Microbiocidal pyrazole derivatives

Abstract

A compound of formula (I): wherein the substituents are as defined in claim 1, as well as agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds, which can be used as fungicides. # imgabs0 #

Description

[0001] 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.

[0002] According to a first aspect of the present invention, there is provided a compound having formula (I):

[0003]

[0004] in

[0005] R 1 Selected from hydrogen, C1-C 4- Alkyl, C2-C 4- alkenyl, C2-C4-alkynyl, or C3-C6 cycloalkyl;

[0006] R 2 Selected from hydrogen, halogen, C1-C 4- Alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C3-C6 cycloalkyl, C1-C 4- Alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimino, N-hydroxy-C-C1-C4 alkyl-carbonimino, or C1-C 4- Alkoxycarbonyl;

[0007] R 3 and R 4 independently selected from hydrogen, halogen, or C1-C4-alkyl;

[0008] R 5 and R 6 Independently selected from hydrogen, or C1-C4 alkyl;

[0009] R 7is selected from hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimino, N-hydroxy-C-C1-C4 alkyl-carbonimino, C1-C4 alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4 alkylaminocarbonyl, di(C1-C6 alkylamino)carbonyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- or 6-membered heteroaryl includes 1, 2, 3, or 4 individual wherein the phenyl and 5- to 6-membered heteroaryl groups are unsubstituted or substituted by 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, cyano, carboxyl, C1-C4 alkyl, or C1-C4 alkoxy; and wherein the C3-C6-cycloalkyl group is unsubstituted or substituted by 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0010] B 1 Selected from CR 10 , or N;

[0011] B 2 Selected from CR 11 , or N;

[0012] R 8 , R 9 , R 10 and R 11 independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, NC 1-4 Alkylamino, N,N-diC 1-4 Alkylamino, C1-C6 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimino, N-hydroxy-C1-C4 alkyl-carbonimino, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxyl, amino, phenyl, 5- or 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, 5- to 6-membered heteroaryl, and C3-C6-cycloalkyl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy;

[0013] A 1 Selected from CR 12a , or N;

[0014] A 2 Selected from CR 13a , or N;

[0015] A 3 Selected from CR 14a , or N;

[0016] R 12a , R 13a and R 14a are independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, or C2-C4 alkynyl; and

[0017] Z 1 is selected from C1-C4 alkyl, phenyl, 5- or 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, 5- or 6-membered heteroaryl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, or C2-C4 alkynyl and wherein the C3-C6 cycloalkyl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy;

[0018] or an agrochemically acceptable salt, stereoisomer or N-oxide thereof.

[0019] Surprisingly, it has been found that, for practical purposes, the compounds of formula (I) have very advantageous levels of biological activity for protecting plants against diseases caused by fungi.

[0020] According to a second aspect of the present invention, there is provided an agrochemical composition comprising a fungicidally 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 agrochemically acceptable diluent or carrier.

[0021] According to a third aspect of the present invention, there is provided a method for controlling or preventing infection of useful plants 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 locus.

[0022] 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 methods of treating the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body.

[0023] 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.

[0024] Compounds of the formula I with 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 hydrohalic acids, strong organic carboxylic acids, such as unsubstituted or, for example, halogen-substituted C1-C4-alkanecarboxylic acids, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or 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, for example, form salts 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 morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, for example ethylamine, diethylamine, triethylamine or dimethylpropylamine, or mono-, di- or tri-hydroxy lower alkylamines, for example monoethanolamine, diethanolamine or triethanolamine).

[0025] In each case, the compounds of formula (I) according to the invention are in free form, oxidized form (such as N-oxide), or salt form (eg, agronomically usable salt form).

[0026] 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.

[0027] The compounds of formula (I) according to the invention also include hydrates which may be formed during salt formation.

[0028] When substituents are indicated as being "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 xSubstituent. For example, the C1-C6 alkyl substituted by 1, 2 or 3 halogens may include, but is not limited to -CH2Cl, -CHCl2, -CCl3, -CH2F, -CHF2, -CF3, -CH2CF3 or -CF2CH3 groups. As another example, the C1-C6 alkoxy substituted by 1, 2 or 3 halogens may include, but is not limited to CH2ClO-, CHCl2O-, CCl3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O- or CH3CF2O- groups. As used herein, the term "optionally substituted" may be used interchangeably with "unsubstituted or substituted".

[0029] As used herein, the term "halogen" or "halo" refers to fluorine (fluorine, fluoro), chlorine (chlorine, chloro), bromine (bromine, bromo) or iodine (iodine, iodo), preferably fluorine, chlorine or bromine. This also applies to halogen in combination with other meanings, such as haloalkyl, haloalkenyl, haloalkynyl, haloalkoxy, and halocycloalkyl.

[0030] As used herein, amino refers to a -NH2 group.

[0031] As used herein, cyano refers to a -CN group.

[0032] As used herein, the term "hydroxyl" or "hydroxy" refers to an -OH group.

[0033] As used herein, the term "carboxylic acid" refers to a -COOH group.

[0034] As used herein, the term "C1-C n "Alkyl" refers to a saturated straight or branched hydrocarbon 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.

[0035] As used herein, the term "C2-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.

[0036] As used herein, the term "C2-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,

[0037] As used herein, the term "C3-C n "-cycloalkyl" refers to a tri(3) to n-membered cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0038] As used herein, the term "C1-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 "C2-C n "Alkenyloxy" refers to a straight or branched alkenyl chain (as mentioned above) having two (2) to n carbon atoms, attached via an oxygen atom.

[0039] As used herein, the term "C1-C n -alkoxy-C1-C n -alkyl" refers to a C1-C n - Alkoxy-substituted alkyl (as mentioned above). Examples are methoxymethyl, methoxyethyl, ethoxymethyl and propoxymethyl.

[0040] As used herein, the term "C1-C n“Haloalkyl” refers to a straight-chain 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 these 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. Accordingly, the term "C1-C2 fluoroalkyl" will refer to a C1-C2 alkyl group with 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 "C2-C n -haloalkenyl" or "C2-C n "-haloalkynyl" refers to a C2-C4 substituted by one or more halogen atoms which may be the same or different. n -alkenyl or C2-C n -alkynyl. Similarly, as used herein, the term "C3-C n -halogenated cycloalkyl" or "C1-C n "-haloalkoxy" refers to a C3-C4 substituted by one or more halogen atoms which may be the same or different. n -cycloalkyl or C1-C n -alkoxy.

[0041] As used herein, the term "C1-C n -alkylthio" or "C1-C n -alkenylsulfanyl" refers to a C1-C n -alkyl.

[0042] As used herein, the term "C1-C n "Haloalkylthio" or "C1-C n "Haloalkylsulfanyl" refers to a C1-C nHalogenated alkyl.

[0043] As used herein, the term "C1-C n "-alkylsulfinyl" refers to a C1-C2-alkyl group attached through the sulfur atom of a sulfinyl (or S(=O)-) group. n alkyl.

[0044] As used herein, the term "C1-C n "-alkylsulfonyl" refers to a C1-C2- alkyl group attached through the sulfur atom of a sulfonyl (or S(=O)2-) group. n alkyl.

[0045] As used herein, the term "C1-C n -Alkylsulfonyl-C1-C n -alkyl" refers to a C1-C n Alkylsulfonyl substituted C1-C n alkyl.

[0046] As used herein, the term "C1-C n "-alkylcarbonyl" refers to a C1-C n -alkyl.

[0047] As used herein, the term "C1-C n "-alkoxycarbonyl" refers to a C1-C2- n -alkoxy moiety.

[0048] As used herein, the term "benzoyl" refers to a phenyl group attached through the carbon atom of a carbonyl group (C=O).

[0049] As used herein, the term "C1-C n "-alkylaminocarbonyl" refers to a C1-C n -alkylamino (or R a NHC(=O)-, where R a It is C1-C n -alkyl).

[0050] As used herein, the term "aminocarbonyl-C1-C n "-alkyl" refers to a C1-C1-substituted by an aminocarbonyl (or NH2C(=O)-) n -alkyl.

[0051] As used herein, the term "N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimino" refers to a a )=NO(R b ) group, wherein Ra is C as generally defined above 1- C4 alkyl, and R b is C as generally defined above 1- C4 alkyl.

[0052] As used herein, the term "N-hydroxy-C-C1-C4 alkyl-carbonimino" refers to a a )=NOH group, wherein R a is C as generally defined above 1- C4 alkyl.

[0053] 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, pyrazinyl, pyridazinyl, pyrimidinyl or pyridinyl. The term "heteroaryl-C1-C1 n -alkyl" or "heteroaryl-C3-C n -cycloalkyl" refers to a C1-C n -alkyl or C3-C n -cycloalkyl. Heteroaryl-C1-C n -alkyl or heteroaryl-C3-C n -Cycloalkyl groups may, if appropriate, be substituted on the heteroaryl, alkyl and / or cycloalkyl groups.

[0054] As used herein, the term "control" means reducing the number of pests, eliminating pests, and / or preventing further pest damage, such that damage to plants or to plant-derived products is reduced.

[0055] As used herein, the term "pest" 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 damage to man-made structures. The term pest covers all stages of the life cycle of the pest.

[0056] 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.

[0057] 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 being applied; the type of application; and other relevant circumstances.

[0058] 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.

[0059] The following list provides substituents R for compounds of formula (I) of the present invention: 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 Definitions of and Z, including preferred definitions. For any of these substituents, any definition given below may be combined with any definition of any other substituent given below or elsewhere in this document.

[0060] In the embodiment of the present invention, R 1 Selected from hydrogen, C1-C 4- Alkyl, C2-C 4- In another embodiment of the present invention, R 1 Selected from hydrogen, C1-C 4- Alkyl, C2-C 4- Preferably R 1 is a C1-C4 alkyl group. More preferably, R 1 is methyl, ethyl, or isopropyl. Most preferably, R 1 It's methyl.

[0061] In the embodiment of the present invention, R 2 Selected from hydrogen, halogen, C1-C 4- Alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C3-C6 cycloalkyl, C1-C 4- Alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimino, N-hydroxy-C-C1-C4 alkyl-carbonimino, or C1-C 4- In another embodiment of the present invention, R 2 Selected from hydrogen, halogen, C1-C 4- Alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C3-C6 cycloalkyl, C1-C 4-Alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimino, N-hydroxy-C-C1-C4 alkyl-carbonimino, or C1-C 4- In yet another embodiment, R 2 is selected from hydrogen, halogen, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimino, or N-hydroxy-C1-C4 alkyl-carbonimino. Preferably, R 2 is selected from hydrogen, halogen, methyl, ethyl, cyclopropyl, C1-C2 alkylcarbonyl, N-C1-C2 alkoxy-C1-C2 alkyl-carbonimino, or N-hydroxy-C1-C2 alkyl-carbonimino. More preferably, R 2 is selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, cyclopropyl, acetyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, or -C(CH3)=NOH. In a preferred embodiment of the present invention, R 2 is selected from hydrogen, halogen, or C1-C4 alkyl. 2 is hydrogen, chlorine, or methyl.

[0062] In one embodiment, R 3 is selected from hydrogen, halogen, or C1-C4 alkyl. In another embodiment, R 3 is selected from hydrogen, halogen, or C1-C4 alkyl. 3 is hydrogen or C1-C4 alkyl. More preferably, R 3 is hydrogen or methyl. Most preferably, R 3 It's hydrogen.

[0063] In one embodiment of the present invention, R 4 is selected from hydrogen, halogen, or C1-C4-alkyl. In another embodiment of the present invention, R 4 is hydrogen, halogen, or C1-C4 alkyl. 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 In another embodiment of the present invention, R 4 It's methyl.

[0064] In one embodiment of the present invention, R 5 and R 6 In another embodiment of the present invention, R 5 and R 6are independently selected from hydrogen or C1-C4-alkyl. 5 and R 6 are independently selected from hydrogen, methyl, or ethyl. More preferably, R 5 and R 6 is independently selected from hydrogen or methyl. Even more preferably, R 5 and R 6 It's hydrogen.

[0065] In the embodiment of the present invention, R 7 is selected from hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimino, N-hydroxy-C-C1-C4 alkyl-carbonimino, N-methoxy-N-methyl-carbonyl, C1-C4 alkylaminocarbonyl, di(C1-C6 alkylamino)carbonyl, phenyl, 5 to 6 membered heteroaryl, or C3-C6-cycloalkyl, wherein the 5 to 6 membered heteroaryl includes 1 heteroatom selected from N and wherein the phenyl and 5 to 6 membered heteroaryl are unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, C1-C4 haloalkyl, cyano, or C1-C4 alkyl; and wherein the C3-C6-cycloalkyl is unsubstituted or substituted by 1 substituent selected from cyano. Preferably, R 7 R is selected from hydrogen, methyl, acetyl, C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=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(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=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.

[0066] In another embodiment, R 7 is selected from hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl. 7 is hydrogen, methyl, cyclopropyl, or 1-cyanocyclopropyl. Even more preferably, R 7is hydrogen, methyl, or cyclopropyl. In one embodiment, R 7 is hydrogen or methyl. In another embodiment, R 7 In yet another embodiment, R 7 It's methyl.

[0067] In the embodiment of the present invention, R 8 and R 9 is independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy. 8 and R 9 are independently selected from hydrogen, halogen, methyl, methoxy, or cyano. More preferably, R 8 and R 9 is independently selected from hydrogen, methyl, chlorine, fluorine, bromine, or methoxy. Even more preferably, R 8 and R 9 is hydrogen or methoxy.

[0068] 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 It's hydrogen.

[0069] In another embodiment, R 9 is selected from hydrogen, halogen, C1-C3 alkyl, C1-C2 haloalkyl, C1-C3 haloalkoxy, C1-C4 alkoxy, C1-C3 alkenyloxy, C1-C3 alkynyloxy, C1-C2 alkylsulfanyl, C1-C2 alkylsulfinyl, C1-C2 alkylsulfonyl, C1-C2 alkoxy-C1-C2 alkyl, C1-C3 alkoxycarbonyl, C1-C2 alkylcarbonyl, N-C1-C2 alkoxy-C-C1-C2 alkyl-carbonimino, N-hydroxy-C-C1-C2 alkyl-carboniminohydroxy, C1-C2 alkylaminocarbonyl, di(C1-C2 alkylamino)carbonyl, trifluoromethylsulfonyloxy, cyano, carboxyl, phenyl, 2-cyanophenyl, 3-cyano Preferably, R is phenyl, 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. Preferably, R 9Selected from hydrogen, chlorine, fluorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, difluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, methoxy, ethoxy, propoxy 、 -allyloxy, prop-2-ynyloxy, methylsulfanyl, methylsulfinyl, methylsulfonyl, methoxymethyl, ethoxymethyl, 2-methoxyethoxymethyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, acetyl, propionyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=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), (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. Even more preferably, R 9 is hydrogen, chlorine, fluorine, methyl, or methoxy. Most preferably, R 9 is hydrogen or methoxy.

[0070] In the embodiment of the present invention, B 1 Yes CR 10 And B 2 Yes CR 11 , or B 1 is N and B 2 Yes CR 11 , or B1 Yes CR 10 And B 2 is N. Preferably, B 1 Yes CR 10 And B 2 Yes CR 11 .

[0071] In one embodiment of the present invention, R 10 and R 11 independently selected from hydrogen, halogen, hydroxy, cyano, amino, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, NC 1-4 Alkylamino, N,N-diC 1-4 Alkylamino, C1-C6 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimino, N-hydroxy-C1-C4 alkyl-carbonimino, hydroxy, trifluoromethylsulfonyloxy, carboxyl, phenyl, 5- or 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, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy. Preferably, R 10 and R 11independently 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, methylsulfanyl, methylsulfinyl, methylsulfonyl, methoxymethyl, ethoxymethyl, 2-methoxyethoxymethyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, acetyl, propionyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=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 and 1-hydroxy-2-[4-(trifluoromethyl)pyrazol-1-yl], 1-hydroxy-2-[4-(trifluoromethyl)pyrazol-1-yl], 1-hydroxy-2-[4-(trifluoromethyl)pyrazol-1-yl], 1-hydroxy-3-[4-(trifluoromethyl)pyrazol-1-yl], 1-hydroxy-4-[4-(trifluoromethyl)pyrazol-1-yl], 1-hydroxy-5-[4-(trifluoromethyl)pyrazol-1-yl], 1-hydroxy-6-[4-(trifluoromethyl)pyrazol-1-yl], 1-hydroxy-7-[4-(trifluoromethyl)pyrazol-1-yl], 1-hydroxy-8-[4-(trifluoromethyl)pyrazol-1-yl], 1-hydroxy-9-[4-(trifluoromethyl)pyrazol-1-yl], 1-hydroxy-10-[4-(trifluoromethyl)pyrazol-1-yl], 1-hydroxy-11-[4-(trifluoromethyl)pyrazol-1-yl], 1-hydroxy-2-[4-(trifluoromethyl)pyrazol-1-yl], 1-hydroxy-3-[4-(trifluoromethyl)pyrazol-1-yl], 1-hydroxy-4-[4-(trifluoromethyl)pyrazol-1-yl], 1-hydroxy-5-[4-(trifluoromethyl)pyrazol-1-yl], 1-hydroxy-6-[4-(trifluoromethyl)pyrazol-1-yl], 1-hydroxy-7-[4-(trifluoromethyl)pyrazol-1-yl], 1-hydroxy-1 ... azole-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(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, cyclopropyl, or 1-cyanocyclopropyl.

[0072] In another embodiment, R 10 and R 11 are independently selected from hydrogen, halogen, C1-C3 alkyl, or C1-C4 alkoxy. 10 and R 11 are independently selected from hydrogen, or halogen. More preferably, R 10 and R11 It's hydrogen.

[0073] In an embodiment of the present invention, A 1 Yes CR 12a , or N; A 2 Yes CR 13a , or N; A 3 Yes CR 14a , or N. Preferably, A 1 , A 2 and A 3 At least two of them are selected from N. More preferably, A 1 , A 2 and A 3 It is N.

[0074] In the embodiment of the present invention, R 12a , R 13a and R 14a is independently selected from hydrogen, halogen, C1-C4 alkyl, C3-C6-cycloalkyl, or C1-C4 haloalkyl. 12a , R 13a and R 14a is independently selected from hydrogen, halogen, methyl, cyclopropyl, or trifluoromethyl. More preferably, R 12a , R 13a and R 14a It's hydrogen.

[0075] In another embodiment, A 1 Selected from CR 12a , or N; A 2 Selected from CR 13a , or N; A 3 Selected from CR 14a , or N; where A 1 , A 2 and A 3 At least two of them are selected from N; and wherein R 12a , R 13a , R 14a It's hydrogen.

[0076] In the embodiment of the present invention, Z 1wherein 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 alkylsulfanyl, 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, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy.

[0077] In another embodiment, Z 1 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 by 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 by 1 or 2 substituents selected from methyl.

[0078] In another embodiment, Z 1 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 one of the phenyl and 5 to 6 membered heteroaryl is unsubstituted or substituted by 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 by 1 or 2 substituents selected from methyl. Preferably, Z 1Selected 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-furanyl , 3-fluoro-2-furanyl, 5-fluoro-2-furanyl, 3,5-difluoro-2-thienyl, 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 1 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 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. Still even more preferably, Z 1 Selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, 4-fluorophenyl, or phenyl.

[0079] In another embodiment of the present invention, Z 1 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 by 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 by 1 substituent selected from halogen or C1-C4 alkyl. Preferably, Z 1is 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 by 1 or 2 substituents independently selected from fluorine, chlorine, C1-C4 alkyl, or C1-C4 alkoxy. More preferably, Z 1 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 1 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.

[0080] In another embodiment of the present invention, Z 1 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 by 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 by 1 substituent selected from halogen or C1-C4 alkyl. Preferably, Z 1 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 by 1 or 2 substituents independently selected from fluorine, chlorine, C1-C4 alkyl, or C1-C4 alkoxy.

[0081] Accordingly, the present invention provides compounds of formula (I) having 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 1 As defined above in all combinations / each permutation.

[0082] Embodiments according to the present invention are provided as listed below.

[0083] In one embodiment of the present invention, there is provided a compound having formula (I), wherein

[0084] R 1 Selected from hydrogen, C1-C 6- Alkyl, C2-C 6- alkenyl, C2-C6-alkynyl, or C3-C6-cycloalkyl;

[0085] R 2 Selected from hydrogen, halogen, C1-C 6- Alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C3-C6-cycloalkyl, C1-C 4- Alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimino, N-hydroxy-C-C1-C4 alkyl-carbonimino, or C1-C 6- Alkoxycarbonyl;

[0086] R 3 and R 4 independently selected from hydrogen, halogen, or C1-C6-alkyl;

[0087] R 5 and R 6 Independently selected from hydrogen, or C1-C6 alkyl;

[0088] R 7is selected from hydrogen, C1-C6 alkyl, C1-C6 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimino, N-hydroxy-C-C1-C4 alkyl-carbonimino, 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 independently wherein the phenyl and 5- to 6-membered heteroaryl groups are unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, cyano, carboxyl, C1-C4 alkyl, and C1-C4 alkoxy; and wherein the C3-C6-cycloalkyl group is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, cyano, C1-C4 alkyl, and C1-C4 alkoxy;

[0089] B 1 Selected from CR 10 , and N;

[0090] B 2 Selected from CR 11 , and N;

[0091] R 8 , R 9 , R 10 and R 11 independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, NC 1-4 Alkylamino, N,N-diC 1-4 Alkylamino, C1-C6 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimino, N-hydroxy-C1-C4 alkyl-carbonimino, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxyl, amino, phenyl, 5- or 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, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy;

[0092] A 1 Selected from CR 12a , or N;

[0093] A 2 Selected from CR 13a , or N;

[0094] A 3 Selected from CR 14a , or N;

[0095] R 12a , R 13a and R 14a are independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, or C2-C4 alkynyl; and

[0096] Z 1 is selected from C1-C4 alkyl, phenyl, 5- or 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, 5- or 6-membered heteroaryl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, and C2-C4 alkynyl substituents and wherein the C3-C6 cycloalkyl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy;

[0097] or an agrochemically acceptable salt, stereoisomer or N-oxide thereof.

[0098] In one embodiment, in the compound of formula (I) according to the present invention, wherein

[0099] R 1 is hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or C3-C6 cycloalkyl;

[0100] R 2 is hydrogen, halogen, or C1-C4 alkyl;

[0101] R 3 and R 4 Independently selected from hydrogen, halogen, or C1-C4 alkyl;

[0102] R 5 and R 6 independently selected from hydrogen and C1-C4 alkyl;

[0103] R 7is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl, wherein the C3-C6-cycloalkyl is unsubstituted or substituted by 1 substituent selected from halogen, C1-C4 haloalkyl, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0104] B 1 Selected from CR 10 , and N;

[0105] B 2 Selected from CR 11 , and N;

[0106] R 8 and R 9 independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0107] R 10 and R 11 independently selected from hydrogen, halogen, C1-C3 alkyl, or C1-C4 alkoxy;

[0108] A 1 Selected from CR 12a , or N;

[0109] A 2 Selected from CR 13a , or N;

[0110] A 3 Selected from CR 14a , or N;

[0111] R 12a , R 13a and R 14a is independently selected from hydrogen, halogen, C1-C4 alkyl, C3-C6-cycloalkyl, or C1-C4 haloalkyl; and

[0112] Z 1 is phenyl, 5 to 6 membered heteroaryl, or C3-C6-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, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy and wherein the C3-C6-cycloalkyl is unsubstituted or substituted by 1 substituent selected from halogen or C1-C4 alkyl.

[0113] In an embodiment of the present invention, the compound having formula (I) may be a compound having formula (II):

[0114]

[0115] in

[0116] 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 is as defined for the compounds of formula (I) according to the invention, and

[0117] A is selected from:

[0118]

[0119] in indicates a bond to a C(=O) group, and an asterisk (*) indicates a bond to a Z 1 The nitrogen of the bond of the group, and wherein R 12a , R 13a and R 14a Independently selected from hydrogen, halogen, C1-C4 alkyl, C3-C6 cycloalkyl, or C1-C4 haloalkyl.

[0120] In one embodiment of the present invention, R 12a , R 13a and R 14a are independently selected from hydrogen, halogen, methyl, cyclopropyl, or trifluoromethyl.

[0121] In another embodiment of the present invention, R 12a , R 13a and R 14a It's hydrogen.

[0122] Preferably, in the compound having formula (II), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and Z 1 is as defined for the compounds 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 is hydrogen; B 1 Yes CR 10; and B 2 Yes CR 11 ; where R 10 and R 11 is as defined for the compounds of formula (I) according to the invention.

[0123] More preferably, in the compound having formula (II), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and Z 1 is as defined for the compounds 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 is hydrogen; B 1 is CH and B 2 It is CH.

[0124] In an embodiment of the present invention, in the compound having formula (II), A is selected from:

[0125]

[0126] in indicates a bond to a C(=O) group, and an asterisk (*) indicates a bond to a Z 1 The nitrogen of the bond of the group.

[0127] In a preferred embodiment of the present invention, in the compound having formula (II), A is selected from:

[0128]

[0129] in indicates a bond to a C(=O) group, and an asterisk (*) indicates a bond to a Z 1 The nitrogen of the bond of the group.

[0130] Preferably, in the compound having formula (II), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and Z 1is as defined for the compounds of formula (I) according to the present invention, A is selected from A1, A2, or A3; B 1 Yes CR 10 ; and B 2 Yes CR 11 ; where R 10 and R 11 is as defined for the compounds of formula (I) according to the invention.

[0131] More preferably, in the compound having formula (II), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the present invention, A is selected from A1, A2, or A3; B 1 is CH; and B 2 It is CH.

[0132] Even more preferably, in the compound having formula (II), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the present invention, A is selected from A1, or A2; B 1 is CH; and B 2 It is CH.

[0133] In an embodiment of the present invention, in the compound having formula (II), A is selected from:

[0134]

[0135] in indicates a bond to a C(=O) group, and an asterisk (*) indicates a bond to a Z 1 The nitrogen of the bond of the group.

[0136] In an embodiment of the present invention, the compound having formula (II) may be a compound having formula (II-A), wherein B 1 and B 2 is CH, and A is as defined for compounds of formula (II)

[0137]

[0138] Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0139] In a variation of this embodiment of the invention, the compound of formula (II-A) may be a compound of formula (II-A1), wherein B 1 and B 2 It is CH; R 3 , R 5 , R 6 is hydrogen and A is as defined for compound (II):

[0140]

[0141] Where R 1 , R 2 , R 4 , R 7 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0142] Preferably, in the compounds of the present invention having formula (II-A1),

[0143] R 1 is C1-C4 alkyl, preferably methyl, ethyl, or isopropyl;

[0144] R 2 is hydrogen, fluorine, chlorine, or methyl;

[0145] R 4 is hydrogen or methyl;

[0146] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0147] R 8 and R 9 Independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0148] A is as defined for compound (II), and Z 1 is as defined for the compounds having (I) according to the present invention.

[0149] Preferably, in the compounds of the present invention having formula (II-A1),

[0150] R 1 is C1-C4 alkyl, preferably methyl, ethyl, or isopropyl;

[0151] R 2 is hydrogen, fluorine, chlorine, or methyl;

[0152] R 4 is hydrogen or methyl;

[0153] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0154] R 8 and R 9 Independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0155] A is selected from A1, or A2; and

[0156] Z 1 is as defined for the compounds of formula (I) according to the invention.

[0157] Preferably, in the compounds of the present invention having formula (II-A1),

[0158] R 1 is C1-C4 alkyl, preferably methyl, ethyl, or isopropyl;

[0159] R 2 is hydrogen, fluorine, chlorine, or methyl;

[0160] R 4 is hydrogen or methyl;

[0161] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0162] R 8 and R 9 Independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0163] A is selected from A1, or A2; and

[0164] Z 1is 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 by 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 by 1 substituent selected from halogen or C1-C4 alkyl.

[0165] In an embodiment of the present invention, the compound having formula (II) may be a compound having formula (II-B), wherein B 1 and B 2 is CH, and wherein A is A1,

[0166]

[0167] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0168] In a variation of this embodiment of the invention, the compound of formula (II-B) may be a compound of formula (II-B1), wherein B 1 and B 2 It is CH; R 3 , R 5 , R 6 is hydrogen, and A is A1

[0169]

[0170] Where R 1 , R 2 , R 4 , R 7 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0171] Preferably, in the compound of the present invention having formula (II-B1),

[0172] R 1 is C1-C4 alkyl, preferably methyl, ethyl, or isopropyl;

[0173] R 2 is hydrogen, fluorine, chlorine, or methyl;

[0174] R 4 is hydrogen or methyl;

[0175] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0176] R 8 and R 9 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; and

[0177] Z 1 is as defined for the compounds of formula (I) according to the invention.

[0178] Preferably, in the compound of the present invention having formula (II-B1),

[0179] R 1 is C1-C4 alkyl, preferably methyl, ethyl, or isopropyl;

[0180] R 2 is hydrogen, fluorine, chlorine, or methyl;

[0181] R 4 is hydrogen or methyl;

[0182] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0183] R 8 and R 9 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; and

[0184] Z 1 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 5 to 6 membered heteroaryl are unsubstituted or substituted by 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 by 1 substituent selected from halogen or C1-C4 alkyl.

[0185] In an embodiment of the present invention, the compound having formula (II) may be a compound having formula (II-C), wherein B 1 and B 2 is CH; and wherein A is A2:

[0186]

[0187] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0188] In a variation of this embodiment of the invention, the compound of formula (II-C) may be a compound of formula (II-C1), wherein B 1 and B 2 It is CH; R 3 , R 5 , R 6 is hydrogen; and A is A2

[0189]

[0190] Where R 1 , R 2 , R 4 , R 7 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0191] Preferably, in the compound of formula (II-C1) of the present invention,

[0192] R 1 is C1-C4 alkyl, preferably methyl, ethyl, or isopropyl;

[0193] R 2 is hydrogen, fluorine, chlorine, or methyl;

[0194] R 4 is hydrogen or methyl;

[0195] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0196] R 8 and R 9 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; and

[0197] Z 1is as defined for the compounds of formula (I) according to the invention.

[0198] Preferably, in the compound of formula (II-C1) of the present invention,

[0199] R 1 is C1-C4 alkyl, preferably methyl, ethyl, or isopropyl;

[0200] R 2 is hydrogen, fluorine, chlorine, or methyl;

[0201] R 4 is hydrogen or methyl;

[0202] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0203] R 8 and R 9 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; and

[0204] Z 1 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 5 to 6 membered heteroaryl are unsubstituted or substituted by 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 by 1 substituent selected from halogen or C1-C4 alkyl.

[0205] In an embodiment of the present invention, the compound having formula (II) may be a compound having formula (II-D), wherein B 1 and B 2 is CH, and where A is A3:

[0206]

[0207] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0208] In a variation of this embodiment of the invention, the compound of formula (II-D) may be a compound of formula (II-D1), wherein B 1 and B 2 It is CH; R 3 , R 5 , R 6 is hydrogen; and A is A3

[0209]

[0210] Where R 1 , R 2 , R 4 , R 7 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0211] Preferably, in the compounds of the present invention having formula (II-D1),

[0212] R 1 is C1-C4 alkyl, preferably methyl, ethyl, or isopropyl;

[0213] R 2 is hydrogen, fluorine, chlorine, or methyl;

[0214] R 4 is hydrogen or methyl;

[0215] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0216] R 8 and R 9 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; and

[0217] Z 1 is as defined for the compounds of formula (I) according to the invention.

[0218] Preferably, in the compounds of the present invention having formula (II-D1),

[0219] R 1 is C1-C4 alkyl, preferably methyl, ethyl, or isopropyl;

[0220] R 2 is hydrogen, fluorine, chlorine, or methyl;

[0221] R 4 is hydrogen or methyl;

[0222] R7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0223] R 8 and R 9 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; and

[0224] Z 1 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 5- to 6-membered heteroaryl are unsubstituted or substituted by 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 by 1 substituent selected from halogen or C1-C4-alkyl.

[0225] The following intermediates are novel and themselves form a further aspect of the invention.

[0226] According to a sixth aspect of the present invention, there is provided an intermediate compound having formula (III) or a salt thereof:

[0227]

[0228] Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B 2 is as defined for the compounds of formula (I) according to the invention.

[0229] The intermediate compounds of formula (III) have R corresponding to the compounds of formula (I) according to the present invention and their corresponding preferred embodiments. 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B 2 The same definition.

[0230] The presence of one or more possible asymmetric carbon atoms in the compounds of formula (III) according to the invention means that these compounds may exist in the form of chiral isomers, ie in the form of enantiomers or diastereomers.

[0231] According to a seventh aspect of the present invention, there is provided an intermediate compound having formula (IV):

[0232]

[0233] Where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B 2 is as defined for the compounds of formula (I) according to the invention.

[0234] The intermediate compounds of formula (IV) have R corresponding to the compounds of formula (I) according to the present invention and their corresponding preferred embodiments. 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B 2 The same definition.

[0235] The presence of one or more possible asymmetric carbon atoms in the compounds of formula (IV) according to the invention means that these compounds may exist in the form of chiral isomers, ie in the form of enantiomers or diastereomers.

[0236] According to an eighth aspect of the present invention, there is provided an intermediate compound having formula (IIb) or a salt thereof:

[0237]

[0238] Where R 0 is a C1-C6 alkyl group and wherein A 1 , A 2 , A 3 and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0239] The intermediate compounds of formula (IIb) have the same A as for the compounds of formula (I) according to the present invention and their corresponding preferred embodiments. 1 , A 2 , A 3 and Z 1 The same definition.

[0240] In one embodiment, R 0 is a C1-C4 alkyl group, A 1 , A 2 , A 3 is N and Z 1 is as defined for the compounds of formula (I) according to the invention.

[0241] In one embodiment, the compound having formula (IIb) may be a compound having formula (IIb-1):

[0242]

[0243] in

[0244] Z 1 is as defined for the compounds of formula (I) according to the invention, R 0 is as defined for the compound having formula (IIb) and A is selected from A1, A2, A3, A4, A5, A6, A7, or A8 as defined for the compound having formula (II).

[0245] Preferably, in the compound having formula (IIb-1), A is selected from:

[0246]

[0247] in indicates a bond to a C(=O) group, and an asterisk (*) indicates a bond to a Z 1 The nitrogen of the bond of the group, where Z 1 is as defined for the compounds of formula (I) according to the invention and R 0 is as defined for the compound of formula (IIb).

[0248] More preferably, in the compound having formula (IIb-1), A is selected from A1 or A2, wherein Z 1 is as defined for the compounds of formula (I) according to the invention and R 0 is as defined for the compound of formula (IIb).

[0249] In another embodiment of the present invention, in the compound having formula (IIb-1), A is A1, wherein Z 1is as defined for the compounds of formula (I) according to the invention and R 0 is as defined for the compound of formula (IIb).

[0250] 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 Table P (below) means that these compounds may exist in the form of chiral isomers, i.e., enantiomers or diastereoisomers.

[0251] 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.

[0252] Even more preferably, the compounds of formula (I) according to the invention are chosen from the compounds listed in Table P (below).

[0253] In one embodiment of the present invention, the compound having formula (I) is selected from

[0254] [1-(2-fluorophenyl)pyrazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0255] [1-(2,4-difluorophenyl)pyrazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0256] [1-(2-Fluorophenyl)pyrazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0257] [2,5-dimethyl-1-(2,2,2-trifluoroethyl)pyrrol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0258] (1,5-dimethylpyrazol-3-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0259] (2-phenyltriazol-4-yl)-[4-(1,3,5-trimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0260] (1-phenyltriazol-4-yl)-[4-(1,3,5-trimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0261] [1-(2,4-difluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0262] [1-(4-fluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0263] [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(1-phenylimidazol-4-yl)methanone,

[0264] [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(1-phenyltriazol-4-yl)methanone,

[0265] [2,5-dimethyl-1-(5-methylisoxazol-3-yl)pyrrol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0266] (1-benzyltriazol-4-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0267] [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazolyl-5-yl)methanone,

[0268] (1-isopropyltriazol-4-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0269] [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(1-phenylpyrazol-3-yl)methanone,

[0270] [1-(4-Fluorophenyl)-5-methyl-triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0271] [2-(4-fluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0272] [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(1-phenyl-1,2,4-triazol-3-yl)methanone,

[0273] (1-tert-butylimidazol-4-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0274] [1-(4-fluorophenyl)pyrazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0275] (5-cyclopropyl-1-methyl-pyrazol-3-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0276] [1-(3-fluoro-2-pyridyl)-1,2,4-triazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0277] [1-(3-Fluorophenyl)-3-methyl-pyrazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0278] (5-Benzyl-1-methyl-pyrazol-3-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0279] [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-[1-[5-(trifluoromethyl)-2-pyridyl]triazol-4-yl]methanone,

[0280] [1-(2-methoxyphenyl)imidazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0281] (5-cyclopropyl-1-ethyl-pyrazol-3-yl)-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0282] [1-(2,6-difluorophenyl)pyrazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0283] [1-(3,4-difluorophenyl)pyrazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0284] [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0285] [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone,

[0286] [1-(2,4-difluorophenyl)-1,2,4-triazol-3-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0287] [2-(2,4-difluorophenyl)tetrazol-5-yl]-[6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0288] [6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone,

[0289] [(1R,4R)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone,

[0290] [(1S,4S)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone,

[0291] [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,

[0292] [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,

[0293] [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,

[0294] [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

[0295] [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.

[0296] In a preferred embodiment of the present invention, the compound having formula (I) is selected from:

[0297] [(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,

[0298] [(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,

[0299] [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,

[0300] [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,

[0301] [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,

[0302] [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,

[0303] [(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,

[0304] [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,

[0305] [6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone,

[0306] [2-(2,4-Difluorophenyl)tetrazol-5-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone

[0307] [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazolyl-5-yl)methanone,

[0308] [(1S,4S)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone,

[0309] [1-(2,4-difluorophenyl)triazol-4-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0310] [2-(2,4-difluorophenyl)tetrazol-5-yl]-[6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0311] [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,

[0312] [(1R,4R)-6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(2-phenyltetrazol-5-yl)methanone,

[0313] [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,

[0314] [(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,

[0315] (1-phenyltriazol-4-yl)-[4-(1,3,5-trimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0316] [4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(1-phenyltriazol-4-yl)methanone,

[0317] [2-(4-fluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone,

[0318] [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,

[0319] [(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

[0320] [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone.

[0321] The compounds of formula (I) according to the present invention can be prepared as shown in the following schemes, wherein, unless otherwise stated, the definition of each variable is as defined above for the compounds of formula (I).

[0322] The 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, the definition of each variable is as defined above for the compounds of formula (I).

[0323] In particular, where R 4 and R 6 is hydrogen and R 5 Compounds of formula (I) that are hydrogen or methyl can be prepared as shown in the following schemes, wherein, unless otherwise stated, the definition of each variable is as defined above for compounds of formula (I).

[0324] 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 invention means that these compounds can exist in the form of chiral isomers, ie in the form of enantiomers or diastereomers.

[0325] The compound of formula (I) can be prepared by a person skilled in the art according to known methods. More specifically, the compound of formula (I) can be prepared by 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 is as defined above for compounds of formula (I)) by reacting with a compound of formula (II) (wherein A 1 , A 2 , A 3 and Z 1 is prepared by reaction of (as defined above for compounds of formula (I)). This reaction is shown in Scheme 1.

[0326]

[0327] In Scheme 1, a compound of formula (II) (wherein A 1 , A 2 , A 3 and Z 1 is as defined above for compounds of formula (I)) activated to compounds of formula (IIa). For example, a compound of formula (IIa) wherein X 0 is halogen) is formed by treating a 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. Optionally, treating a compound of formula (III) (wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R7 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I) to produce compounds of formula (I). Alternatively, compounds of formula (II) may be treated 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 X 0 is as follows G 01 , G 02 or G 03 ) to prepare compounds of formula (I). 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 X 0 is as follows G 04 , 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).

[0328]

[0329] The compound of formula (II) can be prepared from a compound of formula (IIb) (wherein A 1 , A 2 , A 3 is N and Z 1 is as described in formula (I), and R 0C1-C4 alkyl) is prepared by ester hydrolysis. A variety of conditions can be used, such as aqueous sodium hydroxide solution, or lithium hydroxide and organic water-soluble solvents, such as THF, or dimethoxyethane, or methanol, or ethanol. Such ester hydrolysis is well known to those skilled in the art. Compounds with formula (IIb) can also be directly converted into compounds with formula (I) by reacting compounds with formula (IIb) with compounds with 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. [tetrahedron communication] 1977, 4171-4174, and Tetrahedron Lett. [tetrahedron communication] 2006, 5767-5769, and references cited therein). Compounds with formula (II) and (IIb) are commercially available or can be synthesized as described below.

[0330] A compound having formula (IIIa) (wherein R 4 and R 6 is 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 is as defined above for compounds of formula (I)) can be prepared by those skilled in the art according to known methods.

[0331] For example, a compound having formula (IIIa) wherein R 4 and R 6 is 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 is as defined above for compounds of formula (I)) can be obtained from compounds of formula (IVa) wherein R 4 and R 6 is hydrogen, R 5 is hydrogen or methyl and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B2 The compound of formula (IIIa) is as defined above for the compound with formula (I)) by treating with a reducing agent (such as NaBH in a protic solvent (such as methanol or ethanol, etc.) CN and an acid (such as hydrochloric acid or acetic acid). Such reactions are well known in the literature, and similar reactions have been described in, for example, Deng, Zeping et al., CN 103772278 and Synthesis [Synthesis] (1979), 4,281-3. Alternatively, the compound with formula (IIIa) can be prepared by reducing a compound with formula (IVa) by using hydrogen and a suitable ligand (such as 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 (such as Pd, Ir, Rh). Similar reactions have been reported, for example, in Reaction Kinetics and Catalysis Letters 2007, 92, 99-104. This reaction is shown in Scheme 2.

[0332]

[0333] Alternatively, compounds of formula (IIIa) can be prepared as shown in Scheme 3.

[0334] As shown in Scheme 3, by methods known to those skilled in the art and by those methods described in Scheme 1, by using a compound having formula (VI) (wherein X 0 is a leaving group, such as a halogen, and R 0 is a C1-C6 alkyl) to treat a compound having the formula (IIIb), the compound having the formula (IIIb) (wherein R 4 , R 6 and R 7 is hydrogen, R 5 is hydrogen or methyl and R 1 , R 2 , R 3 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I)) to compounds of formula (V) (wherein R 4 , R 6 and R 7 is hydrogen, R 5 is hydrogen or methyl and R 1 , R 2 , R 3 , R 8 , R9 , B 1 and B 2 is as defined above for compounds of formula (I). Alternatively, the compound may be prepared by reacting a compound of formula (R) with a 2-hydroxy-2-nitro-2-ol 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. 0 CO)2O anhydride (where R 0 The compound of formula (V) is prepared by treating with a C1-C6 alkyl) and then metallizing the compound of formula (V) with a base (e.g., an alkyl metal base, such as tert-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). X -X 0 Electrophiles (where X 0 is as defined previously, and R X 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 the 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) The anion of formula (V) formed under such conditions is treated to give a compound of formula (Va) (wherein R 4 and R 6 is hydrogen, R 5 is hydrogen or methyl, R 0 is a C1-C6 alkyl group and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I). This reaction is shown in Scheme 3.

[0335]

[0336] The compound of formula (Va) can be converted into a compound of formula (IIIa) (wherein R 4 and R 6 is 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 is as defined above for compounds of formula (I). For example, a compound of formula (Va) wherein R 0 is tert-butyl) to obtain a compound having formula (IIIa). This reaction is shown in Scheme 4.

[0337]

[0338] A compound having formula (IVa) (wherein R 4 and R 6 is 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 is as defined above for compounds of formula (I)) by allowing a compound of formula (VIII) (wherein R 1 , R 2 and R 3 is as defined above for compounds of formula (I), and X 0 is halogen, preferably chlorine, bromine or iodine) and a compound of formula (VII) (wherein R 5 is hydrogen or methyl and R 7 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I)) by means of a CC bond forming reaction typically reacting under palladium catalyzed (alternatively nickel catalyzed) cross coupling conditions. This reaction is shown in Scheme 5.

[0339]

[0340] The Suzuki-Miyaura cross-coupling reaction between compounds of formula (VIII) and compounds of formula (VII) is well known to those skilled in the art and is typically carried out in the presence of a palladium catalyst such as tetrakis(triphenylphosphine)-palladium(0) or [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex and a base such as sodium carbonate or potassium carbonate in a solvent such as 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. [Journal of Organic Metal Chemistry], 1999, 576, 147-168. Those skilled in the art will also recognize that the reaction can be reversed, i.e. by making the compound of formula (X) (where R 1 , R 2 and R 3 is as defined above for compounds of formula (I)) and compounds of formula (IX) (wherein R 5 is hydrogen or methyl, R 7 , R 8 , R 9 , B 1 and B 2 As defined above for compounds of formula (I), and X 0 is a halogen, preferably chlorine, bromine or iodine) to provide a compound of formula (IVa) (wherein R 4 and R 6 is 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 is as defined above for compounds of formula (I). This reaction is shown in Scheme 6.

[0341]

[0342] Alternative cross-coupling chemistry, namely CH activation, can also be used to prepare compounds of formula (IVa) where R 4 and R 6 is hydrogen, R 5 is hydrogen or methyl and R 1 , R 2 , R 3 , R 7 , R 8 , R9 , B 1 and B 2 is as defined above for compounds of formula (I)) (Scheme 7).

[0343]

[0344] As shown in Scheme 7, a compound having formula (IX) (wherein R 5 is hydrogen or methyl, R 7 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I), and X 0 is halogen, preferably chlorine, bromine or iodine) and a compound having formula (XI) (wherein R 1 , R 2 and R 3 is as defined above for compounds of formula (I)) in the presence of a palladium catalyst (typically palladium acetate Pd(OAc)2), 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, e.g. in Chemical Science [Chemical Science] 2013, 4, 2374-2379.

[0345] Additionally, compounds of formula (III) can be prepared from compounds of formula (XVI) (Scheme 8).

[0346]

[0347] As shown in Scheme 8, compounds of formula (III) can be prepared by one skilled in the art by preparing 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 is as defined above for compounds of formula (I), and R 01It can be prepared by deprotection of a carbamate (which may be a member of a common carbamate protecting group substituent, such as methyl, tert-butyl, allyl, 2,2,2-trichloroethyl or benzyl). 01 When it is methyl, the product can be obtained by heating at a temperature between room temperature and 200° C., preferably between 20° C. and the boiling point of the reaction mixture, using a suitable solvent such as dichloromethane and a suitable reagent such as iodotrimethylsilane, as described, for example, in J. Am. Chem. Soc. 1992, 114, 5959. The compound of formula (III) thus obtained is converted into a compound of formula (I) (Scheme 1).

[0348] A compound having the 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 is as defined above for compounds of formula (I), and wherein R 01 is as described above) can be obtained by an aldehyde (including formaldehyde in its various forms) having the formula (XV) (wherein R 7 is as defined above for compounds of formula (I)) and 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 is as defined above for compounds of formula (I), and wherein R 01 is as described above), formed by combination with an acid in a suitable solvent, for example as described in Tetrahedron 1987, 43, 439 (Scheme 9).

[0349]

[0350] When the compound of formula (XIV) (wherein R 1 , R 2 , R 3 , R 8, R 9 As described in formula (I), B 1 Yes CR 10 , B 2 Yes CR 11 , and where R 01 As described above), that is, a compound having formula (XIVa) and a compound having formula (XVa) (wherein R 7 is a C1-C4 alkyl) to obtain a pyrazole ring and R 7 When the substituents are in a cis-relationship and the racemic compound has the formula rac-cis-(XVIa), the Pickett-Spengler reaction is stereospecific (Scheme 10).

[0351]

[0352] A further consequence of the stereospecific formation of compounds of formula rac-cis-(XVIa) in the Pict-Spengler reaction is that chiral compounds of formula (XVIa) can be obtained if the synthesis starts with a chemically pure compound of formula (XIVa). This is illustrated in Scheme 11 for compounds of formula (XIV) wherein R 1 , R 2 is methyl, R 8 , R 9 , R 11 , and R11 is hydrogen, and R 0 is methyl, that is, (S)-(XIVb) and (R)-(XIVb) are described, which are in the case of (XV) (wherein R 7 After the (S,S)-cis-(XVIb) and (R,R)-cis-(XVIb) reaction, the (S,S)-cis-(XVIb) and (R,R)-cis-(XVIb) were obtained.

[0353]

[0354] A compound having the formula (XIV) (wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I), and wherein R 01 is as described above) can be optionally 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 by an amine of formula (XIII) (wherein R1 , R 2 , R3, R 4 , R 5 , R 6 , R 8 , R 9 , B 1 and B 2 is prepared by reaction between (as defined above for compounds of formula (I)) and a suitable protecting agent such as methyl chloroformate, as described, for example, in Org. Biomol. Chem. 2016 14, 6853 (Scheme 12).

[0355]

[0356] A compound having the formula (XIII) or a salt thereof (wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I)) can be prepared by one skilled in the art by preparing a nitrile of formula (XII) wherein R 1 , R 2 , R 3 , R 4 , R 8 , R 9 , B 1 and B 2 The nitrile of formula (XII) can also be prepared by reaction of a nitrile 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. The nitrile of formula (XII) can also be reduced to a primary amine with hydrogen in the presence of a catalyst such as a platinum salt or Raney nickel in the presence of a hydrogen donor such as ethanol or methanol. Many other conditions for reducing the nitrile to a primary amine are well known to those skilled in the art. Alternatively, the Grignard reagent R 5 MgBr or R 6 MgBr (where R 5 and R 6 (as defined above for compounds of formula (I)) can be added sequentially or simultaneously as nucleophiles to compounds of formula (XII) to allow the preparation of more highly substituted amines of formula (XIII).i Such Grignard addition to nitrile is carried out in the presence of Pr)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.

[0357]

[0358] A compound having the formula (XII) (wherein R 1 , R 2 , R 3 , R 4 , R 8 , R 9 , B 1 and B 2 (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.

[0359]

[0360] For example, a compound having formula (XII) (wherein R 1 , R 2 , R 3 , R 8 , R 9 , B 1 and B 2 is as defined above for compounds of formula (I), and R 4 Instead of hydrogen, the alkyl group can be prepared by one skilled in the art by using a strong base (such as n-butyl lithium or sodium hydride) in an inert solvent (such as tetrahydrofuran) at low temperature, followed by the addition of a suitable alkylating agent R 4 -X(where R 4 is C1-C4 alkyl and X is halogen) (eg iodomethane) to a compound of formula (XIIa) (wherein R 1 , R 2 , R 3 , R 8 , R 9 , B 1 and B 2 is prepared by deprotonation of (as defined above for compounds of formula (I)).

[0361] A compound having the formula (XIIa) (wherein R 4 is hydrogen, and R 1 , R 2 , R 3 , R8 , R 9 , B 1 and B 2 (as defined above for compounds of formula (I)) can be prepared from an alcohol of formula (XVII) by treating with cyanotrimethylsilane (TMSCN) in a nonpolar solvent (such as dichloromethane) at a temperature between 0°C and the boiling point of the reaction mixture in the presence of a base (such as lithium carbonate). Such transformations are well known in the literature under various conditions, for example as described in Org. Lett [Organic Express] 2008 10, 4570 and references therein. This reaction is shown in Scheme 14.

[0362] A compound having formula (III) (wherein B 1 Yes CR 10 , B 2 Yes CR 11 , R 1a is a C1-C4 alkyl group, R 2a is hydrogen, halogen or C1-C4 alkyl, R 3 is hydrogen, R 4a , R 5a , R 6a , R 7a is hydrogen or C1-C4 alkyl and R 8 , R 9 , R 10 and R 11 is as previously defined under formula (I)), i.e. further synthesis of a compound having formula (IIIc);

[0363]

[0364] It is also possible to treat a compound having formula (XVIII)

[0365]

[0366] (where R 1a is a C1-C4 alkyl group, R 2a is hydrogen, halogen, or C1-C4 alkyl, R 4a , R 5a , R 6a , R 7a is hydrogen or C1-C4 alkyl, and R 8 , R 9 , R 10 and R 11(as previously defined under formula (I)) 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). These compounds are converted to compounds of formula (I) as described above. Those skilled in the art will recognize that such cyclization can be carried out via intermediates (e.g., compounds of formula (XIX),

[0367]

[0368] And (when R 4a is methyl), a compound having the formula (XX)

[0369]

[0370] and wherein the substituent R in these compounds is 1a , R 2a , R 3a , R 4a , R 5a , R 6a , R 7a , R 8 , R 9 , R 10 , and R 11 Depending on the reaction conditions, these 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 When it is C1-C4 alkyl, a mixture of diastereoisomers 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 over the other (Scheme 15).

[0371]

[0372] Compounds (XVIII), (XIX), and (XX) can be prepared as shown in Scheme 16 below and as described in the experimental section.

[0373]

[0374] As shown in Scheme 16, in the presence of a base such as triethylamine (Et3N), in an inert solvent such as DMF or DMA, a benzylamine of formula (XXI) is used to alkylate a compound of formula (XXII). The compound (XXIII) thus obtained can be separated or directly treated in situ with BOC-anhydride to obtain a compound of formula (XXIV). The compound of formula XXIV can be reduced with a hydride source such as NaBH4 in MeOH / THF to obtain the target molecule (XVIIIb), which can then be cyclized with, for example, camphorsulfonic acid in EtOAc to obtain a compound of formula (XIXb). Alternatively, a compound of formula (XXIV) can be reacted with a Grignard reagent R 4 MgBr is reacted in an inert ethereal solvent (e.g. 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 a C1-C4 alkyl group, R 2a is hydrogen, halogen, or C1-C4 alkyl, R 4a is hydrogen or C1-C4 alkyl, R 5a , R 6a and R 7a is hydrogen or C1-C4 alkyl, and R 8 , R 9 , R 10 and R 11 is as previously defined under formula (I).

[0375] Another aspect of the Friedel-Crafts chemistry should be noted. If the chemistry is with a chiral amine (XXI), i.e. R 7a If the starting compound is a C1-C4 alkyl group, the stereochemistry is retained in the final compound having formula (I). This is shown in Scheme 17 below. 7a When it is methyl:

[0376]

[0377] 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.

[0378] Compounds of formula II are commercially available or can be synthesized as described below.

[0379] A compound having formula (IIb) (wherein A 1 , A 2 , A3 is N and Z 1 is as defined for the compounds of formula (I) of the present invention, and wherein R 0 is a C1-C6 alkyl) that is, a compound having formula (IIba)

[0380]

[0381] This can be accomplished by making a diazonium salt having the formula (XXV)

[0382]

[0383] Where Z 1 is as defined for the compound of formula (I) of the present invention and Y - Depending on the conditions in which the diazotization step is carried out, the counter ion, such as Cl - or BF4 - , and a compound having formula (XXVI),

[0384]

[0385] Where R 0 It is obtained by reaction with a C1-C6 alkyl. The reaction can be catalyzed by various silver salts (preferably the silver salt is silver acetate), and in various solvents (such as 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 (such as sodium carbonate). These dipole [3+2] cycloadditions are highly regioselective and are described, for example, in Tetrahedron [tetrahedron] 2020, 76 (14), 131063. Compounds of formula (XXV) as defined just before can be prepared by reacting a primary amine of formula (XXVII) with a diazotizing agent (such as a nitrite, such as sodium nitrite). The solvent can be an aqueous solution of an acid, such as dilute hydrochloric acid or tetrafluoroboric acid. Counterion Y - Defined by the acid used. Diazotization reactions are commonly used in organic syntheses, even on an industrial scale, and are known to the person skilled in the art.

[0386] In order to reduce the risk of decomposition of the intermediate of formula (XXV), the diazotization step and the cycloaddition step can be carried out sequentially without isolating (XXV). This variant is also described in Tetrahedron 2020, 76 (14), 131063 (Scheme 18).

[0387]

[0388] Compounds of formula (XXVII) are commercially available, as are compounds of formula (XXVI) (e.g. R0 It is methyl, CAS [6832-16-2]).

[0389] Very similarly, compounds of formula (IIba) (wherein A 1 , A 2 , A 3 is N and Z 1 is as described in formula (I)) can be obtained by making a compound having formula (XXVIII):

[0390]

[0391] Where R 0 is a C1-C6 alkyl group and Ar 1 is phenyl or p-tolyl, reacting 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 good precedence in the literature, for example, Chem. Comm. [Chemical Communications] 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 Chemical Society] 2016, 138 (44), 14609-14615. The compound of formula (XXVIII) is prepared as described in the literature cited above and as illustrated in the preparation examples of the present application.

[0392] Alternatively, a compound of formula (IIba) wherein A 1 , A 2 and A 3 is N and Z 1 is as defined in formula (I)) can be obtained by coupling a compound having formula (XXIX),

[0393]

[0394] (A 1 , A 2 and A 3 is N, and R 0 is as described above), and a boronic acid derivative having formula (XXX)

[0395]

[0396] (where Z 1is as defined in formula I). ​​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), in the atmosphere or under oxygen. It should be noted that compounds of formula (XXIX) (wherein A 1 , A 2 and A 3 is N) exists in tautomeric forms, i.e.;

[0397]

[0398] Those skilled in the art will envision that the coupling product of this 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 regioselectivity for compounds of formula (IIba). Those skilled in 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)

[0399]

[0400] Where Z 1 , R 12a , and R 0 As previously defined (see J. Med. Chem. 2018, 61, 8, 3370-3388 and WO 14 / 041106, 2014), compounds of formula (IIbc) and (IIbd)

[0401]

[0402] Where Z 1 , R 12a , R 13a , R 14a , and R 0 is as defined under formula (I) (see WO 15 / 155626, 2015, EP2390252, 2011) and a compound having formula (IIbe)

[0403]

[0404] Where Z 1 , R 12a , R 13a , R 14a , and R 0is as defined under formula (I) (see J. Med. Chem. 2017, 60(14), 6166-6190, Org. Lett. 2008, 10(8), 1653-1655 and Bio. Med. Chem. Lett. 2009, 19(5), 1451-1456) as representative examples.

[0405] For preparing a compound having formula (IIba) (wherein A 1 , A 2 and A 3 is N and Z 1 Another method wherein (i) is as defined in formula (I) is shown in Scheme 19.

[0406]

[0407] As shown in Scheme 19, the sequence begins with the diazotization of a compound of formula (XXVII) as described above, and then with a compound of formula (XXXI) (where R 0 is C1-C6 alkyl), treating the diazonium salt in the presence of a weak base (e.g. sodium acetate) to obtain a compound of formula (XXXII). Then, treating the compound of formula (XXXII) (wherein Z is C1-C6 alkyl) with aqueous ammonia at a temperature between 0°C and 30°C in a miscible organic solvent (e.g. tetrahydrofuran or 2-methyltetrahydrofuran) 1 and R 0 As previously defined), a compound of formula (XXXIII) is obtained. Finally, the compound of formula (XXXIII) is diazotized with a nitrite (e.g. sodium nitrite) in a slightly acidic medium (e.g. acetic acid or hydrochloric acid) aqueous solution at a temperature between -20°C and 0°C resulting in the spontaneous cyclization of the diazonium salt formed to a tetrazole compound of formula (IIba). The reaction sequence has been previously described in WO 13 / 087805, 2013.

[0408] The compound of formula (IIb) can also be prepared by mixing a compound of formula (XXIX) with

[0409]

[0410] Using a compound having formula (XXXIV)

[0411] z 1 -x 0 (XXIV)

[0412] Where Z 1 is as previously described under Formula I and X 0is prepared by alkylation of a halogen (preferably chlorine, bromine or iodine) in the presence of a base (e.g. and an alkaline earth metal base such as NaOH, KOH, LiOH, Cs2CO3, K2CO3, 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 regioisomeric compounds that can be separated by chromatographic techniques, or pure isomers can be obtained by judicious choice of conditions and additives (e.g. palladium catalysts for the so-called Buchwald amination). For Z 1 In the case of heteroaryl or aryl, 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; US18 / 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 [ACS Catalysis] 2019, 9 (12), 10674-10679, Synthesis [Synthesis] 2017, 49 (23), 5120-5130, J. Org. Chem. [Journal of Organic Chemistry] 2019, 84 (12), 8160-8167 and references cited therein).

[0413] 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.

[0414] Salts of compounds of the formula (I) can be converted in a customary manner into the free compounds (I), acid addition salts (for example by treatment with suitable basic compounds or with suitable ion exchanger reagents) and salts with bases (for example by treatment with suitable acids or with suitable ion exchanger reagents).

[0415] Salts of compounds of formula (I) can be converted in a manner known per se into other salts, acid addition salts of compounds of formula (I), for example into other acid addition salts, for example by treating salts of inorganic acids (such as hydrochlorides) with suitable metal salts of the acid (such as sodium, barium or silver salts, for example with silver acetate) in a suitable solvent in which the inorganic salt formed (such as silver chloride) is insoluble and therefore precipitates out of the reaction mixture.

[0416] 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.

[0417] The compounds of formula (I) and, where appropriate, their tautomers, in each case in free form or in salt form, can be present in the form of one of the possible isomers or in the form of mixtures of these isomers, for example in the form of pure isomers (such as enantiomers and / or diastereomers) or in the form of isomer mixtures (such as enantiomeric mixtures, for example racemates or diastereomeric mixtures), depending on the number of asymmetric carbon atoms present in the molecule, the absolute and relative configuration and / or on the configuration of non-aromatic double bonds present in the molecule; the invention relates to the pure isomers and also to all possible isomer mixtures and is to be understood in this sense in each case above and below, even in each case without specific mention of stereochemical details.

[0418] Diastereomeric mixtures or racemic mixtures of compounds of formula (I) in free form or in salt form, which may be obtained depending on the starting materials and procedures chosen, can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and / or chromatography.

[0419] Enantiomeric mixtures that can be obtained in an analogous manner (such as racemates) can be resolved into the optical enantiomers by known methods, for example by recrystallization from optically active solvents; by chromatography on chiral adsorbents, such as high performance liquid chromatography (HPLC) on acetylcellulose; by cleavage with specific immobilized enzymes with the aid of suitable microorganisms; via the formation of containing compounds, for example using chiral crown ethers, in which only one enantiomer is complexed; or by conversion into diastereomeric salts, for example by reacting the basic end product racemate with an optically active acid (such as a carboxylic acid, such as camphoric acid, tartaric acid or malic acid, or a sulfonic acid, such as camphorsulfonic acid), and separating the diastereomeric mixtures that can be obtained in this way, for example by fractional crystallization based on their different solubility, thereby obtaining diastereomers, from which the desired enantiomer can be freed by the action of suitable reagents (such as basic reagents).

[0420] Pure diastereomers or enantiomers can be obtained according to the invention not only by separation of the appropriate isomer mixtures but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the method according to the invention with starting materials having the appropriate stereochemistry.

[0421] If the individual components have different biological activities, it is advantageous to separate or synthesize the biologically more effective isomers, such as enantiomers or diastereomers or isomer mixtures, such as enantiomeric mixtures or diastereomeric mixtures, in each case.

[0422] As an example, compounds with more than one asymmetric carbon atom may exist as diastereoisomers, which may optionally be separated using, for example, supercritical fluid chromatography (SFC) chromatography with a chiral column. Such diastereomers may show different fungicidal activity profiles, but all isomers and diastereomers form part of the present invention.

[0423] The compound of formula (I) has three chiral carbon atoms (three stereocenters, wherein an asterisk (*) indicates a chiral carbon atom), so that there are eight available stereoisomers. These eight stereoisomers consist of four groups of enantiomers.

[0424]

[0425] For compounds having formula (I), the relationship between enantiomers and diastereomers is shown in Scheme 20.

[0426] Those skilled in the art are well aware of these diastereomers and enantiomers 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.

[0427]

[0428] The compounds of the 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 further solvents, such as those which can be used for crystallization of compounds present in solid form.

[0429] As already indicated, surprisingly, it has now been found that the compounds of 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.

[0430] Compounds with formula (I) according to the present invention can be used as active ingredients such as for controlling plant pests in the agricultural sector and related fields of use, or on non-living materials, for controlling spoilage microorganisms or organisms potentially harmful to humans. The feature of these new compounds is that they have excellent activity at low application rates, and plants tolerate well and are safe for the environment. They have very useful therapeutic, preventive and systemic characteristics and can be used to protect a lot of cultivated plants. Compounds with formula (I) can be used to suppress or destroy the harmful organisms 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, the infringement of phytopathogenic microorganisms.

[0431] 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 plant, its part or its locus.

[0432] 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, alters, or prevents fungal growth. The term "fungicide effective amount" when used means the amount of such a compound or a combination of such compounds that can have an effect on fungal growth. The effects of control or alteration include all deviations from natural development, such as killing, retardation, etc., and prevention includes forming a barrier or other defense in or on a plant to prevent fungal infection.

[0433] It is also possible to use the compound with formula (I) according to the present invention as a seed dressing for treating plant propagation materials (for example, seeds, such as fruits, tubers or grains) or plant cuttings, for protecting against fungal infections and against plant pathogenic fungi present in the soil. Propagation materials can be treated with a composition comprising a compound with formula (I) before planting: for example, seed dressing can be used before sowing. The active compound with formula (I) can also be applied to grains (coating) by dipping seeds in a liquid formulation or by coating them with a solid formulation. It is also possible to apply the composition to the planting site when planting propagation materials, for example, to the furrow of the seed during sowing. The invention further relates to such methods for treating plant propagation materials, and to the plant propagation materials so treated.

[0434] 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.

[0435] Additionally, the present invention can be used to protect non-living materials such as wood, siding and paint from fungal attack.

[0436] 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. These fungi and fungal vectors of diseases and phytopathogenic bacteria and viruses are, for example: Psoralea corylifolia, Alternaria species, Aphanomyces species, Aspergillus species, Aspergillus species (including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terreus), A. pullulans species (including A. pullulans), Blastomyces dermatitidis, B. graminis, B. graminis, B. oleraceus ... lactucae), Botrytis species (including B. dothidea, B. obtusa), Botrytis species (including B. cinerea), Candida species (including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis), Cephaloascus fragrans, Cephaloascus species, Cercospora species (including C. arachidicola), Cercosporidium personatum), Cladosporium species, Claviceps, Coccidioides immitis, Coccidioidomyces species, Colletotrichum species (including C. musae), Cryptococcus neoformans, Diaporthe species, Subsporus species, Entomophthora species, Entomophthora species, Epidermophyton species, Erwinia amylovora, Powdery mildew species (including E. cichoracearum), Eutypa lata, Fusarium species (including Fusarium culmorum, Fusarium graminearum, Fusarium langsethiae, Fusarium moniliforme, Fusarium gloeosporium, Fusarium solani, Fusarium oxysporum, Fusarium laminarum), Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena), Gloeosporium musarum, Glomerella cingulate, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium species, H. capsulatum species, Histoplasma species (including H.capsulatum), red thread pathogen, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum species, Streptoceras species, Mucor species, Mycosphaeria species (including Mycosphaeria graminicola and M. pomi), tree blight pathogen, spruce pathogen, Paracoccidioides species, Penicillium species (including Penicillium digitatum and Penicillium italicum), True mold species, Peronospora species (including Peronospora maize, Peronospora philippinarum and Peronospora kaoliang), Peronospora species, Septoria glume, Phellaria pachyrhizi, Phellinus igniarus, Phyllostoma species, Phomopsis species, Phomopsis graminicola viticola), Phytophthora species (including Phytophthora infestans), Plasmopara species (including Plasmopara hallii, 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, Downy Mildew species (including barley rust (P.hordei), wheat leaf rust (P.recondita), stripe rust (P.Striiformis), wheat brown rust (P.triticina)), Sclerotinia species, Pyrocoel species, Pyrocoel species (including rice blast fungus (P.oryzae)), Pythium species (including ultimum Pythium), Columnar septum species, Rhizoctonia species, microscopic root Mucor (Rhizomucor pusillus), Rhizopus arrhizus, Rhizosporium species, Trichosporon species (including Scedosporium apical and Scedosporium prolificum), coal spot disease (Schizothyrium pomi), Sclerotinia species, Sclerotium species, Septoria species (including S.nodorum, S.tritici), Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix species, Stagonosporanodorum, Stemphylium species, Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia species, Trichoderma species (including T. harzianum, T. pseudokoningii, T. viride), Trichophyton species, Pseudomonas species, Grape Uncinaria, Urocystis species, Ustilago species, Venturia species (including V. inaequalis), Verticillium species, and Xanthomonas species. .

[0437] The compounds of formula (I) according to the present invention can be used, for example, for lawns, ornamental plants such as flowers, shrubs, broad-leaved trees or evergreen plants such as pines, as well as tree injection, pest management and the like.

[0438] 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 sisal; 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 zoysia grass; herbs such as basil, borage, chives, cilantro, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes such as beans, lentils, peas and soybeans; nuts such as almonds, cashews, groundnuts, hazelnuts, peanuts, pecans, pistachios and walnuts; palm plants such as oil palms; ornamental plants such as flowers, shrubs and trees; other trees such as cocoa, coconut, olive and rubber trees; vegetables such as asparagus, eggplant, broccoli, cabbage, carrots, cucumbers, garlic, lettuce, zucchini, melon, okra, onions, peppers, potatoes, squash, rhubarb, spinach and tomatoes; and vines such as grapes.

[0439] 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-pyruvate-shikimate-3-phosphate-synthetase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen oxidase) inhibitors as a result of conventional breeding methods or genetic engineering. Examples of crops which have been rendered tolerant to imidazolinones such as imazamox by conventional breeding methods (mutagenesis) are Summer rapeseed (canola). Examples of crops that have been rendered tolerant to herbicides or herbicides by genetic engineering methods include glyphosate-resistant and glufosinate-resistant maize varieties, which are based on and Commercially available under the trade name ANTIQUID®.

[0440] 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.

[0441] Examples of such plants are: (corn variety expressing CryIA(b) toxin); YieldGard (corn variety expressing CryIIIB(b1) toxin); YieldGard (maize varieties expressing CryIA(b) and CryIIIB(b1) toxins); (corn varieties expressing Cry9(c) toxin); (corn varieties expressing the CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) that confer tolerance to the herbicide glufosinate-ammonium); (cotton variety, expressing CryIA(c) toxin); (cotton variety, expressing CryIA(c) toxin); (cotton varieties expressing CryIA (c) and CryIIA (b) toxins); (cotton varieties expressing VIP toxin); (potato variety, expressing CryIIIA toxin); GT Advantage (GA21 glyphosate tolerance trait), CB Advantage (Bt11 corn borer (CB) trait), (corn rootworm traits) and

[0442] The term "crops" is to be understood as also including crop 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, such as are known, for example, from toxigenic bacteria, in particular those of the genus Bacillus.

[0443] 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 □-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or vegetative insecticidal proteins (Vips), for example Vip1, Vip2, Vip3, or Vip3A; or insecticidal proteins of bacterial colony-forming nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophila, or Xenorhabdus spp. nematophilus); toxins produced by animals, such as scorpion toxins, spider toxins, bee toxins and other insect-specific neurotoxins; toxins produced by fungi, such as streptomycin, plant lectins, such as pea lectin, barley lectin or snowdrop lectin; agglutinin; protease inhibitors, such as trypsin inhibitor, silk proteinase inhibitor, potato glycoprotein, cystatin, papain inhibitor; ribosome inactivating protein (RIP), such as ricin, maize-RIP, abrin, luffa seed toxin protein, saponin protein or bryophyllin; steroid metabolizing enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone 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.

[0444] Further, in the context of the present invention, delta-endotoxins (e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C) or vegetative insecticidal proteins (Vips) (e.g., Vip1, Vip2, Vip3 or Vip3A) are understood to include obviously also mixed toxins, truncated toxins and modified toxins. Mixed toxins are recombinantly produced by 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 replacements, it is preferred that a non-naturally occurring protease recognition sequence is inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into the Cry3A toxin (see WO 2003 / 018810).

[0445] 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.

[0446] 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 deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP 0 367 474, EP 0 401 979 and WO 90 / 13651.

[0447] The toxins contained in the transgenic plants render the plants tolerant to harmful insects. Such insects can be found in any insect taxonomic group but are particularly common among beetles (Coleoptera), two-winged insects (Diptera), and moths (Lepidoptera).

[0448] Transgenic plants comprising one or more genes encoding insecticide resistance and expressing one or more toxins are known and some of them are commercially available. Examples of such plants are: (corn variety expressing Cry1Ab toxin); YieldGard (corn varieties expressing Cry3Bb1 toxin); (corn varieties expressing Cry1Ab and Cry3Bb1 toxins); (corn varieties expressing Cry9C toxin); (corn varieties expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) that confer tolerance to the herbicide glufosinate-ammonium); (cotton variety, expressing Cry1Ac toxin); (cotton variety, expressing Cry1Ac toxin); (cotton varieties expressing Cry1Ac and Cry2Ab toxins); (cotton varieties expressing Vip3A and Cry1Ab toxins); (potato variety, expressing Cry3A toxin); GT Advantage (GA21 glyphosate tolerance trait), Advantage (Bt11 corn borer (CB) trait) and

[0449] Further examples of such transgenic crops are:

[0450] 1. Bt11 maize, from Syngenta Seeds SAS, Cheminde l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified maize, which is resistant to attack by European corn borer (Ostrinia nubilalis and Sesamia inermis) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenicly expresses the PAT enzyme to obtain tolerance to the herbicide glufosinate-ammonium.

[0451] 2. Bt176 maize, from Syngenta Seeds, 27 Hobbit Road, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified maize, which is resistant to attack by European corn borer (Ostrinia nubilalis and Sesamia inermis) by transgenic expression of the toxin Cry1Ab. Bt176 maize also transgenic expression of the enzyme PAT to obtain tolerance to the herbicide glufosinate-ammonium.

[0452] 3. MIR604 maize, from Syngenta Seeds, 27 Rue Hobbitt, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. Maize rendered insect resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 2003 / 018810.

[0453] 4. MON 863 maize, from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses the Cry3Bb1 toxin and is resistant to certain coleopteran insects.

[0454] 5. IPC 531 cotton, from Monsanto Europe AB, 270-272 Avenue Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0455] 6.1507 Maize, from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Genetically modified maize expressing the protein Cry1F for resistance to certain lepidopteran insects and the protein PAT for tolerance to the herbicide glufosinate.

[0456] 7. NK603×MON 810 maize, from Monsanto Europe 270-272 Boulevard Tervuren, B 1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. Made from a conventionally bred hybrid maize variety by crossing the genetically modified varieties NK603 and MON 810. NK603×MON 810 maize is transgenic for expressing the protein CP4 EPSPS obtained from the Agrobacterium strain CP4, rendering it tolerant to herbicides (contains glyphosate), and also Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstakia, which confers resistance to certain lepidopteran insects, including the European corn borer.

[0457] 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; Uncinaria vitis on grapes; Cladosporium, bryozoans, powdery mildew and chlorophyll on cucurbits; Cercospora spp. on cucurbits and solanaceous crops; Fusarium spp. on cereals; Leptosphaeria spp. on cereals; and Saccharomyces spp. on cereals.

[0458] As used herein, the term "locus" means a place where 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, together with established vegetation.

[0459] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves and fruits.

[0460] The term "plant propagation material" should be understood as meaning the reproductive parts of a plant, such as seeds, which can be used for the propagation of a plant, and vegetative materials, such as cuttings or tubers (e.g., potatoes). For example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants can be mentioned. Germinated plants and young plants that will be transplanted after germination or after emergence can also be mentioned. These young plants can be treated completely or partially by dipping and protected before transplanting. Preferably, "plant propagation material" should be understood as meaning seeds.

[0461] The compound with formula (I) according to the present invention can be used in unmodified form, or preferably, together with the adjuvant conventionally adopted in the preparation field.For this purpose, they can be conveniently formulated as emulsifiable concentrates, pastes that can be coated, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, particles and also capsules, for example in polymeric substances, in a known manner.For the type of composition, according to the intended purpose and the environment at that time, application methods are selected, such as spraying, atomizing, dusting, sowing, smearing or watering.Composition can also contain other adjuvants, such as stabilizers, defoamers, viscosity modifiers, adhesives or tackifiers, together with fertilizers, micronutrient donors or other preparations for obtaining special effects.

[0462] 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, dispersants, wetting agents, tackifiers, thickeners, adhesives, or fertilizers. Such carriers are for example described in WO 1997 / 33890.

[0463] Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations 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, these 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.

[0464] Wettable powders are in the form of finely divided particles that disperse easily in water or other liquid carriers. These particles contain the active ingredient retained in a solid matrix. Typical solid matrices include Fuller's earth, kaolin, silica and other easily wetted organic or inorganic solids. Wettable powders usually contain from 5% to 95% of the active ingredient plus a small amount of a wetting agent, dispersant or emulsifier.

[0465] Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquids and may consist entirely of the active compound and a liquid or solid emulsifier, or may also contain a liquid carrier such as xylene, heavy aromatic naphtha, isophorone and other non-volatile organic solvents. When used, these concentrates are dispersed in water or other liquids and are usually applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

[0466] Granular formulations include both extrudates and coarser granules and are usually applied to the area to be treated without dilution. Typical carriers for granular formulations include sand, fuller's earth, attapulgite 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 active compounds. Granular formulations usually contain 5% to 25% active ingredients, which may include surfactants such as heavy aromatic naphtha, kerosene and other petroleum fractions, or vegetable oils; and / or adhesives such as dextrins, glues or synthetic resins.

[0467] 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.

[0468] 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 also contain solvents in addition to the active compound. The encapsulated particles are usually porous particles, in which the porous membrane seals the particle pores 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, coagulation or spheroidization, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and carbon fine particles. Shell or membrane materials include natural and synthetic rubbers, fiber materials, styrene-butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

[0469] 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 soluble 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.

[0470] 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.

[0471] Liquid carriers that can be used include, for example, water, toluene, xylene, naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, 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-dimethyl Formamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol (diproxitol), alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, α-pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glycerol diacetate, glycerol monoethyl Acid esters, triacetin, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, cumene, 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, poly Ethylene 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 generally the carrier of choice for diluting concentrates.

[0472] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite, Fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.

[0473] 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. These 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 diethanolammonium lauryl sulfate; alkylaryl sulfonates such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products such as nonylphenol-C.sub.18 ethoxylate; alcohol-alkylene oxide 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.

[0474] Other adjuvants commonly used in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, defoamers, opacifiers, compatibilizing agents, antifoaming agents, masking agents, neutralizing and buffering agents, corrosion inhibitors, dyes, flavor enhancers, spreading agents, penetration aids, micronutrients, emollients, lubricants, and fixatives.

[0475] In addition, further, other biocidal active ingredients or compositions can be combined with the composition of the present invention, and used in the method of the present invention and applied simultaneously or sequentially with the composition of the present invention. When applied simultaneously, these other active ingredients can be prepared or mixed in, for example, a spray tank together with the composition of the present invention. These other biocidal active ingredients can be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and / or plant growth regulators.

[0476] Pesticides referred to herein using their common names are known, for example, from “The Pesticide Manual”, 15th edition, British Crop Protection Council 2009.

[0477] In addition, the compositions of the invention may also be administered with one or more inducers of systemic acquired resistance ("SAR" inducers). SAR inducers are known and described, for example, in U.S. Pat. No. 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.

[0478] The compound with formula (I) according to the present invention is usually used in the form of an agrochemical composition and can be applied to a crop area or a crop to be treated simultaneously or sequentially with other compounds. For example, these other compounds can be fertilizers or micronutrient donors or other preparations that affect plant growth. They can also be selective herbicides or non-selective herbicides, together with insecticides, fungicides, bactericides, nematicides, molluscicides or a mixture of several of these preparations, if desired together with other carriers, surfactants or adjuvants that are commonly used in the formulation field to promote application.

[0479] The compounds of formula (I) according to the invention can be used in the form of a (fungicide) 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 usable salt) and at least one of the above-mentioned adjuvants.

[0480] Therefore, the present invention provides a composition, preferably a fungicidal composition, comprising at least one compound according to the present invention having formula (I), 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 having formula (I), the composition may comprise at least one or more pesticidal active compounds, such as additional fungicidal active ingredients.

[0481] The compound with formula (I) according to the present invention can be the sole active ingredient of composition, or it can be mixed with one or more other active ingredients (such as pesticide, fungicide, synergist, herbicide or plant growth regulator) when appropriate.In some cases, other active ingredients can produce unexpected synergistic activity.

[0482] 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, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged biphenyl fungicides, carbamate fungicides, phenylcarbamate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine fungicides, organophosphorus fungicides, Organotin fungicides, oxathiin fungicides, oxazole fungicides, benzenesulfamide fungicides, polysulfide fungicides, pyrazole fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungicides, quinone fungicides, quinoxaline fungicides, strobilurin fungicides, sulfonanilide fungicides, thiadiazole fungicides, thiazole fungicides, thiazolidine fungicides, thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, valinamide fungicides, and zinc fungicides.

[0483] 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-chlorophenylphenyl sulfone, acetothionil, aldicarb, sirox, fomanphos, fenthion, fenthion hydrogen oxalate, amitraz, cypermethrin, arsenic trioxide, azobenzene, azophos, benomyl, benoxaphos, benzyl benzoate, bifenthion Amine, bromethrin, bromothion, bromophos, bromothion, buprofezin, butanone, butanone sulfone, butyl pyridaben, calcium polysulfide, octachlorocamphene, chlormethin, trithion, cypermethrin, cypermethrin, cypermethrin hydrochloride, cypermethrin, cypermethrin, cypermethrin hydrochloride, cypermethrin, cypermethrin, ethyl cypermethrin, cypermethrin, cypermethrin, propyl cypermethrin, cypermethrin, cypermethrin I, cypermethrin II, cypermethrin, closantel, coumaphos, crotamiton, baclofos, thiocarb Ling, fruit insect phosphorus, DCPM, DDT, dinoxon, dinoxon-O, dinoxon-S, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methyl, demeton-S-methyl, bacteriostatic, dichlorvos, dicliphos, chlorpyrifos, methylphos, dinex, dinex-dic lexine), diclofenac-4, diclofenac-6, ortho-diclofenac, nitropentyl, nitrooctyl ester acaricide, nitrobutyl ester, dimethoate, sulfodiphenyl, dithiocarb, DNOC, phenoxyacetin, doramectin, fenthiophos, eprinomectin, thiophos, ethidium, anti-mite azole, fenbutatin, fenthiocarb, fenpyrad, fenpyrad, fenpyrad, fenpyrad-8, fenpyrad-9, fenpyrad-10, fenpyrad-20, fenpyrad-11, fenpyrad-12, fenpyrad-13, fenpyrad-14, fenpyrad-15, fenpyrad-16, fenpyrad-17, fenpyrad-18, fenpyrad-19, fenpyrad-21, fenpyrad-19, fenpyrad-22, fenpyrad-19, fenpyrad-23, fenpyrad-19, fenpyrad-24 1137, fenthiocarb, fenthiocarb hydrochloride, carbamate, γ-HCH, chlorpyrifos, benzyl methoxyfen, hexadecyl cyclopropane carboxylate, isothiocarb, jasmonate I, jasmonate II, iodine, lindane, propanil, cypermethrin, dithiophos, methylthiophene, cypermethrin, methyl bromide, cypermethrin, chlorpyrifos, milbemid, propylamine, monocrotophos, maoguo, moxidectin, dibromophos, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one, fluazifop, nikkomycin, pencyprodinil, pencyprodinil 1:1 zinc chloride complex 、Oxydemeton, Isopropylamine, Sulfonyl Sulfate, PP'-DDT, Parathion, Permethrin, Fenthion, Phosalone, Sulfonyl Sulfate, Phosphamide, Chlorinated Turpentine, Acaricide, Proclonol, Fenthion, Propoxur, Ethiothioate, Pyrethrin I, Pyrethrin II, Pyrethrin, Pyridazine, Pyrimithioate, Quinalphos, Quinalphos, R-1492, Glyphosate, Rotenone, Octamethoxam, Clamine, Selamectin, Threonalphos, SSI-121, Sufilam, Sulfluram, Sultep, Sulfur, Flumethoxazine, τ-Fluvalinate, TEPP, Terbutaline, Tetrachlorobenzene Sulfone, Acaricide,thiafenox, thiamethoxam, long-acting thiamethoxam, methyl thiocarb, chloranil, thiophanate-methyl, chloranil, thiophanate-methyl, triazophos, chloranil, trichloropropoxyphos, triamcinol, aphidazole, methyl fipronil, chloranil, copper dioctanoate, copper sulfate, cybutryne, dichloronaphthoquinone, dichlorophen, endoxan, triphenyltin, slaked lime, sodium mancozeb, quinone, quinone, simazine, triphenyltin acetate, triphenyltin hydroxide, thiophos, piperazine, thiophanate-methyl, chloralose, fenthion, pyridine-4-amine, strychnine, 1-hydroxy-1 H-pyridine-2-thione, 4-(quinoxalin-2-ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, copper hydroxide, cresol, disipirthiophene, dodesine, sodium sulfone, formaldehyde, mercurygafen, kasugamycin, kasugamycin hydrochloride hydrate, nickel di(dimethyldithiocarbamate), trichloromethylpyridine, octhiothionone, oxolinic acid, oxytetracycline, potassium hydroxyquinoline sulfate, thiabendazole, streptomycin, streptomycin sesquisulfate, chloranthracene, thimerosal, cotton brown banded tormentor GV, Agrobacterium radiobacterium, Amblyseius species (Amblyseius spp.), celery armyworm NPV, Anagrus atomus, short-spur aphid wasp, cotton aphid parasitic wasp (Aphidius colemani), aphid midge (Aphidoletes aphidimyza), clover armyworm NPV, Bacillus sphaericus Neide, Beauveria brongniartii, Chrysoperlacarnea, Cryptolaemus montrouzieri, codling moth GV, Dacnusa sibirica, pea leafminer wasp (Diglyphus isaea), beautiful aphid wasp, paddle-horned aphid wasp (Eretmocerus eremicus), Heterorhabditis bacteriophora) and H.megidis, Hippodamia convergens, Leptomastix dactylopii, Macrolophus caliginosus, Spodoptera exigua NPV, Metaphycus helvolus, Metarhizium anisopliae var.acridum, Metarhizium anisopliae var.anisopliae,Neodiprionsertifer NPV and N.lecontei NPV, Pseudomonas species, Paecilomyces fumosorum, Phytoseiulus persimilis, Steinernema bibionis, Steinernema carpocapsae, Steinernema glaseri, Steinernema riobrave, Steinernema riobravis, Steinernema scapterisci, Steinernema spp., Trichogramma species, Typhlodromus occidentalis, Verticillium lecanii, Steinernema spp. lecanii), oxazolidinone, bis(aziridine)methylaminophosphine sulfide, busulfan, dimethivin, hexamethylmelamine, hexamethylphosphine, methyl tib, methylthiotib, methyloxazolidinone, infertile amine, flufenuron, tib, hexamethylphosphine thioate, thiotib, trothamide, urethaneimide, (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol, (E)-tridec-4-en-1-yl acetate, (E)-6-methylhept-2-en-4- alcohol, (E,Z)-tetradec-4,10-dien-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-dien-1-yl acetate, (9Z,11E)-tetradec-9,11-dien-1-yl acetate, (9Z,12E)-tetradec-9,12-dien-1-yl acetate, 14-methyloctadec-1-ene, 4-methylnonan-5-ol and 4-methylnonan-5-one, α-polymorphin, western pine beetle aggregation pheromone, dodecadienol, available Mon, fly attractant, epoxy nonadecane, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodec-8,10-dien-1-yl acetate, dominicalure, ethyl 4-methyloctanoate, eugenol, southern pine beetle gathering pheromone, trap-killing ene mixture, trap-killing ene mixture I, trap-killing ene mixture II, trap-killing ene mixture III, trap-killing ene mixture IV, hexane attractant, tooth beetle dienol, small stupid enol,Scarab beetle sex attractant, trimethyl dioxytricyclononane, noctuid sex attractant (litlure), cabbage looper sex attractant, trapping ester, (3E,5Z)-tetradecene-3,5-dienoic acid (megatomoic acid), entrapped ether, entrapped ene, octadecyl-2,13-diene-1-yl acetate, octadecyl-3,13-diene-1-yl acetate, Hecon, coconut rhinoceros beetle aggregation pheromone, filcon, entrapped ring, banana corm weevil attractant (sordidin), fungivorous acetic acid, tetradecyl-11-ene-1-yl acetate, Mediterranean fruit fly attractant, Mediterranean fruit fly attractant A, Mediterranean fruit fly attractant B1, Mediterranean fruit fly attractant B2, Mediterranean fruit fly attractant C, trunc-call, 2-(octylthio)ethanol, deetone, butoxy (polypropylene glycol), dibutyl adipate, dibutyl phthalate, dibutyl succinate, DEET, mosquito repellent (dimethyl carbate), dimethyl phthalate, ethyl hexanediol, hexyl urea, mequindine, methyl neodecylamide, oxamate, 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)ethyl thiocyanate, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate, 2-(4-chloro-3,5-xylyloxy)ethanol, 2-chlorovinyl diethyl phosphate, 2-imidazolidinone, 2-isovaleryl indan-1,3-dione, 2-methyl (prop-2-ynyl) aminophenyl methylcarbamate, 2-thiocyanate ethyl laurate, 3-bromo-1-chloroprop-1-ene, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate, 4-methyl (prop-2-ynyl) amino-3,5-dimethylphenylmethylcarbamate, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate, acethion, acrylonitrile, aldrin, alloamicin, cypermethrin, α-decandrin, aluminum phosphide, cypermethrin, neonicotinoid, ethyl methidathion, methyl pyrifos, Bacillus thuringiensis Bacterial δ-endotoxin, barium hexafluorosilicate, barium polysulfide, fumigantrin, Bayer 22 / 190, Bayer 22408, β-cyfluthrin, β-cypermethrin, pentothrin, biological permethrin, bis (2-chloroethyl) ether, borax, bromobenzene phosphine, bromo-DDT, hexamethasone, animal insect carbendazim, temetazoxan, butyl ester phosphine, calcium arsenate, calcium cyanide, carbon disulfide, carbon tetrachloride, Badan hydrochloride, servadine, borneol, chlordane, chlordecone, chloroform, chloropicrin, chloraniloxime phosphine, chlorpyrifos,Cis-resmethrin, cismethrin, cypermethrin, copper acetoarsenite, copper arsenate, copper oleate, cypermethrin, cryolite, CS 708, benzonitrile, cypermethrin, cypermethrin, d-cypermethrin, DAEP, dazomethane, demethylcarbofuran, chloranil, isochlorphos, chloranil, dicresyl, chloranil, dieldrin, diethyl 5-methylpyrazol-3-yl phosphate, chloranil, tetrafluoromethylthiocarb, dimethoate, pyrethrin, pyrethrin, methyl chlorpyrifos, dichlorvos, propanol, pentotropol, dinoflurane, fenthrin, vegetable phosphorus, thiopyraphos, DSP, ecdysterone, EI 1642, EMPC, EPBP, etaphos, ethiobencarb, ethyl formate, ethylene dibromide, ethylene dichloride, ethylene oxide, EXD, pyrifos, ethiobencarb, cypermethrin, fenthion, ethylfenthion, fluchlorbiphenylphos, butylfenthion, phosphoarsenic acid ester, butylfenthion, furathiocarb, pyrethroid, biguanide salt, biguanide acetate, sodium tetrathiocarbonate, benzyl chlorpyrifos, HCH, HEOD, heptachlor, cypermethrin, HHDN, hydrogen cyanide, quinolincarb, IPSP, chlorfenapyr, carbochlorin, isoaldrin, isofenphos, transplanting spirit, rice blast, oxathiophos, juvenile hormone I, juvenile hormone II, juvenile hormone III, chlorpentyl, methoprene, lead arsenate, bromophenylphos, acetamiprid, thiathiophos, m-isopropyl methyl carbamate, phosphorus Magnesium chloride, phosphorus azide, methyl aphid, chlorpyrifos, mercurous chloride, methyl sulfoxide, metamifop, metamifop potassium, metamifop sodium, methylsulfonyl fluoride, butylene phosphonate, methoprene, methyl ether thiocyanate, methoxychlor, methyl isothiocyanate, methyl chloroform, dichloromethane, chlorpyrifos, anthelmintic, naphthiophos, naphthalene, NC-170, nicotine, nicotine sulfate, nithiazine, pronicotine, O-5-dichloro-4 -Iodophenyl O-ethylethyl phosphonothioate, O,O-diethyl O-4-methyl-2-oxo-2H-benzopyran-7-yl phosphonothioate, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphonothioate, O,O,O',O'-tetrapropyl dithiodipyrophosphate, oleic acid, p-dichlorobenzene, methyl parathion, pentachlorophenol, pentachlorophenyl laurate, PH 60-38, fenthion, parachlorothion, phosphine, methyl phoxim, methamidophos, polychlorinated dicyclopentadiene isomers, potassium arsenite, potassium thiocyanate, precocious element I, precocious element II, precocious element III, amidophos, profluthrin, fenthion, pyraclostrobin, anti-pyrethroid, quassia extract, quinalphos-methyl, fenthion, iodosamide, resfurothrin, rotenone, thiamethoxam, ryanitin, lyanodine, sabah, octamethoxam, clethroid, SI-0009, thiamethoxam, sodium arsenite, sodium cyanide, sodium fluoride, sodium hexafluorosilicate, sodium pentachlorophenol, sodium selenate, sodium thiocyanate, sulfophenoxazine, sulfophenoxazine sodium salt, sulfuryl fluoride, sulfophenoxazine, tar, thiamethoxam, TDE,Butyl pyrimidinphos, dimethoate, cyclopentyl thiocarb, tetrachloroethane, thiochlorvos, cyclopentyl thiocarb, cyclopentyl oxalate, cypermethrin, cypermethrin monosodium, tetrabromothrin, trans-permethrin, triazomethin, isothiocyanate-3, chlorpyrifos, cyclopentyl thiocarb, trifluoromethoxycarb, chlorpyrifos-butyl, methoprene, veratridine, veratridine, XMC, ζ-cypermethrin, zinc phosphide, tolfenphos, chlorfluanid, tetrafluanid, bis(tributyl) Tin) oxide, bromoacetamide, iron phosphate, niclosamide-ethanolamine, tributyltin oxide, pyromorph, worm killer, 1,2-dibromo-3-chloropropane, 1,3-dichloropropylene, 3,4-dichlorotetrahydrothiophene 1,1-dioxide, 3-(4-chlorophenyl)-5-methylrhodanine, 5-methyl-6-thio-1,3,5-thiadiazin-3-yl acetic acid, 6-isopentenylaminopurine, fluorophenyladenine , benzothiol, cytokinin, DCIP, furfural, isoamidophos, kinetin, verrucospore mycorrhizal composition, tetrachlorothiophene, xylenol, zeatin, potassium ethyl xanthate, acibenzolar, acibenzolar-S-methyl, Polygonum cuspidatum extract, α-chlorohydrin, antu, barium carbonate, bimuramide, brodifacoum, bromodiolone, bromodiolone, chloranil, cholecalciferol, chloranil, rat-killing naphthalene, rat-killing pyrimidine, rat-killing Gram, thiabendazole, difacoum, calciferol, fludioxaline, fluoroacetamide, fludioxaline, fludioxaline hydrochloride, fumarolin, phosphine, phosphorus, warfarin, warfarin, scillarin, sciline glycoside, sodium fluoroacetate, thallium sulfate, warfarin, 2-(2-butoxyethoxy) ethyl piperate, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, farnesol with nerolidol, synergistic alkynyl ether, MGK 264, piperonyl butoxide, synergistic aldehyde, propyl isomer, S421, synergistic powder, sesame, sulfoxide, anthraquinone, copper cyclohexane, copper oxychloride, dicyclopentadiene, serene, zinc cyclohexane, zinc thiamide, imanin, ribavirin, chloroindole hydrazide, mercuric oxide, methyl thiophanate, azaconazole, bifenthrin, fumarole, cyproconazole, difenoconazole, diniconazole, fluoxiconazole, nitrobenzamide, fluquinconazole, flusilazole, flutriafol, furopyram, hexaconazole, imazalil, imipenem, cyproconazole, metconazole, myclobutrazol, paclobutrazol, rice blast ester, penconazole, prothioconazole, pyraclostrobin, prochloraz, propiconazole, pyraclostrobin, silyfenazole, tebuconazole, flufenoxazole, triadimefon, triadimenol, flubendazole, trichlorfonazole, pyrimidine alcohol, chlorfenapyridine alcohol, flufenapyridine alcohol, pyrimidine alcohol, thiabendazole sulfonate, acetyl pyrimidine, acetyl pyrimidine, dodecacyclic morpholine, fenpropidin, fenpropimorph, spiroxaplanol, tridecanol, cyprodinil, pyrimidine, pyrimidine, fenpicryl, fludioxonil, bensulfuron, furalaxyl, metalaxyl, R-metalaxyl, furamide, oxadixyl, carbendazim, imidacloprid, wheat spike, thiabendazole, acetyl pyrimidine, sclerotin, acetyl pyrimidine, procymidone, vinyl pyrimidine, boscalid, carboxin, furamide, fluamide, oxadiazine, oxycarboxin, penthiopyrad, thiofuran, dodinolide, biguanide, azoxystrobin, ethersoxamyl, enoxadyl, enoxadyl,Fluopyramide, fluoxastrobin, kresoxim-methyl, fenoxystrobin, trifloxystrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, pyraclostrobin, pyraclostrobin, ferram, mancozeb, maneb, mancozeb, methyl propineb, mancozeb, captazole, captan, azole furofurone, folpet, tolylfluanid, Bordeaux mixture, copper oxide, mancozeb, quinoline copper, phthalocyanine, kefansan, isopyruvate, chlorpyrifos, methyl tolclofos, diffluanid, benzathiapiprolin, blastifungin-S, dimethomorph, chlorothalonil, cyfluthrin, cymoxanil, triflupyramide, dichlorocyanamide, dapoxetine, chloranil, dichlorvos ... , fluosulphanone, fluopyram, fluopyram, sulfaquinoxaline, fluopyram, cyclamic acid aluminum, oxazolidinone, propineb, saizumi, sulfaquinoxaline, benfenoxam, pencuron, phthalide, polyoxin, cymoxanil, pyraclostrobin, iodoquinoxaline, pyraclostrobin, pyraclostrobin, quinoxyfen, pentachloronitrobenzene, thiazolin, imidazolin, tricyclazole, triazolin, validamycin, valerian, benzylpyraclostrobin, dimethomorph, fluorophenyletheramide, pyraclostrobin, fluoxazolidinone, benfenoxam, phenylpyraclostrobin, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide, isoprofluoropyraclostrobin, isothiopyraclostrobin, thiazolin, 6-ethyl-5 ,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-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, fluinoxazolidinone, jiaxiangjunzhi, lvbenmixianan, dichlorothiocarb, mandespin, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolinyl)oxy]phenyl]propan-2-ol, thiophene, N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamic acid tert-butyl ester, bifenthrin, indopamidol, trolprocarb, chlorfluanidazole, isotrifluanidazole,2-(Difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-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-bis(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]carbamic acid methyl ester, 3-chloro-6-methyl-5-phenyl-4-(2,4,6- trifluorophenyl) pyridazine, fluopyridazine, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-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, aminopyraclostrobin , pyraclostrobin, indazole sulfaquinamide, fluopicolide, (Z, 2E) -5- [1- (4-chlorophenyl) pyrazol-3-yl] oxy-2-methoxyimino-N, 3-dimethyl-pent-3-enamine, difluoropyrazolamide, benzylpyrimide, pyridine oxamide, isobutyl ethoxyquinoline, isopropyl quinoline, fluopicolide, isopropyl thiocyanate, 1- [[4- [[2- (trifluoromethyl) -1,3-dioxolan-2-yl] methoxy] phenyl] methyl] pyrazole-3-carboxylic acid ethyl ester (can be made from 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-pyridazine-4-carboxamide (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-pyridazine-4-carboxamide (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-pyridazine-4-carboxamide (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, cyanobacterium methyl, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1), fluopyram, flutolanil azole, fluthiazolin, flutoxacillin, pyridinamide, piperacillin, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-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, fluoxathiocarb, enoxastrobin, (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 ] methyl prop-2-enoate, (Z)-2-[5-(3-isopropylpyrazol-1-yl)-2-methyl-phenoxy]-3-methoxy-prop-2-enoate, (Z)-3-methoxy-2-[2-methyl-5-(3-propylpyrazol-1-yl)phenoxy]prop-2-enoate, (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]prop-2-enoate (these compounds can be prepared by the method described in WO 2020 / 079111), (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate,(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-sulfanyl-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-thio-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, trinexapac-ethyl, syringostyrin, zhongshengmycin, thiophanate-methyl, thiophanate-zinc, amitolin, iprodione, cinclorac , 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 obtained by 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 the method described in WO 2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetane-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 the method described in 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-3,3,3-trifluoro-1-methyl-propane 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 by 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-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)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 by the method described in WO2017 / 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 from 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]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, )-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 from 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 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 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound can be prepared by the method described in WO2016 / 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 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetraone (this compound can be prepared by the method described in WO2011 / 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 WO2018 / 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 WO2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (this compound can be prepared by the method described in WO 2014 / 095675); (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-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylic acid ethyl ester (this compound can be prepared by the method described in 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). 、

[0484] The compounds of the present invention can also be used in combination with anthelmintics. Such anthelmintics include compounds selected from macrolide compounds, such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemaketin and milbemycin derivatives, as described in EP 0357460, EP 0444964 and EP0594291. Other anthelmintics include semisynthetic and biosynthetic avermectin / milbemycin derivatives, such as those described in US 5,015,630, WO 9415944 and WO 9522552. Other anthelmintics include benzimidazoles, such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxbendazole, parbendazole and other members of this category. Additional anthelmintics include imidazothiazoles and tetrahydropyrimidines, such as tetramisole, levamisole, pyrantel pamoate, octadalafil or morantel. Additional anthelmintics include flukeicides (such as triclabendazole and clorsulon) and tapewormicides (such as praziquantel and ethacistel).

[0485] The compounds of the present invention may be used in combination with derivatives and analogs of the paraherquamide / marcfortine class of anthelmintics and antiparasitic oxazolines such as those disclosed in US 5478855, US 4639771 and DE-19520936.

[0486] The compounds of the invention can be used in combination with derivatives and analogs of the general class of dioxomorpholine antiparasitic agents as described in WO 9615121 and also with anthelmintic active cyclic depsipeptides such as those described in WO 9611945, WO 9319053, WO9325543, EP 0626375, EP 0382173, WO 9419334, EP 0382173, and EP 0503538.

[0487] The compounds of the present invention can be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as chlorfenuron; ecdysone agonists such as tebufenozide; neonicotinoids such as imidacloprid, etc.

[0488] The compounds of the 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.

[0489] 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:

[0490] Organophosphates: acephate, methyl pyraclofos, ethyl azinphos-methyl, methyl azinphos-methyl, bromophos, ethyl bromophos, cadusin, chlorethoxyphos, chlorpyrifos, chlorfenapyr, chlormethylphos, demeton, demeton-S-methyl, demeton-S-methyl sulfone, chlormet, diazinon, dichlorvos, dicrotophos, dimethoate, ethion, ethion, ethion, oxamethoxam, fenamiphos, fenitrothion, fenthion, fenthion, fenthion, pyrifos, fenfothion, anchovy, thiamethoxam, heptylphos, chlorazophos, isopropylphos, isoxazophos, malathion Phosphorus, acaricide, methamidophos, methidathion, methyl parathion, mefenphos, monocrotophos, dibromophos, omethoate, methyl oxo-demeton, paraoxon, parathion, methyl parathion, fenthion, phosalone, thiocyanate, phosphine, phosmet, phosphamidon, phosphamidon, phosphamidon, phosphamidon, phosphamidon, phosphamidon, phosphamidon, phosphamidon-methyl, bromophos, propanphos, proetamphos, prothiophos, pyraclofos, pyridazinphos, quinalphos, thiocarb, thimeton, terbufos, butylpyrimidinphos, stirofosate, thimeton, triazophos, trichlorfon, and chlorpyrifos.

[0491] Carbamates: aldicarb, 2-sec-butylphenyl methyl carbamate, benfuracarb, carbaryl, chlorpyrifos, carbofuran, butylthiocarb, diflubenzuron, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801, isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-isopropylphenylbutynyl (methyl) carbamate, cypermethrin, pirimicarb, propoxur, thiodicarb, long-lasting carb, triazolam, UC-51717.

[0492] Pyrethroids: flumethrin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E)-(1R)-cis-2,2-dimethyl-3-(2-oxathiolane-3-ylidenemethyl) cyclopropanecarboxylate, bifenthrin, β-cypermethrin, flucythrin, alpha-cypermethrin, β-cypermethrin, bio-allethrin, bio-allethrin ((S)-cyclopentyl isomer), bio-resmethrin, bifenthrin, NCI-85193, Pyrethrins, cyhalothrin, cypermethrin, deltamethrin, d-cypermethrin, esfenvalerate, etherpermethrin, pentothrin, cypermethrin, cypermethrin, flucythrin, fluvalinate (D isomer), imiprothrin, cyhalothrin, lambda-cyhalothrin, permethrin, phenothrin, prallethrin, pyrethrin (natural product), resmethrin, tetramethrin, transfluthrin, theta-cypermethrin, silafluthrin, t-fluvalinate, tefluthrin, tralomethrin, ζ-cypermethrin.

[0493] Arthropod growth regulators: a) Chitin synthesis inhibitors: benzoyl ureas: chlorfenapyr, diflubenzuron, fluazifop, flufenoxuron, flubendiamide, hexaflumuron, chlorfenuron, isoflurane, diflubenzuron, diflubenzuron, thiocarb, buprofezin, benzylfen, hexathiapiprolin, etoxazole, chlorfentazine; b) Ecdysone antagonists: chlorfenapyr, methoxyfenapyr, fenpyroximate; c) Juvenile hormone analogs: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) Lipid biosynthesis inhibitor: spirodiclofen.

[0494] Other antiparasitic drugs: acequinoxaline, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, sulfamethoxazole, bifenazate, binacarb, bromocriptine, BTG-504, BTG-505, toxaphene, cartap, ethyl cypermethrin, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, clothianidin, cypermethrin, diacloden, cypermethrin, DBI-3204, diclofenac, dihydroxy methyl dihydroxypyrrolidine, dimethoate, dimethoate, endosulfan, ethiprole, fenpyroxen, flumite, MTI-800, fenpyroximate, pyrimidine, flumethrin, bromothrin, flumethoate, trifluroxyfen, halofenprox, hydrazone, IKI-220, sodium silicate, NC-196, neem guard), nidinorterfuran, nitenpyram, SD-35651, WL-108477, pyridalyl, propargite, protrifenbute, pymetrozine, pyridabenzane, pyrimidine, NC-1111, R-195, RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601, flutoxin, silomadine, spinosad, tebufenpyrad, trichloroacetic acid sulfone, tetracycline, thiacloprid, thiamethoxam, tolfenpyrad, triacetin, triacylglycerol, synergistic acetyl ether, vertalec, YI-5301.

[0495] Biological agents: Bacillus thuringiensis ssp. aizawai, Bacillus thuringiensis ssp. kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, insect pathogenic bacteria, viruses and fungi.

[0496] Bactericides: chlortetracycline, oxytetracycline, streptomycin.

[0497] Other biologics: enrofloxacin, febantel, pentoxacillin, meloxicam, cephalexin, kanamycin, pimobendan, clenbuterol, omeprazole, tiamulin, benazepril, pyriprole, cefquinome, florfenicol, buserelin, cefuroxime, tolamectin, ceftiofur, carprofen, mefluazione, praziquantel, triclabendazole.

[0498] The following mixtures of compounds of formula (I) with active ingredients 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 invention, or a compound selected from the compounds listed in Tables A-1 to A-24 or Table P (below):

[0499] A compound selected from the group of substances 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-chlorophenylphenyl sulfone + TX, acetofenamide + TX, aldicarb + TX, sirox + TX, fomanphos + TX, ammonium oxalate + TX, ammonium oxalate + TX, amitraz + TX, cypermethrin + TX, arsenic trioxide + TX, azobenzene + TX, azophos + TX, benomyl + TX, benoxaphos + TX, benzyl benzoate + TX, bixafen + TX, bromomethrin + TX, bromophenazine + TX , bromophos + TX, bromopyralid + TX, buprofezin + TX, butanone + TX, butanone sulfone + TX, butyl pyridaben + TX, calcium polysulfide + TX, octachlorocamphene + TX, chlormethoxam + TX, trithion + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin hydrochloride + TX, cypermethrin + TX, cypermethrin + TX, dimethoate + TX, ethyl cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, propyl cypermethrin + TX, cypermethrin + TX, cypermethrin I + TX, cypermethrin II + TX, cypermethrin + TX, closantel + TX, coumaphos + TX, crotamiton + TX, baclofos + TX, thiocarb + TX, fruit insect phosphorus + TX, DCPM + TX, DDT + TX, tianle phosphorus + TX, tianle phosphorus-O + TX, tianle phosphorus-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-methylsulfon + TX, antifungal + TX, dichlorvos + TX, dicliphos + TX, demeton + TX, methylphos + TX, dinex + TX, dinex-diclexine + TX, dimethoate Pu-4+TX, Dimitrop-6+TX, Ortho-Damipro+TX, Nitral+TX, Nitral octyl acaricide+TX, Nitral butyl+TX, Dimethoate+TX, Sulfondiphenyl+TX, Disulfiram+TX, DNOC+TX, Benoxychlorpyrifos+TX, Doramectin+TX, Indox+TX, Eprinomectin+TX, Ethiophos+TX, Ethiophos+TX, Anti-mite+TX, Fenbutatin+TX, Fenthiocarb+TX, Fenpyrad+TX, Fenpyrad+TX, Amifenpyrad+TX, Amifenpyrad+TX, Fenpyrad+TX, Flunitrodiphenylamine+TX, Flufenamid+TX, Flufenamide+TX, Diflubenzuron+TX, Flufenamid+TX, FMC 1137+TX, thiamethoxam+TX, thiamethoxam hydrochloride+TX, carbendazim+TX, γ-HCH+TX, chlorpyrifos+TX, benzyl methoxyfen+TX, hexadecyl cyclopropane carboxylate+TX, isothiocarb+TX, jasmonate I+TX, jasmonate II+TX,Iodophos + TX, lindane + TX, propanil + TX, cypermethrin + TX, dithiophos + TX, methylthiophene + TX, acarb + TX, methyl bromide + TX, cypermethrin + TX, milbemycin + TX, propylamine + TX, monocrotophos + TX, maoguo + TX, moxidectin + TX, dibromophos + TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, fluazifop + TX, nikkomycin + TX, pentamethylenetetracycline + TX, pentamethylenetetracycline 1:1 zinc chloride complex + TX, omethoate + TX, isothiocarb + TX, sulfone + TX, pp'-DDT + TX, parathion + TX, permethrin + TX, fen Sulfur + TX, phosalone + TX, thiophanate + TX, phosphamidon + TX, chlorinated turpentine + TX, acaricide + TX, chloranil + TX, cypermethrin + TX, propoxur + TX, ethidium + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrin + TX, pyrimethoxam + TX, pyrithiophos + TX, quinalphos + TX, quinalphos + TX, R-1492 + TX, glycyrrhizin + TX, rotenone + TX, octamidine + TX, clematid + TX, selamectin + TX, thiophanate + TX, SSI-121 + TX, sulfilam + TX, sulfluramid + TX, sulfotep + TX, sulfur + TX, fluazifop + TX, τ-fluvalinate + TX, TEPP + TX, tert-butylcarb + TX, tetrachloroacarb + TX, acaricide + TX, thiafenox + TX, anthracene + TX, long-lasting carb + TX, methyl thiophos + TX, acaricide + TX, thuringin + TX, fenthion + TX, benzyl thiocarb + TX, triazophos + TX, aphidazole + TX, trichloropropoxyphos + TX, triamcinol + TX, aphidicide + TX, methyl fipronil + TX, baclofen + TX, copper dioctanoate + TX, copper sulfate + TX, cybutryne + TX, dichloronaphthoquinone + TX, dichlorophen + TX, endosin + TX, triphenyltin + TX, slaked lime + TX, sodium mancozeb + TX, azoquinone + TX, quinone + TX, simazine + TX, triphenylacetic acid Tin + TX, triphenyltin hydroxide + TX, folate + TX, piperazine + TX, thiophanate + TX, chloralose + TX, fenthion + TX, pyridine-4-amine + TX, strychnine + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 4-(quinoxaline-2-ylamino)benzenesulfonamide + TX, 8-hydroxyquinoline sulfate + TX, bronopol + TX, copper hydroxide + TX, cresol + TX, dipyrithione + TX, dodesine + TX, sodium sulfone + TX, formaldehyde + TX, mercury + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel di(dimethyldithiocarbamate) + TX, trichloromethylpyridine + TX, octhion + TX, oxolinic acid + TX, oxytetracycline + TX,Hydroxyquinoline sulfate potassium + TX, Thiabendazole + TX, Streptomycin + TX, Streptomycin sesquisulfate + TX, Chloroquine + TX, Thimerosal + TX, Cotton brown banded moth GV + TX, Radiation-forming Agrobacterium + TX, Amblyseius spp. + TX, Spodoptera exigua NPV + TX, Anagrus atomus + TX, Short-spurred aphid wasp + TX, Aphidius colemani + TX, Aphidoletes aphidimyza + TX, Spodoptera exigua NPV + TX, Bacillus sphaericus Neide + TX, Beauveria brongniartii + TX, Chrysoperla carnea + TX, Cryptolaemus spp. montrouzieri+TX, codling moth GV+TX, Siberian jawed braconid wasp (Dacnusasibirica)+TX, pea leafminer wasp (Diglyphus isaea)+TX, beautiful aphid wasp+TX, paddle-horned aphid wasp (Eretmocerus eremicus)+TX, Heterorhabditis bacteriophora and H.megidis+TX, spotted long-legged ladybird (Hippodamia convergens)+TX, orange flour scale parasitic wasp (Leptomastix dactylopii)+TX, blind bug (Macrolophus caliginosus)+TX, cabbage armyworm NPV+TX, yellow broad-handled jumping wasp (Metaphycus helvolus)+TX, Metarhizium anisopliaevar.acridum)+TX, Metarhizium anisopliae var.anisopliae+TX, Neodiprion sertifer NPV and N.lecontei NPV+TX, Pseudomonas species+TX, Paecilomyces fumosorum+TX, Phytoseiulus persimilis+TX, Steinernema bibionis+TX, Steinernema carpocapsae+TX, Steinernema glaseri+TX,Steinernema riobrave+TX, Steinernema riobravis+TX, Steinernema capterisci+TX, Steinernema spp.+TX, Trichogramma species+TX, Typhlodromus occidentalis+TX, Verticillium lecanii+TX, lecanii)+TX, oxazolidinone+TX, bis(aziridine)methylaminophosphine sulfide+TX, busulfan+TX, dimethivin+TX, hexamethylmelamine+TX, hexamethylphosphine+TX, methyl tibac+TX, methyl thiotibac+TX, methyl oxazolidinone+TX, infertile amine+TX, flufenuron+TX, tibac+TX, thiohexamethylphosphine+TX, thiotibac+TX, trothamide+TX, urethaneimine+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-methylnonan-5-ol and 4-methylnonan-5-one + TX, α-polytextine + TX, western pine beetle aggregation pheromone + TX, dodecadienol + TX, decyl pyrophosphate + TX, cyclopentadienol ... Nonadecane + 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 gathering pheromone + TX, trapping ene mixture + TX, trapping ene mixture I + TX, trapping ene mixture II + TX, trapping ene mixture III + TX, trapping ene mixture IV + TX, hexane attractant + TX, tooth beetle dienol + TX, small beetle alcohol + TX,Scarab beetle sex attractant + TX, trimethyldioxytricyclononane + TX, noctuid sex attractant (litlure) + TX, cabbage looper sex attractant + TX, trapping ester + TX, (3E,5Z)-tetradec-3,5-dienoic acid (megatomoic acid) + TX, trapping ether + TX, trapping ene + TX, octadec-2,13-diene-1-yl acetate + TX, octadec-3,13-diene-1-yl acetate + TX, Hekangbi + TX, coconut rhinoceros beetle aggregation pheromone + TX, feilukang + TX, trapping ring + TX, banana corm weevil attractant (sordidin) + TX, fungivorous methyl trapping alcohol + TX, tetradec-11-ene-1-yl acetate + TX, Mediterranean fruit fly attractant +TX, Mediterranean fruit fly attractant A+TX, Mediterranean fruit fly attractant B1+TX, Mediterranean fruit fly attractant B2+TX, Mediterranean fruit fly attractant C+TX, trunc-call+TX, 2-(octylthio)ethanol+TX, diethyltoluene+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, oxamate+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-isovaleryl indan-1,3-dione+TX, 2-methyl (prop-2-ynyl) aminophenyl methylcarbamate+TX, 2-thiocyanatoethyl laurate+TX, 3-bromo-1-chloroprop-1-ene+TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate+TX, 4-methyl (prop-2-ynyl) amino-3,5-xylyl methylcarbamate+TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate+TX, acethion+TX, acrylonitrile+TX, aldrin+TX, alloamicin+TX, cypermethrin+TX, α-decandrin+TX, aluminum phosphide+TX, cypermethrin+TX, neonicotinoid+TX,Ethyl cypermethrin + TX, methyl pyrifos + TX, Bacillus thuringiensis δ-endotoxin + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, cypermethrin + TX, Bayer 22 / 190 + TX, Bayer 22408 + TX, β-cyfluthrin + TX, β-cypermethrin + TX, pentothrin + TX, biological permethrin + TX, bis (2-chloroethyl) ether + TX, borax + TX, bromophenazone + TX, bromo-DDT + TX, hexamethon + TX, cypermethrin + TX, temozolomide + TX, butyl ester + TX, arsenic acid Calcium + TX, calcium cyanide + TX, carbon disulfide + TX, carbon tetrachloride + TX, badan hydrochloride + TX, servadine + TX, bornane + TX, chlordane + TX, chlordecone + TX, chloroform + TX, chloropicrin + TX, chloraniloxime + TX, chlorpyrifos + TX, cis-resmethrin + TX, cis-resmethrin + TX, cypermethrin + TX, copper acetoarsenite + TX, copper arsenate + TX, copper oleate + TX, insecticide + TX, cryolite + TX, CS 708+TX, benzonitrile+TX, cypermethrin+TX, cypermethrin+TX, cypermethrin+TX, d-cypermethrin+TX, DAEP+TX, dazomethane+TX, demethylcarbofuran+TX, chloranil+TX, isochlorphos+TX, chloranil+TX, mixed toluene carbamate (dicresyl)+TX, cypermethrin+TX, dieldrin+TX, diethyl 5-methylpyrazol-3-yl phosphate+TX, chloranil+TX, tetrafluoromethylthiocarb+TX, demacarb+TX, pyrethrin+TX, methylchlorfenapyr+TX, dichlorvos+TX, propanol+TX, pentotropol+TX, dinoseb+TX, benzylfen+TX, vegetable phosphorus+TX, thiopyraphos+TX, DSP+TX, ecdysterone+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, pyrifos+TX, ethylbencarb+TX, fenitrothion+TX, oxazolidinone+TX, cypermethrin+TX, fenthion+TX, ethylfenthion+TX, flucloroxil+TX, butylfenthion+TX, phosphonate+TX, butylthion+TX, furathiocarb+TX, anti-pyrethroid +TX, biguanide salt +TX, biguanide acetate +TX, sodium tetrathiocarbonate +TX, benzyl chlorfenapyr +TX, HCH +TX, HEOD +TX, heptachlor +TX, cypermethrin +TX, HHDN +TX, hydrogen cyanide +TX, quinoline carbendazim +TX, IPSP +TX, chlorfenapyr +TX, carbochlorin +TX, isodrin +TX, isoflavone +TX, transplanting spirit +TX, rice blast spirit +TX, oxathiophos +TX, juvenile hormone I +TX, juvenile hormone II +TX, j juvenile hormone III +TX, chlorpentyl +TX,Methoprene + TX, lead arsenate + TX, bromophenylphos + TX, acetamiprid + TX, thiathion + TX, m-isopropyl methylcarbamate + TX, magnesium phosphide + TX, phosphorus azide + TX, methyl aphidite + TX, chlorpyrifos + TX, mercurous chloride + TX, methyl sulfoxide + TX, metamifop + TX, metamifop potassium salt + TX, metamifop sodium salt + TX, methylsulfonyl fluoride + TX, butenamidophos + TX, methoprene + TX, methyl ether thiocyanate + TX, methoxychlor + TX, methyl isothiocyanate + TX, methyl chloroform + TX, dichloromethane + TX, chlorpyrifos + TX, anticide + TX, Naphthalene + TX, NC-170 + TX, nicotine + TX, nicotine sulfate + TX, nithiazine + TX, orthonicotine + 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, phosphine+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, amidophos+TX, profluthrin+TX, fenthion+TX, pyraclostrobin+TX, anti-pyrethroid+TX, quassia extract+TX, quinalphos-methyl+TX, oxazolidinone+TX, iodophos+TX, resmethrin+TX, rotenone+TX, thiamethoxam+TX, ryanodine+TX, sabah+TX, octamethrin+TX, clostridium+TX, SI-0009+TX, thiamethoxam+TX, sodium arsenite+TX, sodium cyanide+TX, sodium fluoride+TX 、Sodium hexafluorosilicate + TX、Sodium pentachlorophenol + TX、Sodium selenate + TX、Sodium thiocyanate + TX、Sulfonyl sulfosulfate + TX、Sulfonyl sulfosulfate sodium salt + TX、Sulfuryl fluoride + TX、Sulprophos + TX、Tar + TX、Thiamethoxam + TX、TDE + TX、Butyl pyrimidine + TX、Dimephos + TX、Cyclopentyl thiocyanate + TX、Tetrachloroethane + TX、Thiochlorvos + TX、Cyclomethrin + TX、Cyclomethrin oxalate + TX、Cyclomethrin + TX、Cyclomethrin sodium + TX、Tromthrin + TX、Permethrin + TX、Amicarb + TX、Heterozolin-3 + TX、Toxoplasmosis + TX、Mixoxacarb + TX、Trifluoromethocarb + TX、Chlorpyrifos + TX、Methosulfate + TX、Veratridine + TX、Veratrum + TX、XMC + TX、ζ-Cypermethrin + TX、Zinc phosphide + TX、Tolfenphos + TX、Cypermethrin + TX, tetrafluthrin + TX, bis(tributyltin) oxide + TX, bromoacetamide + TX, ferric phosphate + TX, niclosamide-ethanolamine + TX, tributyltin oxide + TX, pyroximate + 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-methylrhodanine + TX, 5-methyl-6-thiophene 1,3,5-thiadiazine-3-yl acetic acid + TX, 6-isopentenylaminopurine + 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 ethylxanthate + TX, acibenzolar + TX , arachidyl benzyl-S-methyl + TX, Polygonum cuspidatum extract + TX, α-chlorohydrin + TX, Antu + TX, barium carbonate + TX, bismuth urea + TX, brodifacoum + TX, brodifacoum + TX, bromodiolone + TX, bromodiolone + TX, chloranone + TX, cholecalciferol + TX, chlorfenapyr + TX, rat-killing naphthalene + TX, rat-killing pyrimidine + TX, rat-killing + TX, thiazolin + TX, thiazolin + TX, calciferol + TX, fludioxaline + TX, fluoroacetamide + TX, Fluorothiazine + TX, Fluorothiazine hydrochloride + TX, Warfarin + TX, Fenfoth + TX, Phosphorus + TX, Fenfoth + TX, Fenfoth + TX, Fenfoth + TX, Fenfoth + TX, Fenfoth + TX, Fenfoth + TX, Fenfoth + TX, Fenfoth + TX, Fenfoth + TX, Fenfoth + TX, Fenfoth + TX, Fenfoth + TX, Fenfoth + TX, Fenfoth + TX, Fenfoth + TX, Fenfoth + TX, Fenfoth + TX, Fenfoth + TX, Fenfoth + TX, Fenfoth + TX, Fenfoth 264+TX, piperonyl butoxide+TX, synergistic aldehyde+TX, propyl isomer+TX, S421+TX, synergistic powder+TX, sesamelin+TX, sulfoxide+TX, anthraquinone+TX, copper cyclohexaneate+TX, copper oxychloride+TX, dicyclopentadiene+TX, salen+TX, zinc cyclohexaneate+TX, zinc thiram+TX, imanin+TX, ribavirin+TX, mercuric oxide+TX, thiophanate-methyl+TX, azaconazole+TX, bifenthrin+TX, oxadiazole+TX, cyproconazole+TX , fenpropimorph + TX, diniconazole + TX, fluepiconazole + TX, cyproconazole + TX, fluquinconazole + TX, flusilazole + TX, flutriafol + TX, furopyram + TX, hexaconazole + TX, imazalil + TX, imipenem + TX, picroconazole + TX, metconazole + TX, myclobutrazol + TX, paclobutrazol + TX, pyraclostrobin + TX, penconazole + TX, prothioconazole + TX, pyraclostrobin + TX, prochloraz + TX, propiconazole + TX, pyraconazole + TX, silyconazole + TX, tebuconazole + TX,Fluconazole + TX, triadimefon + TX, triadimenol + TX, trifloxystrobin + TX, trichlorfon + TX, pyrimidine + TX, chlorfenapyr + TX, flufenapyr + TX, pyrimidine + TX, ethoxyquin + TX, mefenamic acid + TX, dodecacyclic morpholine + TX, fenpropidin + TX, fenbutamide + TX, spiroxaplanol + TX, tridecanamide + TX, cyprodinil + TX, myclobutanil + TX, myclobutanil + TX, fenmethanil + TX, fenpiclonil + TX, fludioxonil + TX, bensulfuron + TX, furalaxyl + TX, metalaxyl + TX, R-metalaxyl + TX, furamide + TX, oxadone + TX, carbendazim + TX, imidacloprid + TX, strychnine + TX, thiabendazole + TX, mefenamic acid + TX, sclerotinol + TX, mefenamic acid Bacillus+TX, Procymidone+TX, Vinclozolin+TX, Boscalid+TX, Carboxin+TX, Furam+TX, Flutolan+TX, Metformin+TX, Carboxin+TX, Penthiopyrad+TX, Thiofuran+TX, Dodinolide+TX, Biguanide+TX, Azoxystrobin+TX, Diclofenac+TX, Enstrobin+TX, Enstrobin+TX, Fluoxastrobin+TX, Fluoxastrobin+TX, Diclofenac+TX, Fenoxystrobin+TX, Fenoxystrobin+TX, Fenoxystrobin+TX, Fenoxystrobin+TX, Fenoxystrobin+TX, Fenoxystrobin+TX, Fenoxystrobin+TX, Fenoxystrobin+TX, Fenoxystrobin+TX, Fenoxystrobin+TX, Fenoxystrobin+TX, Fenoxystrobin+TX, Fenoxystrobin+TX, Fenoxystrobin+TX, Fenoxystrobin+TX, Fenoxystrobin+TX, Fenoxystrobin+TX, Fenoxystrobin+TX, Fenoxystrobin+TX, Fenoxystrobin+TX, Ferbam+TX, Mancozeb+TX, Maneb+TX, Maneb+TX, Methion+TX, Methyl Manb+TX, Maneb+T X、captan+TX、captan+TX、zofuran+TX、foltan+TX、toluidine+TX、Bordeaux mixture+TX、copper oxide+TX、mancozeb+TX、quinoline copper+TX、phthalocyanine+TX、kewensan+TX、isofenoxam+TX、chlorfenapyr+TX、methyl tolclofos+TX、captan+TX、benthiopyrad+TX、blastifungin-S+TX、dimonium chloride+TX、chlorothalonil+TX、cyfluthrin+TX、cymoxanil+TX、triflupyridam+TX、dichlorothiazol+TX、pyridamole+TX、chloranil+TX、dichlorothalonil+TX、dichlorothalonil+TX、chloranil+TX、ethionyl+TX、oxathiapiprolin+TX、oxathiapiprolin+TX、imidazole cypermethrin + TX, blastamide + TX, pyrimidine + TX, fluazinam + TX, fluopyram + TX, sulfaquinoxaline + TX, flupyraclonil + TX, fenacet + TX, fosetyl-aluminum + TX, meconazole + TX, propineb + ​​TX, saizumi + TX, sulfaquinoxaline + TX, mefenacet + TX, pentocycline + TX, pentocycline + TX, iodoquinoxaline + TX, pyraclostrobin + TX, quinacridone + TX, pentachloronitrobenzene + TX, thiazolin + TX, triazolin + TX, tricyclazole + TX, triazine + TX, validamycin + TX, valerian + TX, oxazolidinone + TX, dimethomorph + TX, fluorophenyl ether amide + TX,Pyraclostrobin + TX, fluopyram + TX, benzylidene + TX, fluopyram + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, isopropyram + TX, isothiopyram + TX, thiophene + TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile + TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX, (R)-3-( 1-methyl-N-[1,1,3-trimethylindan-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, fluinoxam + TX, jiaxiangjunzhi + TX, lvbenmixianan + TX, dichlorothiazide + TX, mandespin + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone +TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol+TX, thiophene-1-azol-2-yl+TX, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamate+TX, bixafen +TX, indoppyraclostrobin +TX, trolprocarb +TX, clofopyraclostrobin +TX, isotrifluanid +TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide +TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine +TX, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine +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)pyridazine+TX, fluopicolide+TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-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-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazolyl-5-one+TX, aminopyraclostrobin+TX, pyraclostrobin+TX, indazolesulfazoline+TX, fluopicolide+TX, (Z,2E)-5-[1- (4-chlorophenyl) pyrazol-3-yl] oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine + TX, diflupyrazolamide + TX, benzylpyrimide + TX, isobutylethoxyquinoline + TX, isopropoxyquinoline + TX, fluquinoline + TX, isopropoxyquinoline + 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, benzylpyrimide + TX, cyproconazole + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, fluopyram +TX, fluthiazolinil +TX, fluopicolide +TX, pyridinamide +TX, piperacillin +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, tetrazolin +TX, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-diphenyl]-4-yl]-5-pyrimidine 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(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-sulfanyl-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-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile+TX, trinexapac-ethyl+TX,Syringoxystrobin + TX, Zhongshengmycin + TX, Thiophanate + TX, Thiazole zinc + TX, Amitolin (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'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, 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-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 by 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)oxetane-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-3,3,3-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-carboxamide+TX, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide+TX, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide+TX , N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, 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 by 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 by 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 by the method described in WO2016 / 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-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]propanamide+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 from WO2017 / 055473, WO 2017 / 055469,Prepared by the method described in 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+TX (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+TX (this compound can be prepared by the method described in WO 2017 / 029179); 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); 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]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetraketone + TX (this compound can be prepared by the method described in WO 2011 / 138281) + TX, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]thiobenzamide; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-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; N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-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-indan-4-yl]pyridine-3-carboxamide + TX (this compound can be prepared by the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)-[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-oxo-N-propyl-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-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylic acid ethyl ester + TX (this compound can be prepared by the method described in WO 2018 / 158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide+TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX, N-[N-methoxy-methyl-carbonimino]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX (these compounds can be prepared by WO 2018 / 202428), chloroindole hydrazide + TX, fluopyram + TX, fluopyram + TX, fluopyram + TX, pyraclostrobin + TX. 、

[0500] References in brackets after the active ingredients, e.g. [3878-19-1], refer to Chemical Abstracts registration numbers. The mixed compatibilities described above are known. In the case where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; 13th edition; editor: CDSTomLin; The British Crop Protection Council], they are described therein by the entry number given in parentheses above for the specific compound; e.g. the compound "avermectin" is described by entry number (1). In the case where "[CCN]" is added above to a specific compound, the compound in question is included in the "Compendium of Pesticide Common Names", which can be found on the Internet [A.Wood; Compendium of PesticideCommonNames ,Copyright 1995-2004]; for example, the compound "acetoprole" is described on the Internet at http: / / www.alanwood.net / pesticides / acetoprole.html.

[0501] Most of the above-mentioned active ingredients are referred to above by so-called "common names", in individual cases the corresponding "ISO common name" or another "common name" being 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, an "alternative name" is used. "CAS Registry Number" means the Chemical Abstracts Registry Number.

[0502] Active ingredient mixtures of compounds 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 selected from the compounds listed in Tables A-1 to A-24, or Table P (below) are 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.

[0503] 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.

[0504] 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 a single "ready-to-use" form, as a combined spray mixture (which consists of separate formulations of the single 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 within a suitably 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.

[0505] The compositions according to the invention may also contain further solid or liquid auxiliaries, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soybean oil), defoamers (for example silicone oils), preservatives, viscosity regulators, adhesives and / or tackifiers, fertilizers or other active ingredients for obtaining specific effects, such as bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0506] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries, for example by grinding, screening and / or compressing the solid active ingredient; and in the presence of at least one auxiliary, 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. These methods for preparing the compositions and the use of compound (I) for preparing these compositions are also the subject matter of the present invention.

[0507] Another aspect of the invention relates to the use of a compound of formula (I) or preferably a compound as defined herein, a composition comprising at least one compound of formula (I) or at least one preferred compound as defined herein, or a fungicidal or insecticidal mixture comprising at least one compound of formula (I) or at least one preferred compound as defined herein (in admixture with other fungicides or insecticides as described above) according to the invention for controlling or preventing infestation of plants, such as useful plants (such as crop plants), their propagation materials (such as seeds), harvested crops (such as harvested food crops), or non-living materials by insects or phytopathogenic microorganisms, preferably fungal organisms.

[0508] Another aspect of the present invention relates to a method for controlling or preventing infestation of plants, for example useful plants (such as crop plants), their propagation materials (such as seeds), harvested crops (such as harvested food crops), or non-living materials 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 active ingredients to these plants, parts of these plants or their loci, their propagation materials, or any parts of these non-living materials.

[0509] 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 an improvement is demonstrated.

[0510] The preferred method of controlling or preventing crop plants from being infected by plant pathogenic microorganisms (especially fungal organisms) or insects is foliar application, which includes applying the compound of formula (I) according to the present invention or containing at least one agrochemical composition of the compound of formula (I). Frequency of application and application ratio will depend on the risk of infection by the corresponding pathogen or insect. However, the compound of formula (I) according to the present invention can also penetrate plants by roots (systemic action) through soil by soaking the place of plants with liquid formulations or by applying the compound in solid form, for example, in granular form to soil (soil application). In rice crops, such granules can be applied to the paddy field of irrigation. The compound of formula (I) can also be applied to seeds (coating) by dipping seeds or tubers with liquid formulations of fungicides or coating them with solid formulations.

[0511] Formulations, e.g. compositions containing a compound of formula (I) according to the invention and, if desired, solid or liquid adjuvants or monomers for encapsulating the compound of formula (I) can be prepared in a known manner, typically by intimately mixing and / or grinding the compound with extenders, e.g. solvents, solid carriers and optionally surface-active compounds (surfactants).

[0512] Advantageous application rates are generally from 5 g to 2 kg of active ingredient (ai) / hectare (ha), preferably from 10 g to 1 kg ai / ha, most preferably from 20 g to 600 g ai / ha. When used as a seed drench, a suitable dosage is from 10 mg to 1 g of active substance / kg seed.

[0513] As used herein, the term "gai / ha" refers to the application rate given in grams [g] of active ingredient [ai] per unit surface [ha]. The unit hectare (symbol ha) is equal to a square mile with a side length of 100 m (1 hm 2 ) or a square of 10,000 square meters. The hectare is a commonly used unit of area in the metric system.

[0514] When the combination according to the invention is used to treat seed, a ratio of 0.001 to 50 g of compound of formula (I) per kg of seed, preferably from 0.01 to 10 g per kg of seed, is generally sufficient.

[0515] 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).

[0516] The composition of the present invention can be used in any conventional form, for example in the form of a twin pack, a dry powder for seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water-dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspoemulsion (SE), a capsule suspension (CS), a water-dispersible granule (WG), an emulsifiable granule (EG), an oil-in-water emulsion (EO), an oil-in-water emulsion (EW), a microemulsion (ME), a dispersible oil suspension (OD), an oil suspension (OF), an oil-soluble liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with an agriculturally acceptable adjuvant.

[0517] Such compositions can be produced in a conventional manner, for example by mixing active ingredients with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulation ingredients, such as surfactants, biocides, antifreeze agents, adhesives, thickeners and compounds providing auxiliary effects). Conventional slow-release formulations intended to last for a long time can also be used. In particular, formulations to be applied in a spray form, 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 auxiliary effects, such as condensation products of formaldehyde with naphthalene sulfonates, alkylaryl sulfonates, lignin sulfonates, fatty alkyl sulfates and ethoxylated alkylphenols and ethoxylated fatty alcohols.

[0518] The seed dressing formulation is applied to the seed in a manner known per se using the combination of the invention and the diluent in the form of a suitable seed dressing formulation, for example an aqueous suspension or dry powder with good adhesion to the seed. 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 sustained-release capsule or microcapsule.

[0519] Typically, these formulations comprise by weight from 0.01% to 90% of an 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 being optionally composed together with other active agents (particularly microbicides or preservatives, etc.) by a compound with formula (I) at least according to the present invention. The concentrated form of the composition typically contains by weight between about 2% and 80%, preferably between about 5% and 70% of an active agent. The application form of the formulation can for example contain by weight from 0.01% to 20%, preferably by weight from 0.01% to 5% of an active agent. However, commercial products will preferably be formulated as concentrates, and end users will typically use diluted formulations.

[0520] While it is preferred that commercial products be formulated as concentrates, the end user will generally employ a diluted formulation.

[0521] The application rate varies within a wide range and depends on the nature of the soil, the application method, the crop plants, the harmful organisms to be controlled, the prevailing climatic conditions, and other factors governed by the application method, the application time and the target crop. In general, the compound can be applied at a rate of from 1 l / ha to 2000 l / ha, especially from 10 l / ha to 1000 l / ha.

[0522] Preferred formulations may have the following composition (wt%):

[0523] Emulsifiable concentrates :

[0524] Active ingredient: 1% to 95%, preferably 60% to 90%

[0525] Surfactant: 1% to 30%, preferably 5% to 20%

[0526] Liquid carrier: 1% to 80%, preferably 1% to 35%

[0527] Dust powder :

[0528] Active ingredient: 0.1% to 10%, preferably 0.1% to 5%

[0529] Solid carrier: 99.9% to 90%, preferably 99.9% to 99%

[0530] Suspension concentrate:

[0531] Active ingredient: 5% to 75%, preferably 10% to 50%

[0532] Water: 94% to 24%, preferably 88% to 30%

[0533] Surfactant: 1% to 40%, preferably 2% to 30%

[0534] Wettable powder :

[0535] Active ingredient: 0.5% to 90%, preferably 1% to 80%

[0536] Surfactant: 0.5% to 20%, preferably 1% to 15%

[0537] Solid carrier: 5% to 95%, preferably 15% to 90%

[0538] Granules:

[0539] Active ingredient: 0.1% to 30%, preferably 0.1% to 15%

[0540] Solid carrier: 99.5% to 70%, preferably 97% to 85%

[0541] The disclosure of the present application enables every combination of the embodiments disclosed herein to be achieved.

[0542] Compounds according to the following tables A-1 to A-24 can be prepared according to the above method. These examples are subsequently intended to illustrate the present invention and to show preferred compounds with formula (I). In any one of the following tables A-1 to A-24, the presence of one or more possible asymmetric carbon atoms in compounds with formula (I) according to the present invention means that these compounds can exist in chiral isomer form, i.e., enantiomer or diastereoisomer form.

[0543] Table A : This table discloses 20 substituent definitions (G) of compounds of formula (Ia) according to the present invention:

[0544]

[0545] Wherein the compound G of formula (I) according to the present invention is

[0546]

[0547] and wherein the G substituent is defined as follows:

[0548]

[0549]

[0550] Therefore, the following compounds are specifically described in Tables A-1 to A-24, wherein the substituents of formula (Ia) are:

[0551] 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 is H, and the G substituents are as defined in Table A. For example, compound (A-1.01) has the following structure:

[0552]

[0553] Table A-2: This table provides 20 compounds (A-2.01) to (A-2.20) having formula (Ia), wherein R 2 , R 5 , R 6 , R 7 , R 8 , R 9 , R10 and R 11 Yes H, R 2 is CH3, and the G substituent is as defined in Table A. For example, compound (A-2.09) has the following structure:

[0554]

[0555] Table A-3: This table provides 20 compounds (A-3.01) to (A-3.20) having formula (Ia), wherein R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 Yes H, R 2 is Cl, and the G substituents are as defined in Table A.

[0556] Table A-4: This table provides 20 compounds (A-4.01) to (A-4.20) having formula (Ia), wherein R 2 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 Yes H, R 4 is CH3, and the G substituent is as defined in Table A. For example, compound (A-4.06) has the following structure:

[0557]

[0558] Table A-5: This table provides 20 compounds (A-5.01) to (A-5.20) having formula (Ia), wherein R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 Yes H, R 2 and R 4 is CH3, and the G substituent is as defined in Table A.

[0559] Table A-6: This table provides 20 compounds (A-6.01) to (A-6.20) having formula (Ia), wherein R 5 , R 6 , R7 , R 8 , R 9 , R 10 and R 11 Yes H, R 2 It is Cl, R 4 is CH3, and the G substituent is as defined in Table A.

[0560] Table A-7: This table provides 20 compounds having 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 Yes H, R 7 is CH3, and the G substituent is as defined in Table A. All compounds in this table have R 7 The relationship between the substituent and the cis-form of the pyrazole substituent. For example, the compound racemic-cis-(A-7.06) has the following structure:

[0561]

[0562] Table A-8: This table provides 20 compounds having 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 Yes H, R 2 and R 7 is CH3, and the G substituent is as defined in Table A. All compounds in this table have R 7 The relationship between the substituent and the cis-form of the pyrazole substituent. For example, the compound racemic-cis-(A-8.01) has the following structure:

[0563]

[0564] 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 , R9 , R 10 and R 11 Yes H, R 2 is Cl and R 7 is CH3, and the G substituent is as defined in Table A. All compounds in this table have R 7 The relationship between the substituent and the pyrazole substituent is cis. For example, compound (A-9.14) has the following structure:

[0565]

[0566] Table A-10: This table provides 6 compounds (A-10.01) to (A-10.06) having formula (Ia), wherein R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 Yes H, R 11 is Br, and the G substituents are as defined in Table A.

[0567] Table A-11: This table provides 6 compounds (A-11.01) to (A-11.06) having formula (Ia), wherein R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 Yes H, R 11 is Cl, and the G substituents are as defined in Table A.

[0568] Table A-12: This table provides 6 compounds (A-12.01) to (A-12.06) having formula (Ia), wherein R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 Yes H, R 11 is CN, and the G substituents are as defined in Table A.

[0569] Table A-13: This table provides 6 compounds (A-13.01) to (A-13.06) having formula (Ia), wherein R 2 , R5 , R 6 , R 7 , R 8 , R 9 and R 10 Yes H, R 4 It is CH3, R 11 is Br, and the G substituents are as defined in Table A.

[0570] Table A-14: This table provides 6 compounds (A-14.01) to (A-14.06) having formula (Ia), wherein R 2 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 Yes H, R 4 It is CH3, R 11 is Cl, and the G substituents are as defined in Table A.

[0571] Table A-15: This table provides 6 compounds (A-15.01) to (A-15.06) having formula (Ia), wherein R 2 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 Yes H, R 4 It is CH3, R 11 is CN, and the G substituents are as defined in Table A.

[0572] Table A-16: This table provides 6 compounds having formula (Ia) 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 Yes H, R 7 It is CH3, R 11 is Br, and the G substituent is as defined in Table A. All compounds in this table have R 7 The relationship between the substituent and the cis-form of the pyrazole substituent. For example, the compound racemic-cis-(A-16.04) has the following structure:

[0573]

[0574] Table A-17: This table provides 6 compounds having formula (Ia) rac-cis-(A-17.01) to rac-cis-(A-17.006), wherein R 2 , R 4 , R 5 , R 6 , R 8 , R 9 and R 10 Yes H, R 7 It is CH3, R 11 is Cl, and the G substituent is as defined in Table A. All compounds in this table have R 7 Relationship of substituents to pyrazole substituent cis.

[0575] Table A-18: This table provides 6 compounds having formula (Ia) rac-cis-(A-18.01) to rac-cis-(A-18.006), wherein R 2 , R 4 , R 5 , R 6 , R 8 , R 9 and R 10 Yes H, R 7 It is CH3, R 11 is CN, and the G substituent is as defined in Table A. All compounds in this table have R 7 Relationship of substituents to pyrazole substituent cis.

[0576] Table A-19: This table provides 6 compounds having formula (Ia) rac-cis-(A-19.01) to rac-cis-(A-19.006), wherein R 4 , R 5 , R 6 , R 8 , R 9 , and R 10 Yes H, R 2 and R 7 It is CH3, R 11 is Br, and the G substituent is as defined in Table A. All compounds in this table have R 7 Relationship of substituents to pyrazole substituent cis.

[0577] Table A-20: This table provides 6 compounds having formula (Ia) rac-cis-(A-20.01) to rac-cis-(A-20.006), wherein R 4 , R 5 , R 6, R 8 , R 9 and R 10 Yes H, R 2 and R 7 It is CH3, R 11 is Cl, and the G substituent is as defined in Table A. All compounds in this table have R 7 Relationship of substituents to pyrazole substituent cis.

[0578] Table A-21: This table provides 6 compounds having formula (Ia) 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 Yes H, R 2 and R 7 It is CH3, R 11 is CN, and the G substituent is as defined in Table A. All compounds in this table have R 7 The relationship between the substituent and the cis-form of the pyrazole substituent. For example, the compound racemic-cis-(A-21.01) has the following structure:

[0579]

[0580] Table A-22: This table provides three compounds (A-22.01) to (A-22.03) having formula (Ia), wherein R 4 , R 5 , R 6 , R 7 , R 8 , R 10 and R 11 Yes H, R 2 It is CH3, R 9 is Br, and the G substituents are as defined in Table A.

[0581] Table A-23: This table provides three compounds (A-23.01) to (A-23.03) having formula (Ia), wherein R 4 , R 5 , R 6 , R 7 , R 8 , R 10 and R 11 Yes H, R 2 It is CH3, R 9 is OCH3, and the G substituent is as defined in Table A.

[0582] Table A-24: This table provides three compounds (A-24.01) to (A-24.03) having formula (Ia), wherein R 4 , R 5 , R 6 , R 7 , R 8 , R 10 and R 11 Yes H, R 2 It is CH3, R 9 is CN, and the G substituents are as defined in Table A.

[0583] Examples

[0584] The following examples are provided to illustrate the invention and are not meant to limit the invention in any way.

[0585] The compounds of the invention may be distinguished from known compounds by a greater efficacy at low application rates, which can be demonstrated by one of ordinary skill 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.

[0586] Compounds of formula (I) may have a number of benefits, including, among others, favorable levels of biological activity for protecting plants against diseases caused by fungi or superior properties for use as active ingredients in agrochemicals (e.g., higher biological activity, favorable activity spectrum, increased safety (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).

[0587] Throughout this specification, temperatures are given in degrees Celsius and "mp" means melting point. LC-MS means liquid chromatography-mass spectrometry, and a description of the apparatus and methods follows.

[0588] Recorded on a Bruker 400 MHz spectrometer 1 H NMR and 19 F NMR measurements, chemical shifts relative to TMS ( 1 H) and CFCl3( 19 F) Standards are given in ppm. Spectra were measured in deuterated solvents as specified. The compounds were characterized using any of the following LCMS methods. The characteristic LCMS values ​​obtained for each compound are the retention time ("Rt", reported in minutes) and the measured molecular ion (M+H) + or (MH) - .

[0589] LC-MS Method A:Spectra were recorded on a mass spectrometer from Waters Corporation (SQD, SQDII or QDA single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ions), capillary voltage: 0.8-3.00 kV, cone: 5-30 V, source temperature: 120°C-150°C, desolvation temperature: 350°C-600°C, cone gas flow: 50-150 l / h, desolvation gas flow: 650-1000 l / h, mass range: 50 to 900 Da, and Acquity UPLC from Waters Corporation: binary pump, heated column compartment, diode array detector and ELSD. Column: Waters UPLCHSS T3, 1.8 μm, 30x2.1 mm, temperature: 60°C, DAD wavelength range (nm): 210 to 400, run time: 1.5 min; solvent: 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.

[0590] LC-MS Method B: Spectra were recorded on a mass spectrometer from Waters (SQD, SQDII or QDA single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ions) with optimized mass parameters: ionization method: electrospray (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 with 0.1% formic acid: acetonitrile = 95:5 v / v; solvent B: acetonitrile with 0.05% formic acid

[0591]

[0592] 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

[0593] LC-MS Method C:Spectra were recorded on a mass spectrometer from Waters (SQD, SQDII or QDA single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ions) with optimized mass parameters: ionization method: electrospray (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 with 0.1% formic acid: acetonitrile = 95:5 v / v; solvent B: acetonitrile with 0.05% formic acid

[0594]

[0595] PDA wavelength range: 200 to 400nm,

[0596] 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

[0597] LC-MS Method D: Spectra were recorded on a mass spectrometer from Waters (SQD, SQDII or QDA single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ions) with optimized mass parameters: ionization method: electrospray (ESI); polarity: positive and negative polarity switching, scan type: MS2 scan; capillary (kV): 4.00; fragmentor voltage (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 with 0.1% formic acid: acetonitrile = 95:5 v / v; solvent B: acetonitrile with 0.1% formic acid

[0598]

[0599] Column: KINETEX EVO C18, column length: 50 mm; column inner diameter: 4.6 mm; particle size: 2.6 μ, column oven temperature: 40 °C

[0600] LC-MS Method E:Instrument specifications: UHPLC Agilent 1290 series LCMSD system with DAD\ELSD and Agilent LC\MSD (G6125B) mass spectrometer; Column: Agilent Poroshell 120SB-C18 4.6x30mm 2.7μm; Column temperature: 60°C; Mobile phase: A-water (0.1% formic acid), B-acetonitrile (0.1% formic acid); Flow rate: 3ml / min; Gradient: 0.01min-1%B, 1.5min-100%B, 1.73min-100%B; MS ionization mode: electrospray ionization (ESI); MS scan range: 83-600m / z; UV detection: 215nm, 254nm, 280nm

[0601] LC-MS Method F: Spectra were recorded on a mass spectrometer from Agilent Technologies (6410 triple quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative ion, MS2 scan, 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, 50x4.6 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.

[0602] LC-MS Method G:Spectra were recorded on a mass spectrometer from Waters (SQD2 or QDA single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative switching, capillary: 0.8-3.00 kV, cone range: 25 source temperature: 120°C-150°C, desolvation temperature: 500°C-600°C, cone gas flow: 50 L / h, desolvation gas flow: 1000 L / h, mass range: 110 to 850 Da) and an Acquity UPLC from Waters: quaternary solvent manager, heated column compartment, diode array detector. Column: Acquity UPLC HSS T3 C18, 1.8 μm, 30x2.1 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.

[0603] LC-MS Method H: Spectra were recorded on an ACQUITY mass spectrometer from Waters (SQD or SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative, 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 a solvent degasser, binary pump, heated column compartment and diode array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30x2.1 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.

[0604] Preparation Examples

[0605]

[0606] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain wettable powders which can be diluted with water to give a suspension of the desired concentration.

[0607]

[0608] The combination is thoroughly mixed with adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a dust that can be used directly for seed treatment.

[0609] Emulsifiable concentrates

[0610]

[0611] Emulsions of any desired dilution which can be used in plant protection can be obtained from these concentrates by dilution with water.

[0612]

[0613] A ready-to-use dust is obtained by mixing the combination with a carrier and grinding the mixture in a suitable grinder. Such a dust can also be used for dry seed dressing of seeds.

[0614] Extruder pellets

[0615]

[0616] The combination is mixed with the auxiliaries and ground, and the mixture is moistened with water. The mixture is extruded and then dried in an air stream.

[0617] Coated granules

[0618] Active ingredient 8%

[0619] Polyethylene glycol (molecular weight 200) 3%

[0620] Kaolin 89%

[0621] The finely ground combination is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

[0622] Suspension concentrates

[0623]

[0624] The finely ground combination is intimately mixed with adjuvants to give a suspension concentrate from which any desired dilution can be obtained by dilution with water. Using such a dilution, living plants together with plant propagation materials can be treated and protected against microbial infestation by spraying, pouring or immersion.

[0625] Flowable concentrate for seed treatment

[0626]

[0627] The finely ground combination is intimately mixed with adjuvants to give a suspension concentrate from which any desired dilution can be obtained by dilution with water. Using such a dilution, living plants together with plant propagation materials can be treated and protected against microbial infestation by spraying, pouring or immersion.

[0628] Extended-release capsule suspension

[0629] 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 are added 2.8 parts of a 1,6-hexanediamine mixture in 5.3 parts of water. The mixture is stirred until the polymerization reaction is complete. The capsule suspension obtained 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 capsules is 8-15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for this purpose.

[0630] Formulation types include emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifiable granules (EG), emulsions, water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oil dispersions (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), soluble granules (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0631] abbreviation

[0632] CDCl3 deuterated chloroform

[0633] DABCO 1,4-diazabicyclo[2.2.2]octane, also known as triethylenediamine or TEDADCC dicyclohexylcarbodiimide

[0634] DIPEA Diisopropylethylamine (N,N-diisopropylethylamine)

[0635] DMA Dimethylacetamide

[0636] DMF Dimethylformamide

[0637] DMSO Dimethyl sulfoxide

[0638] DMSO-d6 deuterated dimethyl sulfoxide

[0639] EDC 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide

[0640] Et3N Triethylamine

[0641] EtOAc Ethyl acetate

[0642] HATU 1-[Bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate

[0643] HCl

[0644] hr / hrs hours

[0645] LC-MS Liquid chromatography mass spectrometry (LC-MS, LC / MS or LCMS)

[0646] rh relative humidity

[0647] rt room temperature

[0648] Rt retention time

[0649] ssp. subspecies

[0650] TBME tert-butyl methyl ester or tert-butyl methyl ester

[0651] Preparation Example:

[0652] The compounds of formula (I) according to the present invention can be prepared using the synthetic techniques described above and below.

[0653] "Mp" refers to the melting point in ° C. Free radical means methyl group.

[0654] Example P1: [2-(2,4-difluorophenyl)tetrazol-5-yl]-[6-methoxy-1-methyl-4-(1-methylpyrazole-4- Preparation of [(4-(2- ...

[0655] Step 1: Preparation of 4-(1,5-dimethylpyrazol-4-yl)isoquinoline

[0656]

[0657] 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 a few minutes, and then tetrakis(triphenylphosphonium)palladium (0.545 g, 0.471 mmol) was added. The reaction mixture was heated and stirred at 100 °C for 1 hour under microwave irradiation. After cooling to room temperature, the reaction mixture was poured into water, extracted with EtOAc, and the organic layer was separated, dried over Na2SO4, filtered and concentrated in vacuo. The crude material was purified by flash chromatography on silica gel (eluting with EtOAc / 30% methanol) to give the title product.

[0658] LCMS (method A): m / z 225 [M+H], retention time 0.51 min

[0659] Step 2: Preparation of 4-(1,5-dimethylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline

[0660]

[0661] 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 the pH reached 2-3. After stirring at room temperature for 30 minutes, the reaction mixture was diluted with water and basified with 2N sodium hydroxide and the mixture was extracted with EtOAc (3x25 mL). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo. The resulting yellow oil was used without further purification.

[0662] LCMS (Method A): m / z 228 [M+H]. Retention time 0.29 min

[0663] The hydrochloride salt 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 2M HCl in diethyl ether and then concentrating in vacuo.

[0664] Step 3: Preparation of ethyl (2E)-2-(p-toluenesulfonylhydrazono)acetate

[0665]

[0666] At room temperature, 4-methylbenzenesulfonyl hydrazide (2g, 10.7mmol) is treated with 2-oxoethyl acetate (2.63g, 12.8mmol) in ethanol (40mL).Reaction mixture is stirred for 1 hour, and ethanol is removed by vacuum concentration.The residue obtained is diluted with water and extracted with EtOAc.Organic phase is separated, and solvent is evaporated in vacuo to obtain (2E)-2-(tosylhydrazono)ethyl acetate, which is used in the next step as it is.

[0667] LCMS (Method B): m / z 271 [M+H], retention time 1.06 min.

[0668] 1 H NMR (400MHz, CDCl3) δppm 9.31(s,1H),7.85(d,J=8.31Hz,2H),7.34(d,J=8.07Hz,2H),7.23(s,1H),4.27(q,J=7.09Hz,2H),2.44(s,3H)1.23-1.37(m,3H).

[0669] Step 4: Preparation of ethyl 2-(2,4-difluorophenyl)tetrazolyl-5-carboxylate

[0670]

[0671] A solution of 2,4-difluoroaniline (1.00 g, 7.74 mmol) in 6M 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 (2E)-2-(tosylhydrazono)ethyl 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 1N HCl, and the aqueous layer was extracted with EtOAc. The combined organic layer was dried over Na2SO4 and concentrated in vacuo to obtain a crude product, which was purified by column chromatography, eluted with 30% EtOAc / hexane to obtain 2-(2,4-difluorophenyl)tetrazolyl-5-carboxylic acid ethyl ester as a light red oil.

[0672] 1 H NMR (400MHz, CDCl3) δppm 7.86-7.94(m,1H),7.11-7.21(m,2H),4.60(q,J=7.21Hz,2H),1.51(t,J=7.13Hz,3H)

[0673] Step 5: [[2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro- Preparation of 1H-isoquinolin-2-yl]methanone (Compound P-31, Table P).

[0674]

[0675] 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 cooled with an ice bath. A solution of trimethylaluminum in toluene (0.6 mL, 1.18 mmol) (2.0 mol / L) was added dropwise at 0°C and the resulting mixture was heated to 80°C for 2 hours. After completion of the reaction, the mixture was diluted with EtOAc and washed with aqueous 1N 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.

[0676] LCMS (Method C): m / z 436 (M+H). Retention time 1.07 min.

[0677] Example P2: [1-(2,4-difluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H- Preparation of [2-isoquinolinyl]methanone (Compound P-8, Table P)

[0678] Step 1: Preparation of methyl 1-(2,4-difluorophenyl)triazole-4-carboxylate:

[0679]

[0680] The solution of 1-azido-2,4-difluoro-benzene (0.30g, 1.8mmol) in methanol (3.6mL) is successively treated with anhydrous copper sulfate (II) (0.053g, 0.33mmol), sodium ascorbate (0.46g, 2.3mmol) in water (3.6mL), and then methyl propionate-2-ynoate (0.14g, 0.14mL, 1.7mmol). The reddish reaction mixture is stirred at room temperature for 2 days, monitored by LCMS. The reaction mixture is then concentrated in a vacuum, and the residue is absorbed in water and EtOAc. The organic layer is separated, washed with salt water and the separated organic layer is dried over MgSO4, filtered and concentrated in a vacuum. The crude product is purified through a silica gel column (Rf200), eluted with cyclohexane / EtOAc, to give the title compound as a white solid.

[0681] LCMS (Method A): m / z 240 (M+H), retention time 0.79 min.

[0682] 1 H NMR (400MHz, CDCl3) δppm; 8.59 (d, J = 2.57Hz, 1H), 7.96-8.05 (m, 1H), 7.09-7.17 (m, 2H), 4.02 (s, 3H)

[0683] Step 2: Preparation of 1-(2,4-difluorophenyl)triazole-4-carboxylic acid

[0684]

[0685] Under argon, 1-(2,4-difluorophenyl) triazole-4-methyl formate sample (0.31g, 1.3mmol) is dissolved in tetrahydrofuran (6.5mL) and water (3.2mL) to obtain a light brown solution. Lithium hydroxide monohydrate (0.047g, 1.9mmol) is added thereto and the mixture is stirred at room temperature. After 3 hours, LCMS shows the desired quality and consumption of starting materials. Tetrahydrofuran is evaporated in vacuo, and then aqueous HCl 2N (about 0.5mL) is added so that the pH of the aqueous phase is 3-4. The obtained light red suspension is filtered, the white filter cake is washed with water and cyclohexane and dried in vacuo at 55°C to obtain 1-(2,4-difluorophenyl) triazole-4-carboxylic acid as a white solid.

[0686] LCMS (Method A): m / z 226 (M+H), retention time 0.63 min.

[0687] 1 H NMR(400MHz,DMSO-d6)δppm 7.27-7.52(m,1H),7.73(ddd,J=11.10,8.71,2.57Hz,1H),7.95(td,J=8.80,5.87Hz,1H),9.15(d,J=1.47Hz,1H),13.26-13.60(bs,1H).

[0688] Step 3: Preparation of 4-(1-methylpyrazol-4-yl)isoquinoline

[0689]

[0690] Similar to Example P1, Step 1 Prepare

[0691] LCMS (Method A): m / z 210 (M+H), retention time 0.41 min

[0692] 1H NMR (400MHz, CDCl3) δppm: 9.20 (s, 1H), 8.51 (s, 1H), 8.10-8.18 (m, 1H), 8.03 (d, J = 8.07Hz, 1 H),7.78-7.81(m,1H),7.70-7.76(m,1H),7.66-7.68(m,1H),7.62-7.66(m,1H),4.06(s,3H)

[0693] Step 4: Preparation of 4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline

[0694]

[0695] Prepared analogously to Example P1, step 2. The crude product was used without further purification.

[0696] Step 5: [1-(2,4-difluorophenyl)triazol-4-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-iso Preparation of [quinolin-2-yl]methanone (Compound P-8, Table P)

[0697]

[0698] Under argon, 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) 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 1M HCl, water and brine. The organic layer was dried over Na2SO4 and concentrated in vacuo. The crude material was purified by flash chromatography on silica gel (eluted with EtOAc in cyclohexane) to provide the title product.

[0699] LCMS (Method A) m / z 421 (M+H), retention time 0.92 min.

[0700] Example P3: [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-1,3-difluorophenyl]- Preparation of [2-[(2-Hydroisoquinolin-2-yl)]methanone (Compound P-32, Table P)

[0701] Step 1: Preparation of (1-methylpyrazol-4-yl)-phenyl-methanol

[0702]

[0703] 1-Methyl-1H-pyrazole-4-carboxaldehyde (2.20 g, 19.2 mmol) and tetrahydrofuran (40 mL) were loaded into a single-necked round-bottom flask equipped with a magnetic stirring bar. At 0°C-5°C, under an argon atmosphere, 1 mol of phenylmagnesium bromide in THF (21 mL, 21.1 mmol) was added dropwise to the colorless solution for 15 minutes. After 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 (2x40 mL). The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo to obtain a crude product as a colorless oil. The crude product was purified by combi flash (silica gel, gradient: EtOAc in cyclohexane) to obtain the desired product (1-methylpyrazole-4-yl)-phenyl-methanol as a colorless oil.

[0704] LCMS (Method A) m / z 189 [M+H], retention time: 0.62 min.

[0705] 1 H NMR (400MHz, CDCl3) δppm 7.26-7.43(m,6H),7.18(s,1H),5.80(s,1H),3.81(s,3H),2.89(br s,1H)

[0706] Step 2: Preparation of 2-(1-methylpyrazol-4-yl)-2-phenyl-acetonitrile

[0707]

[0708] A round-bottom flask equipped with a magnetic stirring bar and a condenser was charged with (1-methylpyrazole-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 sequentially 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 solution of sodium thiosulfate (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 a crude product, which was purified by combi flash (silica gel, gradient: EtOAc in cyclohexane) to give the desired title compound as a yellow oil.

[0709] LCMS (Method A) m / z 198 [M+H], retention time: 0.78 min.

[0710] 1H NMR (400MHz, CDCl3) δppm 7.33-7.43(m,6H),7.32(s,1H),5.09(s,1H),3.87(s,3H)

[0711] Step 3: Preparation of 2-(1-methylpyrazol-4-yl)-2-phenyl-propionitrile

[0712]

[0713] 2-(1-methylpyrazol-4-yl)-2-phenyl-acetonitrile (3.22 g, 16.3 mmol) and tetrahydrofuran (65 mL) were loaded into a 250 mL-3-neck flask equipped with a magnetic stirring bar and a condenser. A solution of n-butyl lithium in hexane (7.8 mL, 19.6 mmol) was added dropwise at -70 ° C under a nitrogen atmosphere (a small amount of exotherm was observed to -65 ° C). 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 it was warmed 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 Na2SO4, and concentrated in vacuo to obtain a 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.

[0714] LCMS (Method A) m / z 211 [M+H], retention time: 0.84 min.

[0715] 1 H NMR (400MHz, CDCl3) δppm 7.28-7.49(m,7H),3.88(s,3H),2.04(s,3H)

[0716] Step 4: Preparation of 2-(1-methylpyrazol-4-yl)-2-phenyl-propan-1-amine

[0717]

[0718] 2-(1-methylpyrazole-4-yl)-2-phenyl-propionitrile (2.82 g, 13.3 mmol) and tetrahydrofuran (40 mL) were loaded into a 250 mL-3-neck flask equipped with a magnetic stirring bar. Borane dimethyl sulfide complex (4.0 mL, 40.0 mmol) was added dropwise to the yellow solution at room temperature under an argon atmosphere, and the resulting colorless mixture was stirred at 65 ° C for 2 hours. The reaction mixture was cooled to 0 ° C, and hydrochloric acid (8.9 mL, 53.7 mmol) was then added dropwise (strong gas evolution), and the mixture was stirred at 65 ° C for 1 hour and allowed to stand overnight at room temperature. The mixture was diluted with water (80 mL), basified (pH 12) with 13 mL NaOH 6M, and the mixture was extracted twice with EtOAc. The combined organic layer was 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.

[0719] LCMS (method A) m / z 216 [M+H], retention time: 0.39 min

[0720] Step 5: Preparation of methyl N-[2-(1-methylpyrazol-4-yl)-2-phenyl-propyl]carbamate

[0721]

[0722] Into a sealed tube equipped with a magnetic stirring bar, 2-(1-methylpyrazol-4-yl)-2-phenyl-propan-1-amine (3.01 g, 11.2 mmol) and dichloromethane (45 mL) were loaded. Methyl chloroformate (1.1 mL, 13.4 mmol) was added dropwise at 0°C-10°C under an argon atmosphere, 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 Na2SO4 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.

[0723] LCMS (Method A) m / z 274 [M+H], retention time: 0.80 min.

[0724] Step 6: Preparation of methyl 4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinoline-2-carboxylate

[0725]

[0726] Into a single-necked round-bottom flask equipped with a magnetic stirring bar, N-[2-(1-methylpyrazole-4-yl)-2-phenyl-propyl]carbamic acid methyl ester (422mg, 1.54mmol), hydrochloric acid (5.00mL / mmol, 9.26g, 7.72mL, 94.0mmol) and paraformaldehyde (93mg, 0.97mmol) were loaded. The mixture was stirred at room temperature for 40min, where LCMS analysis showed that the reaction was complete. The reaction mixture was slowly poured into water (30mL), neutralized with sodium bicarbonate, and extracted with EtOAc (3×20mL). The combined organic layer was washed with brine, dried over Na2SO4 and concentrated in vacuo to obtain the crude title compound as a colorless gum, which was used as is without further purification.

[0727] LCMS (Method A) m / z 286 [M+H], retention time: 0.87 min.

[0728] Step 7: Preparation of 4-methyl-4-(1-methylpyrazol-4-yl)-2,3-dihydro-1H-isoquinoline

[0729]

[0730] A single-necked round-bottom flask equipped with a magnetic stirring bar was charged with 4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinoline-2-carboxylic acid methyl ester (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 argon atmosphere 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 Na2SO4, and concentrated in vacuo to give the title compound as a dark orange gum.

[0731] LCMS (Method A), m / z 228 [M+H], retention time: 0.61 min.

[0732] Step 8: [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-1,3-difluorophenyl]- Preparation of [2-[(2-Hydroisoquinolin-2-yl)]methanone (Compound P-32, Table P)

[0733]

[0734] 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 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 1N 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 cyclohexane / EtOAc gradient to give [2-(2,4-difluorophenyl)tetrazol-5-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone.

[0735] LCMS (Method C); m / z 436 [M+H], retention time: 1.06 min.

[0736] 1H NMR (400MHz, CDCl3) δppm 7.79-7.88(m,1H),6.99-7.22(m,7H),6.72(s,1H),5.10-5.21(m,1H),4.87-5. 00(m,1H),4.23(d,J=13.45Hz,1H),3.84-3.96(m,1H),3.67(s,3H),1.59(s,3H)

[0737] Example P4: [1-(2,4-difluorophenyl)-1,2,4-triazol-3-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3, Preparation of 4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-33, Table P)

[0738] Step 1: Preparation of methyl 1-(2,4-difluorophenyl)-1,2,4-triazole-3-carboxylate

[0739]

[0740] Prepared similarly to that described in Lett. [Organic Letters] 2018, 20, 6930-6933. Therefore, a solution of 2,4-difluorobenzenediazonium-tetrafluoroborate (prepared as described in J. Am. Chem. Soc. [American Chemical Society] 1956, 78, 2593-6, 500 mg, 0.5 g, 2.1939 mmol) in tetrahydrofuran (8.8 mL) was added at 0°C, 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), and the mixture was stirred at this temperature for 4 h. LCMS analysis showed that the reaction was complete after this time. The reaction mixture was poured into water (25 mL) and the mixture was extracted with EtOAc (2 × 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 obtain the title compound in an oily state.

[0741] 1 H NMR (400MHz, CDCl3) δppm 8.68 (d, J = 2.81Hz, 1H), 7.93-8.00 (m, 1H), 7.08-7.14 (m, 2H), 4.08 (s, 3H)

[0742] Step 2: [1-(2,4-difluorophenyl)-1,2,4-triazol-3-yl]-[4-(1,5-dimethylpyrazol-4-yl)-3, Preparation of 4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-33, Table P)

[0743]

[0744] 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 argon atmosphere 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 stirred in a microwave at 70°C 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 Na2SO4 and concentrated in vacuo. The crude product was purified by silica gel chromatography using 50%-70% cyclohexane / EtOAc as 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 sticky material.

[0745] LCMS (method D): m / z (M+H) 435, retention time 1.38 min

[0746] 1 H NMR (400MHz, CDCl3) δppm 8.59-8.50(m,1H),7.89-7.75(m,1H),7.25-6.92(m,7H),5.24 -5.13(m,1H)4.78(d,1H)4.15-4.49(m,2H),3.70-3.52(m,4H),2.18-1.98(m,3H)

[0747] Example P5: [2-(2,4-difluorophenyl)triazol-4-yl]-[rac-(1S,4S)-4-(1,5-dimethylpyrazole- Preparation of 4-methyl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-40, Table P)

[0748] Step 1: (1,5-Dimethylpyrazol-4-yl)-phenyl-methanol

[0749]

[0750] Similar to Example 3, step 1 prepare

[0751] LCMS (method A): m / z (M+H) 203, retention time 0.68 min

[0752] 1H NMR (400MHz, CDCl3) δppm 2.23 (s, 3H) 2.28 (d, J = 4.00Hz, 1H) 3.76 (s, 3H) 5.80 (d, J = 3.63Hz, 1H) 7.22 (s, 1H) 7.27-7.32 (m, 1H) 7.33-7.44 (m, 4H)

[0753] Step 2: 2-(1,5-dimethylpyrazol-4-yl)-2-phenyl-acetonitrile

[0754]

[0755] Similar to Example 3, step 2 prepared

[0756] LCMS (method A): m / z (M+H) 212, retention time 0.82 min

[0757] 1 H NMR (400MHz, CDCl3) δ = 7.46-7.28 (m, 6H), 5.05 (s, 1H), 3.78 (s, 3H), 2.18 (s, 3H)

[0758] Step 3: 2-(1,5-dimethylpyrazol-4-yl)-2-phenyl-ethylamine

[0759]

[0760] Similar to Example 3, step 3 prepare

[0761] LCMS (method A): m / z (M+H) 216, retention time 0.60 min

[0762] 1 H NMR (400MHz, CDCl3) δppm 2.09(s,3H)3.20(dd,J=7.45,2.00Hz,2H)3.75(s,3H)3.79(t,J=7.27Hz,1H)7.16-7.25(m,3H)7.26-7.33(m,2H)7.42(s,1H)

[0763] Step 4: Methyl N-[2-(1,5-dimethylpyrazol-4-yl)-2-phenyl-ethyl]carbamate

[0764]

[0765] Similar to Example 3, step 4 prepares

[0766] LCMS (method A): m / z (M+H) 274, retention time 0.76 min

[0767] 1H NMR (400MHz, CDCl3) δppm 1.57 (d, J = 6.90Hz, 3H) 2.18 (br d, J = 6.90Hz, 3H) 3.05-3.27 (m, 1H) 3.78 (br s,3H)3.84(s,3H)3.99-4.09(m,1H)4.09-4.38(m,1H)5.22-5.47(m,1H)6.92-7.01(m,1H)7.07-7.27(m,4H

[0768] 1 H NMR (400MHz, CDCl3) δppm 2.03-2.13(m,3H)3.62-3.74(m,5H)3.77(s,3H)3.94-4.05(m,1H)4.72(br s,1H)7.21-7.26(m,3H)7.27-7.34(m,2H)7.38(s,1H)

[0769] Step 5: Racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline Preparation of methyl phenoxyline-2-carboxylate

[0770]

[0771] N-[2-(1,5-dimethylpyrazole-4-yl)-2-phenyl-ethyl] methyl carbamate (2.0 g, 7.3 mmol), hydrochloric acid (37 mL, 450 mmol) and acetaldehyde (0.83 mL, 15 mmol) were loaded into a single-necked round-bottom flask equipped with a magnetic stirring bar. The mixture was stirred at room temperature for 2 h. The reaction mixture was slowly poured into water (500 mL) and neutralized with NaHCO (intense gas evolution). The mixture was extracted with EtOAc (3 × 50 mL), and the combined organic layer was washed with salt water, dried over NaSO, filtered and concentrated in vacuo. The crude product was purified by chromatography to obtain the title compound in an oily state.

[0772] LC-MS (method A): retention time 0.87 min, 300 (M+H)

[0773] 1 H NMR (400MHz, CDCl3) δppm 1.57 (d, J = 6.90Hz, 3H) 2.18 (br d, J = 6.90Hz, 3H) 3.05-3.27 (m, 1H) 3.78 (br s,3H)3.84(s,3H)3.99-4.09(m,1H)4.09-4.38(m,1H)5.22-5.47(m,1H)6.92-7.01(m,1H)7.07-7.27(m,4H

[0774] Step 6. Racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-1,2,3,4-tetrahydroisoquinoline Preparation of morphine

[0775]

[0776] 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) was treated with iodotrimethylsilane (1.7 mL, 12 mmol) in 1,2-dichloroethane (21 mL), and the mixture was stirred at 60 ° C for 1 h under argon, at which time LCMS analysis showed that the reaction was complete. The reaction was cooled to room temperature, and 10% HCl (22 mL) was then added to the reaction under ice cooling. The mixture was concentrated in vacuo to remove volatiles, and the residual aqueous solution was adjusted to pH 8 with 10% NaOH (aq). The mixture was extracted with CH2Cl2 (4x25 mL), and the organic layers were combined, dried over Mg2SO4, filtered and concentrated in vacuo to give the title product as a single diastereomer of the title compound (>97:3 cis:trans), which was pure enough for subsequent steps.

[0777] LC-MS (Method A): m / z 242 (M+H), retention time 0.35 min

[0778] 1 H NMR (600MHz, CDCl3) δppm 1.86(d,J=6.9Hz,3H)2.23(s,3H)3.27(dd,J=12.5,10.8Hz,1H)3.59(dd,J=12.8,5.6Hz,1H)3.83(s,3H)4.58(dd,J=10.6, 5.4Hz,1H)4.80(q,J=6.8Hz,1H)7.00(d,J=7.8Hz,1H)7.11(s,1H)7.16(d,J=7.6Hz,1H)7.18-7.22(m,1H)7.25-7.28(m,1H)

[0779] Step 7: Preparation of ethyl 2-[(2,4-difluorophenyl)hydrazono]-3-oxo-propionate

[0780]

[0781] At room temperature, in a double-necked round-bottom flask equipped with a nitrogen inlet, 2,4-difluoroaniline (4.00g, 30.9mmol), water (32mL) and concentrated HCl (12mL, 35%) were added. The reaction mixture was cooled to 0°C and a cold solution of sodium nitrite (2.56g, 37.1mmol) in water (32mL) was added to the solution, and the resulting mixture was stirred at 0°C for 5min. In another round-bottom flask, a solution of 3-(dimethylamino)prop-2-enoic acid ethyl ester (12.0g, 23.4mmol) and potassium acetate (4.61g, 46.4mmol) in ethanol (40mL) was stirred and cooled to 0°C. The above-mentioned diazotization solution was added dropwise thereto at 0°C, and the reaction mixture was warmed to room temperature and stirred for 18 hours. LCMS shows the formation of the desired product. The reaction was diluted with water and extracted with EtOAc (3x50mL). The combined organic layers were washed with brine, dried over Na 2 SO 4 , and concentrated in vacuo to give ethyl 2-[(2,4-difluorophenyl)hydrazono]-3-oxo-propanoate as a brown solid, which was used as such in the next step.

[0782] LCMS (Method B): m / z 257 [M+H], retention time = 1.09 min

[0783] Step 8: Preparation of 2-[(2,4-difluorophenyl)hydrazono]-3-hydroxyimino-propionic acid ethyl ester

[0784]

[0785] To a solution of 2-[(2,4-difluorophenyl)hydrazono]-3-oxo-propionic acid ethyl 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 shows complete conversion to the desired product. The reaction mixture was allowed to cool to room temperature, diluted with water and extracted with EtOAc (3x50 mL). The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo to give the title compound as a brown solid, which was used as is in the next step.

[0786] LCMS (Method B): m / z 272 [M+H], retention time = 1.16 min

[0787] Step 9: Preparation of ethyl 2-(2,4-difluorophenyl)triazole-4-carboxylate

[0788]

[0789] 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 the reaction was completed, 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 with Na2SO4 and concentrated in vacuo to give a crude product. It was purified by combiflash using EtOAc / cyclohexane as eluent (5:95) to give the title compound as a brown solid.

[0790] LCMS (Method C): m / z 254 [M+H], retention time = 1.19 min

[0791] Step 10: Preparation of lithium 2-(2,4-difluorophenyl)triazole-4-carboxylate

[0792]

[0793] 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 ground with methyl tert-butyl methyl ether (TBME). This produces lithium; 2-(2,4-difluorophenyl)triazole-4-carboxylate, which was used as is in the next step.

[0794] LCMS (Method B): m / z 224 [M+H], retention time = 0.29 min

[0795] Step 11: [2-(2,4-difluorophenyl)triazol-4-yl]-[rac-(1S,4S)-4-(1,5-dimethylpyrazole- Preparation of 4-methyl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-40, Table P)

[0796]

[0797] A suspension of 2-(2,4-difluorophenyl)triazole-4-carboxylic acid lithium (0.231 g, 1.0 mmol, 100% by mass) and racemic-(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% by mass in EtOAc) at 0 ° C and the reaction mixture was stirred at room temperature for 2 h. After the reaction was complete, the reaction mixture was diluted with water (15 mL) and extracted with EtOAc (3x20 mL). The combined organic layers were washed with water and brine (20 mL), dried over Na2SO4, filtered and concentrated in vacuo to give a crude product. This was purified by combiflash using 0-80% cyclohexane / EtOAc as eluent to give the title compound as a brown solid.

[0798] LCMS (Method B), m / z 449 (M+H), retention time 1.14 min.

[0799] Example P6: [2-(2,4-difluorophenyl)tetrazol-5-yl]-[6-methoxy-1-methyl-4-(1-methylpyrazole-4- Preparation of

[0147] -3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-34, Table P).

[0800] Step 1: Preparation of (3-methoxyphenyl)-(1-methylpyrazol-4-yl)methanol

[0801]

[0802] 4-iodo-1-methyl-1h-pyrazole (5.14g, 23.5mmol) and tetrahydrofuran (64mL) were loaded into a single-necked round-bottom flask equipped with a magnetic stirring bar. At 0°C, under argon, a solution of isopropylmagnesium chloride lithium chloride complex (1.3mol / L) in THF (25mL, 32.0mmol) was added dropwise. The mixture was stirred at 0°C for 45min, and then, at 0°C under argon, 3-methoxybenzaldehyde (2.68mL, 21.3mmol) was added dropwise. The mixture was stirred at this temperature for 10min, and then it was brought to room temperature and stirred for 2 hours. The reaction mixture was then poured into water (100mL) and extracted with EtOAc (2X80mL). The organic layer merged was washed with salt water, through Na2SO4 and concentrated in vacuo. The crude material was purified by flash chromatography (80 g SiO2, EtOAc / cyclohexane gradient) to give (3-methoxyphenyl)-(1-methylpyrazol-4-yl)methanol.

[0803] LCMS (Method B): m / z 219 [M+H], retention time 0.21 min.

[0804] 1 H NMR (400MHz, CDCl3) δppm: 7.39 (s, 1H), 7.26-7.33 (m, 1H), 7.28 (s, 1H), 6.96 -7.05(m,2H),6.82-6.90(m,1H),5.72-5.88(m,1H),3.84(s,3H),3.82(s,3H)

[0805] Step 2: Preparation of 2-(3-methoxyphenyl)-2-(1-methylpyrazol-4-yl)acetonitrile

[0806]

[0807] A solution of (3-methoxyphenyl)-(1-methylpyrazole-4-yl)methanol (4g, 9.16mmol) in acetonitrile (18mL) was treated with iodine (4.18g, 16.5mmol) and lithium carbonate (0.13g, 1.83mmol), and then trimethylsilyl cyanide (5.26mL, 41.2mmol) was added dropwise at room temperature. The resulting mixture was stirred at 50°C for 8 hours. The reaction mixture was then cooled to room temperature and poured into a saturated solution of sodium thiosulfate (400mL) and extracted with EtOAc (2X100mL). The combined organic layers were washed with brine, dried over Na2SO4 and concentrated in vacuo. The crude product was purified by silica gel chromatography to obtain 2-(3-methoxyphenyl)-2-(1-methylpyrazole-4-yl)acetonitrile.

[0808] LCMS (Method B): m / z 228 [M+H], retention time 1.00 min.

[0809] 1 H NMR (400MHz, CDCl3) δppm 7.41(s,1H),7.27-7.37(m,2H),6.87-6.99(m,3H),5.06(s,1H),3.89(s,3H),3.83(s,3H)

[0810] Step 3: Preparation of 2-(3-methoxyphenyl)-2-(1-methylpyrazol-4-yl)ethylamine

[0811]

[0812] At room temperature under argon, a solution of 2-(3-methoxyphenyl)-2-(1-methylpyrazole-4-yl)acetonitrile (3.2g, 14mmol) in tetrahydrofuran (42mL) was treated dropwise with borane dimethyl sulfide complex (4.0mL, 42mmol). The resulting yellow solution was stirred at 65°C for 3 hours, and then cooled to 0°C, and then hydrochloric acid 6M (9.4mL, 4.0, 57mmol) was added dropwise (strong gas evolution!). The reaction mixture was then stirred at 50°C for 1 hour, and then allowed to cool to room temperature. The reaction mixture was diluted with water, and then basified to pH 12 with NaOH 6N. 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 obtain 2-(3-methoxyphenyl)-2-(1-methylpyrazole-4-yl)ethylamine as a brown oil, which can be used as is for further chemical reactions.

[0813] LCMS (Method B): m / z 232 [M+H], retention time 0.36 min.

[0814] 1 H NMR(400MHz,DMSO-d6)δppm 7.52(s,1H),7.29(s,1H),7.20(t,J=7.44Hz,1H),6.72-6.87(m,3H),3.77(s,3H),3.80(m,1H),3.73(s,3H),3.42(s,1H)3.03-2.99(m,2H).

[0815] Step 4: Preparation of 6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline

[0816]

[0817] Into a 25mL round-bottom flask equipped with a magnetic stirring bar, 2-(3-methoxyphenyl)-2-(1-methylpyrazole-4-yl)ethylamine (80g, 0.34mmol), hydrochloric acid 37% (1.7mL) and acetaldehyde (0.19mL, 3.46mmol) were charged. The mixture was stirred at room temperature for 3 hours, and then slowly poured into water and neutralized with saturated NaHCO3 aqueous solution (strong gas evolution) until pH 8. The mixture was extracted with EtOAc, and the combined organic layers were washed with brine, dried with Na2SO4, and concentrated in vacuo to obtain the title compound.

[0818] LCMS (Method B): m / z 258 [M+H], retention time 0.19 min.

[0819] Step 5: [2-(2,4-difluorophenyl)tetrazol-5-yl]-[6-methoxy-1-methyl-4-(1-methylpyrazole-4-yl)- Preparation of

[0147] -3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-34, Table P).

[0820]

[0821] 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 stirred at room temperature overnight. The mixture was diluted with water and EtOAc, and the organic layer was removed. The aqueous layer was then stripped three times using EtOAc, and the combined organic layers were dried over Na2SO4, 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-methylpyrazole-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.

[0822] The racemic mixture was further purified by chiral phase chromatography, where the major cis isomer was isolated:

[0823] Chiralpak-IG (250x20mm; 5μm), mobile phase A: TBME (97%), mobile phase B: EtOH (3%) isocratic, flow rate: 17mL / min, DAD detection: DAD, run time: 40min, sample preparation: 350mg, in 6mL EtOH + 4mL TBME, the cis isomer was obtained in the form of rotational isomers.

[0824] 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)

[0825]

[0826] LCMS (Method D): m / z 466 [M+H], retention time 1.50 min.

[0827] 1H NMR (400 MHz, CDCl3) δ ppm (rotamer ratio 65:35) 7.87-7.97 (m, 1H), 7.39-7.43 (m, 1H), 7.31 (s, 1H), 7.11-7.20 (m, 3H), 6.84 (dd, J = 8.57, 2.19 Hz, 1H), 6.60 (d, J = 2.50 Hz, 1H), 5.85 (q, J = 6.67 Hz, 1H), 4.47 (dd, J = 11.63, 5.13 Hz, 1H), 4.25-4.37 (m, 1H), 3.91 (s, 3H), 3.71 (s, 3H), 3.53 (dd, J = 13.6, 11.7 Hz, 1H), 1.68 (d, J = 6.75 Hz, 3H)

[0828] 19 F NMR(376MHz, CDCl3)δ-103.71(s,1F),-115.07(s,1F)

[0829] 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)

[0830]

[0831] LCMS (Method D): m / z 466 [M+H], retention time 1.50 min.

[0832] NMR is identical to isomer 1

[0833] Example P7: [6-methoxy-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]- Preparation of (2-phenyltetrazolyl-5-yl)methanone (Compound P-35, Table P)

[0834] Prepared similarly to Example 5. Thus, 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% by mass) in EtOAc (4.08 g, 3.78 mL, 6.41 mmol) was stirred overnight at room temperature in ethyl acetate (11 mL). After this time, LCMS showed product formation. 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 afford diastereomeric mixture of the title compound as a white solid (cis:trans ratio 63:37).

[0835] The racemic mixture was further purified by column: Chiral pak-IG (250x20mm; 5μm), mobile phase A: TBME (80%), mobile phase B: EtOH (20%) isocratic, flow rate: 17mL / min, DAD detection: DAD, run time: 45min, sample preparation: 580mg, in 10mL EtOH+4mL THF+1mL TBME, the cis isomer was obtained in the form of rotamers.

[0836] 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)

[0837]

[0838] LCMS (Method D): m / z 430 [M+H], retention time 1.50 min.

[0839] 1H NMR (400 MHz, CDCl3) δ ppm (rotamer ratio 64:36) 8.16-8.22 (m, 2H), 7.53-7.62 (m, 3H), 7.40-7.44 (m, 1H), 7.32 (s, 1H), 7.12-7.20 (m, 1H), 6.84 (dd, J=8.57, 2.19 Hz, 1H), 6.58 -6.61(m,1H),5.89-5.80(m,1H),4.47(dd,J=11.57,5.19Hz,1H),4.33-4.40(m,1H) ,3.91(s,3H),3.72(s,3H),3.53(dd,J=13.63,11.76Hz,1H),1.68(d,J=6.75Hz,3H)

[0840] 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)

[0841]

[0842] LCMS (Method D): m / z 430 [M+H], retention time 1.50 min.

[0843] 1 H NMR (400 MHz, CDCl3) δ ppm (rotamer ratio 61:39) 8.16-8.22 (m, 2H), 7.53-7.62 (m, 3H), 7.40-7.44 (m, 1H), 7.32 (s, 1H), 7.12-7.20 (m, 1H), 6.84 (dd, J=8.57, 2.19 Hz, 1H), 6.58 -6.61(m,1H),5.89-5.80(m,1H),4.47(dd,J=11.57,5.19Hz,1H),4.33-4.40(m,1H) ,3.91(s,3H),3.68(s,3H),3.53(dd,J=13.63,11.76Hz,1H),1.68(d,J=6.75Hz,3H).

[0844] Further examples of synthesized compounds of formula (I) are shown in Table P.

[0845] Table P: Synthesized compounds with spectroscopic and physicochemical data.

[0846]

[0847]

[0848]

[0849]

[0850]

[0851]

[0852]

[0853]

[0854]

[0855]

[0856]

[0857] Example B1: Alternaria solani / tomato / leaf disc (early blight)

[0858] Tomato leaf disks cultivar Baby were placed on agar in a multiwell plate (24-well format) and sprayed with the prepared test compound diluted in water. After application for 2 days, the leaf disks were inoculated with a spore suspension of fungi. In a climate chamber under a light scheme of 12 / 12h (light / darkness), the leaf disks inoculated were incubated at 23°C / 21°C (day / night) and 80% rh, and the activity of the compound was assessed as the disease control percentage compared to untreated when appropriate levels of disease damage occurred on untreated inspection leaf disks (after application for 5-7 days).

[0859] The following compounds gave at least 80% control of Alternaria solani at 200 ppm when compared to untreated controls which showed extensive disease development under the same conditions:

[0860] P-14, P-31, P-41, P-42, P-43, P-48, P-49, P-51, P-53, P-54, P-56, P-57

[0861] Example B2: Botryotiniafuckeliana or Botrytiscinerea / Liquid culture (Botryotiniafuckeliana or Botrytiscinerea mildew)

[0862] Fungal conidia from frozen storage were directly mixed into nutrient broth (Vogels broth). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient broth 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.

[0863] The following compounds gave at least 80% control of Botrytis cinerea at 20 ppm when compared to untreated controls which showed extensive disease development under the same conditions:

[0864] 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

[0865] Example B3: Melon small bush shell / liquid culture (anthracnose)

[0866] The fungal conidia from frozen storage were directly mixed into the nutrient broth (PDB-potato dextrose broth). After the (DMSO) solution of the test compound was placed in a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. The test plate was incubated at 24°C and the inhibition of growth was measured photometrically 3-4 days after application.

[0867] The following compounds gave at least 80% control of Melon Bushworm at 20 ppm when compared to untreated controls which showed extensive disease development under the same conditions:

[0868] 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

[0869] Example B4: Blumeria graminis f. sp. tritici (Wheat Powdery Mildew (Erysiphegraminis f.sp.tritici) / wheat / leaf disc preventive (powdery mildew on wheat)

[0870] 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, leaf disks were inoculated by shaking powdery mildew infected plants over these test plates. Inoculated leaf disks were incubated at 20° C. and 60% rh in a climate chamber under a light regime 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).

[0871] 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:

[0872] P-37, P-42, P-43, P-48, P-49, P-51, P-53, P-54, P-56

[0873] Example B5: Fusarium erythrorhizium / liquid culture (head blight)

[0874] The fungal conidia from frozen storage were directly mixed into the nutrient broth (PDB-potato dextrose broth). After the (DMSO) solution of the test compound was placed in a microtiter plate (96-well format), the nutrient broth containing the fungal spores was added. The test plate was incubated at 24°C and the inhibition of growth was determined photometrically 3-4 days after application.

[0875] The following compounds gave at least 80% control of Fusarium oxysporum at 20 ppm when compared to untreated controls showing extensive disease development under the same conditions:

[0876] P-42, P-43, P-48, P-53, P-54

[0877] Example B6: Corn Gibberellic acid (Fusarium graminearum) / Wheat / Spikelet Preventive (Fusarium graminearum)

[0878] Wheat spikelet cultivar Amber is placed on agar in a multiwell plate (24-well format) and sprayed with the prepared test compound diluted in water. One day after application, the spikelet is inoculated with a spore suspension of the fungus. In a climate chamber, under a light scheme of 12h illumination / 12h darkness followed by 72h semi-darkness, the inoculated test leaf disks are incubated at 20°C and 60% rh, and the activity of the compound is evaluated as the disease control percentage when compared with the untreated spikelet when the appropriate level of disease damage occurs (6-8 days after application).

[0879] The following compounds gave at least 80% control of Gibberella zeae at 200 ppm when compared to untreated controls which showed extensive disease development under the same conditions:

[0880] P-54

[0881] Example B7: Phaeosphaerianodorum, Septorianodorum / wheat / leaf disc Prevention (glume blight)

[0882] 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. 2 days after application, the leaf disks were inoculated with a spore suspension of the fungus. The inoculated test leaf disks 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 the appropriate level of disease damage appeared on the untreated test leaf disks (5-7 days after application).

[0883] The following compounds gave at least 80% control of Septoria nodosum at 200 ppm when compared to untreated controls which showed extensive disease development under the same conditions:

[0884] 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

[0885] Example B8: Thielavia nivalis (nival leaf blight) / liquid culture (cereal root rot)

[0886] Fungal conidia from frozen storage were directly mixed into nutrient broth (PDB-potato dextrose broth). After the (DMSO) solution of the test compound was placed in a microtiter plate (96-well format), the nutrient broth 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.

[0887] The following compounds gave at least 80% control of Thielavia nivalis at 20 ppm when compared to untreated controls showing extensive disease development under the same conditions:

[0888] 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

[0889] Example B9: Mycosphaerella arachidis (Mycosphaerella arachidis) (Cercosporaarachidicola)) / Liquid culture (early leaf spot)

[0890] Fungal conidia from frozen storage were directly mixed into nutrient broth (PDB-potato dextrose broth). After the (DMSO) solution of the test compound was placed in a microtiter plate (96-well format), the nutrient broth 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.

[0891] The following compounds gave at least 80% control of Mycosphaeria arachidis at 20 ppm when compared to untreated controls which showed extensive disease development under the same conditions:

[0892] 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

[0893] Example B10: Puccinia recondita f. sp. tritici / wheat / leaf disc treatment Method (Brown Rust)

[0894] 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 compound diluted in water was applied. The leaf segments were incubated at 19°C and 75% rh in a climate chamber under a light regime of 12h light / 12h dark, and the activity of the compound was assessed as the percentage of disease control compared to the untreated when the appropriate level of disease damage appeared on the untreated test leaf segments (6-8 days after application).

[0895] The following compounds gave at least 80% control of Puccinia reconditatis of wheat at 200 ppm when compared to untreated controls showing extensive disease development under the same conditions:

[0896] P-42

[0897] Example B11: Puccinia recondita f. sp. tritici / wheat / leaf disc prevention Sex (Brown Rust)

[0898] 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 disks 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).

[0899] The following compounds gave at least 80% control of Puccinia reconditatis of wheat at 200 ppm when compared to untreated controls showing extensive disease development under the same conditions:

[0900] P-37, P-41, P-42, P-49

[0901] Example B12: Pyricularia terrestris / barley / leaf disc preventive (net spot)

[0902] Barley leaf segments cv. Hasso are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. 2 days after application, the leaf segments are inoculated with a spore suspension of the fungus. The inoculated leaf segments are incubated at 20°C and 65% rh in a climate chamber under a light regime of 12h light / 12h dark, and the activity of the compound is assessed as disease control compared to the untreated when an appropriate level of disease damage appears on the untreated test leaf segments (5-7 days after application).

[0903] The following compounds gave at least 80% control of Pyricularia terrestris at 200 ppm when compared to untreated controls which showed extensive disease development under the same conditions:

[0904] 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

[0905] Example B13: Sclerotinia sclerotiorum / liquid culture (cotton rot)

[0906] Mycelial fragments of freshly grown liquid cultures of the fungus are mixed directly into nutrient broth (PDB (potato dextrose broth)). After placing a (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal material is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3-4 days after application.

[0907] The following compounds gave at least 80% control of Sclerotinia sclerotiorum at 20 ppm when compared to untreated controls showing extensive disease development under the same conditions:

[0908] P-42, P-48.

[0909] Example B14: Mycosphaeria graminearum (Septoria graminearum) / liquid culture (Septoria blotch)

[0910] Fungal conidia from frozen storage were directly mixed into nutrient broth (PDB-potato dextrose broth). After the (DMSO) solution of the test compound was placed in a microtiter plate (96-well format), the nutrient broth 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.

[0911] The following compounds gave at least 80% control of Mycosphaeria graminearum at 20 ppm when compared to untreated controls which showed extensive disease development under the same conditions:

[0912] 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

Claims

1. A compound having formula (I): in in R 1 Selected from hydrogen, C1-C 4- Alkyl, C2-C 4- alkenyl, C2-C4-alkynyl, or C3-C6 cycloalkyl; R 2 Selected from hydrogen, halogen, C1-C 4- Alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C3-C6 cycloalkyl, C1-C 4- Alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimino, N-hydroxy-C-C1-C4 alkyl-carbonimino, or C1-C 4- Alkoxycarbonyl; R 3 and R 4 independently selected from hydrogen, halogen, or C1-C4-alkyl; R 5 and R 6 Independently selected from hydrogen, or C1-C4 alkyl; R 7 is selected from hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimino, N-hydroxy-C-C1-C4 alkyl-carbonimino, C1-C4 alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4 alkylaminocarbonyl, di(C1-C6 alkylamino)carbonyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- or 6-membered heteroaryl includes 1, 2, 3, or 4 individual wherein the phenyl and 5- to 6-membered heteroaryl groups are unsubstituted or substituted by 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, cyano, carboxyl, C1-C4 alkyl, or C1-C4 alkoxy; and wherein the C3-C6-cycloalkyl group is unsubstituted or substituted by 1, 2, or 3 substituents independently selected from halogen, C1-C4 haloalkyl, cyano, C1-C4 alkyl, or C1-C4 alkoxy; B 1 Selected from CR 10 , or N; B 2 Selected from CR 11 , or N; R 8 , R 9 , R 10 and R 11 independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, NC 1-4 Alkylamino, N,N-diC 1-4 Alkylamino, C1-C6 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimino, N-hydroxy-C1-C4 alkyl-carbonimino, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxyl, amino, phenyl, 5- or 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, 5- to 6-membered heteroaryl, and C3-C6-cycloalkyl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy; A 1 Selected from CR 12a , or N, A 2 Selected from CR 13a , or N; A 3 Selected from CR 14a , or N; R 12a , R 13a and R 14a are independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, or C2-C4 alkynyl; and Z 1 is selected from C1-C4 alkyl, phenyl, 5- or 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, 5- or 6-membered heteroaryl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, or C2-C4 alkynyl and wherein the C3-C6 cycloalkyl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy; or an agrochemically acceptable salt, stereoisomer or N-oxide thereof.

2. The compound of formula (I) according to claim 1, wherein R 1 is methyl; and wherein R 2 is selected from hydrogen or methyl.

3. A compound of formula (I) according to claim 1 or claim 2, wherein R 3 is hydrogen; and R 4 is selected from hydrogen or methyl.

4. A compound of formula (I) according to any one of claims 1 to 3, wherein R 5 and R 6 are independently selected from hydrogen or methyl.

5. A compound of formula (I) according to any one of claims 1 to 4, wherein R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl.

6. A compound of formula (I) according to any one of claims 1 to 5, wherein A 1 Selected from CR 12a or N; A 2 Selected from CR 13a or N; A 3 Selected from CR 14a or N; where A 1 , A 2 and A 3 At least two of them are selected from N; and wherein R 12a , R 13a , and R 14a It's hydrogen.

7. A compound of formula (I) according to any one of claims 1 to 6, wherein B 1 Yes CR 10 ; and B 2 Yes CR 11 .

8. A compound of formula (I) according to any one of claims 1 to 7, wherein R 8 and R 9 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; and R 10 and R 11 Independently selected from hydrogen, halogen, C1-C3 alkyl, or C1-C4 alkoxy.

9. The compound of formula (I) according to claim 8, wherein R 10 and R 11 It's hydrogen.

10. A compound of formula (I) according to any one of claims 1 to 9, wherein The compound having formula (I) is a compound having formula (II): Where 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 is as defined for a compound of formula (I) according to 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 bond to a Z 1 The nitrogen of the bond of the group, and wherein R 12a , R 13a and R 14a are independently selected from hydrogen, halogen, methyl, cyclopropyl, or trifluoromethyl.

11. The compound of formula (II) according to claim 10, wherein A is selected from in indicates a bond to a C(=O) group, and an asterisk (*) indicates a bond to a Z 1 The nitrogen of the bond of the group.

12. A compound of formula (I) according to any one of claims 1 to 11, wherein Z 1 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.

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

14. 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 said compound of formula (I) is applied to these plants, parts thereof or the locus thereof.

15. Use of a compound according to any one of claims 1 to 12 as a fungicide.

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