example, from WO 95/34656, EP 0367474, EP 0401979 and WO 90/13651.

The toxins contained in the transgenic plants make the plants tolerant to harmful insects. Such insects can be found in any insect taxonomic group but are particularly common in beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).

Transgenic plants comprising one or more genes encoding insecticide resistance and expressing one or more toxins are known and some are commercially available. Examples of such plants are: YieldGard® (a corn variety expressing the Cry1Ab toxin); YieldGard Rootworm® (a corn variety expressing the Cry3Bb1 toxin); YieldGard Plus® (a corn variety expressing the Cry1Ab and Cry3Bb1 toxins); Starlink® (a corn variety expressing the Cry9C toxin); Herculex I® (a corn variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) which confers tolerance to the herbicide ammonium phosphinothricin); NuCOTN 33B® (a cotton variety expressing the Cry1Ac toxin); Bollgard I® (a cotton variety expressing the Cry1Ac toxin); Bollgard II® (cotton variety expressing Cry1Ac and Cry2Ab toxins); VipCot® (cotton variety expressing Vip3A and Cry1Ab toxins); NewLeaf® (potato variety expressing Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Other examples of such GM crops are: 1.   Bt11 maize, from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified maize, transgenic to express a truncated Cry1Ab toxin, making it resistant to attack by the European corn borer (Ostrinia nubilalis and C. cerevisiae). Bt11 maize is also transgenic to express the PAT enzyme to confer tolerance to the herbicide glufosinate. 2.   Bt176 maize, from Syngenta Seeds, 27 rue de Hobit, F-31 790 Saint-Sauviere, France, registration number C/FR/96/05/10. Genetically modified maize, transgenic to express the Cry1Ab toxin, which makes it resistant to attack by the European corn borer (Ostrinia nubilalis and Ceratitis oleracea). Bt176 maize is also transgenic to express the enzyme PAT to obtain tolerance to the herbicide glufosinate. 3.   MIR604 maize, from Syngenta Seeds, 27 rue de Hobit, F-31 790 Saint-Sauviere, France, registration number C/FR/96/05/10. Maize rendered insect-resistant by transgenic expression of a modified Cry3A toxin. The toxin is Cry3A055 modified by insertion of a cathepsin-G-proteinase recognition sequence. The preparation of such transgenic maize plants is described in WO 2003/018810. 4.   MON 863 maize from Monsanto Europe S.A., 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses the Cry3Bb1 toxin and confers resistance to certain coleopteran insects. 5.   IPC 531 Cotton, from Monsanto Europe 270-272 Avenue Teveren, 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 expressing the protein Cry1F to confer resistance to certain lepidopteran insects and the protein PAT to confer tolerance to the herbicide glufosinate. 7.   NK603 × MON 810 maize, from Monsanto Europe AB 270-272 Boulevard Tervuren, B 1150 Brussels, Belgium, registration number C/GB/02/M3/03. A conventionally bred hybrid maize variety formed by crossing the genetically modified varieties NK603 and MON 810. NK603 × MON 810 maize transgenics expresses the protein CP4 EPSPS obtained from Agrobacterium strain CP4, which confers resistance to the herbicide Roundup® (containing glyphosate), and the Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstak, which confers resistance to certain Lepidoptera, including the European corn borer.

The compounds of formula (I) according to the invention can be used to control or prevent phytopathogenic diseases, in particular phytopathogenic fungi, such as Alternaria on fruits, vegetables and potatoes; Botrytis cinerea on strawberries, tomatoes, sunflowers, legumes, vegetables and grapes; Rhizoctonia solani on potatoes and vegetables; Rhizoctonia solani on grapes; Cladosporium, moss borer, powdery mildew and cucurbitaceous nematodes on cucurbits; Cercospora spp. on cucurbits and solanaceous crops; Sicklings spp. on cereals; Leptosphaeria spp. on cereals; and Saccharomyces spp. on cereals.

As used herein, the term "location" means a place in or on which plants grow, or where seeds of cultivated plants are sown, or where seeds are to be placed in the soil. It includes soil, seeds and seedlings, as well as established vegetation.

The term "plant" refers to all visible parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves and fruits.

The term "plant propagation material" is to be understood as meaning reproductive parts of plants, such as seeds, which can be used for the propagation of the plants, and vegetative material, such as cuttings or tubers (e.g. potatoes). Mention may be made, for example, of seeds (in the strict sense), roots, fruits, tubers, scales, rhizomes and parts of plants. Mention may also be made of germinated plants and young plants to be transplanted after germination or after emergence. Such young plants may be protected before transplanting by a complete or partial treatment by immersion. Preferably, "plant propagation material" is to be understood as meaning seeds.

The compounds of formula (I) according to the invention can be used in unmodified form or, preferably, together with adjuvants conventionally employed in the art of formulation. For this purpose, they can be conveniently formulated in a known manner as emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granules and also capsules, for example in polymeric substances. For the type of composition, the method of application is selected according to the intended purpose and the prevailing circumstances, such as spraying, atomizing, dusting, spreading, spreading or pouring. The compositions may also contain further adjuvants, such as stabilizers, defoamers, viscosity regulators, binders or tackifiers, as well as fertilizers, trace nutrient donors or other formulations for obtaining special effects.

Suitable carriers and adjuvants, for example, for agricultural use, can be solid or liquid and are substances useful in formulation technology, such as natural or regenerated mineral substances, solvents, dispersions, wetting agents, tackifiers, thickeners, adhesives, or fertilizers. Such carriers are described, for example, in WO 1997/33890.

Suspension concentrates are aqueous preparations in which finely divided solid particles of the active compound are suspended. Such preparations contain anti-settling agents and dispersants, and may further contain wetting agents to enhance activity, as well as defoamers and crystal growth inhibitors. When used, the concentrates are diluted in water and usually applied as a spray to the area to be treated. The amount of active ingredient can range from 0.5% to 95% of the concentrate.

Wettable powders are in the form of finely divided particles that 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, silica and other readily wettable organic or inorganic solids. Wettable powders usually contain from 5% to 95% active ingredient plus a small amount of a wetting agent, dispersant or emulsifier.

Emulsifiable concentrates are uniform liquid compositions dispersible in water or other liquids and may consist entirely of active compounds and liquid or solid emulsifiers, or may also contain liquid carriers such as xylene, heavy aromatic naphtha, isophorone and other non-volatile organic solvents. When used, the concentrates are dispersed in water or other liquids and are usually applied as sprays 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 coarser granules and are usually applied undiluted to the area to be treated. Typical carriers for granular formulations include sand, fuller's earth, magnesium aluminum sepiolite clay, bentonite, montmorillonite, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, crushed corn cobs, crushed peanut shells, sugar, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesium oxide, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate, and other organic or inorganic materials that absorb or can be coated with the active compound. Granular formulations usually contain 5% to 25% active ingredients, which may include surfactants such as heavy aromatic naphtha, kerosene and other petroleum distillates, or vegetable oils; and/or adhesives such as dextrins, glues or synthetic resins.

Dusts are free-flowing mixtures 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 particles of active ingredients encapsulated in an inert porous shell that allows the encapsulated material to escape into the environment at a controlled rate. The diameter of the encapsulated droplets is typically 1 to 50 microns. The encapsulated liquid typically accounts for 50% to 95% of the weight of the capsule and can contain solvents in addition to the active compound. Encapsulated particles are usually porous particles, wherein the porous membrane seals the particle orifice and retains the active species in the form of a liquid inside the particle pores. The diameter of the particles typically ranges from 1 mm to 1 cm and preferably 1 mm to 2 mm. The particles are formed by extrusion, agglomeration or granulation, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, magnesium aluminum sepiolite clay, sawdust and carbon pellets. Shell or membrane materials include natural and synthetic rubbers, fiber materials, styrene-butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

Other useful formulations for agrochemical applications include simple solutions of the active ingredient in a solvent such as acetone, alkylated naphthalenes, xylene and other organic solvents in which the active ingredient is completely dissolved at the desired concentration. Pressurized sprays may also be used in which the active ingredient is dispersed in finely divided form due to evaporation of a low-boiling dispersant solvent carrier.

Suitable agricultural adjuvants and carriers useful for formulating the compositions of the present invention in the above-mentioned formulation types are well known to those skilled in the art.

The liquid carrier that can be used includes, for example, water, toluene, xylene, naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetobenzene, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetate, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol rosin acid ester, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformyl Amine, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol (diproxitol), alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethyl carbonate, 1,1,1-trichloroethane, 2-heptanone, α-pinene, d-oxadiene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, 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, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, dichloromethane, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine 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, glycerol and N-methyl-2-pyrrolidone. Water is usually the carrier of choice for diluting concentrates.

Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, magnesium aluminum sepiolite clay, kieselguhr, chalk, diatomaxeous earth, limestone, calcium carbonate, bentonite, Fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.

A wide range of surfactants may be advantageously employed in the liquid and solid compositions, especially those designed to be diluted with a carrier prior to application. Such agents, when used, generally comprise from 0.1% to 15% by weight of the formulation. They may be anionic, cationic, nonionic or polymeric in nature and may be employed as emulsifiers, wetting agents, suspending agents or for other purposes. Typical surfactants include alkyl sulfates such as diethyl ammonium lauryl sulfate; alkyl aryl sulfonates such as calcium dodecylbenzene sulfonate; alkylphenol-epoxy addition products such as nonylphenol-C.sub.18 ethoxylate; alcohol-epoxy addition products such as tridecanol-C.sub.16 ethoxylate; soaps such as sodium stearate; alkylnaphthalene sulfonates such as sodium dibutylnaphthalene sulfonate; salts of dialkyl sulfosuccinates such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitan esters such as sorbitan oleate; quaternary amines such as lauryltrimethylammonium 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 phosphates.

Other adjuvants commonly used in agricultural compositions include crystallization inhibitors, viscosity regulators, suspending agents, spray droplet regulators, pigments, antioxidants, foaming agents, defoamers, opacifiers, compatibility agents, defoamers, clamps, neutralizers and buffers, corrosion inhibitors, dyes, odorants, spreaders, penetration aids, trace nutrients, emollients, lubricants and fixatives.

In addition, further, other biocidal active ingredients or compositions can be combined with the compositions of the present invention and used in the methods of the present invention and applied simultaneously or sequentially with the compositions of the present invention. When applied simultaneously, the additional active ingredients can be formulated or mixed together with the compositions of the present invention, for example, in a spray can. The additional biocidal active ingredients can be fungicides, herbicides, insecticides, bactericides, miticides, nematicides and/or plant growth regulators.

Pesticides referred to herein using their common names are known, for example, from “The Pesticide Manual”, 15th edition, British Crop Protection Council 2009.

In addition, the compositions of the invention may be administered with one or more systemic acquired resistance inducers ("SAR" inducers). SAR inducers are known and described, for example, in U.S. Patent No. 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 usually used in the form of agrochemical compositions and can be applied to the crop area or the crop to be treated simultaneously or successively with further compounds. For example, these further compounds can be fertilizers or micronutrient donors or other preparations that influence plant growth. They can also be selective or non-selective herbicides, together with insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or adjuvants that facilitate application that are usually used in the field of formulation.

The compounds of formula (I) according to the invention can be used in the form of a (fungicidal) composition for controlling or protecting against phytopathogenic microorganisms, comprising as active ingredients at least one compound of formula (I) or at least one preferred individual compound as defined herein (in free form or in the form of an agrochemically acceptable salt) and at least one adjuvant as described above.

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

The compound of formula (I) according to the present invention can be the sole active ingredient of the composition, or it can be mixed with one or more additional active ingredients (such as pesticides, fungicides, synergists, herbicides or plant growth regulators) as appropriate. In some cases, the additional active ingredients can produce unexpected synergistic activities.

Examples of suitable additional active ingredients include the following: acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, aniline fungicides, antibiotic fungicides, aromatic fungicides, arsenic-containing fungicides, arylphenylketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, cross-linked biphenyl fungicides, Fungicides, carbamate fungicides, aniline formate fungicides, conazole fungicides, copper fungicides, dimethylimide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, Pyridoxine fungicides, organophosphorus fungicides, organotin fungicides, oxathiin fungicides, oxazole fungicides, phenylsulfonamide fungicides, polysulfide fungicides, pyrazole fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungicides, quinone fungicides, quinoline fungicides, euphorbia fungicides fungicides, sulfonanilide fungicides, thiadiazole fungicides, thiazole fungicides, tetrahydrothiazole fungicides, thiocarbamate fungicides, thiophene fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, valinamide fungicides, and zinc fungicides.

Examples of suitable additional active ingredients include the following: petroleum, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenylbenzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylacetamide, 4-chlorophenylphenylsulfonate, acetothionil, aldicarb, sirox, fosfoline, amitriptyline, oxalothioate, cypermethrin, chlorpyrifos, arsenic trioxide, azobenzene, azophos, benomyl, benzyl benzoate, bifenthrin Amine, bromethrin, bromothion, bromothion, bromothion, thiophene, butacarb, butacarb, butylated chlorfenapyr, calcium polysulfide, octachlorocamphene, chlorfenapyr, trithion, cypermethrin, cypermethrin, cypermethrin hydrochloride, cypermethrin, cypermethrin ester, cypermethrin, ethyl cypermethrin, cypermethrin, cypermethrin urea, propyl cypermethrin, cypermethrin, cypermethrin I, cypermethrin II, cypermethrin, closantel, cypermethrin, crotamiton, cypermethrin, thiothion , fruit bug phosphorus, DCPM, DDT, fenvalerate, fenvalerate-O, fenvalerate-S, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methyl, demeton-S-methyl, demeton-S-methylsulfon, bacteriostatic, dichlorvos, dicliphos, chlorpyrifos, chlorpyrifos, dinex, dinex-dicl exine), dimethoate-4, dimethoate-6, lindane, nitropentyl, nitrooctyl ester miticide, nitrobutyl, dimethoate, sulfodiphenyl, disulfiram, DNOC, phenoxyacetin, doramectin, indole, eprinomectin, phosphothion, ethidium, anti-mite azole, fenbutin, fenthiocarb, fenpyrad, fenazolidinone, fenpyrad, fluazifop, flufenazol, fluazifop, FMC 1137, fenvalerate, fenvalerate hydrochloride, carbendazim, γ-HCH, chloranil, benzyl chloranil, hexadecyl cyclopropane carboxylate, isothiocarb, jasmonate I, jasmonate II, iodine, lindane, propionamide, cypermethrin, dithiophos, methylthiophene, cypermethrin, methyl bromide, cypermethrin, chloranil, milbemidoxim, propylamine, monocrotophos, malathion, moxidectin, dibromophos, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy] tantalum -3-Keto, flufenamic acid, nikomycin, pentothiocarb, pentothiocarb 1:1 zinc chloride complex, omethoate, isothiophos, sulfophos, pp'-DDT, parathion, permethrin, fenthion, phosphamidon, thiocyanate, phosphamidon, chlorinated turpentine, acaricide, proclonol, cypermethrin, chlorfenapyr, ethidium, pyrethrin I, pyrethrin II, pyrethrin, tadalafil, pyrimithiophos, quinalphos, quinalphos, R-1492, glyphosate, rotenone, octamidine, chlorpyrifos, stearamide, stearamide Keding, Suthion, SSI-121, Sufilam, flumitriptyline, Sultep, sulfur, fluazifop, τ-fluvalinate, TEPP, tert-bucarb, tetrachlorvinphos, miticide, thiafenox, cypermethrin, long-acting carb, methyl sulfothion, chlorpyrifos, sulfamethoxam, sulfamethoxam, triazophos, chlorpyrifos, trichlorfon, triamcinol, triamcinol, trifloxystrobin ... Cybutryne, dichloronaphthoquinone, dichlorophenol, mycophenolic acid, triphenyltin, slaked lime, mancozeb, quinone, quinone, simazine, triphenyltin acetate, triphenyltin hydroxide, oxazolidinone, piperidine, thiophanate, chloralose, fenthion, pyridine-4-amine, strychnine, 1-hydroxy-1H-pyridine-2-thione, 4-(quinolin-2-ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, Copper hydroxide, cresol, dipyrithione, dodesine, sodium sulfonate, formaldehyde, mercurygaphene, kasugamycin, kasugamycin hydrochloride hydrate, nickel di(dimethyldithiocarbamate), trichloromethylpyridine, octhilthione, oxolinic acid, terpenoid, potassium hydroxyquinoline sulfate, thiabendazole, streptomycin, streptomycin sesquisulfate, chlorthalidone, thimerosal, GV, Geobacillus radiobacter, Amblyseius spp.), celery armyworm NPV, Anagrus atomus, short-spur aphid wasp, cotton aphid parasitic wasp (Aphidius colemani), aphid-eating gall midge (Aphidoletes aphidimyza), clover armyworm NPV, Bacillus sphaericus Neide, Beauveria brongniartii, Chrysoperla carnea, Cryptolaemus montrouzieri, apple moth GV, Siberian jawed wasp (Dacnusa sibirica), pea leaf-diving wasp (Diglyphus isaea), Encarsia formosa, Eretmocerus eremicus), Heterorhabditis bacteriophora and H. megidis, Hippodamia convergens, Leptomastix dactylopii, Macrolophus caliginosus, Cabbage armyworm NPV, Metaphycus helvolus, Metarhizium anisopliae var. acridum, Metarhizium anisopliae var. anisopliae, Neodiprion sertifer NPV and Neodiprion rufa (Neodiprion sertifer) NPV. lecontei) NPV, Steinernema species, Rose-colored pseudo-blue mold, Phytoseiulus persimilis, Steinernema bibionis, Steinernema carpocapsae, Steinernema lancelet, Steinernema glaseri, Steinernema riobrave, Steinernema riobravis, Steinernema scapterisci, Steinernema spp., Trichogramma species, Typhlodromus occidentalis), Verticillium lecanii, oxazolidinone, bis(aziridine)methylaminophosphine sulfide, busulfan, dimethivin, hexamethylmelamine, hexamethylphosphine, methyl tibactam, methyl oxazolidinone, infertile, flufenuron, tibactam, hexamethylphosphine thioate, thibactam, trothamide, urethaneimide, (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol, (E)-trideca-4-en-1-yl acetate, (E)-6-methylhept-2-en-4-ol, (E,Z)-tetradec-4,10-dione 1-yl acetate, (Z)-dodec-7-en-1-yl acetate, (Z)-hexadec-11-enal, (Z)-hexadec-11-en-1-yl acetate, (Z)-hexadec-13-en-11-yn-1-yl acetate, (Z)-eicos-13-en-10-one, (Z)-tetradec-7-en-1-al, (Z)-tetradec-9-en-1-ol, (Z)-tetradec-9-en-1-yl acetate, (7E,9Z)-dodec-7,9-diene-1- acetate, (9Z,11E)-tetradec-9,11-dien-1-yl acetate, (9Z,12E)-tetradec-9,12-dien-1-yl acetate, 14-methyloctadec-1-ene, 4-methylnon-5-ol and 4-methylnon-5-one, α-polystyrene, western pine beetle aggregation information, dodecadienol, codmon, oxadione, epoxynonadecane, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodec-8, 10-dien-1-yl acetate, acetic acid ester, dominicalure, ethyl 4-methyloctanoate, eugenol, southern pine beetle aggregation information, ene mixture, ene mixture I, ene mixture II, ene mixture III, ene mixture IV, hexane attractant, halogenated beetle dienol, styrene alcohol, golden turtle attractant, trimethyldioxytricyclononane, noctuid attractant (litlure), powdery mildew bud attractant, ester of attractant, (3E,5Z)-tetradec-3,5-dienoic acid (megatomoic acid), chloranthate, chloranthene, octadec-2,13-dien-1-yl acetate, octadec-3,13-dien-1-yl acetate, Hercon, Coconut borer rhinoceros turtle aggregation pheromone, filcon, chloranthide, banana bulb weevil attractant (sordidin), mycophagous methylindole, tetradec-11-en-1-yl acetate, Mediterranean fruit fly attractant Attractants, Mediterranean fly attractant A, Mediterranean fly attractant B1, Mediterranean fly attractant B2, Mediterranean fly attractant C, trunc-call, 2-(octylthio)ethanol, dimethoate, butoxy (polypropylene glycol), dibutyl adipate, dibutyl phthalate, dibutyl succinate, DEET, dimethyl carbate), dimethyl phthalate, ethyl hexanediol, hexyl urea, mequindine, methyl neodecanamide, oxalyl esters, picaridin, 1-dichloro-1-nitroethane, 1,1-dichloro-2,2-di(4-ethylphenyl)ethane, 1,2-dichloropropane and 1,3-dichloropropylene, 1-bromo-2-chloroethane, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate, 2-(2-butoxyethoxy)ethylthiocyanate, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenylmethylcarbamate, 2-(4-chloro-3,5-xylyloxy)ethanol, 2-chlorovinyldiethylphosphate, 2-imidazolidinone, 2-isopentyldihydroindane-1,3-dione, 2-methyl(prop-2-ynyl)aminophenylmethylcarbamate, 2-thiocyanatoethyllaurate, 3-bromo-1-chloroprop-1-ene, 3-methyl-1-phenylpyrazole-5- 4-Methyl (prop-2-ynyl) amino-3,5-dimethylphenylmethyl carbamate, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethyl carbamate, acethion, acrylonitrile, aldrin, alloamicin, cypermethrin, α-cortin, aluminum phosphide, cypermethrin, nicotine, ethyl cypermethrin, methyl pyriphos, Bacillus thuringiensis delta-endotoxin, barium hexafluorosilicate, barium polysulfide, cypermethrin, Bayer 22/190, Bayer 22408, β-cyfluthrin, β-cypermethrin Ester, amylthrin, biopermethrin, bis(2-chloroethyl) ether, borax, bromophenazone, bromo-DDT, chlorpyrifos, chloranil, termidor, butyl phosphate, calcium arsenate, calcium cyanide, carbon disulfide, carbon tetrachloride, badan hydrochloride, servadine, bornyl, chlordane, chlordecone, chloroform, chloropicrin, chloraniloxime, chlorpyrifos, cis-resmethrin, cismethrin, cypermethrin, copper acetyl arsenite, copper arsenate, copper oleate, chloranil, cryolite, CS 708, benzonitrile, cypermethrin, cypermethrin, d-methanthrin, DAEP, dazomethane, demethyl carbofuran, chloranil, isochlorophos, chloranil, dimethoate, dicresyl, cypermethrin, dieldrin, diethyl 5-methylpyrazol-3-yl phosphate, cypermethrin, tetrafluthrin, demacarb, pyrethrin, methyl chlorpyrifos, cypermethrin, propanol, pentotropol, chloranil, fenthrin, vegetable phosphorus, thiopyrasulfate, DSP, cyclohexanone, EI 1642, EMPC, EPBP, etaphos, ethiofencarb, ethyl formate, ethylene dibromide, ethylene dichloride, ethylene oxide, EXD, fenthion, ethylfencarb, chlorpyrifos, cypermethrin, fenthion, ethylfenthion, fluazifop, butylfenthion, phosphamidon, butylfenthion, furathiocarb, pyrethroid, biguanide, biguanide acetate, tetramethrin Sodium thiocarbonate, benzyl chloramine, HCH, HEOD, heptachlor, mefenthion, HHDN, hydrogen cyanide, quinoline carbendazim, IPSP, chlorfenapyr, carbofuran, isothrin, isoflavone, transplanting spirit, rice blast spirit, chlorfenapyr, juvenile hormone I, juvenile hormone II, juvenile hormone III, chlorfenapyr, methoxyfen, lead arsenate, bromophenylphos, pyraclofos, thiathion, m-isopropyl methylcarbamate, phosphorus Magnesium chloride, chlorpyrifos, methyl chlorpyrifos, chlorpyrifos, mercurous chloride, chlorpyrifos, metabendazole, metabendazole potassium salt, metabendazole sodium salt, methylsulfonyl fluoride, butenamidophos, methoprene, methoxythrin, methoxychlor, methyl isothiocyanate, methyl chloroform, dichloromethane, chlorpyrifos, chlorpyrifos, naphthiophos, naphthalene, NC-170, niacin, niacin sulfate, nitrobenzene, proton nicotinoids, O-5-dichloro-4- Iodophenyl O-ethylethylphosphonothioate, O,O-diethyl O-4-methyl-2-oxo-2H-benzopyran-7-ylphosphonothioate, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-ylphosphonothioate, O,O,O',O'-tetrapropyl dithiodipyrophosphate, oleic acid, p-dichlorobenzene, methyl parathion, pentachlorophenol, pentachlorophenyl laurate, PH 60-38, fenthion, parachlorothion, hydrogen phosphide, methyl phoxim, methamidophos, polychlorinated dicyclopentadiene isomers, potassium arsenite, potassium thiocyanate, precocious hormone I, precocious hormone II, precocious hormone III, pyrimethamine, profluthrin, fenthion, pyraclostrobin, pyraclostrobin, quassia extract, quinalphos-methyl, cypermethrin, iodophos, resmethrin, rotenone, thiamethoxam, ryanodine, sabah, octamphos, clostridium, SI-0009, thiamethoxam, sodium arsenite, sodium cyanide, sodium fluoride, sodium hexafluorosilicate, sodium pentachlorophenol, sodium selenate, thiocyanate Sodium, sulfofensulfuron, sulfofensulfuron sodium salt, sulfofensulfuron, sulfofensulfuron, tar, thiocarb, TDE, butylpirimiphos, chlorpyrifos, cypermethrin, tetrachloroethane, thiochlorvos, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr sodium, tralomethrin, permethrin, trichlorfon, isoflurane Fenphos-3, chlorpyrifos, chloranil, triflumethocarb, chlorpyrifos-butyl, methoxystrobin, veratrimide, veratrine, XMC, ζ-cypermethrin, zinc phosphide, cypermethrin, tetrafluthrin, dibutyltin oxide, bromoacetamide, iron phosphate, niclosamide-ethanolamine, tributyltin Tin oxide, pyridine, snail killer, 1,2-dibromo-3-chloropropane, 1,3-dichloropropylene, 3,4-dichlorotetrahydrothiophene 1,1-dioxide, 3-(4-chlorophenyl)-5-methylrosenin, 5-methyl-6-thioketo-1,3,5-thiadiazole-3-ylacetic acid, 6-isoprenylamidin, fluphenyladenine, benzylchlorothiol, cytokinin, DCIP, furfural, isoamidophos, kinetin, verrucospore mycorrhizal composition, tetrachlorothiophene, xylenol, zeatin, potassium ethylxanthate, acibenzolar, acibenzolar-S-methyl, Polygonum cuspidatum extract, α- Chlorohydrin, Antu, barium carbonate, bifenthion, brodifacoum, bromidron, bromidron, bromidramine, chlorfenthion, bile calcification alcohol, chlorfenthion, chlorfenthion, chlorfenthion, chlorfenthion, chlorfenthion, chlorfenthion, chlorfenthion, calcification alcohol, flufenthion, fluoroacetamide, flufenthion, flufenthion hydrochloride, flufenthion, chlorfenthion, phosphorus, chlorfenthion, chlorfenthion, chlorfenthion, chlorfenthion, chlorfenthion, sodium fluoroacetate, potassium sulfate, chlorfenthion, 2-(2-butoxyethoxy)ethyl piperate, 5-(1,3-benzodioxolane-5-yl)-3-hexylcyclohex-2-enone, bacteriochlorenol with nerolidol, synergistic alkynyl ether, MGK 264, piperonyl butoxide, synergistic aldehyde, propyl isomer, S421, synergistic powder, sesame, sulfoxide, anthraquinone, copper cycloalkanoate, copper oxychloride, dicyclopentadiene, salamine, zinc cycloalkanoate, fenamic acid, imazoline, ribavirin, chlorindole hydrazide, mercuric oxide, thiophanate-methyl, azaconazole, bifenthrin, oxadiazole, cyclaconazole, difenocyclazole, diniconazole, fluazifop, fenbuconazole, Fluquinconazole, flusilazole, flutriafol, furapyramide, hexaconazole, imidacloprid, imipenem, cyproconazole, metconazole, myclobutrazol, paclobutrazol, pyraclostrobin, penconazole, prothioconazole, pyraclostrobin, prochloraz, propiconazole, pyraclostrobin, sifazole, tebuconazole, fluconazole, triadimefon, triadimenol, triflumizole, meconazole, pyrimidine alcohol, chlorfenapyr, flufenapyr, pyrimidine alcohol, ethoxybenzene sulfonate, mefenamic acid, Ethiocarb, dodecanol, phenoxydim, fenbutol, spiroxafil, tridecanol, pyraclostrobin, pyraclostrobin, pyraclostrobin, fenpiclonil, fludioxonil, bensulfuron, furalaxyl, metalaxyl, R-metalaxyl, furamide, oxalyl, carbendazim, imidacloprid, mesugine, thiabendazole, ethiocarb, sclerotin, mesugine, fumonisol, vinclozolin, pyraclostrobin, fumarate, furalaxyl, mesugine, fluazifop, fumarate Amine, sulfamethoxam, oxysulfamethoxam, penthiopyrad, thiofuran, dodinolide, biguanide, azoxystrobin, ethersoxim, enestrobin, enestrobin, flutoxin, fluoxastrobin, ethersoxim, fenoxystrobin, trifloxystrobin, trifloxystrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, ferric iron, mancozeb, mancozeb, methanamide, methyl mancozeb, mancozeb, dimethoate, chlorpyrifos, Dan, azole furan, cypermethrin, tolylfluanid, Bordeaux mixture, copper oxide, mancozeb, quinoline copper, phthalocyanine, kefansan, isoflavone, chlorpyrifos, methyl tolclofos, dichlorvos, benzathiapiprolin, blastifungin-S, chlorpyrifos, chlorothalonil, cyfluanid, cymoxanil, triflupyramide, dichloropyralid, cypermethrin, chloranil, chlordiazepoxide, chloranil, chlorpyrifos, fluopyramide, fluopyramide, dithiocarb, chloranil ... Bacillus thiocarb, oxadazole, oxathiapiprolin, imidacloprid, pyraclostrobin, fluazinam, fluopyram, fluopyram, fluopyram, sulfaquinoxaline, fluopyram, cypermethrin, fosetyl-aluminum, oxadazole, propanezid, cypermethrin, sulfaquinoxaline, mefenamic acid, pentocyclan, phthalide, polyoxamic acid, cypermethrin, pyraclostrobin, iodoquinoxaline, pyraquinoxaline, quinoxyfen, pentachloronitrobenzene Benzene, thiamethoxam, imidacloprid, tricyclazole, oxadiazine, effective mycophenolate mofetil, pyraclostrobin, benzathine, dimethomorph, flufenoxam, pyraclostrobin, flutoxafen, pyraclostrobin, flutoxafen, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide, isoprofenoxam, isothiazolin , thiabendazole, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiazol-(dithiino)[1,2-c]isothiazole-3-carbonitrile, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-dihydroindan-4-yl]pyridine-3-carboxamide, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-1-thiazol-2-one -3-carbonitrile, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethyldihydroindane-4-yl]pyrazole-4-carboxamide, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, fluopyram, Jiaxiangjunzhi, lvbenmixianan, dichlorothiazide, mandesbin, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolinone, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolinone] 1-[(1-methyltetrazolyl)oxy]phenyl]propan-2-ol, thiophene, N-[6-[[[(1-methyltetrazolyl-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamic acid tributyl ester, bixafen, indopamidol, trolprocarb, clofoconazole, isotrifluanid, 2-(difluoromethyl)-N-[(3R)-3 -ethyl-1,1-dimethyl-dihydroindan-4-yl]pyridine-3-carboxamide, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, [2-[3-[2-[1-[2-[3,5 [(1-(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl]methanesulfonate, N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamic acid but-3-ynyl ester, N-[[5-[4-(2, 4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl) tetramethyleneimine, fluopicolide, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethyldihydroindane-4-yl]pyrazole-4-carboxamide, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one, pyraclostrobin, pyraclostrobin, indazolesulfazolide, fluopicolide, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one oxazolidin-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine, diflupyrazolamide, benzylpyrimide, pyridine sulfamethoxazole, isobutyl ethoxyquinoline, isopropyl quinoline, flutoquinoline, isopropyl thiopyrad, 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylic acid ethyl ester (can be prepared by WO 2020/056090), ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enyloxy]phenyl]methyl]pyrazole-3-carboxylate (can be prepared by the method described in WO 2020/056090), methyl N-[[4-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (can be prepared by the method described in WO 2020/097012), methyl N-[[4-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate (can be prepared by the method described in WO 2020/097012), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl- -4-formamide (which can be prepared by the method described in WO 2020/109391), 6-chloro-N-[2-(2-chloro-4-methyl-phenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-tantalum -4-formamide (which can be prepared by the method described in WO 2020/109391), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl- -4-carboxamide (which can be prepared by the method described in WO 2020/109391), N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide, benzathiostrobin, cyanothiostrobin, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2: 1), Fluopyram, fluopyram, fluthiazolin, fluopyram, pyridoxamide, piperidine, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indane-4-yl)pyridine-3-carboxamide, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindane-4-yl)pyridine-3-carboxamide, 4-[ [6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, tetrazobactam, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-diphenyl]-4-yl]-5-pyrimidinemethanol, fluazifop-butyl, enoxime oxadiazole, (Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop-2-enoic acid methyl ester, (Z)-3-methoxy-2-[2-methyl-5-[4-propyltriazol-2-yl)phenoxy]prop-2-enoic acid methyl ester, (Z)-2-[5-(3-isopropylpyrazol-1-yl)-2-methyl-phenoxy]-3-methoxy-prop-2-enoic acid methyl ester, (Z)-3-methoxy-2-[2-methyl-5-(3-propylpyrazol-1-yl)phenoxy]prop-2-enoic acid methyl ester, (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]prop-2-enoic acid methyl ester (these compounds can be prepared by WO 2020/079111), (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoic acid methyl ester, (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoic acid methyl ester (these compounds can be prepared by the method described in WO 2020/193387), 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-hydrosulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile )propyl]-3-pyridyl]oxy]benzonitrile, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioketone-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, trinexapac-ethyl, syringoxystrobin, zhongshengmycin, thiophanate-methyl, thiabendazim, amitotractin, iprodione, succinimide Amine, N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-isopropyl-N-methyl-formamidine (these compounds are prepared from WO 2015/155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared by the method described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine (these compounds can be prepared by WO 2018/228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxacyclobutane-2-yl]phenyl]-N-methyl-formamidine, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine (these compounds can be prepared by WO 2019/110427); N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, 8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline -3-carboxamide, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide Amine, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide (these compounds can be prepared from WO 2017/153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline, 4,4-difluoro-3,3-dimethyl isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline (these compounds can be prepared from WO 2017/025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole (these compounds can be prepared by WO 2016/156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide )-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea 4-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl) -1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylic acid ethyl ester, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine (these compounds can be prepared by WO 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared by the method described in WO 2017/029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared by the method described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689); 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared by the method described in WO 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester (this compound can be prepared by the method described in WO 2016/156290); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound can be prepared by the method described in WO 2016/156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound can be prepared by the method described in WO 2016/156290); 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester (this compound can be prepared by the method described in WO 2,6-dimethyl-1H,5H-[1,4]dithiazo[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetraone (this compound can be prepared by the method described in WO 2011/138281), N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]thiobenzamide; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine (this compound can be prepared by the method described in WO 2011/138281); 2018/153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine;N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared by the method described in WO 2016/202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-dihydroindan-4-yl]pyridine-3-carboxamide (this compound can be prepared by the method described in WO 2-O-(2-(4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)methanone (these compounds can be prepared by the method described in WO 2017/220485); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone (these compounds can be prepared by the method described in WO 2017/220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide (this compound can be prepared by the method described in WO 2018/065414); 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylic acid ethyl ester (this compound can be prepared by WO 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[N-methoxy-methyl-carbonimino]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (these compounds can be prepared by the method described in WO 2018/202428).

The compounds of the present invention may also be used in combination with anthelmintics. Such anthelmintics include compounds selected from the class of macrolide compounds, such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemaketin and milbemycin derivatives, such as those described in EP 0357460, EP 0444964 and EP 0594291. Additional anthelmintics include semisynthetic and biosynthetic avermectin/milbemycin derivatives, such as those described in US 5,015,630, WO 9415944 and WO 9522552. Additional anthelmintics include benzimidazoles, such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of this class. Additional anthelmintics include imidazothiazoles and tetrahydropyrimidines, such as tetramisole, levamisole, pyrantel pamoate, occutane, or moroentel. Additional anthelmintics include trematodes (such as triclabendazole and clorsulon) and tapeworms (such as praziquantel and ethacryl).

The compounds of the present invention may be used in combination with derivatives and analogs of paraherquamide/marcfortine class anthelmintics and antiparasitic oxazolines such as those disclosed in US Pat. No. 5,478,855, US Pat. No. 4,639,771 and DE-19520936.

The compounds of the present invention can be used with dioxygen compounds of the general type as described in WO 9615121. Derivatives and analogs of phenoxyethanol antiparasitic agents and also in combination with anthelmintic active cyclic ester peptides (such as those described in WO 9611945, WO 9319053, WO 9325543, EP 0626375, EP 0382173, WO 9419334, EP 0382173, and EP 0503538).

The compounds of the present invention can be used in combination with other ectoparasiticides; for example, flubendiamide; pyrethroids; organophosphates; insect growth regulators such as chlorfenuron; dermatophyte agonists such as chlorfenapyr; neonicotinoids such as pyridoxine; and the like.

The compounds of the present invention may be used in combination with terpene alkaloids, such as those described in WO 95/19363 or WO 04/72086, in particular the compounds disclosed therein.

Other examples of such biologically active compounds that can be used in combination with the compounds of the present invention include, but are not limited to, the following: Organophosphates: acetylmethamidophos, methylpyraphos, ethyl glutamate, methyl glutamate, bromophos, ethyl bromophos, cadusin, chlorethoxyphos, chlorpyrifos, chlorfenapyr, chlormethylphos, demeton, demeton-S-methyl, demeton-S-methylsulfuron, chlormet, dithiophos, chlorfenapyr, dicrotophos, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate, dimethoate , chlorpyrifos, methamidophos, chlorpyrifos, methyl parathion, cypermethrin, monocrotophos, dibromophos, omethoate, methyl parathion, paraoxon, parathion, methyl parathion, chlorpyrifos, thiophanate-methyl, phosphamidon, phosphamidon, phosphamidon, phosphamidon, phosphamidon, oxathiophos, chlorpyrifos, chlorpyrifos-methyl, profenofos, profenofos, proetamphos, profenofos, pyraclofos, tadalaphos, quinalphos, thiomethoate, thimeton, terbufos, butylpyrimidinphos, stirofos, thimeton, triazophos, cypermethrin, cypermethrin. Carbamates: chloranil, chloranil, 2-butylphenyl methyl carbamate, benfuracarb, carbaryl, carbofuran, carbofuran, dithiocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801, isoprocarb, indocarb, cypermethrin, cypermethrin, 5-methyl-m-isopropylphenyl butynyl (methyl) carbamate, cypermethrin, cypermethrin, thiocarb, chloranil, thiocarb, chloranil, UC-51717. Pyrethroids: acralthrin, allethrin, alphametrin, 5-benzyl-3-furanylmethyl (E)-(1R)-cis-2,2-dimethyl-3-(2-oxathiocyclopent-3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, β-cypermethrin, cypermethrin, α-cypermethrin, β-cypermethrin, bio-allethrin, bio-allethrin ((S)-cyclopentyl isomer), bio-resmethrin, bifenthrin, NCI-85193, pyrethroids Permethrin, cyhalothrin, cypermethrin (cythithrin), cypermethrin, deltamethrin, d-cypermethrin, esfenvalerate, ethathrin, pentothrin, cypermethrin, cypermethrin, flucythrin, fluvalinate, flumethrin, fluvalinate (D isomer), imiprothrin, cyhalothrin, lambda-cyhalothrin, permethrin, phenothrin, prallethrin, pyrethrin (natural product), resmethrin, tetramethrin, transfluthrin, theta-cypermethrin, flucythrin, t-fluvalinate, tefluthrin, tralomethrin, ζ-cypermethrin. Arthropod growth regulators: a) Chitosan synthesis inhibitors: Benzyl urea: cyfluthrin, cyfluthrin, fluazifop, flufenuron, fluazifop, chlorfenuron, flufenuron, flufenuron, flufenuron, flufenuron, flufenuron, flufenuron, thiocarb, benzyl methacrylate, thiomethoxam, ethidium bromide, chlorfenapyr, chlorfenapyr; b) Corticosterone antagonists: chloranil, methoxyfenazine, chlorfenapyr; c) Juvenile hormone analogs: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) Lipid biosynthesis inhibitor: spiromethoxam. Other antiparasitic drugs: chloranil, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, chloranil, bifenazate, chloranil, bromocriptine, BTG-504, BTG-505, toxaphene, chloranil, ethyl chloranil, chloranil, bromocriptine, Cyclohexidine, thiamethoxam, cypermethrin, diacloden, cypermethrin, DBI-3204, diactin, dihydroxymethyl dihydroxypyrrolidine, dimethoate, dimethoate, endosulfan, ethopropenil, quinamoxadone, flumite, MTI-800, cyfluthrin, cyfluthrin, flumethrin, flumethrin, triflumuron, fluproxyfen, halofenprox, flufenhydrin, IKI-220, sodium silicate, NC-196, neem guard), nidinorterfuran, nitenpyram, SD-35651, WL-108477, pyraclostrobin, cyfluthrin, protrifenbute, pymetrozine, cyfluthrin, NC-1111, R-195, RH-0345, RH-2485, RYI -210, S-1283, S-1833, SI-8601, flucythrin, silomadine, polysaccharide, pyrimidine, triclosan, tetracycline, thiamethoxam, cypermethrin, thiamethoxam, trimethoprim, trifloxystrobin, triacylglycerol, pyralidone, vertalec, YI-5301. Biological agents: Bacillus thuringiensis ssp aizawai, Bacillus thuringiensis ssp kurstaki, Bacillus thuringiensis delta endotoxin, bacillary viruses, insect pathogenic bacteria, viruses and fungi. Bactericidal agents: aureomycin, terephthalate, streptomycin. Other biological agents: enrofloxacin, febantel, pentoxacillin, meloxicam, ceftriaxone, conmycin, pimobendan, clenbuterol, omeprazole, tiamulin, benazepril, pyriprole, cefquinome, florfenicol, buserelin, cefuroxime, toramectin, ceftiofur, carprofen, mefluazione, praziquantel, triclabendazole.

The following mixtures of a compound of formula (I) and an active ingredient are preferred. The abbreviation "TX" means a compound selected from the compounds of formula (I), (II), (II-A), (II-A1), (II-B), (II-B1), (II-C), (II-C1), (II-D) or (II-D1) according to the present invention, or a compound selected from the compounds listed in Tables A-1 to A-24 or Table P (below): A compound selected from the group consisting of: petroleum + TX, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX, 2,4-dichlorophenylbenzenesulfonate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 4-chlorophenylphenylsulfonate + TX, acetothionil + TX, aldicarb + TX, sago + TX, fomanphos + TX, amitriptyline + TX, amitriptyline + TX, oxalate + TX, amitraz + TX, cypermethrin + TX, chlorpyrifos + TX, arsenic trioxide + TX, azobenzene + TX, azophos + TX, benomyl + TX, benzyl benzoate + TX, bixafen + TX, bromomethrin + TX, bromomethrin + TX X, bromophos + TX, bromofenacet + TX, thiamethoxam + TX, butanone + TX, butanone + TX, butyl chlorpyrifos + TX, calcium polysulfide + TX, octachlorocamphene + TX, chlorfenapyr + TX, trithion + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin hydrochloride + T X, cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, ethyl cypermethrin + TX, cypermethrin + TX, propyl cypermethrin + TX, cypermethrin + TX, cypermethrin I + TX, cypermethrin II + TX, cypermethrin + TX, closantel + TX, cypermethrin + TX, crotamiton + TX, baclofos + TX, thiophanate+TX, chlorfenapyr+TX, DCPM+TX, DDT+TX, dinafop+TX, dinafop-O+TX, dinafop-S+TX, demeton-methyl+TX, demeton-O+TX, demeton-O-methyl+TX, demeton-S+TX, demeton-S-methyl+TX, demeton-S-methyl+TX, demeton-S-methyl+TX, demeton-S-methyl+TX, demeton-S-methyl+TX, demeton-S-methylsulfon+TX, chlorfenapyr+TX, chlorfenapyr+TX, dicliphos+TX, chlorfenapyr+TX, chlorfenapyr+TX, chlorfenapyr+TX, dinex+TX, dinex-diclexine+TX, chlorfenapyr Pu-4+TX, Dimitrop-6+TX, Lindimit+TX, Nitral+TX, Nitral+TX, Nitral+TX, Nitral+TX, Nitral+TX, Dimethoate+TX, Sulfondiphenyl+TX, Disulfiram+TX, DNOC+TX, Benoxyacetin+TX, Doramectin+TX, Indox+TX, Eprinomectin+TX, Ethiophos+TX, Ethiophos+TX, Antimitox+TX, Fenbuterol+TX, Fenthiocarb+TX, Fenpyrad+TX, Afenpyrad+TX, Afenpyrad+TX, Afenpyrad+TX, Afenpyrad+TX, Afenpyrad+TX, Flunitrodiphenylamine+TX, Flufenamid+TX, Flufenazuron+TX, Diflumex+TX, Flumethoate+TX, FMC 1137+TX, fenvalerate+TX, fenvalerate hydrochloride+TX, carbendazim+TX, γ-HCH+TX, chloranil+TX, benzyl chloranil+TX, hexadecyl cyclopropane carboxylate+TX, isocarbophos+TX, jasmonate I+TX, jasmonate II+TX, iodine+TX, lindane+TX, propiconazole+TX, cypermethrin+TX, dithiophos+TX, methylthiophene+TX, cypermethrin+TX, methyl bromide+TX, cypermethrin+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil+TX, chloranil -3-Keto+TX, Flufenamic Acid+TX, Nicomycin+TX, Pentocyancarb+TX, Pentocyancarb 1: 1 Zinc chloride complex + TX, omethoate + TX, isothiophos + TX, sulfophos + TX, pp'-DDT + TX, parathion + TX, permethrin + TX, fenthion + TX, phosphamidon + TX, thiophanate + TX, chlorinated turpentine + TX, acarb + TX, chlorfenapyr + TX, chlorfenapyr + TX, chlorfenapyr + TX, chlorfenapyr + TX, ethidium + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrin + TX, pyrethrin + TX, pyrethiophos + TX, pyrethiophos + TX, quinalphos + TX, quinalphos + TX, R-1492 + TX, glyphosate + TX, rotenone + TX, octamidine + T X, chloranil + TX, selamectin + TX, sulfothion + TX, SSI-121 + TX, sulphidon + TX, flumethrin + TX, sulfur + TX, fluazifop + TX, τ-fluvalinate + TX, TEPP + TX, terbutaline + TX, tetrachlorvinphos + TX, chloranil + TX, thiafenox + TX, cypermethrin + TX, thiafenox + TX, chloranil + TX, methyl sulfamethoxam + TX, chloranil + TX, sulfothion + TX, sulfothion + TX, sulfothion + TX, chloranil + TX, sulfothion + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil Methoxazine + TX, copper dioctanoate + TX, copper sulfate + TX, cybutryne + TX, dichloronaphthoquinone + TX, dichlorophenol + TX, mycophenolic acid + TX, triphenyltin + TX, slaked lime + TX, mancozeb + TX, quinone + TX, quinone + TX, simazine + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, oxadiazine + TX, piperidine + TX, thiophanate + TX, chloralose + TX, fenthion + TX, pyridin-4-amine + TX, strychnine + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 4-(quinolin-2-ylamino)benzenesulfonamide + TX, 8-hydroxyquinoline sulfate Salt + TX, bronopol + TX, copper hydroxide + TX, cresol + TX, dipyrithione + TX, dodesine + TX, sodium sulfonate + TX, formaldehyde + TX, mercury plus phen + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel di(dimethyldithiocarbamate) + TX, trichloromethylpyridine + TX, octhilthione + TX, oxolinic acid + TX, terpenoid + TX, hydroxyquinoline potassium sulfate + TX, thiabendazole + TX, streptomycin + TX, streptomycin sesquisulfate + TX, chlorothiazide + TX, thimerosal + TX, cotton brown banded moth GV + TX, radiobacterium + TX, Amblyseius spp.)+TX, celery armyworm NPV+TX, original cherry-winged wasp (Anagrus atomus)+TX, short-spurred aphid wasp+TX, cotton aphid parasitic wasp (Aphidius colemani)+TX, aphid-eating gall midge (Aphidoletes aphidimyza)+TX, alfalfa silver moth NPV+TX, sphaericus neide (Bacillus sphaericus Neide)+TX, Beauveria brongniartii (Beauveria brongniartii)+TX, common lacewing (Chrysoperla carnea)+TX, Meng's hidden lip ladybird (Cryptolaemus montrouzieri)+TX, apple moth GV+TX, Siberian sibirica wasp (Dacnusa sibirica)+TX, pea leaf divers (Diglyphus isaea + TX, Encarsia formosa + TX, Eretmocerus eremicus + TX, Heterorhabditis bacteriophora and Heterorhabditis spp. megidis+TX, Hippodamia convergens+TX, Leptomastix dactylopii+TX, Macrolophus caliginosus+TX, Cabbage armyworm NPV+TX, Metaphycus helvolus+TX, Metarhizium anisopliae var. acridum+TX, Metarhizium anisopliae var. anisopliae+TX, Neodiprion sertifer NPV and N. lecontei NPV+TX, Microstomus species+TX, Pseudomonas spp.+TX, Phytoseiulus spp.+TX, persimilis +TX, Steinernema bibionis +TX, Steinernema carpocapsae +TX, Steinernema lanceolata +TX, Steinernema glaseri +TX, Steinernema riobrave +TX, Steinernema riobravis +TX, Steinernema scapterisci +TX, Steinernema spp. +TX, Trichogramma species +TX, Typhlodromus occidentalis +TX, Verticillium lecanii）+TX、oxazolidinone+TX、bis(aziridine)methylaminophosphine sulfide+TX、busulfan+TX、dimetif+TX、hexamethylmelamine+TX、hexamethylphosphine+TX、methyl tibac+TX、methylthiotibac+TX、methyloxazolidinone+TX、infertilizer+TX、flufenuron+TX、tibac+TX、thiohexamethylphosphine+TX、thiotibac+TX、trothamide+TX、urethaneimide+TX、(E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol+TX、(E)-tridec-4-en-1-yl acetate+TX、(E)-6-methylhept-2-en-4-ol+TX、(E ,Z)-tetradec-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-eicos-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, (7E,9Z)-dodec-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradec-9,12-dien-1-yl acetate + TX, 14-methyloctadec-1-ene + TX, 4-methylnon-5-ol and 4-methylnon-5-one + TX, α-polystyrene + TX, western pine beetle aggregation information + TX, dodecadienol + TX, codmon + TX, oxadifenone + TX, epoxynonadecane + TX, dodec-8-en-1-yl acetate + TX, dodec-9-en-1-yl acetate + TX, dodec-8 + TX, 10-dien-1-yl acetate + TX, Dominicalure + TX, 4-methyloctanoic acid ethyl ester + TX, eugenol + TX, southern pine beetle aggregation information + TX, ene mixture + TX, ene mixture I + TX, ene mixture II + TX, ene mixture III + TX, ene mixture IV + TX, hexane attractant + TX, halogenated beetle dienol + TX, small beetle alcohol + TX, golden turtle attractant + TX, trimethyldioxytricyclononane + TX, noctuid attractant (litlure) + TX, powdery mildew bud attractant + TX, attractant ester + TX, (3E,5Z)-tetradec-3,5-dienoic acid (megatomoic acid) + TX, cypermethrin + TX, cypermethrin + TX, octadec-2,13-dien-1-yl acetate + TX, octadec-3,13-dien-1-yl acetate + TX, Heconbi + TX, Coconut rhinoceros turtle aggregation pheromone + TX, Felocon + TX, Cypermethrin + TX, Banana bulb weevil attractant (sordidin) + TX, Mycophagous foram + TX, Tetradec-11-en-1-yl acetate + TX, Mediterranean fruit fly attractant +TX, Mediterranean fly attractant A+TX, Mediterranean fly attractant B1+TX, Mediterranean fly attractant B2+TX, Mediterranean fly attractant C+TX, trunc-call+TX, 2-(octylthio)ethanol+TX, dimethoate+TX, butoxy(polypropylene glycol)+TX, dibutyl adipate+TX, dibutyl phthalate+TX, dibutyl succinate+TX, DEET+TX, dimethyl carbate) + TX, dimethyl phthalate + TX, ethyl hexanediol + TX, hexylurea + TX, mequindine + TX, methyl neodecylamide + TX, oxalamide + TX, picaridin + TX, 1-dichloro-1-nitroethane + TX, 1,1-dichloro-2,2-di(4-ethylphenyl)ethane + TX, 1,2-dichloropropane and 1,3-dichloropropylene + TX, 1-bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-( 2-Butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenylmethylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidinone + TX, 2-isopentyldihydroindane-1,3-dione + TX, 2-methyl (prop-2-ynyl) aminophenylmethylcarbamate + TX, 2-thiocyanatoethyl laurate + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-methyl-1-phenylpyrazol-5-yldimethylcarbamate + TX, 4-methyl (prop-2-ynyl) amino-3,5-xylylmethylcarbamate +TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate +TX, acethion +TX, acrylonitrile +TX, aldrin +TX, alloamido +TX, chlorfenapyr +TX, α-chlorpyrifos +TX, aluminum phosphide +TX, chlorfenapyr +TX, nicotine +TX, ethyl chlorfenapyr +TX, methyl pyrifos +TX, Bacillus thuringiensis δ-endotoxin +TX, barium hexafluorosilicate +TX, barium polysulfide +TX, fumonisin +TX, Bayer 22/190 +TX, Bayer 22408 +TX, β-cyfluthrin +TX, β-cypermethrin +TX, pentothrin +TX, biopermethrin +TX, bis(2-chloroethyl) ether +TX, borax +TX, bromophenazone +TX, bromo-DDT +TX, chlorpyrifos +TX, cypermethrin +TX, cypermethrin +TX, butyl phosphate +TX, calcium arsenate +TX, calcium cyanide +TX, carbon disulfide +TX, carbon tetrachloride +TX, cypermethrin hydrochloride +TX, servadine +TX, borneol +TX, chlordane +TX, chlordecone +TX, chloroform +TX, chloropicrin +TX, chlornitrothion +TX, chlorpyrifos +TX, cis-resmethrin +TX, cismethrin +TX, cypermethrin +TX, copper acetylarensite +TX, copper arsenate +TX, copper oleate +TX, cypermethrin +TX, cryolite +TX, CS 708+TX, benzonitrile+TX, cypermethrin+TX, cypermethrin+TX, cypermethrin+TX, d-cypermethrin+TX, DAEP+TX, dazomethane+TX, demethylcarbofuran+TX, chlorpyrifos+TX, isochlorophos+TX, chlorpyrifos+TX, dicresyl+TX, cypermethrin+TX, dieldrin+TX, diethyl 5-methylpyrazol-3-yl phosphate+TX, cypermethrin+TX, tetrafluthrin+TX, demacarb+TX, pyrethrin+TX, methylcarbazin+TX, cypermethrin+TX, methylcarbazin+TX, cypermethrin+TX, propanol+TX, pentotropol+TX, dimethoate+TX, fenthrin+TX, fenthion+TX, vesiculophos+TX, thiopyrafos+TX, DSP+TX, cyclohexanone+TX, EI 1642+TX, EMPC+TX, EPBP+TX, etaphos+TX, ethiofencarb+TX, ethyl formate+TX, ethylene dibromide+TX, ethylene dichloride+TX, ethylene oxide+TX, EXD+TX, chlorpyrifos+TX, ethylbencarb+TX, chlorpyrifos+TX, cypermethrin+TX, fenthion+TX, ethylfenthion+TX, fluazifop+TX, butylfenthion+TX, phosphamidon+TX, butylfenthion+TX, furamidocarb+TX, antipyrethroid+TX, biguanide+TX, biguanide Octyl acetate + TX, sodium tetrathiocarbonate + TX, benzyl chloramine + TX, HCH + TX, HEOD + TX, heptachlor + TX, mefenphos + TX, HHDN + TX, hydrogen cyanide + TX, quinoline carbendazim + TX, IPSP + TX, chlorfenapyr + TX, carbofuran + TX, isoflurane + TX, isoflurane + TX, transplanting spirit + TX, rice blast spirit + TX, oxazophos + TX, juvenile hormone I + TX, juvenile hormone II + TX, j juvenile hormone III + TX, chlorfenapyr + TX, methoxyfen + TX, lead arsenate + TX, bromophenylphos + TX, pyraclostrobin + T X, thiathiazophos + TX, methyl cumyl methylcarbamate + TX, magnesium phosphide + TX, chlorpyrifos + TX, methyl chlorpyrifos + TX, chlorpyrifos + TX, mercurous chloride + TX, methyl chlorpyrifos + TX, metabolite + TX, metabolite potassium salt + TX, metabolite sodium salt + TX, methyl sulfonyl fluoride + TX, butylene phosphonate + TX, methoprene + TX, methyl ether thiocyanate + TX, methoxychlor + TX, methyl isothiocyanate + TX, methyl chloroform + TX, dichloromethane + TX, chlorpyrifos + TX, anthelmintic + TX, naphthiophos + TX, naphthalene + TX, NC-170 + T X, nicotine + TX, nicotine sulfate + TX, nitrobenzene + TX, protonycin + TX, O-5-dichloro-4-iodophenyl O-ethylethyl phosphonothioate + TX, O,O-diethyl O-4-methyl-2-oxo-2H-benzopyran-7-yl phosphonothioate + TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphonothioate + TX, O,O,O',O'-tetrapropyl dithiodipyrophosphate + TX, oleic acid + TX, p-dichlorobenzene + TX, methyl parathion + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH 60-38+TX, fenthion+TX, parachlorothion+TX, hydrogen phosphide+TX, methyl phoxim+TX, methamidophos+TX, polychlorinated dicyclopentadiene isomers+TX, potassium arsenite+TX, potassium thiocyanate+TX, precocious element I+TX, precocious element II+TX, precocious element III+TX, pyrimethamine+TX, profluthrin+TX, cypermethrin+TX, prothiophene+TX, pyraclostrobin+TX, pyraclostrobin+TX, bitter Wood extract + TX, quinalphos-methyl + TX, cypermethrin + TX, iodophos + TX, resmethrin + TX, rotenone + TX, thiamethoxam + TX, ryanodine + TX, saba quinoa + TX, octamethoxazole + TX, chloranthate + TX, SI-0009 + TX, thiamethoxam + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium hexafluorosilicate + TX, sodium pentachlorophenol + TX, selenic acid Sodium + TX, sodium thiocyanate + TX, sulfofensulfuron + TX, sulfofensulfuron sodium + TX, sulfofensulfuron + TX, tar + TX, thiocarb + TX, TDE + TX, butylpyrimidinphos + TX, chlorpyrifos + TX, cypermethrin + TX, tetrachloroethane + TX, thiochlorvos + TX, chlorfenapyr + TX, chlorfenapyr + TX, chlorfenapyr sodium + TX, tralomethrin + TX , trans-permethrin + TX, triazolam + TX, isoflurane + TX, chlorpyrifos + TX, chlorpyrifos + TX, chlorpyrifos + TX, chlorpyrifos + TX, veratrum + TX, veratrum + TX, XMC + TX, ζ-cypermethrin + TX, zinc phosphide + TX, toxaphene + TX, chlorfluanidine + TX, tetrafluanidine + TX, bis(tributyltin) oxide + TX, bromoacetamide + TX, phosphoric acid Iron + TX, niclosamide-ethanolamine + TX, tributyltin oxide + TX, pyridine + TX, snail killer + TX, 1,2-dibromo-3-chloropropane + TX, 1,3-dichloropropylene + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-(4-chlorophenyl)-5-methylrosenin + TX, 5-methyl-6-thioxo-1,3,5-thiadioxadiazole-3-acetic acid + TX, 6-isoprenylamidopurine + TX, 2-fluoro-N-(3-methoxyphenyl)-9H-purine-6-amine + TX, benzothiol + TX, cytokinin + TX, DCIP + TX, furfural + TX, isoamidophos + TX, kinetin + TX, verrucosporium mycorrhizal composition + TX, tetrachlorothiophene + TX, xylenol + TX, zeatin + TX, potassium ethyl xanthate + TX, acibenzolar + TX, acibenzolar-S-methyl + TX, Polygonum cuspidatum extract + TX, α-chlorohydrin + TX, antu + TX, barium carbonate + TX, bifenthion + TX, brodifacoum + TX, bromodifacoum + TX, bromodifacoum + TX, chlorodifacoum + TX, cholecalciferol + TX, chlordifacoum + TX, chloranil ... Salt + TX, cypermethrin + TX, cypermethrin + TX, phosphorus + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, sodium fluoroacetate + TX, potassium sulfate + TX, cypermethrin + TX, 2-(2-butoxyethoxy)ethyl piperate + TX, 5-(1,3-benzodioxolane-5-yl)-3-hexylcyclohex-2-enone + TX, nerolidol + TX, synergistic acetyl ether + TX, MGK 264+TX, piperonyl butoxide+TX, synergistic aldehyde+TX, propyl isomers+TX, S421+TX, synergistic powder+TX, sesamelin+TX, sulfoxide+TX, anthraquinone+TX, copper cycloalkanoate+TX, copper ronate+TX, dicyclopentadiene+TX, salene+TX, zinc cycloalkanoate+TX, fenamidate+TX, imanin+TX, ribavirin+TX, mercuric oxide+TX, thiophanate-methyl+TX, azaconazole+TX, bifenthrin+TX, oxadiazole+TX, oxadiazole+TX, oxadiazole+TX, oxadiazole+TX, oxadiazole+TX , fenbuconazole + TX, fluquinconazole + TX, flusilazole + TX, flutriafol + TX, furopyram + TX, hexaconazole + TX, imidacloprid + TX, imipenem + TX, methconazole + TX, myclobutrazol + TX, paclobutrazol + TX, pyraclostrobin + TX, penconazole + TX, prothioconazole + TX, pyraclostrobin + TX, prochloraz + TX, cypermethrin + TX, propiconazole + TX, pyraclostrobin + TX, sifazole + TX, tebuconazole + TX, fluconazole + TX, triadimefon + TX, triadimenol + TX, triflumizole + TX, meconazole + TX, pyrimidine + TX, chlorfenapyr Alcohol + TX, flufenamic acid + TX, pyrimidine + TX, pyrimidine + TX, mefenamic acid + TX, dodecanol + TX, pheniramine + TX, butylfenamic acid + TX, spiroxafil + TX, tridecanol + TX, pyraclostrobin + TX, pyraclostrobin + TX, pyrimidine + TX, fenpicrol + TX, fludioxonil + TX, bensulfuron + TX, furalaxyl + TX, metalaxyl + TX, R-metalaxyl + TX, furamide + TX, oxaloxaline + TX, carbendazim + TX, imidacloprid + TX, mysuining + TX, thiabendazole + TX, mefenamic acid + TX, sclerotinol + T X, carbendazim + TX, humic acid + TX, vinclozolin + TX, pyraclostrobin + TX, chloranil + TX, chloranil + TX, fluazifop + TX, chloranil + TX, oxychloranil + TX, penthiopyrad + TX, thiofuran + TX, docodine + TX, guanidine + TX, azoxystrobin + TX, pyraclostrobin + TX, fenoxam + TX, fenoxam + TX, flutostrobin + TX, fluoxastrobin + TX, fenoxam + TX, pyraclostrobin + TX, oxazolidinone + TX, oxazolidinone + TX, pyraclostrobin + TX, oxazolidinone Strombolin+TX, pyraclostrobin+TX, ferram+TX, mancozeb+TX, mancozeb+TX, methanal+TX, methanal+TX, methanzine+TX, methanal+TX, mefentanil+TX, mefentanil+TX, mefentanil+TX, mefentanil+TX, mefentanil+TX, mefentanil+TX, Bordeaux mixture+TX, copper oxide+TX, mancozeb+TX, quinoline copper+TX, phthalostrobin+TX, fenvalerate+TX, fenvalerate+TX, fenvalerate+TX, fenvalerate+TX, fenvalerate+TX, fenvalerate+TX, fenvalerate-S+TX, fenvalerate+TX , chlorothalonil+TX, cyfluanid+TX, cymoxanil+TX, triflupyralid+TX, dichlorocyanamide+TX, cyclohexanil+TX, chloranil+TX, ethocarb+TX, oxadiazine+TX, flutolan+TX, dithiazone+TX, ethaboxam+TX, oxadone+TX, fenamidone+TX, pyraclostrobin+TX, meconium+TX, fluopyram+TX, sulfaquinoxaline+TX, fluazinam+TX, fluopyram+TX, cypermethrin+TX, fosetyl-aluminum+TX, oxadone+TX, propionyl+TX, saizomide+TX , sulfamethoxam + TX, mefenamic acid + TX, pencuron + TX, phthalide + TX, polyoxamic acid + TX, cypermethrin + TX, pyraclostrobin + TX, iodoquinolone + TX, pyraclostrobin + TX, benpyram + TX, quinoxyfen + TX, pentachloronitrobenzene + TX, thiamethoxam + TX, imidacloprid + TX, tricyclazole + TX, oxadiazine + TX, effective mycobacterium + TX, cypermethrin + TX, benzylpyridin + TX, dimethomorph + TX, flufenoxam + TX, pyraclostrobin + TX, flutoxafen + TX, fenpyrad + TX, flutoxafen + TX, flutoxafen + TX X, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, isopropyram + TX, isothiopyram + TX, thiophanate-methyl + TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiazo[1,2-c]isothiazole-3-carbonitrile + TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-dihydroindan-4-yl]pyridine-3-carboxamide + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-tantalum -3-carbonitrile + TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethyldihydroindan-4-yl]pyrazole-4-carboxamide + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine + TX , flutolanil + TX, jiaxiangjunzhi + TX, lvbenmixianan + TX, dichlorothiocarb + TX, mandesbin + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolinone + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol + TX, thiophene Bacillus+TX, N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamic acid tributyl ester+TX, bixafen+TX, indoppyraclostrobin+TX, trolprocarb+TX, clofodilazuron+TX, isotrifloxacin+TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-dihydroindane-4-yl] Pyridine-3-carboxamide + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-carboxamidine + TX, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-carboxamidine + TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]thiazol-4-yl]-4, 5-dihydroisoxazol-5-yl]-3-chloro-phenyl] methanesulfonate + TX, N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamic acid but-3-ynyl ester + TX, N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester + TX, 3-chloro-6-methyl-5-phenyl-4-( 2,4,6-trifluorophenyl) pyridine + TX, fluphenazine + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethyldihydroindane-4-yl]pyrazole-4-carboxamide + TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazolyl-5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethyl [(4-( ... , flutolanil + TX, isoprenaline + TX, N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, benzathiostrobin + TX, cyproconazole + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2: 1) + TX, fluopyram + TX, fluthiazolin + TX, fluopyram + TX, pyridinamide + TX, piperidine + TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, 4-[[6-[2-( 2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, tetrazobactam + TX, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-diphenyl]-4-yl]-5-pyrimidinemethanol + TX, fluazifop-butyl + TX, enestrobin + TX, 4-[[6-[2-(2,4- 1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-hydrosulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-hydrosulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 1-Difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, trinexapac-ethyl + TX, syringoxystrobin + TX, zhongshengmycin + TX, thiophanate-methyl + TX, thiabendazim + TX, amethoxam + TX, ametolin (amectotractin) + TX, iprodione + TX, N-octyl-N'-[2-(octylamino)ethyl]ethane-1,2-diamine +TX, N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine +TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine +TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds are prepared from WO 2015/155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared by the method described in IPCOM 000249876 D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine + TX, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds can be prepared by WO 2018/228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxacyclobutane-2-yl]phenyl]-N-methyl-formamidine + TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine + TX (these compounds can be prepared by WO 2019/110427); N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]- 8-Fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3- Formamide + TX, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-formamide + TX, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-formamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-formamide + T X, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX (these compounds can be prepared from WO 2017/153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline+TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline+TX, 4,4-difluoro-3,3-dimethyl -1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline+TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline+TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline+TX (these compounds can be prepared from WO 2017/025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1 -(4-methylbenzimidazol-1-yl)isoquinoline + TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole + TX (these compounds can be prepared from WO 2016/156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide + TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide + TX, )-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide+TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX, 3-ethyl-1-methoxy-1-[[4-[ 5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide+TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one+TX, 5,5-dimethyl-2-[[4-[5 -(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one+TX, 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylic acid ethyl ester+TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine+TX. The compounds in this paragraph can be prepared by the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689: 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridinyl]-1-(1,2,4-triazol-1-yl)propan-2-ol+TX (this compound can be prepared by the method described in WO 2017/029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridinyl]-1-(1,2,4-triazol-1-yl)propan-2-ol+TX (this compound can be prepared by the method described in WO 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester + TX (this compound can be prepared by the method described in WO 2016/156290); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl] imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016/156290); 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester + TX (this compound can be prepared by the method described in WO 2016/156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl] imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016/156290); 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester + TX (this compound can be prepared by the method described in WO 2014/006945); 2,6-dimethyl-1H,5H-[1,4]dithiazo[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetraone + TX (this compound can be prepared by WO 2011/138281) + TX, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]thiobenzamide + TX; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide + TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine + TX (this compound can be prepared by WO 2018/153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX; N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared by the method described in WO 2016/202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-dihydroindan-4-yl]pyridine-3-carboxamide + TX (this compound can be prepared by the method described in WO 2-O-(2-(4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)methanone+TX, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone+TX (these compounds can be prepared by the method described in WO 2017/220485); 2-(2-(4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)acetamide+TX (this compound can be prepared by the method described in WO 2018/065414); 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylic acid ethyl ester + TX (this compound can be prepared by WO 2018/158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]acetamide + TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide + TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide + TX, N-[N-methoxy-methyl-carbonimino]-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide + TX (these compounds can be prepared by WO 2018/202428), chloroindole hydrazide + TX, fluopyram + TX, fluopyram + TX, trifloxystrobin + TX, pyraclostrobin + TX.

References in brackets after the active ingredient, e.g. [3878-19-1] , refer to the Chemical Abstracts Registration Number. The mixtures described above are known. In case the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; 13th edition; editor: CDS TomLin; The British Crop Protection Council]], they are described therein by the entry number given in brackets above for the specific compound; e.g. the compound "abamectin" is described by the entry number (1). Where "[CCN]" is added above to a particular compound, the compound in question is included in the "Compendium of Pesticide Common Names", which is available on the Internet [A. Wood; Compendium of Pesticide Common Names, Copyright © 1995-2004]; for example, the compound "acetoprole" is described at the Internet address http://www.alanwood.net/pesticides/acetoprole.html.

Most of the above active ingredients are referred to above by so-called "common names", in a single case the corresponding "ISO common name" or another "common name" is used. If a name is not a "common name", the kind of name used is replaced by the name given in parentheses for the specific compound; in this case, the IUPAC name, IUPAC/Chemical Abstracts name, "Chemical Name", "Conventional Name", "Compound Name" or "Development Code" is used, or, if neither one of those names nor the "common name" is used, a "synonym" is used. "CAS registration number" means the Chemical Abstracts registration number.

The active ingredient mixture of a compound selected from the compounds of formula (I), (II), (II-A), (II-A1), (II-B), (II-B1), (II-C), (II-C1), (II-D), or (II-D1) according to the present invention or a compound selected from the compounds listed in Tables A-1 to A-24, or Table P (below) is preferably in a mixing ratio of from 100:1 to 1:100, in particular from 50:1 to 1:50, more particularly from 20:1 to 1:20, even more particularly from 10:1 to 1:10, and still more particularly from 5:1 to 1:5, those mixing ratios being by weight.

The mixtures as described above may 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, except for methods for treating the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body.

Mixtures comprising a compound selected from compounds of formula (I), (II), (II-A), (II-A1), (II-B), (II-B1), (II-C), (II-C1), (II-D), or (II-D1) according to the present invention or a compound selected from the compounds listed in Tables A-1 to A-24, or Table P (below) and one or more active ingredients as described above can be applied, for example, in the form of a single "ready-mix", in a combined spray mixture (which mixture consists of individual formulations of the individual active ingredients) (e.g., a "tank-mix"), and in combination with the individual active ingredients when applied in a sequential manner (i.e., one after another appropriately short period of time, such as a few hours or days). A compound selected from the compounds of formula (I), (II), (II-A), (II-A1), (II-B), (II-B1), (II-C), (II-C1), (II-D) or (II-D1) according to the present invention, or a compound selected from the compounds listed in Tables A-1 to A-24, or Table P (below), and one or more active ingredients as described above are not essential for the implementation of the present invention.

The compositions according to the invention may also contain further solid or liquid adjuvants, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (e.g. epoxidized coconut oil, rapeseed oil or soybean oil), defoamers (e.g. silicone oils), preservatives, viscosity regulators, binders and/or tackifiers, fertilizers or other active ingredients for achieving specific effects, such as bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

The compositions according to the invention are prepared in a manner known per se in the absence of auxiliary agents, for example by grinding, sieving and/or compressing the solid active ingredient; and in the presence of at least one auxiliary agent, for example by intimately mixing the active ingredient with one or more auxiliary agents and/or grinding the active ingredient with one or more auxiliary agents. Such methods for preparing the compositions and the use of compound (I) for preparing such compositions are also subject matter of the present invention.

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

Another aspect of the present invention relates to a method for controlling or preventing plants (e.g. useful plants (e.g. crop plants)), their propagation materials (e.g. seeds), harvested crops (e.g. harvested food crops), or non-living materials from being infested by phytopathogenic microorganisms or spoilage microorganisms or organisms potentially harmful to humans (especially fungal organisms), which method comprises applying a compound of formula (I) according to the present invention or preferably various compounds as defined herein as an active ingredient to the plants, parts of the plants or their loci, their propagation materials, or any part of the non-living materials.

Control or prevention means the reduction of infestation by insects or phytopathogenic or spoilage microorganisms or organisms potentially harmful to humans (especially fungal organisms) to such a level that improvement is demonstrated.

A preferred method for controlling or preventing infestation of crop plants by phytopathogenic microorganisms (especially fungal organisms) or insects is foliar application, which comprises applying a compound of formula (I) according to the invention, or an agrochemical composition containing at least one compound of formula (I). The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogens or insects. However, the compound of formula (I) according to the invention can also penetrate the plant via the soil through the roots (systemic action) by soaking the plant locus with a liquid formulation or by applying the compound in solid form, for example in granular form, to the soil (soil application). In rice crops, such granules can be applied to irrigated rice fields. The compounds of formula (I) can also be applied to seeds (coating) by impregnating the seeds or tubers with a liquid formulation of the fungicide, or coating them with a solid formulation.

Formulations (e.g., compositions containing a compound of formula (I) according to the invention and, if desired, a solid or liquid adjuvant or monomer for encapsulating the compound of formula (I)) can be prepared in a known manner, typically by intimately mixing and/or grinding the compound with an extender (e.g., a solvent, a solid carrier and, if desired, a surface-active compound (surfactant)).

Advantageous application rates are usually from 5 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha, most preferably from 20 g to 600 g a.i./ha. When used as a seed drench, a suitable dosage is from 10 mg to 1 g active substance/kg seed.

As used herein, the term "gai/ha" refers to an application rate given in grams [g] of active ingredient [ai] per unit surface [ha]. The unit hectare (symbol ha) is a metric unit of area equivalent to a square with a side length of 100 m (1 hm ² ) or 10,000 square meters. The hectare is a commonly used unit of area in the metric system.

When the combination of the invention is used to treat seeds, a ratio of 0.001 to 50 g of compound of formula (I) per kg of seeds, preferably from 0.01 to 10 g per kg of seeds, is generally sufficient.

Suitably, the composition according to the invention comprising a compound of formula (I) is administered prophylactically (meaning before development of the disease) or therapeutically (meaning after development of the disease).

The composition of the present invention can be used in any conventional form, such as double packaging, dry seed treatment powder (DS), seed treatment emulsion (ES), seed treatment flowable concentrate (FS), seed treatment solution (LS), seed treatment water dispersible powder (WS), seed treatment capsule suspension (CF), seed treatment gel (GF), emulsion concentrate (EC), suspension concentrate (SC), suspension emulsion (SE), capsule suspension (CS), water The invention can be used in the form of dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), dispersible oil suspensions (OD), oil suspensions (OF), oil-soluble liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), master batches (TK), dispersible concentrates (DC), wettable powders (WP) or any technically feasible formulations in combination with agriculturally acceptable adjuvants.

Such compositions can be produced in a conventional manner, for example by mixing the active ingredient with appropriate formulation inerts (diluents, solvents, fillers and, if necessary, other formulation ingredients such as surfactants, biocides, antifreeze agents, adhesives, thickeners and compounds providing auxiliary effects). Conventional sustained-release formulations intended to provide long-lasting effects can also be used. In particular, formulations to be applied in the form of a spray, such as water-dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO, etc.), wettable powders and granules may contain surfactants such as wetting agents and dispersants and other compounds providing an auxiliary effect, such as condensation products of formaldehyde with naphthalenesulfonates, alkylarylsulfonates, ligninsulfonates, fatty alkyl sulfates and ethoxylated alkylphenols and ethoxylated fatty alcohols.

Using the combination and diluent of the invention, the seed dressing formulation is applied to the seeds in a manner known per se in the form of a suitable seed dressing formulation, for example an aqueous suspension or dry powder having good adhesion to the seeds. Such seed dressing formulations are known in the art. The seed dressing formulation may contain a single active ingredient or a combination of active ingredients in encapsulated form, for example as a slow-release capsule or microcapsule.

Typically, such formulations contain from 0.01% to 90% by weight of active agent, from 0% to 20% of an agriculturally acceptable surfactant and 10% to 99.99% of a solid or liquid formulation inert agent and one or more adjuvants, the active agent consisting of at least a compound of formula (I) according to the present invention, optionally together with other active agents (especially microbicides or preservatives, etc.). Concentrated forms of the composition typically contain between about 2% and 80% by weight, preferably between about 5% and 70% by weight of active agent. The application form of the formulation may, for example, contain from 0.01% to 20% by weight, preferably from 0.01% to 5% by weight of active agent. While commercial products will preferably be formulated as concentrates, the end user will generally employ dilute formulations.

While it is preferred that commercial products be formulated as concentrates, the end user will generally employ a dilute formulation.

The application rates vary within a wide range and depend on the nature of the soil, the method of application, the crop plants, the pests to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. In general, the compounds can be applied at a rate of from 1 l/ha to 2000 l/ha, in particular from 10 l/ha to 1000 l/ha.

Preferred formulations may have the following composition (weight %): Emulsifiable concentrates: Active ingredient:                         1% to 95%, preferably 60% to 90% Surfactant:                       1% to 30%, preferably 5% to 20% Liquid carrier:                            1% to 80%, preferably 1% to 35% Dust: 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% Surfactant:                           1% to 40%, preferably 2% to 30% Wettable powder: Active ingredient:                              0.5% to 90%, preferably 1% to 80% Surfactant:                           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 of this application makes available every combination of the embodiments disclosed herein.

The compounds according to the following Tables A-1 to A-24 can be prepared according to the above methods. The following examples are intended to illustrate the present invention and to show preferred compounds of formula (I). In any of the following Tables A-1 to A-24, the presence of one or more possible asymmetric carbon atoms in the compounds of formula (I) according to the present invention means that the compounds can exist in the form of chiral isomers, i.e., mirror isomers or non-mirror isomers.

Table A: This table discloses 20 substituent definitions (G) of compounds of formula (Ia) according to the present invention: (Ia) wherein the compound G according to the present invention having the formula (I) is (G) and wherein the G substituent is as defined below: index G index G 1 [2-(2,4-difluorophenyl)tetrazolyl-5-carbonyl] 11 [2-(2-Fluorophenyl)tetrazolyl-5-carbonyl] 2 [2-(2,4-difluorophenyl)triazole-4-carbonyl] 12 [2-(2-Fluorophenyl)triazole-4-carbonyl] 3 [1-(2,4-difluorophenyl)triazole-4-carbonyl] 13 [1-(2-Fluorophenyl)triazole-4-carbonyl] 4 [2-(3,5-difluoro-2-pyridyl)tetrazolyl-5-carbonyl] 14 (2-phenyltetrazolyl-5-carbonyl) 5 [2-(3,5-difluoro-2-pyridyl)triazole-4-carbonyl] 15 (2-phenyltriazole-4-carbonyl) 6 [1-(3,5-difluoro-2-pyridyl)triazole-4-carbonyl] 16 (1-phenyltriazole-4-carbonyl) 7 [2-(4-Fluorophenyl)tetrazolyl-5-carbonyl] 17 [1-(2,4-difluorophenyl)pyrazol-4-carbonyl] 8 [2-(5-Fluoro-2-pyridyl)tetrazolyl-5-carbonyl] 18 [1-(2,4-difluorophenyl)pyrazol-3-carbonyl] 9 [2-(4-Fluorophenyl)triazole-4-carbonyl] 19 [1-(2,4-difluorophenyl)-1,2,4-triazole-3-carbonyl] 10 [1-(4-Fluorophenyl)triazole-4-carbonyl] 20 [1-(2,4-difluorophenyl)pyrrole-3-carbonyl]

Thus, the following compounds are specifically described in Tables A-1 to A-24, wherein the substituents of formula (Ia) are: Table A-1: This table provides 20 compounds (A-1.01) to (A-1.20) having formula (Ia), wherein R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are H, and the G substituent is as defined in Table A. For example, compound (A-1.01) has the following structure: Compound (A-1.01)

Table A-2: This table provides 20 compounds (A-2.01) to (A-2.20) of formula (Ia), wherein R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are H, R ² is CH ₃ , and the G substituent is as defined in Table A. For example, compound (A-2.09) has the following structure: Compound (A-2.09)

Table A-3: This table provides 20 compounds (A-3.01) to (A-3.20) of formula (Ia) wherein ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 and ^R11 are H, ^R2 is Cl, and the G substituent is as defined in Table A.

Table A-4: This table provides 20 compounds (A-4.01) to (A-4.20) of formula (Ia), wherein R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are H, R ⁴ is CH ₃ , and the G substituent is as defined in Table A. For example, compound (A-4.06) has the following structure: Compound (A-4.06)

Table A-5: This table provides 20 compounds (A-5.01) to (A-5.20) of formula (Ia) wherein ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 and ^R11 are H, ^R2 and ^R4 are _CH3 , and the G substituent is as defined in Table A.

Table A-6: This table provides 20 compounds (A-6.01) to (A-6.20) of formula (Ia) wherein ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 and ^R11 are H, ^R2 is Cl, ^R4 is _CH3 , and the G substituent is as defined in Table A.

Table A-7: This table provides 20 compounds of formula (Ia) rac - cis- (A-7.01) to rac- cis- ( A -7.20), wherein R ² , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are H, R ⁷ is CH ₃ , and the G substituent is as defined in Table A. All compounds in this table have a cis relationship between the R ⁷ substituent and the pyrazole substituent. For example, compound rac - cis- (A-7.06) has the following structure: Compound racemic - cis- (A-7.06)

Table A-8: This table provides 20 compounds of formula (Ia) rac - cis- (A-8.01) to rac-cis- ( A - 8.020), wherein R ⁴ , R ⁵ , R ⁶ , R7 , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are H, R ² and R ⁷ are CH ₃ , and the G substituent is as defined in Table A. All compounds in this table have a cis relationship between the R ⁷ substituent and the pyrazole substituent. For example, compound rac - cis- (A-8.01) has the following structure: Compound racemic - cis- (A-8.01)

Table A-9: This table provides 20 compounds having formula (Ia) rac - cis- (A-9.01) to rac- cis- ( A -9.20), wherein R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are H, R ² is Cl and R ⁷ is CH ₃ , and the G substituent is as defined in Table A. All compounds in this table have a cis relationship between the R ⁷ substituent and the pyrazole substituent. For example, compound (A-9.14) has the following structure: Compound racemic - cis- (A-9.14)

Table A-10: This table provides 6 compounds (A-10.01) to (A-10.06) wherein ^R2 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 and ^R10 are H, ^R11 is Br, and the G substituent is as defined in Table A.

Table A-11: This table provides 6 compounds (A-11.01) to (A-11.06) wherein ^R2 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 and ^R10 are H, ^R11 is Cl, and the G substituent is as defined in Table A.

Table A-12: This table provides 6 compounds (A-12.01) to (A-12.06) wherein ^R2 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 and ^R10 are H, ^R11 is CN, and the G substituent is as defined in Table A.

Table A-13: This table provides 6 compounds (A-13.01) to (A-13.06) wherein ^R2 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 and ^R10 are H, ^R4 is _CH3 , ^R11 is Br, and the G substituent is as defined in Table A.

Table A-14: This table provides 6 compounds (A-14.01) to (A-14.06) wherein ^R2 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 and ^R10 are H, ^R4 is _CH3 , ^R11 is Cl, and the G substituent is as defined in Table A.

Table A-15: This table provides 6 compounds (A-15.01) to (A-15.06) wherein ^R2 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 and ^R10 are H, ^R4 is _CH3 , ^R11 is CN, and the G substituent is as defined in Table A.

Table A-16: This table provides six compounds rac - cis- (A-16.01) to rac - cis- (A-16.006), wherein R ² , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ and R ¹⁰ are H, R ⁷ is CH ₃ , R ¹¹ is Br, and the G substituent is as defined in Table A. All compounds in this table have a cis relationship between the R ⁷ substituent and the pyrazole substituent. For example, compound rac - cis- (A-16.04) has the following structure: Compound racemic - cis- (A-16.04)

Table A-17: This table provides 6 compounds rac - cis- (A-17.01) to rac - cis- (A-17.006), wherein ^R2 , ^R4 , ^R5 , ^R6 , ^R8 , ^R9 and ^R10 are H, ^R7 is _CH3 , ^R11 is Cl, and the G substituent is as defined in Table A. All compounds in this table have a cis relationship between the ^R7 substituent and the pyrazole substituent.

Table A-18: This table provides 6 compounds rac - cis- (A-18.01) to rac - cis- (A-18.006), wherein ^R2 , ^R4 , ^R5 , ^R6 , ^R8 , ^R9 and ^R10 are H, ^R7 is _CH3 , ^R11 is CN, and the G substituent is as defined in Table A. All compounds in this table have a cis relationship between the ^R7 substituent and the pyrazole substituent.

Table A-19: This table provides six compounds rac - cis- (A-19.01) to rac - cis- (A-19.006) wherein ^R4 , ^R5 , ^R6 , ^R8 , ^R9 , and ^R10 are H, ^R2 and ^R7 are _CH3 , ^R11 is Br, and the G substituent is as defined in Table A. All compounds in this table have a cis relationship of the ^R7 substituent to the pyrazole substituent.

Table A-20: This table provides 6 compounds rac - cis- (A-20.01) to rac - cis- (A-20.006), wherein ^R4 , ^R5 , ^R6 , ^R8 , ^R9 and ^R10 are H, ^R2 and ^R7 are _CH3 , ^R11 is Cl, and the G substituent is as defined in Table A. All compounds in this table have a cis relationship between the ^R7 substituent and the pyrazole substituent.

Table A-21: This table provides six compounds rac - cis- (A-21.01) to rac - cis- (A-21.006), wherein R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ and R ¹⁰ are H, R ² and R ⁷ are CH ₃ , R ¹¹ is CN, and the G substituent is as defined in Table A. All compounds in this table have a cis relationship between the R ⁷ substituent and the pyrazole substituent. For example, compound rac - cis- (A-21.01) has the following structure: Compound racemic - cis- (A-21.01)

Table A-22: This table provides three compounds (A-22.01) to (A-22.03) wherein ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R10 and ^R11 are H, ^R2 is _CH3 , ^R9 is Br, and the G substituent is as defined in Table A.

Table A-23: This table provides 3 compounds (A-23.01) to (A-23.03) wherein ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R10 and ^R11 are H, ^R2 is _CH3 , ^R9 is _OCH3 , and the G substituent is as defined in Table A.

Table A-24: This table provides three compounds (A-24.01) to (A-24.03) wherein R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ are H, R ² is CH ₃ , R ⁹ is CN, and the G substituent is as defined in Table A. Examples

The following examples are provided to illustrate the present invention and are not intended to limit the present invention in any way.

The compounds of the invention may be distinguished from known compounds by their greater efficacy at low application rates, which can be demonstrated by one skilled in the art using the experimental procedures outlined in the examples, using lower application rates (if necessary), e.g., 60 ppm, 20 ppm, or 2 ppm.

Compounds of formula (I) may have numerous benefits, including, among others, favorable levels of biological activity for protecting plants against diseases caused by fungi or superior properties for use as agrochemical active ingredients (e.g., higher biological activity, favorable activity spectrum, increased safety (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).

Throughout this specification, temperatures are given in degrees Celsius and "m.p." means melting point. LC-MS means liquid chromatography-mass spectrometry, and a description of the apparatus and methods is as follows.

^1H NMR and ^19F NMR measurements were recorded on a Bruker 400MHz spectrometer and chemical shifts are given in ppm relative to TMS ( ^1H ) and CFCl3 ( ^19F ) standards. Spectra were measured in deuterated solvents as indicated. The compounds were characterized by any of the following LCMS methods. Characteristic LCMS values obtained for each compound are the retention time ("Rt", reported in minutes) and the measured molecular ion (M+H) ⁺ or (MH) ^- .

LC-MS Method A : Spectra were recorded on a mass spectrometer from Waters Corporation (SQD, SQDII or QDA single quadrupole mass spectrometer) equipped with a sputtering source (polarity: positive and negative ions), capillary voltage: 0.8-3.00 kV, taper: 5-30 V, source temperature: 120°C-150°C, desolvation temperature: 350°C-600°C, taper gas flow: 50-150 l/h, desolvation gas flow: 650-1000 l/h, mass range: 50 to 900 Da, and Acquity UPLC: binary pump, heated column compartment, diode array detector, and ELSD. Column: Waters UPLC HSS T3, 1.8 µm, 30 x 2.1 mm, temperature: 60°C, DAD wavelength range (nm): 210 to 400, run time: 1.5 min; solvents: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; flow rate (ml/min) 0.85, gradient: 10% B isocratic for 0.2 min, then 10%-100% B in 1.0 min, 100% B isocratic for 0.2 min, 100%-10% B in 0.05 min, 10% B isocratic for 0.05 min.

LC-MS Method B : Spectra were recorded on a mass spectrometer from Waters (SQD, SQDII or QDA single quadrupole mass spectrometer) equipped with a sputtering source (polarity: positive and negative ions), with optimized mass parameters: Ionization method: Sputtering (ESI); Polarity: positive and negative polarity switching; Scan type: full scan; Capillary (kV): 0.8; Cone voltage (V): 23; Source temperature (°C): 120; Desolvation gas flow (L/Hr): 1000; Desolvation temperature (°C): 600; Cone gas flow (L/Hr): 50; Mass range: 110 to 1200 Da gradient conditions: solvent A: water containing 0.1% formic acid: acetonitrile = 95:5 v/v; solvent B: acetonitrile containing 0.05% formic acid Time (min) A ( % ) B ( % ) Flow rate ( ml/min ) 0 9 0 10 0.6 0.2 90 10 0.6 0.3 50 50 0.6 0.6 0 100 0.6 1.3 0 100 0.6 1.4 90 10 0.6 1.6 90 10 0.6 PDA wavelength range: 200 to 400 nm, column: Acquity UPLC HSS T3 C18; column length: 30 mm; column inner diameter: 2.1 mm; particle size: 1.8 µ; column oven temperature: 40°C

LC-MS Method C : Spectra were recorded on a mass spectrometer from Waters (SQD, SQDII or QDA single quadrupole mass spectrometer) equipped with a sputtering source (polarity: positive and negative ions), with optimized mass parameters: Ionization method: Sputtering (ESI); Polarity: positive and negative polarity switching; Scan type: full scan; Capillary (kV): 3.00; Cone voltage (V): 41.00; Source temperature (°C): 150; Desolvation gas flow (L/Hr): 1000; Desolvation temperature (°C): 500; Cone gas flow (L/Hr): 50; Mass range: 110 to 1000 Da gradient conditions: solvent A: water containing 0.1% formic acid: acetonitrile = 95:5 v/v; solvent B: acetonitrile containing 0.05% formic acid Time (min) A ( % ) B ( % ) Flow rate ( ml/min ) 0 90 10 0.6 0.2 90 10 0.6 0.3 50 50 0.6 0.6 0 100 0.6 1.3 0 100 0.6 1.4 90 10 0.6 1.6 90 10 0.6 PDA wavelength range: 200 to 400 nm, column: Acquity UPLC HSS T3 C18; column length: 30 mm; column inner diameter: 2.1 mm; particle size: 1.8 µ; column oven temperature: 40°C

LC-MS Method D: Spectra were recorded on a mass spectrometer from Waters (SQD, SQDII or QDA single quadrupole mass spectrometer) equipped with a sputtering source (polarity: positive and negative ionization), optimized mass parameters: Ionization method: sputtering (ESI); Polarity: positive and negative polarity switching, Scan type: MS2 scan; Capillary (kV): 4.00; Fragmentor (V): 100.00; Gas temperature (°C): 350; Gas flow (L/min): 11; Nebulizer gas (psi): 40; Mass range: 110 to 1000 Da Detection (VWD): 254 nm; Gradient conditions: Solvent A ： Water containing 0.1% formic acid:acetonitrile = 95:5 v/v; Solvent B: Acetonitrile containing 0.1% formic acid Time (min) A ( % ) B ( % ) Flow rate ( ml/min ) 0 90 10 1.8 0.9 0 100 1.8 1.8 0 100 1.8 2.2 90 10 1.8 2.5 90 10 1.8 Column: KINETEX EVO C18, column length: 50 mm; column inner diameter: 4.6 mm; particle size: 2.6 µ, column oven temperature: 40°C

LC-MS Method E: Instrumental specifications: UHPLC Agilent 1290 Series LCMSD system with DAD\ELSD and Agilent LC\MSD (G6125B) mass spectrometer; Column: Agilent Poroshell 120 SB-C18 4.6 x 30 mm 2.7 µm; Column temperature: 60°C; Mobile phase: A - water (0.1% formic acid), B - acetonitrile (0.1% formic acid); Flow rate: 3 ml/min; Gradient: 0.01 min - 1%B, 1.5 min - 100%B, 1.73 min - 100%B; MS ionization mode: electrospray ionization (ESI); MS scan range: 83 - 600 m/z; UV detection: 215 nm, 254 nm, 280 nm

LC-MS Method F : Spectra were recorded on a mass spectrometer from Agilent Technologies (6410 Triple Quadrupole Mass Spectrometer) equipped with a sputtering source (polarity: positive or negative ion, MS2 scanning, capillary voltage: 4.00 kV, fragmentor voltage: 100 V, desolvation temperature: 350 °C, gas flow: 11 L/min, nebulizer gas: 45 psi, mass range: 110 to 1000 Da) and a 1200 series HPLC from Agilent: quaternary pump, heated column compartment and VWD detector. Column: KINETEX EVO C18, 2.6 µm, 50 x 4.6 mm, temperature: 40°C, detector VWD wavelength: 254 nm, solvent gradient: A = water + 5% acetonitrile + 0.1% HCOOH, B = acetonitrile + 0.1% HCOOH; gradient: 0 min 10% B, 90% A; 0.9-1.8 min 100% B; 1.8-2.2 min 100%-10% B; 2.2-2.5 min 10% B; flow rate (mL/min) 1.8.

LC-MS Method G : Spectra were recorded on a mass spectrometer from Waters (SQD2 or QDA single quadrupole mass spectrometer) equipped with a sputtering source (polarity: positive and negative switching, capillary: 0.8-3.00 kV, taper range: 25 source temperature: 120°C-150°C, desolvation temperature: 500°C-600°C, taper gas flow: 50 L/h, desolvation gas flow: 1000 L/h, mass range: 110 to 850 Da) and Acquity UPLC from Waters: quaternary solvent manager, heated column compartment, diode array detector. Column: Acquity UPLC HSS T3 C18, 1.8 µm, 30 x 2.1 mm, temperature: 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 rate (mL/min) 0.6.

LC-MS Method H: Spectra were recorded on an ACQUITY mass spectrometer from Waters (SQD or SQDII single quadrupole mass spectrometer) equipped with a sputtering source (polarity: positive or negative ion, capillary: 3.0 kV, cone: 30 V, 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 with solvent degasser, binary pump, heated column compartment, and diode array detector. Column: Waters UPLC HSS T3, 1.8 µm, 30 x 2.1 mm, temperature: 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 3.0 min; flow rate (ml/min) 0.75.

Formulation Examples Wettable powders a) b) c) Active ingredient 25% 50% Sodium lignin sulfonate 5% 5% - Sodium lauryl sulfate 3% - 5% Sodium diisobutylnaphthalene sulfonate - 6% 10% Phenol polyglycol 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 grinder to obtain a wettable powder which can be diluted with water to give a suspension of the desired concentration. Powder for dry seed treatment a) b) c) Active ingredient 25% 50% 75% Light mineral oil 5% 5% 5% Highly dispersed silicic acid 5% 5% - Kaolin 65% 40% - Talc - - 20% Mix the combination thoroughly with the adjuvants and grind the mixture thoroughly in a suitable grinder to obtain a powder that can be used directly for seed treatment. Emulsifiable concentrate active ingredient 10% Octylphenol polyglycol ether (4-5 mol of ethylene oxide) 3% Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (35 mol of ethylene oxide) 4% Cyclohexanone 30% Xylene mixture 50% Emulsions of any desired dilution which can be used in plant protection can be obtained from this concentrate by diluting with water. Dusts a) b) c) Active ingredient 5% 6% 4% Talc 95% - - Kaolin - 94% - Mineral filler - - 96% Ready-to-use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable grinder. Such a powder can also be used for dry seed dressing of seeds. Extruder granules Active ingredient 15% Sodium lignin sulfonate 2% Carboxymethylcellulose 1% Kaolin 82% The combination is mixed with the adjuvants and ground, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air. Coated granules Active ingredient 8% Polyethylene glycol (molecular weight 200) 3% Kaolin 89% The finely ground combination is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. Dust-free coated granules are obtained in this way. Suspension concentrate active ingredient 40% Propylene glycol 10% Nonylphenol polyglycol ether (15 mol of ethylene oxide) 6% Sodium lignin sulfonate 10% Carboxymethyl cellulose 1% Silicone oil (in the form of a 75% emulsion in water) 1% Water 32% Intimately mixing the finely ground combination with the auxiliaries gives a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such a dilution, living plants as well as plant propagation material can be treated by spraying, pouring or immersion and protected against infestation by microorganisms. Flowable concentrate for seed treatment Active ingredient 40% Propylene glycol 5% Copolymer butanol PO/EO 2% Tristyrylphenol with 10-20 mol 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 mixed intimately with the auxiliaries to give 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 by spraying, pouring or immersion and protected against infestation by microorganisms.

Sustained release capsule suspension

28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate/polymethylene-polyphenyl isocyanate mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is reached. To this emulsion is added 2.8 parts of a 1,6-hexanediamine mixture in 5.3 parts of water. The mixture is stirred until the polymerization is complete. The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% of active ingredient. The diameter of the medium capsule is 8-15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in an apparatus suitable for this purpose.

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

Abbreviations CDCl ₃ -deuterated chloroform DABCO 1,4-diazobicyclo[2.2.2]octane, also known as triethylenediamine or TEDA DCC Dicyclohexylcarbodiimide DIPEA Diisopropylethylamine (N,N-diisopropylethylamine) DMA Dimethylacetamide DMF Dimethylformamide DMSO Dimethylsulfoxide DMSO-d6 Deuterated dimethylsulfoxide EDC 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Et ₃ N Triethylamine EtOAc Ethyl acetate HATU 1-[Bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide Hexafluorophosphate HCl Hydrochloric acid hr/hrs Hours LC-MS Liquid chromatography mass spectrometry (LC-MS, LC/MS or LCMS) rh relative humidity rt room temperature Rt retention time ssp. Subspecies TBME tert-butyl methyl ether or tert-butyl methyl ether Preparation Example:

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

"Mp" refers to the melting point in ° C. Free radical refers to methyl group.

Example P1 : Preparation of [2-(2,4-difluorophenyl)tetrazol-5-yl]-[6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-31, Table P) Step 1 : Preparation of 4-(1,5-dimethylpyrazol-4-yl)isoquinoline In a microwave vial, a suspension of 4-bromoisoquinoline (2.0 g, 9.4204 mmol), 1,5-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazolyl (2.3484 g, 10.362 mmol) and potassium carbonate (1.4322 g, 10.362 mmol) in a toluene/methanol mixture (30 mL, 5:1) was degassed with argon for several minutes, and then tetrakis(triphenylphosphonium)palladium (0.545 g, 0.471 mmol) was added. The reaction mixture was heated at 100 °C and stirred for 1 hour under microwave irradiation. After cooling to room temperature, the reaction mixture was poured into water and extracted with EtOAc. _The organic layer was separated, dried over _Na2SO4 , filtered and concentrated in vacuo. The crude material was purified by silica gel flash chromatography (eluting with EtOAc/30% methanol) to give the title product. LCMS (Method A): m/z 225 [M+H], retention time 0.51 min Step 2 : Preparation of 4-(1,5-dimethylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline To a solution of 4-(1,5-dimethylpyrazol-4-yl)isoquinoline (2.00 g, 8.96 mmol) in methanol (90 mL) was added sodium cyanoborohydride (3.55 g, 53.7 mmol) at room temperature. The reaction mixture was stirred at rt (room temperature) and then hydrochloric acid (1.25 M in methanol) was added until a pH of 2-3 was reached. After stirring at room temperature for 30 minutes, the reaction mixture was diluted with water and basified with 2 N sodium hydroxide and the mixture was extracted with EtOAc (3 x 25 mL). The combined organic layers were dried over Na ₂ SO ₄ , filtered and concentrated in vacuo. The resulting yellow oil was used without further purification. LCMS (Method A): m/z 228 [M+H]. Retention time 0.29 min The hydrochloride of the title product (4-(1,5-dimethylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline; hydrochloride) can be obtained by treating the yellow oil with 2 M HCl in ether and then concentrating in vacuo . Step 3 : Preparation of ethyl (2E)-2-(p-toluenesulfonylhydrazono)acetate A solution of 4-methylbenzenesulfonylhydrazine (2 g, 10.7 mmol) in ethanol (40 mL) was treated with ethyl 2-oxoacetate (2.63 g, 12.8 mmol) at room temperature. The reaction mixture was stirred for 1 hour and the ethanol was removed by vacuum concentration. The residue obtained was diluted with water and extracted with EtOAc. The organic phase was separated and the solvent was evaporated in vacuo to give ethyl (2E)-2-(p-toluenesulfonylhydrazono)acetate which was used as such in the next step. LCMS (Method B): m/z 271 [M+H], retention time 1.06 min. ¹ H NMR (400 MHz, CDCl ₃ ) δ ppm 9.31 (s, 1 H), 7.85 (d, J = 8.31 Hz, 2 H), 7.34 (d, J = 8.07 Hz, 2 H), 7.23 (s, 1 H), 4.27 (q, J = 7.09 Hz, 2 H), 2.44 (s, 3 H) 1.23 - 1.37 (m, 3 H). Step 4 : Preparation of ethyl 2-(2,4-difluorophenyl)tetrazolyl-5-carboxylate A solution of 2,4-difluoroaniline (1.00 g, 7.74 mmol) in 6 M hydrochloric acid in deionized water (6 mL, 36 mmol) and ethanol (5 mL) was cooled to 0°C. Sodium nitrite (0.64 g, 9.29 mmol) was added to the solution and the resulting solution was stirred for 1 hour and then added dropwise to a solution of ethyl (2E)-2-(p-toluenesulfonylhydrazono)acetate (2.3 g, 8.51 mmol) in pyridine (20 mL) at -20°C. The reaction mixture was slowly warmed to room temperature and then stirred for 5 h. The resulting mixture was diluted with 1 N HCl and the aqueous layer was extracted with EtOAc. The combined organic layers were dried over _Na2SO4 and concentrated in vacuo to give the crude product, which _was purified by column chromatography eluting with 30% EtOAc/hexanes to give ethyl 2-(2,4-difluorophenyl)tetrazolyl-5-carboxylate as a light red oil. ¹ H NMR (400 MHz, CDCl ₃ ) δ ppm 7.86 - 7.94 (m, 1 H), 7.11 - 7.21 (m, 2 H), 4.60 (q, J = 7.21 Hz, 2 H), 1.51 (t, J = 7.13 Hz, 3 H) Step 5 : Preparation of [[2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-31, Table P). (Compound P-31, Table P). A solution of ethyl 2-(2,4-difluorophenyl)tetrazole-5-carboxylate (0.1 g, 0.39 mmol) in toluene (2 mL) was treated with 4-(1,5-dimethylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline-hydrochloride (0.12 g, 0.47 mmol) and then the solution was cooled with an ice bath. A solution (2.0 mol/L) of trimethylaluminum in toluene (0.6 mL, 1.18 mmol) was added dropwise thereto at 0°C and then the resulting mixture was heated to 80°C for 2 hours. After the reaction was completed, the mixture was diluted with EtOAc and washed with aqueous 1 N HCl. The organic layer was separated and the aqueous layer was back-extracted with EtOAc. The combined organic layers _were dried over _Na2SO4 , filtered and concentrated in vacuo. The crude product was purified by column chromatography to give [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone as a white solid. LCMS (Method C): m/z 436 (M+H). Retention time 1.07 min.

Example P2 : Preparation of [1-(2,4-difluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-8, Table P) Step 1 : Preparation of 1-(2,4-difluorophenyl)triazole-4-carboxylic acid methyl ester: A solution of 1-azido-2,4-difluoro-benzene (0.30 g, 1.8 mmol) in methanol (3.6 mL) was treated sequentially with anhydrous copper(II) sulfate (0.053 g, 0.33 mmol), sodium ascorbate (0.46 g, 2.3 mmol) in water (3.6 mL), and then methyl prop-2-ynoate (0.14 g, 0.14 mL, 1.7 mmol). The reddish reaction mixture was stirred at room temperature for 2 days, monitored by LCMS. The reaction mixture was then concentrated in vacuo, and the residue was taken up in water and EtOAc. The organic layer was separated, washed with brine and dried over MgSO4, filtered and concentrated in vacuo. The crude product was purified by silica gel column (Rf200) eluting with cyclohexane/EtOAc to give the title compound as a white solid. LCMS (Method A): m/z 240 (M+H), retention time 0.79 min. ¹ H NMR (400 MHz, CDCl ₃ ) δ ppm; 8.59 (d, J = 2.57 Hz, 1 H), 7.96 - 8.05 (m, 1 H), 7.09 - 7.17 (m, 2 H), 4.02 (s, 3 H) Step 2 : Preparation of 1-(2,4-difluorophenyl)triazole-4-carboxylic acid A sample of methyl 1-(2,4-difluorophenyl)triazole-4-carboxylate (0.31 g, 1.3 mmol) was dissolved in tetrahydrofuran (6.5 mL) and water (3.2 mL) under argon to give a light brown solution. To this was added lithium hydroxide monohydrate (0.047 g, 1.9 mmol) and the mixture was stirred at room temperature. After 3 hours, LCMS showed the desired mass and consumption of the starting material. Tetrahydrofuran was evaporated in vacuo and then aqueous HCl 2 N (about 0.5 mL) was added to bring the pH of the aqueous phase to 3-4. The resulting light red suspension was filtered, the white filter cake was washed with water and cyclohexane and dried in vacuo at 55°C to give 1-(2,4-difluorophenyl)triazole-4-carboxylic acid as a white solid. LCMS (Method A): m/z 226 (M+H), retention time 0.63 min. ¹ H NMR (400 MHz, DMSO-d6) δ ppm 7.27 - 7.52 (m, 1 H), 7.73 (ddd, J = 11.10, 8.71, 2.57 Hz, 1 H), 7.95 (td, J = 8.80, 5.87 Hz, 1 H), 9.15 (d, J = 1.47 Hz, 1 H), 13.26-13.60 (bs, 1H). Step 3 : Preparation of 4-(1-methylpyrazol-4-yl)isoquinoline Analogously to Example P1, Step 1 Preparative LCMS (Method A): m/z 210 (M+H), retention time 0.41 min ¹ H NMR (400 MHz, CDCl ₃ ) δ ppm: 9.20 (s, 1 H), 8.51 (s, 1 H), 8.10 - 8.18 (m, 1 H), 8.03 (d, J = 8.07 Hz, 1 H), 7.78 - 7.81 (m, 1 H), 7.70 - 7.76 (m, 1 H), 7.66 - 7.68 (m, 1 H), 7.62 - 7.66 (m, 1 H), 4.06 (s, 3 H) Step 4 : Preparation of 4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline Prepared similarly to Example P1, Step 2. The crude product was used without further purification. Step 5 : Preparation of [1-(2,4-difluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-8, Table P) (Compound P-8, Table P) A mixture of 4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline (0.090 g, 0.40 mmol) and 1-(2,4-difluorophenyl)triazole-4-carboxylic acid (0.090 g, 0.40 mmol) was dissolved in EtOAc (3 mL) under argon and treated with 1-propanephosphonic anhydride (0.60 mL, 1.0 mmol) and N,N -diisopropylethylamine (0.28 mL, 1.6 mmol). The resulting solution was stirred at room temperature. After 17 hours, LCMS showed that the reaction was complete. The reaction mixture was poured into water and extracted with EtOAc. The organic layer was washed with saturated sodium bicarbonate solution followed by 1 M HCl, water and _brine . The organic layer was dried over _Na2SO4 and concentrated in vacuo. The crude material was purified by silica gel flash chromatography eluting with EtOAc in cyclohexane to provide the title product. LCMS (Method A) m/z 421 (M+H), retention time 0.92 min.

Example P3 : Preparation of [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone (Compound P-32, Table P) Step 1 : Preparation of (1-methylpyrazol-4-yl)-phenyl-methanol A single-necked round-bottom flask equipped with a magnetic stir bar was charged with 1-methyl-1H-pyrazole-4-carbaldehyde (2.20 g, 19.2 mmol) and tetrahydrofuran (40 mL). To the colorless solution was added 1 mol of phenylmagnesium bromide in THF (21 mL, 21.1 mmol) dropwise at 0°C-5°C under an atmosphere of argon for 15 minutes. After the addition, the ice bath was removed and the white suspension was stirred at room temperature for 2.5 hours. The reaction mixture was poured into a saturated ammonium chloride solution (40 mL) and extracted with EtOAc (2 x 40 mL). The combined organic layers were washed with _brine , dried over _Na2SO4 , and concentrated in vacuo to give the crude product as a colorless oil. The crude product was purified by combi flash (silica gel, gradient: EtOAc in cyclohexane) to give the desired product (1-methylpyrazol-4-yl)-phenyl-methanol as a colorless oil. LCMS (Method A) m/z 189 [M+H], retention time: 0.62 min. ¹ H NMR (400 MHz, CDCl ₃ ) δ ppm 7.26 - 7.43 (m, 6 H), 7.18 (s, 1 H), 5.80 (s, 1 H), 3.81 (s, 3 H), 2.89 (br s, 1 H) Step 2 : Preparation of 2-(1-methylpyrazol-4-yl)-2-phenyl-acetonitrile A round-bottom flask equipped with a magnetic stirring bar and a condenser was charged with (1-methylpyrazol-4-yl)-phenyl-methanol (3.45 g, 15.6 mmol) and dichloromethane (156 mL). Then, lithium carbonate (0.23 g, 3.1 mmol), trimethylsilyl cyanide (9.0 mL) and iodine (7.23 g, 28.0 mmol) were added in sequence at room temperature. The mixture was stirred at 35°C for 1 hour. The reaction mixture was then cooled to room temperature and poured into a saturated sodium thiosulfate solution (250 mL), and extracted with dichloromethane (2 × 150 mL). The combined organic layers were washed with _brine , dried over _Na2SO4 , and concentrated in vacuo to give the crude product, which was purified by combi flash (silica gel, gradient: EtOAc in cyclohexane) to give the desired title compound as a yellow oil. LCMS (Method A) m/z 198 [M+H], retention time: 0.78 min. ^1H NMR (400 MHz, _CDCl3 ) δ ppm 7.33 - 7.43 (m, 6 H), 7.32 (s, 1 H), 5.09 (s, 1 H), 3.87 (s, 3 H) Step 3 : Preparation of 2-(1-methylpyrazol-4-yl)-2-phenyl-propionitrile A 250 mL-3-neck flask equipped with a magnetic stir bar and condenser was charged with 2-(1-methylpyrazol-4-yl)-2-phenyl-acetonitrile (3.22 g, 16.3 mmol) and tetrahydrofuran (65 mL). A solution of n-butyl lithium in hexanes (7.8 mL, 19.6 mmol) was added dropwise at -70°C under a nitrogen atmosphere (a small exotherm to -65°C was observed). The orange solution was stirred at this temperature for 30 minutes, and then iodomethane (1.54 mL, 24.5 mmol) was added dropwise at -70°C. The resulting yellow solution was stirred at -78°C for 5 minutes, and then allowed to warm to ambient temperature and stirred for 30 minutes. The reaction mixture was then poured into water (90 mL) and extracted with EtOAc. The organic layer was washed with brine, dried over Na ₂ SO ₄ , and concentrated in vacuo to give the crude product as an orange oil. It was purified by combi flash (silica gel, gradient: EtOAc in cyclohexane) to give the title compound as a yellow oil. LCMS (Method A) m/z 211 [M+H], retention time: 0.84 min. ¹ H NMR (400 MHz, CDCl ₃ ) δ ppm 7.28 - 7.49 (m, 7 H), 3.88 (s, 3 H), 2.04 (s, 3 H) Step 4 : Preparation of 2-(1-methylpyrazol-4-yl)-2-phenyl-propan-1-amine A 250 mL-3-neck flask equipped with a magnetic stirring bar was charged with 2-(1-methylpyrazol-4-yl)-2-phenyl-propionitrile (2.82 g, 13.3 mmol) and tetrahydrofuran (40 mL). Borane dimethyl sulfide complex (4.0 mL, 40.0 mmol) was added dropwise to the yellow solution under an argon atmosphere at room temperature, and the resulting colorless mixture was stirred at 65° C. for 2 hours. The reaction mixture was cooled to 0° C., and then hydrochloric acid (8.9 mL, 53.7 mmol) was added dropwise (strong gas evolution), and the mixture was stirred at 65° C. for 1 hour and allowed to stand at room temperature overnight. The mixture was diluted with water (80 mL), alkalized (pH 12) with 13 mL NaOH 6 M, and the mixture was extracted twice with EtOAc. The combined organic layers were washed with _brine , dried over _Na2SO4 , and concentrated in vacuo to give the title compound as a yellow oil, which was used in the next step without further purification. LCMS (Method A) m/z 216 [M+H], retention time: 0.39 min Step 5 : Preparation of N-[2-(1-methylpyrazol-4-yl)-2-phenyl-propyl]carbamic acid methyl ester A sealed tube equipped with a magnetic stirring bar was charged with 2-(1-methylpyrazol-4-yl)-2-phenyl-propan-1-amine (3.01 g, 11.2 mmol) and dichloromethane (45 mL). Methyl chloroformate (1.1 mL, 13.4 mmol) was added dropwise at 0°C-10°C under an atmosphere of argon, followed by triethylamine (4.7 mL, 33.6 mmol). The ice bath was removed and the mixture was stirred at room temperature for 1 hour. The reaction mixture was poured into water and the organic phase was separated. The aqueous phase was extracted twice with EtOAc. The combined organic layers were dried over Na ₂ SO ₄ and concentrated in vacuo. The crude material was purified by combiflash (silica gel, gradient: EtOAc in cyclohexane) to give the title compound as a colorless gum. LCMS (Method A) m/z 274 [M+H], retention time: 0.80 min. Step 6 : Preparation of methyl 4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinoline-2-carboxylate A single-necked round-bottom flask equipped with a magnetic stir bar was charged with methyl N-[2-(1-methylpyrazol-4-yl)-2-phenyl-propyl]carbamate (422 mg, 1.54 mmol), hydrochloric acid (5.00 mL/mmol, 9.26 g, 7.72 mL, 94.0 mmol), and paraformaldehyde (93 mg, 0.97 mmol). The mixture was stirred at room temperature for 40 min, where LCMS analysis showed the reaction was complete. The reaction mixture was slowly poured into water (30 mL), neutralized with sodium bicarbonate, and extracted with EtOAc (3 × 20 mL). The combined organic layers were washed with _brine , dried over _Na2SO4 and concentrated in vacuo to give the crude title compound as a colorless gum which was used as is without further purification. LCMS (Method A) m/z 286 [M+H], retention time: 0.87 min. Step 7 : Preparation of 4-methyl-4-(1-methylpyrazol-4-yl)-2,3-dihydro-1H-isoquinoline A single-necked round-bottom flask equipped with a magnetic stirring bar was charged with methyl 4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinoline-2-carboxylate (3.86 g, 13.5 mmol), 1,2-dichloroethane (5.00 ml/mmol, 68 mL) and trimethylsilyl iodide (8.37 g, 5.69 mL, 40.6 mmol). The mixture was stirred at 60°C under an atmosphere of argon for 45 min (LCMS analysis showed that the reaction was complete). After cooling to room temperature, the reaction mixture was slowly poured into a saturated sodium bicarbonate solution (30 mL). The resulting mixture was extracted with EtOAc (2 × 50 ml), and the combined organic layers were washed with brine, dried over Na ₂ SO ₄ , and concentrated in vacuo to afford the title compound as a dark orange gum. LCMS (Method A), m/z 228 [M+H], retention time: 0.61 min. Step 8 : Preparation of [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone (Compound P-32, Table P) (Compound P-32, Table) To a cooled solution of ethyl 2-(2,4-difluorophenyl)tetrazole-5-carboxylate (0.2 g, 0.78 mmol) and 4-methyl-4-(1-methylpyrazol-4-yl)-2,3-dihydro-1H-isoquinoline (0.21 g, 0.94 mmol) in toluene (48 mL) was added dropwise a solution of trimethylaluminum (2.0 mol/L) in toluene (1.2 mL, 2.36 mmol) at 0°C. The resulting mixture was heated to 90°C for 3 hours, where LCMS analysis showed the reaction was complete. The reaction mixture was diluted with EtOAc and quenched with 1 N HCl solution. The mixture was extracted with EtOAc (3 x 25 mL) and the combined organic layers were dried over _Na2SO4 , filtered and concentrated in vacuo. The crude product was purified by silica gel chromatography using a gradient of cyclohexane/EtOAc to give [2-( _2,4 -difluorophenyl)tetrazol-5-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone. LCMS (Method C); m/z 436 [M+H], retention time: 1.06 min. 1H NMR (400 MHz, CDCl ₃ ) δ ppm 7.79 - 7.88 (m, 1 H), 6.99 - 7.22 (m, 7 H), 6.72 (s, 1 H), 5.10 - 5.21 (m, 1 H), 4.87-5.00 (m, 1 H), 4.23 (d, J = 13. 45 Hz, 1 H), 3.84 - 3.96 (m, 1 H), 3.67 (s, 3 H), 1.59 (s, 3 H)

Example P4 : Preparation of [1-(2,4-difluorophenyl)-1,2,4-triazol-3-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-33, Table P) Step 1 : Preparation of 1-(2,4-difluorophenyl)-1,2,4-triazole-3-carboxylic acid methyl ester Prepared similarly as described in Lett. [ Organ Express ] 2018 , 20, 6930-6933. Therefore , a solution of 2,4-difluorobenzenediazonium-tetrafluoroborate (prepared as described in J. Am. Chem. Soc. 1956 , 78 , 2593-6, 500 mg, 0.5 g, 2.1939 mmol) in tetrahydrofuran (8.8 mL) was cooled to 0°C and treated with lithium acetate dihydrate (0.44765 g, 4.3879 mmol), Cu(OAc) ₂ (0.10 eq., 0.03985 g, 0.21939 mmol) and methyl 2-isocyanatoacetate (1.20 eq., 0.2609 g, 0.239 mL, 2.6327 mmol) at 0°C was added and the mixture was stirred at this temperature for 4 h. LCMS analysis showed the reaction was complete after this time. The reaction mixture was poured into water (25 mL) and the mixture was extracted with EtOAc (2 X 20 mL). The combined organic layers _were washed with brine, dried over _Na2SO4 and concentrated in vacuo. The crude material was purified by column chromatography (24 g _SiO2 , eluted with EtOAc/cyclohexane gradient) to give the title compound as an oil. ¹ H NMR (400 MHz, CDCl ₃ ) δ ppm 8.68 (d, J = 2.81 Hz, 1 H), 7.93 - 8.00 (m, 1 H), 7.08 - 7.14 (m, 2 H), 4.08 (s, 3 H) Step 2 : Preparation of [1-(2,4-difluorophenyl)-1,2,4-triazol-3-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-33, Table P) (Compound P-33, Table P) A sample of 4-(1,5-dimethylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline hydrochloride (0.13 g, 0.50 mmol, prepared as described in Example P1) was added to a solution of methyl 1-(2,4-difluorophenyl)-1,2,4-triazole-3-carboxylate (0.100 g, 0.41 mmol) in toluene (3.0 mL) in a microwave vial. The reaction mixture was stirred under an atmosphere of hydrogen for 5 minutes, and then bis(trimethylaluminum)-1,4-diazabicyclo[2.2.2]octane adduct (0.27 g, 1.04 mmol) was added. The reaction mixture was stirred at room temperature for 5 minutes and then at 70°C in a microwave for 2 hours. After cooling to room temperature, the reaction mixture was diluted with water and extracted with EtOAc (×3). The combined organic layers were washed with brine, dried over Na ₂ SO ₄ and concentrated in vacuo. The crude product was purified by silica gel chromatography using 50%-70% cyclohexane/EtOAc as the eluent system to give [1-(2,4-difluorophenyl)-1,2,4-triazol-3-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone as a viscous material. LCMS (Method D): m/z (M+H) 435, retention time 1.38 min ¹ H NMR (400 MHz, CDCl ₃ ) δ ppm 8.59-8.50 (m, 1 H), 7.89 - 7.75 (m, 1 H), 7.25 - 6.92 (m, 7 H), 5.24 -5.13 (m, 1 H) 4.78 (d, 1 H) 4.15-4.49 (m, 2 H), 3.70-3.52 (m, 4 H), 2.18-1.98 (m, 3 H)

Example P5 : Preparation of [2-(2,4-difluorophenyl)triazol-4-yl]-[rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-40, Table P) Step 1 : (1,5-dimethylpyrazol-4-yl)-phenyl-methanol Analogously to Example 3, Step 1 Preparative LCMS (Method A): m/z (M+H) 203, retention time 0.68 min ¹ H NMR (400 MHz, CDCl ₃ ) δ ppm 2.23 (s, 3 H) 2.28 (d, J = 4.00 Hz, 1 H) 3.76 (s, 3 H) 5.80 (d, J = 3.63 Hz, 1 H) 7.22 (s, 1 H) 7.27 - 7.32 (m, 1 H) 7.33 - 7.44 (m, 4 H) Step 2 : 2-(1,5-dimethylpyrazol-4-yl)-2-phenyl-acetonitrile Similar to Example 3, Step 2 Preparative LCMS (Method A): m/z (M+H) 212, retention time 0.82 min ¹ H NMR (400 MHz, CDCl ₃ ) δ = 7.46 - 7.28 (m, 6H), 5.05 (s, 1H), 3.78 (s, 3H), 2.18 (s, 3H) Step 3 : 2-(1,5-dimethylpyrazol-4-yl)-2-phenyl-ethylamine Analogously to Example 3, Step 3 Preparative LCMS (Method A): m/z (M+H) 216, retention time 0.60 min ¹ H NMR (400 MHz, CDCl ₃ ) δ ppm 2.09 (s, 3 H) 3.20 (dd, J = 7.45, 2.00 Hz, 2 H) 3.75 (s, 3 H) 3.79 (t, J = 7.27 Hz, 1 H) 7.16 - 7.25 (m, 3 H) 7.26 - 7.33 (m, 2 H) 7.42 (s, 1 H) Step 4 : Methyl N-[2-(1,5-dimethylpyrazol-4-yl)-2-phenyl-ethyl]carbamate Analogously to Example 3, Step 4 Preparative LCMS (Method A): m/z (M+H) 274, retention time 0.76 min ¹ H NMR (400 MHz, CDCl ₃ ) δ ppm 1.57 (d, J = 6.90 Hz, 3 H) 2.18 (br d, J = 6.90 Hz, 3 H) 3.05 - 3.27 (m, 1 H) 3.78 (br s, 3 H) 3.84 (s, 3 H) 3.99 - 4.09 (m, 1 H) 4.09 - 4.38 (m, 1 H) 5.22 - 5.47 (m, 1 H) 6.92 - 7.01 (m, 1 H) 7.07 - 7.27 (m, 4 H ¹ H NMR (400 MHz, CDCl ₃ ) δ ppm 2.03-2.13 (m, 3H) 3.62-3.74 (m, 5 H) 3.77 (s, 3H) 3.94-4.05 (m, 1H) 4.72 (br s, 1 H) 7.21-7.26 (m, 3H) 7.27-7.34 (m, 2H) 7.38 (s, 1H) Step 5 : Preparation of rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxylic acid methyl ester A single-necked round-bottom flask equipped with a magnetic stir bar was charged with methyl N-[2-(1,5-dimethylpyrazol-4-yl)-2-phenyl-ethyl]carbamate (2.0 g, 7.3 mmol), hydrochloric acid (37 mL, 450 mmol) and acetaldehyde (0.83 mL, 15 mmol). The mixture was stirred at room temperature for 2 h. The reaction mixture was slowly poured into water (500 mL) and neutralized with NaHCO ₃ (strong gas evolution). The mixture was extracted with EtOAc (3 X 50 mL), and the combined organic layers were washed with brine, dried over Na ₂ SO ₄ , filtered and concentrated in vacuo. The crude product was purified by chromatography to give the title compound as an oil. LC-MS (Method A): retention time 0.87 min, 300 (M+H) ¹ H NMR (400 MHz, CDCl ₃ ) δ ppm 1.57 (d, J = 6.90 Hz, 3 H) 2.18 (br d, J = 6.90 Hz, 3 H) 3.05 - 3.27 (m, 1 H) 3.78 (br s, 3 H) 3.84 (s, 3 H) 3.99 - 4.09 (m, 1 H) 4.09 - 4.38 (m, 1 H) 5.22 - 5.47 (m, 1 H) 6.92 - 7.01 (m, 1 H) 7.07 - 7.27 (m, 4 H Step 6 .Preparation of racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-1,2,3,4-tetrahydroisoquinoline A sample of rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxylic acid methyl ester (1.3 g, 4.1 mmol) in 1,2-dichloroethane (21 mL) was treated with iodotrimethylsilane (1.7 mL, 12 mmol), and the mixture was stirred under argon at 60°C for 1 h, at which time LCMS analysis showed the reaction was complete. The reaction was cooled to room temperature, and 10% HCl (22 mL) was then added to the reaction with ice cooling. The mixture was concentrated in vacuo to remove volatiles, and the remaining aqueous solution was adjusted to pH 8 with 10% NaOH (aq). The mixture was extracted with _CH2Cl2 ( ₄ x 25 mL) and the organic layers were combined, dried _{over Mg2SO4} , filtered and concentrated in vacuo to afford the title product as a single non-mirror isomer of the title compound (>97:3 cis:trans) pure enough for subsequent steps. LC-MS (Method A): m/z 242 (M+H), retention time 0.35 min ¹ H NMR (600 MHz, CDCl ₃ ) δ ppm 1.86 (d, J = 6.9 Hz, 3 H) 2.23 (s, 3 H) 3.27 (dd, J = 12.5, 10.8 Hz, 1 H) 3.59 (dd, J = 1 2.8, 5.6 Hz, 1 H) 3.83 (s, 3H) 4.58 (dd, J = 10.6, 5.4 Hz, 1 H) 4.80 (q, J = 6.8 Hz, 1 H) 7.00 (d, J = 7.8 Hz, 1 H) 7.11 (s, 1 H) 7.16 (d, J = 7.6 Hz, 1 H) 7.18 - 7.22 (m, 1 H) 7.25 - 7.28 (m, 1H) Step 7 : Preparation of 2-[(2,4-difluorophenyl)hydrazono]-3-oxo-propionic acid ethyl ester In a double-necked round-bottom flask equipped with a nitrogen inlet at room temperature, 2,4-difluoroaniline (4.00 g, 30.9 mmol), water (32 mL) and concentrated HCl (12 mL, 35%) were added. The reaction mixture was cooled to 0°C and a cold solution of sodium nitrite (2.56 g, 37.1 mmol) in water (32 mL) was added to the solution, and the resulting mixture was stirred at 0°C for 5 min. In another round-bottom flask, a solution of ethyl 3-(dimethylamino)prop-2-enoate (12.0 g, 23.4 mmol) and potassium acetate (4.61 g, 46.4 mmol) in ethanol (40 mL) was stirred and cooled to 0°C. The above diazotized solution was added dropwise at 0°C, and the reaction mixture was warmed to room temperature and stirred for 18 hours. LCMS showed the formation of the desired product. The reaction was diluted with water and extracted with EtOAc (3 x 50 mL). The combined organic layers were washed with _brine , dried over _Na2SO4 , and concentrated in vacuo to give 2-[(2,4-difluorophenyl)hydrazono]-3-hydroxy-propionic acid ethyl ester as a brown solid, which was used as is in the next step. LCMS (Method B): m/z 257 [M+H], retention time = 1.09 min Step 8 : Preparation of 2-[(2,4-difluorophenyl)hydrazono]-3-hydroxyimino-propionic acid ethyl ester To a solution of ethyl 2-[(2,4-difluorophenyl)hydrazono]-3-oxo-propionic acid ester (3.00 g, 5.85 mmol) in ethanol (30 mL) was added potassium acetate (1.45 g, 14.6 mmol) and hydroxylamine hydrochloride (0.49 g, 7.02 mmol) at room temperature. The reaction mixture was stirred at 80 ° C for 2 hours. LCMS showed complete conversion to the desired product. The reaction mixture was allowed to cool to room temperature, diluted with water and extracted with EtOAc (3 x 50 mL). The combined organic layers were washed with brine, dried over Na ₂ SO ₄ , and concentrated in vacuo to give the title compound as a brown solid, which was used as is in the next step. LCMS (Method B): m/z 272 [M+H], retention time = 1.16 min Step 9 : Preparation of ethyl 2-(2,4-difluorophenyl)triazole-4-carboxylate A sample of 2-[(2,4-difluorophenyl)hydrazono]-3-hydroxyimino-propionic acid ethyl ester (3.4 g, 6.3 mmol) was treated with acetic anhydride (34 mL, 10 mL/g) at room temperature. The reaction mixture was then stirred at 140°C for 1 h. The reaction mass was monitored by LC-MS and after completion of the reaction, the reaction mixture was cooled and quenched with ice and cold brine. The reaction mixture was extracted with EtOAc (3 × 25 mL) and the combined organic layers were dried over Na2SO4 and concentrated in vacuo to get the crude product. It was purified by combiflash using EtOAc/cyclohexane as eluent (5:95) to afford the title compound as a brown solid. LCMS (Method C): m/z 254 [M+H], retention time = 1.19 min Step 10 : Lithium 2-(2,4-difluorophenyl)triazole-4-carboxylate A stirred solution of ethyl 2-(2,4-difluorophenyl)triazole-4-carboxylate (0.10 g, 0.31 mmol) in tetrahydrofuran (0.4 mL) and water (0.1 mL) was treated with lithium hydroxide (11.0 mg 0.47 mmol) and the reaction was stirred at room temperature for 3 hours. After the reaction was complete, the reaction mixture was concentrated in vacuo and the residue was triturated with tert-butyl methyl ether (TBME). This yielded lithium 2-(2,4-difluorophenyl)triazole-4-carboxylate, which was used as is in the next step. LCMS (Method B): m/z 224 [M+H], retention time = 0.29 min Step 11 : Preparation of [2-(2,4-difluorophenyl)triazol-4-yl]-[rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-40, Table P) (rac-cis-compound P-40, Table P) A suspension of lithium 2-(2,4-difluorophenyl)triazole-4-carboxylate (0.231 g, 1.0 mmol, 100 mass %) and rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-1,2,3,4-tetrahydroisoquinoline (0.241 g, 1.0 mmol) was taken up in EtOAc (9 mL), treated with DIPEA (0.7 g, 5 mmol) and 1-propanephosphonic anhydride (TP3, 2 mL, 3 mmol, 50 mass % in EtOAc) at 0°C and the reaction mixture was stirred at room temperature for 2 h. After completion of the reaction, the reaction mixture was diluted with water (15 mL) and extracted with EtOAc (3 x 20 mL). The combined organic layers were washed with water and brine (20 mL), dried _{over Na2SO4} , filtered and concentrated in vacuo to give the crude product. It was purified by combiflash using 0-80% cyclohexane/EtOAc as eluent to give the title compound as a brown solid. LCMS (Method B), m/z 449 (M+H), retention time 1.14 min.

Example P6 : Preparation of [2-(2,4-difluorophenyl)tetrazol-5-yl]-[6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-34, Table P). Step 1 : Preparation of (3-methoxyphenyl)-(1-methylpyrazol-4-yl)methanol A single-necked round-bottom flask equipped with a magnetic stirring bar was charged with 4-iodo-1-methyl-1h-pyrazole (5.14 g, 23.5 mmol) and tetrahydrofuran (64 mL). To this solution was added dropwise a solution of isopropylmagnesium lithium chloride complex (1.3 mol/L) in THF (25 mL, 32.0 mmol) at 0°C under argon. The mixture was stirred at 0°C for 45 min, and then 3-methoxybenzaldehyde (2.68 mL, 21.3 mmol) was added dropwise at 0°C under argon. The mixture was stirred at this temperature for 10 min, and then allowed to reach room temperature and stirred for 2 hours. The reaction mixture was then poured into water (100 mL) and extracted with EtOAc (2 × 80 mL). The combined organic layers were washed with brine, dried over Na ₂ SO ₄ and concentrated in vacuo. The crude material was purified by flash chromatography (80 g SiO ₂ , EtOAc/cyclohexane gradient) to give (3-methoxyphenyl)-(1-methylpyrazol-4-yl)methanol. LCMS (Method B): m/z 219 [M+H], retention time 0.21 min. ¹ H NMR (400 MHz, CDCl ₃ ) δ ppm: 7.39 (s, 1 H), 7.26 - 7.33 (m, 1 H), 7.28 (s, 1 H), 6.96 - 7.05 (m, 2 H), 6.82 - 6.90 (m, 1 H), 5.72 - 5.88 (m, 1 H), 3.84 (s, 3 H), 3.82 (s, 3 H) Step 2 : Preparation of 2-(3-methoxyphenyl)-2-(1-methylpyrazol-4-yl)acetonitrile A solution of (3-methoxyphenyl)-(1-methylpyrazol-4-yl)methanol (4 g, 9.16 mmol) in acetonitrile (18 mL) was treated with iodine (4.18 g, 16.5 mmol) and lithium carbonate (0.13 g, 1.83 mmol), followed by the dropwise addition of trimethylsilyl cyanide (5.26 mL, 41.2 mmol) at room temperature. The resulting mixture was stirred at 50 °C for 8 h. The reaction mixture was then cooled to room temperature and poured into a saturated sodium thiosulfate solution (400 mL) and extracted with EtOAc (2 × 100 mL). The combined organic layers were washed with brine, dried over Na ₂ SO ₄ and concentrated in vacuo. The crude product was purified by silica gel chromatography to give 2-(3-methoxyphenyl)-2-(1-methylpyrazol-4-yl)acetonitrile. LCMS (Method B): m/z 228 [M+H], retention time 1.00 min. ¹ H NMR (400 MHz, CDCl ₃ ) δ ppm 7.41 (s, 1 H), 7.27 - 7.37 (m, 2 H), 6.87 - 6.99 (m, 3 H), 5.06 (s, 1 H), 3.89 (s, 3 H), 3.83 (s, 3 H) Step 3 : Preparation of 2-(3-methoxyphenyl)-2-(1-methylpyrazol-4-yl)ethanamine A solution of 2-(3-methoxyphenyl)-2-(1-methylpyrazol-4-yl)acetonitrile (3.2 g, 14 mmol) in tetrahydrofuran (42 mL) is treated dropwise with borane dimethyl sulfide complex (4.0 mL, 42 mmol) at room temperature under argon. The resulting yellow solution is stirred at 65°C for 3 hours and then cooled to 0°C, and then hydrochloric acid 6 M (9.4 mL, 4.0, 57 mmol) is added dropwise (strong gas evolution!). The reaction mixture is then stirred at 50°C for 1 hour and then allowed to cool to room temperature. The reaction mixture is diluted with water and then basified to pH 12 with NaOH 6 N. The mixture was extracted three times with EtOAc, and the combined organic layers were washed once with brine, dried over _{anhydrous Na2SO4} and concentrated under vacuum to give 2-(3-methoxyphenyl)-2-(1-methylpyrazol-4-yl)ethanamine as a brown oil, which was used as such in further chemical reactions. LCMS (Method B): m/z 232 [M+H], retention time 0.36 min. ¹ H NMR (400 MHz, DMSO-d6) δ ppm 7.52 (s, 1 H), 7.29 (s, 1 H), 7.20 (t, J = 7.44 Hz, 1 H), 6.72 - 6.87 (m, 3 H), 3.77 (s, 3 H), 3.80 (m, 1H), 3.73 (s, 3 H), 3.42 (s,1 H) 3.03-2.99 (m, 2H). Step 4 : Preparation of 6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline A 25 mL round-bottom flask equipped with a magnetic stir bar was charged with 2-(3-methoxyphenyl)-2-(1-methylpyrazol-4-yl)ethanamine (80 g, 0.34 mmol), hydrochloric acid 37% (1.7 mL) and acetaldehyde (0.19 mL, 3.46 mmol). The mixture was stirred at room temperature for 3 hours and then slowly poured into water and neutralized with saturated aqueous NaHCO ₃ solution (strong gas evolution) until pH 8. The mixture was extracted with EtOAc, and the combined organic layers were washed with brine, dried over Na ₂ SO ₄ , and concentrated in vacuo to give the title compound. LCMS (Method B): m/z 258 [M+H], retention time 0.19 min. Step 5 : Preparation of [2-(2,4-difluorophenyl)tetrazol-5-yl]-[6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-34, Table P). (Compound P-34, Table P). A mixture of 6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline (0.25 g, 0.97 mmol), 2-(2,4-difluorophenyl)tetrazole-5-carboxylic acid (0.24 g, 1.06 mmol), N,N - diisopropylethylamine (0.39 g, 2.91 mmol) and T3P (50 mass %) in EtOAc (1.72 mL, 2.91 mmol) was stirred in EtOAc (5 mL) at room temperature overnight. The reaction mixture was diluted with water and EtOAc, and the organic layer was removed. The aqueous layer was then back-extracted three times with EtOAc, and the combined organic layers were purified by Na ₂ SO ₄ , dried, filtered and concentrated in vacuo to give a crude product. It was purified by silica gel chromatography to give [2-(2,4-difluorophenyl)tetrazol-5-yl]-[6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone as a racemic mixture of cis and trans isomers in a ratio of 82:18, respectively. The racemic mixture was further purified by chiral phase chromatography, wherein the major cis isomer was separated: Chiralpak-IG (250 x 20 mm; 5 µm), mobile phase A: TBME (97%), mobile phase B: EtOH (3%) isocratic, flow rate: 17 mL/min, DAD detection: DAD, run time: 40 min, sample preparation: 350 mg, in 6 mL EtOH + 4 mL TBME, the cis isomer was obtained as a rotamer. Isomer 1: [2-(2,4-difluorophenyl)tetrazol-5-yl]-[(1S,4S)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-38, Table P) LCMS (Method D): m/z 466 [M+H], retention time 1.50 min. ¹ H NMR (400 MHz, CDCl ₃ ) δ ppm (rotanomeric ratio 65 : 35) 7.87 - 7.97 (m, 1 H), 7.39 - 7.43 (m, 1 H), 7.31 (s, 1 H), 7.11 - 7.20 (m, 3 H), 6.84 (dd, J = 8.57, 2.19 Hz, 1 H), 6.60 (d, J = 2.50 Hz, 1 H), 5.85 (q, J = 6.67 Hz, 1 H), 4.47 (dd, J = 11.63, 5.13 Hz, 1 H), 4.25 - 4.37 (m, 1 H), 3.91 (s, 3 H), 3.71 (s, 3 H), 3.53 (dd, J = 13.6,11.7 Hz, 1 H), 1.68 (d, J = 6.75 Hz, 3 H) ¹⁹ F NMR (376 MHz, CDCl ₃ ) δ -103.71 (s, 1 F), -115.07 (s, 1 F) Isomer 2: [2-(2,4-difluorophenyl)tetrazol-5-yl]-[(1R,4R)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-39, Table P) (Compound P-39, Table P) LCMS (Method D): m/z 466 [M+H], retention time 1.50 min. NMR is the same as isomer 1

Example P7 : Preparation of [6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone (Compound P-35, Table P) was prepared similarly to Example 5. Therefore, a mixture of 6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline (0.55 g, 2.14 mmol), 2-phenyltetrazole-5-carboxylic acid (0.45 g, 2.35 mmol), N,N -diisopropylethylamine (1.17 mL, 6.41 mmol) and T3P (50 mass %) in EtOAc (4.08 g, 3.78 mL, 6.41 mmol) was stirred in ethyl acetate (11 mL) at room temperature overnight. After this time, LCMS showed the formation of the product. The reaction mixture was diluted with water and EtOAc. The EtOAc was decanted and the aqueous was back extracted with EtOAc. The combined organic layers _were dried over _Na2SO4 , filtered and concentrated in vacuo. The crude product was purified by column to give a non-mirror isomer mixture of the title compound as a white solid (cis: trans ratio 63:37). The racemic mixture was further purified by column: Chiral pak-IG (250 x 20 mm; 5 µm), mobile phase A: TBME (80%), mobile phase B: EtOH (20%) isocratic, flow rate: 17 mL/min, DAD detection: DAD, run time: 45 min, sample preparation: 580 mg, in 10 mL EtOH+4 mL THF+1 mL TBME, the cis isomer was obtained as a rotomeric isomer. Isomer 1: [(1R,4R)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazolyl-5-yl)methanone (Compound P-36, Table P) (Compound P-36, Table P) LCMS (Method D): m/z 430 [M+H], retention time 1.50 min. ¹ H NMR (400 MHz, CDCl ₃ ) δ ppm (rotational isomer ratio 64 : 36) 8.16 - 8.22 (m, 2 H), 7.53 - 7.62 (m, 3 H), 7.40 - 7.44 (m, 1 H), 7.32 (s, 1 H), 7.12 - 7.20 (m, 1 H), 6.84 (dd, J = 8.57, 2.19 Hz, 1 H), 6.58 - 6.61 (m, 1 H), 5.89-5.80 (m, 1 H), 4.47 (dd, J = 11.57, 5.19 Hz, 1 H), 4.33 - 4.40 (m, 1 H), 3.91 (s, 3 H), 3.72 (s, 3 H), 3.53 (dd, J = 13.63, 11.76 Hz, 1 H), 1.68 (d, J = 6.75 Hz, 3 H) Isomer 2: [(1S,4S)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazolyl-5-yl)methanone (Compound P-36, Table P) (Compound P-36, Table P) LCMS (Method D): m/z 430 [M+H], retention time 1.50 min. ¹ H NMR (400 MHz, CDCl ₃ ) δ ppm (rotational isomer ratio 61 : 39) 8.16 - 8.22 (m, 2 H), 7.53 - 7.62 (m, 3 H), 7.40 - 7.44 (m, 1 H), 7.32 (s, 1 H), 7.12 - 7.20 (m, 1 H), 6.84 (dd, J = 8.57, 2.19 Hz, 1 H), 6.58 - 6.61 (m, 1 H), 5.89-5.80 (m, 1 H), 4.47 (dd, J = 11.57, 5.19 Hz, 1 H), 4.33 - 4.40 (m, 1 H), 3.91 (s, 3H), 3.68 (s, 3 H), 3.53 (dd, J = 13.63, 11.76 Hz, 1 H), 1.68 (d, J = 6.75 Hz, 3 H).

Further examples of synthesized compounds of formula (I) are shown in Table P. [ Table P ] : Synthesized compounds and spectral and physicochemical data. Article IUPAC name molecular RT ( min ) [M+H] (measured) method P-1 [1-(2-Fluorophenyl)pyrazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 0.98 402 A P-2 [1-(2,4-Difluorophenyl)pyrazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 0.98 420 A P-3 [1-(2-Fluorophenyl)pyrazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 0.92 403 A P-4 [2,5-Dimethyl-1-(2,2,2-trifluoroethyl)pyrrol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 0.98 417 A P-5 (1,5-dimethylpyrazol-3-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 0.23 335 A P-6 (2-phenyltriazol-4-yl)-[4-(1,3,5-trimethylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 1.01 413 A P-7 (1-phenyltriazol-4-yl)-[4-(1,3,5-trimethylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 0.94 413 A P-8 [1-(2,4-Difluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 0.92 421 A P-9 [1-(4-Fluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 1.21 403 E P-10 [4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]-(1-phenylimidazol-4-yl)methanone 1.27 384 E P-11 [4-(1-Methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]-(1-phenyltriazol-4-yl)methanone 1.19 385 E P-12 [2,5-Dimethyl-1-(5-methylisoxazol-3-yl)pyrrol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 1.39 416 E P-13 (1-Benzyltriazol-4-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 1.29 399 E P-14 [4-(1-Methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone 1.35 386 E P-15 (1-Isopropyltriazol-4-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 1.18 351 E P-16 [4-(1-Methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]-(1-phenylpyrazol-3-yl)methanone 1.33 384 E P-17 [1-(4-Fluorophenyl)-5-methyl-triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 1.34 417 E P-18 [2-(4-Fluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 1.41 403 E P-19 [4-(1-Methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]-(1-phenyl-1,2,4-triazol-3-yl)methanone 1.24 385 E P-20 (1-Tributylimidazol-4-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 1.06 364 E P-21 [1-(4-Fluorophenyl)pyrazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 1.40 402 E P-22 (5-Cyclopropyl-1-methyl-pyrazol-3-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 1.28 362 E P-23 [1-(3-Fluoro-2-pyridinyl)-1,2,4-triazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 1.70 404 E P-24 [1-(3-Fluorophenyl)-3-methyl-pyrazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 1.39 416 E P-25 (5-Benzyl-1-methyl-pyrazol-3-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 1.38 412 E P-26 [4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]-[1-[5-(trifluoromethyl)-2-pyridyl]triazol-4-yl]methanone 1.27 454 E P-27 [1-(2-Methoxyphenyl)imidazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 1.20 414 E P-28 (5-Cyclopropyl-1-ethyl-pyrazol-3-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 1.32 376 E P-29 [1-(2,6-Difluorophenyl)pyrazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 1.36 420 E P-30 [1-(3,4-difluorophenyl)pyrazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 1.42 420 E P-31 [2-(2,4-Difluorophenyl)tetrazol-5-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 1.07 436 G P-32 [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone 1.06 436 G P-33 [1-(2,4-Difluorophenyl)-1,2,4-triazol-3-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 1.38 435 F P-34 [2-(2,4-difluorophenyl)tetrazol-5-yl]-[6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]methanone 1.50 466 F P-35 [6-Methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro- 1H -isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone 1.52 430 F P-36 [(1R,4R)-6-Methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone 1.50 430 F P-37 [(1S,4S)-6-Methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone 1.50 430 F P-38 [2-(2,4-difluorophenyl)tetrazol-5-yl]-[(1S,4S)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone 1.50 466 F P-39 [2-(2,4-difluorophenyl)tetrazol-5-yl]-[(1R,4R)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone 1.50 466 F P-40 [2-(2,4-difluorophenyl)triazol-4-yl]-[rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone 1.14 449 G P-41 [1-(2,4-difluorophenyl)triazol-4-yl]-[rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone 1.13 449 G P-42 [2-(2,4-difluorophenyl)tetrazol-5-yl]-[rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone 1.12 450 G P-43 [1-(3,5-difluoro-2-pyridyl)triazol-4-yl]-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone 1.06 450 G P-44 [1-(3,5-difluoro-2-pyridyl)triazol-4-yl]-[(1R,4R)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone 1.05 450 G P-45 [(1S,4S)-4-(5-Chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[2-(2,4-difluorophenyl)triazol-4-yl]methanone 1.23 469 G P-46 [(1R,4R)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[2-(2,4-difluorophenyl)triazol-4-yl]methanone 1.23 469 G P-47 [(1R,4R)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[1-(2,4-difluorophenyl)triazol-4-yl]methanone 1.18 469 G P-48 [(1S,4S)-4-(5-Chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[1-(2,4-difluorophenyl)triazol-4-yl]methanone 1.18 469 G P-49 [(1S,4S)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[2-(2,4-difluorophenyl)tetrazol-5-yl]methanone 1.05 470 G P-50 [(1R,4R)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[2-(2,4-difluorophenyl)tetrazol-5-yl]methanone 1.05 470 G P-51 [1-(3,5-difluoro-2-pyridyl)triazol-4-yl]-[(1S,4S)-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone 1.07 436 G P-52 [1-(3,5-difluoro-2-pyridyl)triazol-4-yl]-[(1R,4R)-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone 1.07 436 G P-53 [1-(3,5-difluoro-2-pyridyl)triazol-4-yl]-[rac-(1S,4S)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone 1.17 470 G P-54 [(1S,4S)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[1-(3,5-difluoro-2-pyridyl)triazol-4-yl]methanone 1.15 470 G P-55 [(1R,4R)-4-(5-chloro-1-methyl-pyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-[1-(3,5-difluoro-2-pyridyl)triazol-4-yl]methanone 1.15 470 G P-56 [1-(2,4-difluorophenyl)triazol-4-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone 1.77 435 H P-57 [1-(3,5-difluoro-2-pyridyl)triazol-4-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone 1.67 436 H

Example B1 : Leptospora solani / tomato / leaf disc (early blight) Tomato leaf discs cv. Baby were placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. 2 days after application, the leaf discs were inoculated with a spore suspension of the fungus. The inoculated leaf discs were incubated at 23°C/21°C (day/night) and 80% rh in a climate chamber under a light regime of 12/12 h (light/darkness), and the activity of the compound was assessed as the percentage of disease control compared to the untreated test leaf discs when appropriate levels of disease damage appeared (5-7 days after application). The following compounds at 200 ppm gave at least 80% control of L. solani when compared to untreated controls which showed extensive disease development under the same conditions: P-14, P-31, P-41, P-42, P-43, P-48, P-49, P-51, P-53, P-54, P-56, P-57

Example B2 : Botryotinia fuckeliana or Botrytis cinerea / liquid culture (gray mold) Conidia of the fungus from frozen storage are mixed directly into the nutrient medium (Vogels broth). After placing a (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient medium containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3-4 days after application. The following compounds at 20 ppm gave at least 80% control of Botrytis cinerea when compared to untreated controls which showed extensive disease development under the same conditions: P-14, P-31, P-35, P-37, P-41, P-42, P-43, P-48, P-49, P-51, P-53, P-54, P-56

Example B3 : Melon husk /liquid culture (anthracnose) Fungal conidia from frozen storage were mixed directly into the nutrient medium (PDB-potato dextrose broth). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient medium containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was measured photometrically 3-4 days after application. The following compounds at 20 ppm gave at least 80% control of melon bush husk when compared to untreated controls which showed extensive disease development under the same conditions: P-11, P-14, P-31, P-35, P-41, P-42, P-43, P-44, P-48, P-49, P-51, P-53, P-54, P-56

Example B4 : Blumeria graminis f. sp. tritici ( Erysiphe graminis f. sp. Tritici ) / Wheat / Leaf discs Preventive (Powdery mildew on wheat) Wheat leaf segments cv . Kanzler were placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. One day after application, the leaf discs were inoculated by shaking powdery mildew infected plants on the test plates. Inoculated leaf disks were incubated at 20°C and 60% rh in a climate chamber under a light regimen of 24 h dark followed by 12 h light/12 h dark and the activity of the compounds was assessed as the percentage of disease control compared to the untreated when appropriate levels of disease damage appeared on untreated test leaf segments (6-8 days after application). The following compounds gave at least 80% control of wheat powdery mildew at 200 ppm when compared to untreated controls showing extensive disease development under the same conditions: P-37, P-42, P-43, P-48, P-49, P-51, P-53, P-54, P-56

Example B5 : Yellow sickle fungus /liquid culture (head mold) Fungal conidia from frozen storage were mixed directly into the nutrient medium (PDB-potato dextrose broth). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient medium containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 3-4 days after application. The following compounds gave at least 80% control of yellow sickle fungus at 20 ppm when compared to untreated controls that showed extensive disease development under the same conditions: P-42, P-43, P-48, P-53, P-54

Example B6 : Corn rudaria (Sickling fungus of cereals) /wheat/spikelet preventive (rudaria) Wheat spikelets cv. Miscanthus were placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. One day after application, the spikelets were inoculated with a spore suspension of the fungus. Inoculated test leaf disks were cultured at 20°C and 60% rh in a climatic chamber under a light regime of 72 h semi-darkness followed by 12 h light/12 h dark, and the activity of the compound was evaluated as the percentage of disease control compared to the untreated spikelets when appropriate levels of disease damage appeared (6-8 days after application). The following compounds at 200 ppm gave at least 80% control of corn rutabaga when compared to untreated controls which showed extensive disease development under the same conditions: P-54

Example B7 : Phaeosphaeria nodorum , Septoria nodorum / wheat / leaf disc preventive (grain blight) Wheat leaf segments cv. Kanzler were placed on agar in multiwell plates (24-well format) and sprayed with formulated test compounds diluted in water. 2 days after application, the leaf discs were inoculated with a spore suspension of the fungus. The inoculated test leaf discs were incubated at 20°C and 75% rh in a climate chamber under a light regime of 12 h light/12 h dark, and the activity of the compound was assessed as the percentage of disease control compared to the untreated when appropriate levels of disease damage appeared on the untreated test leaf discs (5-7 days after application). The following compounds at 200 ppm gave at least 80% control of Septoria sphaerocephala when compared to untreated controls which showed extensive disease development under the same conditions: P-14, P-31, P-37, P-41, P-42, P-43, P-48, P-49, P-51, P-53, P-54, P-56, P-57

Example B8 : Thielavia nivalis (Leaf Blight Fungus) / Liquid Culture (Cereal Root Rot) Fungal conidia from frozen storage were mixed directly into the nutrient medium (PDB-Potato Dextrose Broth). After placing a (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient medium containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 4-5 days after application. The following compounds at 20 ppm gave at least 80% control of Thielavia nivalis when compared to untreated controls which showed extensive disease development under the same conditions: P-14, P-18, P-31, P-34, P-35, P-36, P-37, P-38, P-41, P-42, P-43, P-48, P-49, P-51, P-53, P-54, P-56

Example B9 : Mycosphaerella arachidis ( Cercospora arachidicola ) / Liquid culture (early leaf spot) Fungal conidia from frozen storage were directly mixed into the nutrient medium (PDB-potato dextrose broth). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient medium containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 4-5 days after application. The following compounds at 20 ppm gave at least 80% control of Mycosphaeria arachidis when compared to untreated controls which showed extensive disease development under the same conditions: P-7, P-14, P-31, P-34, P-35, P-36, P-37, P-38, P-41, P-42, P-43, P-44, P-47, P-48, P-49, P-51, P-53, P-54, P-56

Example B10 : Puccinia recondita f . sp. tritici / wheat / leaf disc treatment (brown rust) Wheat leaf segments cv. Cansler were placed on agar in multiwell plates (24-well format). The leaf segments were inoculated with a spore suspension of the fungus. The plates were stored in the dark at 19°C and 75% rh. One day after inoculation, the formulated test compounds diluted in water were applied. The leaf segments were incubated at 19°C and 75% rh in a climate chamber under a light regime of 12 h light/12 h dark, and the activity of the compounds was assessed as the percentage of disease control compared to the untreated when appropriate levels of disease damage appeared on the untreated test leaf segments (6-8 days after application). The following compounds at 200 ppm gave at least 80% control of P. truncatula when compared to untreated controls which showed extensive disease development under the same conditions: P-42

Example B11 : Puccinia recondita f. sp. tritici / wheat / leaf disc preventive (brown rust) Wheat leaf segments cv. Kanzler were placed on agar in multiwell plates (24-well format) and sprayed with formulated test compounds diluted in water. One day after application, the leaf discs were inoculated with a spore suspension of the fungus. The inoculated leaf segments were incubated at 19°C and 75% rh in a climate chamber under a light regime of 12 h light/12 h dark, and the activity of the compound was assessed as the percentage of disease control compared to the untreated when appropriate levels of disease damage appeared in the untreated test leaf segments (7-9 days after application). The following compounds at 200 ppm gave at least 80% control of P. truncatula at wheat when compared to untreated controls which showed extensive disease development under the same conditions: P-37, P-41, P-42, P-49

Example B12 : Pyricularia tergoniae / barley / leaf disc preventive (net blotch) Barley leaf segments cv. Hasso were placed on agar in multiwell plates (24-well format) and sprayed with formulated test compounds diluted in water. 2 days after application, the leaf segments were inoculated with a spore suspension of the fungus. The inoculated leaf segments were incubated at 20°C and 65% rh in a climate chamber under a light regime of 12 h light/12 h dark, and the activity of the compounds was assessed as disease control compared to the untreated when appropriate levels of disease damage appeared on untreated test leaf segments (5-7 days after application). The following compounds at 200 ppm gave at least 80% control of Pyrrolizidine occludinium when compared to untreated controls which showed extensive disease development under the same conditions: P-8, P-14, P-31, P-35, P-37, P-40, P-41, P-42, P-43, P-48, P-49, P-51, P-53, P-54, P-56, P-57

Example B13 : Sclerotinia sclerotiorum /liquid culture (cotton rot) Mycelial fragments of a newly grown liquid culture of the fungus were mixed directly into a nutrient medium (PDB (potato dextrose broth)). After placing a (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient medium containing the fungal material was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 3-4 days after application. The following compounds gave at least 80% control of Sclerotinia sclerotiorum at 20 ppm when compared to untreated controls that showed extensive disease development under the same conditions: P-42, P-48.

Example B14 : Mycosphaeria graminicola (Septoria graminicola) / liquid culture (Septoria blotch) Fungal conidia from frozen storage were mixed directly into the nutrient medium (PDB-potato dextrose broth). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient medium containing the fungal spores was added. The test plates were incubated at 24°C and the inhibition of growth was determined photometrically 4-5 days after application. The following compounds at 20 ppm gave at least 80% control of Mycosphaeria graminearum when compared to untreated controls which showed extensive disease development under the same conditions: P-7, P-11, P-14, P-18, P-31, P-32, P-34, P-35, P-36, P-37, P-38, P-40, P-41, P-42, P-43, P-44, P-45, P-47, P-48, P-49, P-50, P-51, P-53, P-54, P-56, P-57

without

without

without

Claims (15)

A compound having formula (I), (I) wherein R ¹ is selected from hydrogen, C ₁ -C _4- alkyl, C ₂ -C _4- alkenyl, C ₂ -C ₄ -alkynyl, or C ₃ -C ₆ cycloalkyl; R ² is selected from hydrogen, halogen, C ₁ -C ₄ -alkyl, C ₂ -C ₄ -alkenyl, C ₂ -C ₄ -alkynyl, C ₁ -C ₄ -halogenated alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C _4- alkylcarbonyl, N-C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl-carboimido, N-hydroxy-C ₁ -C ₄ alkyl-carboimido, or C ₁ -C ₄ -alkoxycarbonyl; R ³ and R ⁴ are independently selected from hydrogen, halogen, or C ₁ -C ₄ -alkyl; R ⁵ and R R ⁶ is independently selected from hydrogen, or C ₁ -C ₄ alkyl; R ⁷ is selected from hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylcarbonyl, N-C ₁ -C ₄ alkoxy-C C ₁ -C ₄ alkyl-carboimido, N-hydroxy-C C ₁ -C ₄ alkyl-carboimido, C ₁ -C ₄ alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C ₁ -C ₄ alkylaminocarbonyl, di(C ₁ -C ₆ alkylamino)carbonyl, phenyl, 5 to 6 membered heteroaryl, or C ₃ -C ₆ -cycloalkyl; wherein the 5- or 6-membered heteroaryl includes 1, 2, 3, or 4 heteroatoms independently selected from N, O, or S and wherein the phenyl and the 5- to 6-membered heteroaryl are unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C ₁ -C ₄ haloalkyl, cyano, carboxyl, C ₁ -C ₄ alkyl, or C ₁ -C ₄ alkoxy; and wherein the C ₃ -C ₆ -cycloalkyl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C ₁ -C ₄ haloalkyl, cyano, C ₁ -C ₄ alkyl, or C ₁ -C ₄ alkoxy; B ¹ is selected from CR ¹⁰ , or N; B ² is selected from CR ¹¹ , or N; R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are independently selected from hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ halogenated alkyl, C ₁ -C 4 alkoxy, C ₁ -C ₄ halogenated alkoxy, C ₂ -C ₄ alkenyloxy, C ₂ -C ₄ alkynyloxy, C ₁ -C ₄ alkylthio, C 1 -C ₄ alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ alkoxy-C ₁ -C ₄ alkyl, N-C _1-4 alkylamino, N,N-diC _1-4 alkylamino, C _{1 -C 6} alkoxycarbonyl _, C ₁ -C ₄ alkylcarbonyl, N-C _{1 -C 4 alkoxy-C 1 -C 4 alkyl} -carboimido, N-hydroxy-C ₁ -C wherein the phenyl, the 5- to 6-membered heteroaryl and the C ₃ -C ₆ -cycloalkyl are unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C 1 -C 4 alkyl, C ₁ -C ₄ halogenated alkyl, or C _{1 -C 4} alkoxy; A ¹ is selected from CR _12a , or N, A ² is selected from CR ^13a , or N; A ³ is selected ^{from CR 14a ,} _{or N} ; R ^12a _, R R ^13a and R ^14a are independently selected from hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ halogenated alkyl, C ₂ -C ₄ alkenyl, or C ₂ -C ₄ alkynyl; and Z ¹ is selected from C ₁ -C ₄ alkyl, phenyl, 5- or 6-membered heteroaryl, or C ₃ -C ₆ cycloalkyl, wherein the 5- or 6-membered heteroaryl includes 1, 2, 3, or 4 heteroatoms independently selected from N, O, or S, and wherein any of the phenyl, 5- or 6-membered heteroaryl is unsubstituted or substituted by 1, 2, or 3 halogenated, cyano, C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₁ -C ₄ halogenated alkyl, C 1 -C ₄ alkoxy, C ₁ -C ₄ halogenated alkoxy, C ₃ -C 6 cycloalkyl, The present invention relates _{to an} agrochemically acceptable salt, stereoisomer _or N-oxide _{thereof wherein the C3-C6 cycloalkyl group is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl , C1 - C4 halogenated alkyl or C1 - C4 alkoxy} . The compound of claim 1 having the formula (I), wherein R ¹ is methyl; and wherein R ² is selected from hydrogen or methyl. The compound of claim 1 or claim 2 having the formula (I), wherein R ³ is hydrogen; and R ⁴ is selected from hydrogen or methyl. The compound of formula (I) as described in any one of claims 1 to 3, wherein R ⁵ and R ⁶ are independently selected from hydrogen or methyl. The compound of formula (I) as described in any one of claims 1 to 4, wherein R ⁷ is hydrogen, C ₁ -C ₄ alkyl, or C ₃ -C ₆ cycloalkyl. A compound of formula (I) as described in any one of claims 1 to 5, wherein ^A1 is selected from ^CR12a or N; ^A2 is selected from ^CR13a or N; ^A3 is selected from ^CR14a or N; wherein at least two of ^A1 , ^A2 and ^A3 are selected from N; and wherein ^R12a , ^R13a , and ^R14a are hydrogen. The compound of formula (I) as claimed in any one of claims 1 to 6, wherein B ¹ is CR ¹⁰ ; and B ² is CR ¹¹ . The compound of formula (I) as described in any one of claims 1 to 7, wherein ^R8 and ^R9 are independently selected from hydrogen, halogen, cyano, _C1 - _C4 alkyl, or _C1 - _C4 alkoxy; and ^R10 and ^R11 are independently selected from hydrogen, halogen, _C1 - _C3 alkyl, or _C1 - _C4 alkoxy. The compound of claim 8 having the formula (I), wherein R ¹⁰ and R ¹¹ are hydrogen. The compound of formula (I) as described in any one of claims 1 to 9, wherein the compound of formula (I) is a compound of formula (II): (II) wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , B ¹ and B ² and Z ¹ are as defined for the compound of formula (I) as described in any one of claims 1 to 9, and A is selected from: in indicates a bond to a C(═O) group, and an asterisk (*) indicates a nitrogen having a bond to a Z ¹ group, and wherein R ^12a , R ^13a and R ^14a are independently selected from hydrogen, halogen, methyl, cyclopropyl, or trifluoromethyl. The compound of claim 10 having the formula (II), wherein A is selected from in indicates a bond to a C(═O) group, and an asterisk (*) indicates a nitrogen with a bond to a Z ¹ group. A compound of formula (I) as described in any one of claims 1 to 11, wherein Z ¹ is selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 3,5-difluoro-2-pyridyl, 2,4-difluorophenyl, 2-fluorophenyl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, cyclobutyl, cyclohexyl, cyclopentyl, or phenyl. An agrochemical composition comprising a fungicidal effective amount of a compound of formula (I) as defined in any one of claims 1 to 12. A method for controlling or preventing infection 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 12 or a composition comprising the compound of formula (I) is applied to the plants, parts thereof or the locus thereof. A use of the compound as claimed in any one of claims 1 to 12 as a fungicide.