Microbiocidal tetrahydroisoquinoline derivatives

Abstract

A compound of formula (I) wherein the substituents are as defined in claim 1 and 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 tetrahydroisoquinoline derivatives, for example as active ingredients, which have microbicidal activity, especially fungicidal activity. The present invention also relates to the preparation of these tetrahydroisoquinoline derivatives, to intermediates useful in the preparation of these tetrahydroisoquinoline derivatives, to the preparation of these intermediates, to agrochemical compositions comprising at least one of these tetrahydroisoquinoline derivatives, to the preparation of these compositions and to the use of these tetrahydroisoquinoline derivatives or compositions in agriculture or horticulture for controlling or preventing the infestation of plants, harvested food crops, seeds or inanimate materials by phytopathogenic microorganisms, especially fungi.

[0002] According to a first aspect of the present invention, there is provided a compound of formula (I) or an agrochemically acceptable salt, stereoisomer, or N-oxide thereof,

[0003]

[0004] wherein,

[0005] Q is selected from 5- or 6-membered heteroaryl, wherein any one of said 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that not more than one is O or S; and wherein any one of said heteroaryl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C 4- alkyl, C1-C4-haloalkyl, or C3-C6-cycloalkyl;

[0006] R 1 is selected from hydrogen, halogen, C1-C4-haloalkyl, C3-C6-cycloalkyl, or C1-C4-alkyl;

[0007] R 2 and R 3 are independently selected from hydrogen, or C1-C4-alkyl;

[0008] R 4 is selected from hydrogen, C1-C4-alkyl, C1-C4-alkylcarbonyl, N-C1-C4-alkoxy-C-C1-C4alkyl-carbimino, N-hydroxy-C-C1-C 4-alkyl-carbonimino, C1-C4-alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4-alkylaminocarbonyl, di(C1-C4-alkyl)aminocarbonyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that no more than one is O or S; wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, carboxyl, or C1-C4-alkoxy; 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;

[0009] B 1 selected from CR 7 or N;

[0010] B 2 selected from CR 8 or N;

[0011] R 5 R 6 R 7 and R 8 are 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-alkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-alkoxy-C1-C4-alkyl, N-C1-C4-alkylamino, N,N-di(C1-C4-alkyl)amino, C1-C4-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 contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that no more than one is O or S; and wherein any one 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;

[0012] A 1 A 2 A 4 are independently selected from methylene, N, NR 10, O, or S, provided that A 1 , A 2 and A 4 at least one of which is selected from N, O or S, and A 1 , A 2 and A 4 no more than one of which is O or S, wherein R 10 is selected from hydrogen or C1-C4-alkyl;

[0013] A 3 is C or N, provided that when A 3 is N, A 1 , A 2 and A 4 is methylene, N or NR 10 , wherein R 10 is selected from hydrogen or C1-C4-alkyl; and

[0014] Z 1 is selected from C1-C4-alkyl, phenyl, 5- or 6-membered heteroaryl, or C3-C6-cycloalkyl, wherein any one of the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that no more than one is O or S; wherein any one of the phenyl, and 5- or 6-membered heteroaryl is unsubstituted or substituted by 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-alkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, or C2-C4-alkynyl; and wherein the C3-C6-cycloalkyl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, or C1-C4-alkoxy,

[0015] provided that the compound having formula (I) is not

[0016]

[0017]

[0018]

[0019] or its agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide.

[0020] The PubChem Compound ID given for each of the compounds excluded above refers to the identification number of each compound on the PubChem website https: / / pubchem.ncbi.nlm.nih.gov / for each compound.

[0021] Surprisingly, it has been found that, for practical purposes, the compounds of formula (I) have a very advantageous level of biological activity for protecting plants against diseases caused by fungi.

[0022] According to a second aspect of the invention, there is provided an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) according to the invention. Such an agricultural composition may further comprise at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

[0023] According to a third aspect of the invention, there is provided a method for controlling or preventing useful plants from being infested by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I) according to the invention, or a composition comprising the compound of formula (I), is applied to these plants, parts thereof or their sites.

[0024] According to a fourth aspect of the invention, there is provided the use of a compound of formula (I) or an agrochemically acceptable salt, stereoisomer or N-oxide thereof as a fungicide,

[0025]

[0026] Herein,

[0027] Q is selected from 5- or 6-membered heteroaryl, wherein any one of the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that not more than one is O or S; and wherein any one of the heteroaryl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C 4- alkyl, C1-C4-haloalkyl, or C3-C6-cycloalkyl;

[0028] R 1 is selected from hydrogen, halogen, C1-C4-haloalkyl, C3-C6-cycloalkyl, or C1-C4-alkyl;

[0029] R 2 and R 3 are independently selected from hydrogen, or C1-C4-alkyl;

[0030] R 4 is selected from hydrogen, C1-C4-alkyl, C1-C4-alkylcarbonyl, N-C1-C4-alkoxy-C-C1-C4alkyl-carbimino, N-hydroxy-C-C1-C 4-alkyl-carbonimino, C1-C4-alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4-alkylaminocarbonyl, di(C1-C4-alkyl)aminocarbonyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that no more than one is O or S; wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, carboxyl, or C1-C4-alkoxy; 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;

[0031] B 1 selected from CR 7 、or N;

[0032] B 2 selected from CR 8 、or N;

[0033] R 5 、R 6 、R 7 and R 8 are 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-alkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-alkoxy-C1-C4-alkyl, N-C1-C4-alkylamino, N,N-di(C1-C4-alkyl)amino, C1-C4-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 contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that no more than one is O or S; and wherein any one 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;

[0034] A 1 、A 2 、A 4 are independently selected from methylene, N, NR 10 、O, or S, provided that A1 and at least one of A 2 and A 4 is selected from N, NR 10 , O or S, and A 1 and A 2 and A 4 has no more than one being O or S, where R 10 is selected from hydrogen or C1-C4 alkyl;

[0035] A 3 is C or N, provided that when A 3 is N, A 1 and A 2 and A 4 is methylene, N or NR 10 , where R 10 is selected from hydrogen or C1-C4 alkyl; and

[0036] Z 1 is selected from C1-C4 alkyl, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl, where the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that no more than one is O or S; where any one of the phenyl, 5- or 6-membered heteroaryl is unsubstituted or substituted by 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 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, or C2-C4 alkynyl, and where the C3-C6 cycloalkyl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy.

[0037] According to this particular aspect of the invention, the use may exclude methods of treating the human or animal body by surgery or therapy and diagnostic methods practiced on the human or animal body.

[0038] Compounds of formula (I) having at least one basic center can, for example, form acid addition salts with, for example: 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 halogen-substituted C1-C4 alkanoic 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 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 salts, potassium salts 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).

[0039] In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form (such as N-oxides) or in salt form (for example in the form of an agrochemically acceptable salt).

[0040] N-oxides are the oxidized form of tertiary amines or 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.

[0041] The compounds of formula (I) according to the invention also include the hydrates that may form during salt formation.

[0042] When a substituent is indicated as being “optionally substituted”, this means that it may or may not carry one or more identical or different substituents, for example one, two or three R x Substituents. For example, C1-C6 alkyl substituted by 1, 2 or 3 halogens can include, but are not limited to, the groups -CH2Cl, -CHCl2, -CCl3, -CH2F, -CHF2, -CF3, -CH2CF3, or -CF2CH3. As another example, C1-C6 alkoxy substituted by 1, 2 or 3 halogens can include, but are not limited to, the groups CH2ClO-, CHCl2O-, CCl3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O-, or CH3CF2O-.

[0043] As used herein, the term "halogen" or "halo" means fluorine, chlorine, bromine, or iodine, preferably fluorine, chlorine, or bromine. This also applies correspondingly to halogens in combination with other meanings, such as haloalkyl, haloalkenyl, haloalkynyl, haloalkoxy, and halocycloalkyl.

[0044] As used herein, amino means the -NH2 group.

[0045] As used herein, cyano means the -CN group.

[0046] As used herein, the term "hydroxyl" or "hydroxy" means the -OH group.

[0047] As used herein, the term "carboxylic acid" means the -COOH group.

[0048] As used herein, the term "C1-C n -alkyl" refers to a saturated straight-chain 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.

[0049] As used herein, the term "C2-C n -alkenyl" refers to a straight-chain or branched alkenyl chain moiety having two to n carbon atoms and one or two double bonds, such as vinyl, prop-1-enyl, but-2-enyl.

[0050] As used herein, the term "C2-C n -alkynyl" refers to a straight-chain or branched alkynyl chain moiety having two to n carbon atoms and one triple bond, such as ethynyl, prop-2-ynyl, but-3-ynyl.

[0051] As used herein, the term "C3-C n -cycloalkyl" refers to a three (3)- to n-membered cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0052] As used herein, the term "C1-C n -alkoxy" refers to a straight-chain or branched-chain saturated alkyl group having one (1) to n carbon atoms attached via an oxygen atom (as mentioned above), 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-chain or branched-chain alkenyl chain having two (2) to n carbon atoms attached via an oxygen atom (as mentioned above).

[0053] As used herein, the term "C1-C n -alkoxy-C1-C n -alkyl" refers to an alkyl group substituted with C1-C n -alkoxy (as mentioned above). Examples are methoxymethyl, methoxyethyl, ethoxymethyl, and propoxymethyl.

[0054] As used herein, the term "C3-C n -cycloalkyl-C1-C n -alkyl" refers to an alkyl group substituted with C3-C n -cycloalkyl (as mentioned above). Examples are cyclopropylmethyl and cyclopropylethyl. Similarly, the term "C3-C n -halocycloalkyl-C1-C n -alkyl" refers to an alkyl group substituted with a cycloalkyl group, wherein the cycloalkyl group is substituted with one or more identical or different halogen atoms. Examples are 3,3-difluorobutylmethyl and 1-chlorocyclopropylmethyl.

[0055] As used herein, the term "C1-C n"-Halogenoalkyl" means a straight-chain or branched-chain saturated alkyl group having from 1 to n carbon atoms attached via any one of the carbon atoms (as mentioned above), 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 one of the following groups: 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 mean a C1-C2 alkyl group bearing 1, 2, 3, 4, or 5 fluorine atoms, such as any one of the following groups: 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 -halogenoalkenyl" or "C2-C n -halogenoalkynyl" refers respectively to a C2-C n -alkenyl or C2-C n -alkynyl substituted by one or more halogen atoms which may be the same or different. Similarly, as used herein, the term "C3-C n -halogenocycloalkyl" or "C1-C n -halogenoalkoxy" refers respectively to a C3-C n -cycloalkyl or C1-C n -alkoxy substituted by one or more halogen atoms which may be the same or different.

[0056] As used herein, the term "C1-C n -alkylthio" or "C1-C n -alkylsulfanyl" means a C1-C n -alkyl group linked via a sulfur atom.

[0057] As used herein, the term "C1-C n -halogenoalkylthio" or "C1-C n -halogenoalkylsulfanyl" means a C1-Cn Halogenated alkyl group.

[0058] As used herein, the term "C1-C n -alkylsulfinyl" refers to a C1-C alkyl group attached through the sulfur atom of a sulfinyl (or S(=O)-) group. n alkyl group.

[0059] As used herein, the term "C1-C n -alkylsulfonyl" refers to a C1-C alkyl group attached through the sulfur atom of a sulfonyl (or S(=O)2-) group. n alkyl group.

[0060] As used herein, the term "C1-C n -alkylsulfonyl-C1-C n -alkyl" refers to a C1-C alkyl group substituted with a C1-C n alkylsulfonyl group. n alkyl group.

[0061] As used herein, the term "C1-C n -alkylcarbonyl" refers to a C1-C alkyl group attached through the carbon atom of a carbonyl (C=O) group. n -alkyl group.

[0062] As used herein, the term "C1-C n -alkoxycarbonyl" refers to a C1-C alkoxy moiety attached through the carbon atom of a carbonyl (or C=O) group. n -alkoxy moiety.

[0063] As used herein, the term "C1-C n -alkoxycarbonyl-C1-C n -alkyl" refers to a C1-C alkyl group substituted with a C1-C n -alkoxycarbonyl group. n -alkyl group.

[0064] As used herein, the term "benzoyl" refers to a phenyl group attached through the carbon atom of a carbonyl (C=O) group.

[0065] As used herein, the term "C1-C n -haloalkoxycarbonyl" refers to a C1-C haloalkoxy group attached through the carbon atom of a carbonyl (C=O) group. n -haloalkoxy group.

[0066] As used herein, the term "C2-C n -alkenyloxycarbonyl" refers to a C2-C alkenyloxycarbonyl group attached through the carbon atom of a carbonyl (C=O) group. n -alkenyloxycarbonyl group.

[0067] As used herein, the term "C1-C n -alkylaminocarbonyl" refers to a group having the formula R a NHC(=O)- that is attached through the carbon atom of the carbonyl (C=O) group, where R a is C1-C n -alkyl as generally defined above.

[0068] As used herein, the term "di(C1-C n alkyl)aminocarbonyl" refers to a group having the formula R a NR b C(=O) that is attached through the carbon atom of the carbonyl (C=O) group, where R a is C 1- C n alkyl as generally defined above, and R b is C 1- C n alkyl as generally defined above.

[0069] As used herein, the term "N-C1-C n alkylamino" refers to a group having the formula -NH-R a where R a is C1-C n alkyl as defined above.

[0070] As used herein, the term "N,N-di(C1-C n alkyl)amino" refers to a group having the formula -N(R a )R a where each R a is C1-C n alkyl as defined above, which may be the same or different.

[0071] As used herein, the term "C1-C n -alkylcarbonyloxy-C1-C n -alkyl" refers to a C1-C n -alkyl that is substituted with a C1-C a -alkylcarbonyloxy (or R n C(=O)O-) group, where R a is C1-C n -haloalkyl.

[0072] As used herein, the term "C1-C n -alkoxycarbonyloxy-C1-C n -alkyl" refers to a C1-C n -alkyl that is substituted with a C1-C c -alkoxycarbonyloxy (or Rn -alkyl, where R c is C1-C n -alkoxy. The C1-C n -alkoxy attached to nitrogen may be substituted.

[0073] As used herein, the term "N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimino" refers to a group having the formula -C(R a )=NO(R b ), where R a is C 1- C4 alkyl as generally defined above, and R b is C 1- C4 alkyl as generally defined above.

[0074] As used herein, the term "N-hydroxy-C-C1-C4 alkyl-carbonimino" refers to a group having the formula -C(R a )=NOH, where R a is C 1- C4 alkyl as generally defined above.

[0075] As used herein, the term "aminocarbonyl-C1-C n -alkyl" refers to a C1-C n -alkyl substituted by an aminocarbonyl (or NH2C(=O)-) group.

[0076] As used herein, the term "C1-C n -alkylaminocarbonyl-C1-C n -alkyl" refers to a C1-C n -alkyl substituted by a C1-C a -alkylaminocarbonyl (or R n NHC(=O)-) group, where R a is C1-C n -alkyl. The C1-C n -alkyl attached to nitrogen may be substituted.

[0077] 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, furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidinyl, or pyridyl. The term "heteroaryl-C1-C n -alkyl" or "heteroaryl-C3-C n -cycloalkyl" refers to a C1-C n -alkyl or C3-Cn -cycloalkyl. Heteroaryl-C1-C n -alkyl or heteroaryl-C3-C n -cycloalkyl may optionally be substituted on the heteroaryl, alkyl, and / or cycloalkyl.

[0078] As used herein, the term "control" means reducing the number of pests, eliminating pests, and / or preventing further pest damage such that damage to the plant or to plant-derived products is reduced.

[0079] As used herein, the term "pest" means insects and mollusks present in agriculture, horticulture, forestry, and the storage of plant-derived products (such as fruits, grains, and wood); and those pests associated with damage to man-made structures. The term pest encompasses all stages of the pest life cycle.

[0080] As used herein, the term "effective amount" means the amount of a compound or its salt that provides the desired effect upon single or multiple applications.

[0081] The effective amount is readily determined by those skilled in the art using known techniques and by observing the results obtained in 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 treated; the pest to be controlled and its life cycle; the particular compound to be applied; the type of application; and other relevant circumstances.

[0082] As used herein, the term "room temperature" or "RT" or "rt" means a temperature of from about 15°C to about 35°C. For example, rt can mean a temperature of from about 20°C to about 30°C.

[0083] The following list provides definitions for the substituents R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , B 1 , B 2 , A 1 , A 2 , A 3 , A 4 , Q 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.

[0084] In one embodiment of the invention, R 1Selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, or C3-C6 cycloalkyl. Preferably, R 1 is hydrogen, chlorine, bromine, fluorine, methyl, ethyl, trifluoromethyl, difluoromethyl, or cyclopropyl. More preferably, R 1 is hydrogen, chlorine, bromine, or methyl. Even more preferably, R 1 is hydrogen, or methyl. Most preferably, R 1 is hydrogen. In one embodiment of the present invention, R 1 is hydrogen. In another embodiment of the present invention, R 1 is methyl.

[0085] In one embodiment of the present invention, R 2 and R 3 are independently selected from hydrogen, or C1-C4-alkyl. Preferably, R 2 and R 3 are independently selected from hydrogen, methyl, or ethyl. More preferably, R 2 and R 3 are independently selected from hydrogen, or methyl. Even more preferably, R 2 and R 3 are hydrogen.

[0086] In one embodiment of the present invention, R 4 is selected from hydrogen, C1-C4-alkyl, C1-C4-alkylcarbonyl, N-C1-C4-alkoxy-C-C1-C4 alkyl-carbodiimide, N-hydroxy-C-C1-C 4- alkyl-carbodiimide, C1-C4-alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4 alkylaminocarbonyl, di(C1-C4 alkyl)aminocarbonyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that no more than one is O or S; wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, carboxyl, or C1-C4-alkoxy; 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.

[0087] In another embodiment of the present invention, R 4Selected from hydrogen, C1-C4 alkyl, C3-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-C4 alkyl)aminocarbonyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl, wherein the 5- to 6-membered heteroaryl contains 1 heteroatom selected from N and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with 1 to 2 substituents independently selected from halogen, C1-C4 haloalkyl, cyano, or C1-C4 alkyl; and wherein the C3-C6-cycloalkyl is unsubstituted or substituted with 1 substituent selected from cyano. Preferably, R 4 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 4 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 4 Selected from hydrogen, methyl, cyclopropyl, or 1-cyanocyclopropyl.

[0088] In another embodiment, R 4 Selected from hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl. Preferably, R 4 is hydrogen, methyl, ethyl, cyclopropyl, or 1-cyanocyclopropyl. Even more preferably, R 4 is hydrogen, methyl, ethyl, or cyclopropyl.

[0089] In another preferred embodiment, R 4 is hydrogen, or C1-C4 alkyl. Preferably, R 4 is hydrogen, methyl, or ethyl. More preferably, R 4 is hydrogen, or methyl.

[0090] In an embodiment of the present invention, B 1 is CR 7 and B2 is CR 8 , or B 1 is N and B 2 is CR 8 , or B 1 is CR 7 and B 2 is N. Preferably, B 1 is CR 7 and B 2 is CR 7 .

[0091] In one embodiment of the present invention, R 5 and R 6 are 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 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, N-C1-C4 alkylamino, N,N-bis(C1-C4 alkyl)amino, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbodiimide, N-hydroxy-C1-C4 alkyl-carbodiimide, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, amino, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that no more than one is O or S; and wherein any one 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] In one embodiment of the present invention, R 5 and R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy. Preferably, R 5 and R 6 are independently selected from hydrogen, halogen, methyl, methoxy, or cyano. More preferably, R 5 and R 6 are independently selected from hydrogen, methyl, chlorine, fluorine, bromine, or methoxy. Even more preferably, R 5 and R 6 are independently selected from hydrogen, or methoxy.

[0093] In another embodiment of the present invention, R 5 is hydrogen, halogen, or cyano. Preferably, R 5is hydrogen, bromine, chlorine, or cyano. More preferably, R 5 is hydrogen, cyano, or bromine. Even more preferably, R 5 is hydrogen.

[0094] In another embodiment, R 6 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 alkylthio, 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-carbodiimide, N-hydroxy-C-C1-C2 alkyl-carbodiimide, hydroxy, C1-C2 alkylaminocarbonyl, di(C1-C2 alkyl)aminocarbonyl, trifluoromethylsulfonyloxy, cyano, carboxy, 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. Preferably, R 6is hydrogen, chlorine, fluorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, difluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, methoxy, ethoxy, propoxy, allyloxy, prop-2-ynyloxy, methylthio, methylsulfinyl, methylsulfonyl, methoxymethyl, ethoxymethyl, 2-methoxyethoxymethyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, acetyl, propionyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methylaminocarbonyl, bis(methylamino)carbonyl, trifluoromethylsulfonyloxy, cyano, carboxy, 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 6 is hydrogen, chlorine, bromine, fluorine, cyano, 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 6 is hydrogen, chlorine, bromine, cyano, methyl, or methoxy. Most preferably, R 6 is hydrogen, or methoxy.

[0095] In one embodiment of the present invention, R 7 and R 8Independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, N-C1-C4 alkylamino, N,N-bis(C1-C4 alkyl)amino, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbodiimide, N-hydroxy-C1-C4 alkyl-carbodiimide, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, amino, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that no more than one is O or S; wherein any one of the phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy. Preferably, R 7 and R 8 Independently selected from hydrogen, chlorine, fluorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, difluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, methoxy, ethoxy, propoxy, allyloxy, prop-2-ynyloxy, methylthio, methylsulfinyl, methylsulfonyl, methoxymethyl, ethoxymethyl, 2-methoxyethoxymethyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, acetyl, propionyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methylaminocarbonyl, bis(methylamino)carbonyl, trifluoromethylsulfonyloxy, cyano, carboxy, 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 7 and R 8Independently selected from hydrogen, chlorine, bromine, fluorine, cyano, methyl, methoxy, propoxy, allyloxy, methoxymethyl, 2-methoxyethoxymethyl, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, [4-(trifluoromethyl)pyrazol-1-yl], [3-(trifluoromethyl)pyrazol-1-yl], 3-cyanopyrazol-1-yl, 4-cyanopyrazol-1-yl, 5-chloropyrazol-1-yl, 4-chloropyrazol-1-yl, 3-chloropyrazol-1-yl, 5-fluoropyrazol-1-yl, 4-fluoropyrazol-1-yl, 3-fluoropyrazol-1-yl, 3,5-dimethylpyrazol-1-yl, 5-methylpyrazol-1-yl, 4-methylpyrazol-1-yl, 3-methylpyrazol-1-yl, pyrazol-1-yl, C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, cyclopropyl, or 1-cyanocyclopropyl. Even more preferably, R 7 and R 8 are independently selected from hydrogen, chlorine, bromine, or cyano.

[0096] In another embodiment, R 7 and R 8 are independently selected from hydrogen, halogen, C1-C3 alkyl, or C1-C4 alkoxy. Preferably, R 7 and R 8 are independently selected from hydrogen, or halogen. More preferably, R 7 and R 8 are hydrogen, bromine, or chlorine. Even more preferably, R 7 and R 8 are hydrogen.

[0097] In one embodiment of the present invention, A 1 , A 2 , A 4 are independently selected from methylene, N, O or S, provided that at least one of A 1 , A 2 and A 4 is selected from N, O or S, and no more than one of A 1 , A 2 or A 4 is O or S.

[0098] In one embodiment of the present invention, A 3 is C or N, provided that when A 3 is N, A 1 , A 2 and A 4 are methylene or N.

[0099] In one embodiment of the present invention, Z 1Selected from C1-C4 alkyl, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that no more than one is O or S; wherein any one of the phenyl, 5- or 6-membered heteroaryl is unsubstituted or substituted by 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 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, or C2-C4 alkynyl; and wherein the C3-C6 cycloalkyl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy.

[0100] In another embodiment, Z 1 Selected from C1-C4 alkyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- or 6-membered heteroaryl contains 1, 2 or 3 heteroatoms independently selected from N, O or S, provided that no more than one is O or S; wherein any one 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.

[0101] In another embodiment, Z 1 Selected from C1-C4 alkyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N, O or S, 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.

[0102] In still another embodiment, Z 1 Selected from C1-C4 alkyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N; 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.

[0103] 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-methoxyphenyl, 2-fluoro-4-methylsulfonylphenyl, 2-fluorophenyl, 3-fluorophenyl, 4-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, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3-methoxyphenyl, 4-ethynyl-2-fluorophenyl, 4-fluoro-2-methoxyphenyl, cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, n-propyl, or phenyl. More preferably, Z 1 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-methoxyphenyl, 4-fluorophenyl, 4-methylphenyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, or phenyl. Even more preferably, 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-methoxyphenyl, 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.

[0104] In another embodiment of the present invention, Z 1 Selected from C 1- C4 alkyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- or 6-membered heteroaryl contains 1, 2 or 3 heteroatoms independently selected from N, O or S, provided that no more than one is O or S; 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, Z1 selected from phenyl or a 5- to 6-membered heteroaryl; wherein the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N or S; and wherein the phenyl and the 5- to 6-membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from fluorine, chlorine, C1-C4 alkyl, or C1-C4 alkoxy. More preferably, Z 1 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-methoxyphenyl, 4-fluorophenyl, cyclobutyl, cyclohexyl, cyclopentyl, or methyl. Even 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.

[0105] In another embodiment of the present invention, Z 1 selected from phenyl, a 5- to 6-membered heteroaryl, or a C3-C6-cycloalkyl; wherein the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N or S, and wherein the phenyl and the 5- to 6-membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy and wherein the C3-C6-cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen, or C1-C4 alkyl. Preferably, Z 1 selected from phenyl, or a 5- to 6-membered heteroaryl; wherein the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N or S, and wherein the phenyl and the 5- to 6-membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from fluorine, chlorine, C1-C4 alkyl, or C1-C4 alkoxy.

[0106] In a further embodiment of the present invention, Z 1 selected from phenyl or a 5- to 6-membered heteroaryl; wherein the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N, and wherein the phenyl and the 5- to 6-membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from fluorine, chlorine, C1-C4 alkyl, or C1-C4 alkoxy. Preferably, Z1 selected from 1-methylpyrazol-4-yl, 2,3,4-trifluorophenyl, 2,3-difluorophenyl, 3,4-difluorophenyl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2-pyridyl, 2-fluoro-4-methoxyphenyl, 2-fluoro-4-methylsulfonylphenyl, 2-fluorophenyl, 3-fluorophenyl, 4-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, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3-methoxyphenyl, 4-ethynyl-2-fluorophenyl, 4-fluoro-2-methoxyphenyl, cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, n-propyl or phenyl. More preferably, Z 1 selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2-chlorophenyl, 2-fluorophenyl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-fluorophenyl, 3-methylphenyl, 3-thienyl, 4-fluoro-2-methoxyphenyl, 4-fluorophenyl, 4-methylphenyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl or phenyl. Even more preferably, 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-methoxyphenyl, 4-fluorophenyl, cyclobutyl, cyclohexyl, cyclopentyl or phenyl. Even still more preferably, Z 1 selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, 4-fluorophenyl or phenyl.

[0107] In one embodiment of the present invention, Q is selected from 5- or 6-membered heteroaryl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that no more than one is O or S; and wherein the heteroaryl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C 4- alkyl, C1-C4-haloalkyl, or C3-C6 cycloalkyl.

[0108] In another embodiment of the present invention, Q is selected from Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, Q9, Q10, Q11, Q12, Q13, Q14, Q15, or Q16,

[0109]

[0110] and any one of said Q1 to Q16 is unsubstituted or substituted by 1, 2 or 3 substituents selected from C1-C 4- alkyl, halogen, C1-C4-haloalkyl, or C3-C6 cycloalkyl, and wherein R 9 is selected from hydrogen or C1-C4 alkyl, wherein represents the position attached to the tetrahydroisoquinoline moiety.

[0111] In a preferred embodiment of the present invention, Q is selected from Q1, Q2, Q3, Q4, Q6, Q7, Q9, Q10, Q11, Q12, Q14, or Q16,

[0112]

[0113] wherein any one of said Q-groups is unsubstituted or substituted by 1, 2 or 3 substituents selected from C1-C 4- alkyl, halogen, C1-C4-haloalkyl, or C3-C6 cycloalkyl, and wherein R 9 is selected from hydrogen or C1-C4 alkyl,

[0114] wherein represents the position attached to the tetrahydroisoquinoline moiety.

[0115] In a more preferred embodiment of the present invention, Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12, or Q16,

[0116]

[0117] wherein any one of said Q-groups is unsubstituted or substituted by 1, 2 or 3 substituents selected from C1-C 4- alkyl, halogen, C1-C4-haloalkyl, or C3-C6 cycloalkyl, and wherein R 9 is selected from hydrogen or methyl, and

[0118] wherein represents the position attached to the tetrahydroisoquinoline moiety.

[0119] In an even more preferred embodiment of the present invention, Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12, or Q16, wherein any one of said Q-groups is unsubstituted or substituted by 1, 2 or 3 substituents selected from C1-C 4- alkyl, halogen, C1-C4-haloalkyl, or C3-C6 cycloalkyl, and wherein R 9 is methyl, and

[0120] wherein represents the position attached to the tetrahydroisoquinoline moiety.

[0121] In a still more preferred embodiment of the present invention, Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12, or Q16, wherein any one of the Q groups is unsubstituted or substituted with 1 or 2 substituents selected from fluorine, chlorine, bromine, cyano, or methyl, and wherein R 9 is methyl.

[0122] In an even more preferred embodiment of the present invention, Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, or Q12, wherein any one of the Q groups is unsubstituted or substituted with 1 or 2 substituents selected from fluorine, chlorine, bromine, cyano, or methyl, and wherein R 9 is methyl.

[0123] In an even more preferred embodiment of the present invention, Q is selected from Q1, Q2, or Q3, wherein any one of the Q groups is unsubstituted or substituted with 1 or 2 substituents selected from fluorine, chlorine, bromine, cyano, or methyl, and wherein R 9 is methyl.

[0124] In an additionally even more preferred embodiment of the present invention, Q is selected from Q1, Q2, or Q3, wherein any one of the Q groups is unsubstituted or substituted with 1 substituent selected from methyl.

[0125] Preferably, O is selected from

[0126]

[0127] wherein represents the position attached to the tetrahydroisoquinoline moiety.

[0128] More preferably, O is selected from

[0129]

[0130] wherein represents the position attached to the tetrahydroisoquinoline moiety.

[0131] Even more preferably, O is selected from

[0132]

[0133] wherein represents the position attached to the tetrahydroisoquinoline moiety. Most preferably, Q is selected from Q1, Q2a, Q3, or Q4,

[0134]

[0135] wherein represents the position attached to the tetrahydroisoquinoline - moiety.

[0136] Accordingly, the present invention enables the obtaining of compounds of formula (I), which have R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q, B 1 , B 2 , A 1 , A 2 , A 3 , A 4 and Z 1 as defined above in all combinations / each permutation.

[0137] In one embodiment of the present invention, the compound of formula (I) can be a compound of formula (I - A)

[0138]

[0139] wherein

[0140] R 1 , R 2 , R 3 , R 4 , R 5 , B 1 and B 2 , Q and Z 1 are as defined for the compound of formula (I) according to the present invention, and A is selected from A1 to A38:

[0141]

[0142] wherein represents the position attached to the C(=O) group and the arrow represents the position attached to the Z 1 group, and wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q, B 1 , B 2 and Z 1 are as defined for the compound of formula (I) according to the present invention, and wherein R 10 is selected from hydrogen or C1 - C4 alkyl.

[0143] Preferably, the compound of formula (I) may be a compound of formula (IA), wherein R 1 , R 2 , R 3 , R 4 , R 5 , B 1 and B 2 , Q, and Z 1 is as defined for the compounds of formula (I) according to the invention, and A is selected from A1 to A38, and wherein R 10 Selected from methyl.

[0144] In an embodiment of the present invention, in the compound having formula (IA), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q, B 1 , B 2 and Z 1 is as defined for the compounds of formula (I) according to the invention, and A is selected from

[0145]

[0146] in indicates the position of attachment to the C(=O) group and the arrow indicates the position of attachment to Z 1 The position of the group.

[0147] In another embodiment of the present invention, in the compound having formula (IA), wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q, B 1 , B 2 and Z 1 is as defined for the compounds of formula (I) according to the invention, and A is selected from

[0148]

[0149] in indicates the position of attachment to the C(=O) group and the arrow indicates the position of attachment to Z 1 The position of the group.

[0150] In another preferred embodiment of the present invention, in the compound having formula (IA), wherein R 1 , R 2 , R3 , R 4 , R 5 , R 6 , Q, B 1 , B 2 and Z 1 are as defined for the compounds of formula (I) according to the invention, and A is selected from

[0151]

[0152] wherein represents the position attached to the C(=O) group and the arrow represents the position attached to the Z 1 group.

[0153] Thus, the present invention makes it possible to obtain compounds of formula (I) which have R in all combinations / each permutation as defined above 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q, B 1 , B 2 , A and Z 1 .

[0154] Embodiments according to the invention are provided, as listed below.

[0155] In one embodiment of the invention, the compound of formula (I) can be a compound of formula (I-A), wherein

[0156] R 1 is hydrogen, or C1-C4 alkyl;

[0157] R 2 , R 3 are hydrogen;

[0158] R 4 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0159] R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0160] B 1 is N, or CR 7 ;

[0161] B 2 is N, or CR 8 ;

[0162] R 7 and R8 independently selected from hydrogen or halogen; and

[0163] Q and Z 1 are as defined for the compounds of formula (I), and A is as defined for the compounds of formula (I-A).

[0164] In another embodiment of the present invention, the compound of formula (I) may be a compound of formula (I-A), wherein

[0165] R 1 is hydrogen, or C1-C4 alkyl;

[0166] R 2 , R 3 is hydrogen;

[0167] R 4 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0168] R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0169] B 1 is N, or CR 7 ;

[0170] B 2 is N, or CR 8 ;

[0171] R 7 and R 8 are independently selected from hydrogen or halogen;

[0172] Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12, or Q16, wherein any one of the Q groups is unsubstituted or substituted by 1 or 2 substituents selected from fluorine, chlorine, bromine, cyano or methyl, and wherein R 9 is methyl;

[0173] A is selected from A4, A6, A7, A9, A10, A37, or A39; and

[0174] Z 1 is as defined for the compounds of formula (I).

[0175] In another preferred embodiment of the present invention, the compound of formula (I) may be a compound of formula (I-A), wherein

[0176] R 1 is hydrogen, or C1-C4 alkyl;

[0177] R 2 and R 3 is hydrogen;

[0178] R 4 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0179] R 5 and R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0180] B 1 is N, or CR 7 and B 2 is N, or CR 8 ; where R 7 and R 8 are independently selected from hydrogen, halogen, C1-C3 alkyl, or C1-C4 alkoxy;

[0181] Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12, or Q16, where any one of the Q-groups is unsubstituted or substituted with 1 or 2 substituents selected from fluorine, chlorine, bromine, cyano or methyl, and where R 9 is methyl;

[0182] A is selected from A4, A6, A7, A9, A10, A37, or A39; and

[0183] Z 1 is selected from C1-C4 alkyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl, where the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N, and where any one of the phenyl and 5- to 6-membered heteroaryl is unsubstituted or substituted with 1 or 2 substituents independently selected from fluorine, chlorine, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and where the C3-C6-cycloalkyl is unsubstituted or substituted with 1 or 2 substituents selected from methyl.

[0184] In another preferred embodiment of the present invention, the compound having formula (I) can be a compound having formula (I-A), where

[0185] R 1 is hydrogen, or C1-C4 alkyl;

[0186] R 2 and R 3 are hydrogen;

[0187] R 4 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0188] R 5 and R6 independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0189] B 1 is CR 7 and B 2 is CR 8 ; wherein R 7 and R 8 are independently selected from hydrogen or halogen;

[0190] Q is selected from Q1, Q2, or Q3, wherein any one of the Q groups is unsubstituted or substituted by 1 or 2 substituents selected from fluorine, chlorine, bromine, cyano, or methyl, and wherein R 9 is methyl;

[0191] A is selected from A4, A6, A7, A9, A10, A37, or A39; and

[0192] 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 contains 1 heteroatom selected from N, 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.

[0193] In a further preferred embodiment of the present invention, the compound having formula (I) may be a compound having formula (I-A), wherein

[0194] R 1 is hydrogen, or C1-C4 alkyl;

[0195] R 2 、R 3 is hydrogen;

[0196] R 4 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0197] R 5 、R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0198] B 1 is CR 7 and B 2 is CR 8 ; wherein R 7 and R 8 are independently selected from hydrogen or halogen;

[0199] Q is selected from Q2, Q3, or Q4, wherein any one of the Q groups is unsubstituted or substituted with one substituent selected from methyl;

[0200] A is selected from A4, A7, A9, A10, A37, or A39; and

[0201] 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 contains one heteroatom selected from N, and wherein any one of the phenyl and 5- to 6-membered heteroaryl is unsubstituted or substituted with 1 or 2 substituents independently selected from fluorine, chlorine, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and wherein the C3-C6-cycloalkyl is unsubstituted or substituted with 1 or 2 substituents selected from methyl.

[0202] In still another preferred embodiment of the present invention, the compound having formula (I) can be a compound having formula (I-A), wherein

[0203] R 1 is hydrogen, or C1-C4 alkyl;

[0204] R 2 , R 3 is hydrogen;

[0205] R 4 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0206] R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0207] B 1 is CR 7 and B 2 is CR 8 ; wherein R 7 and R 8 are independently selected from hydrogen or halogen;

[0208] Q is selected from Q2, Q3, or Q4, wherein any one of the Q groups is unsubstituted or substituted with one substituent selected from methyl;

[0209] A is selected from A4, A7, A9, A10, A37, or A39; and

[0210] Z 1is 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.

[0211] In still another preferred embodiment of the present invention, the compound having the formula (I) may be a compound having the formula (I-A), wherein

[0212] R 1 is hydrogen, or C1-C4 alkyl;

[0213] R 2 , R 3 is hydrogen;

[0214] R 4 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0215] R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0216] B 1 is CH and B 2 is CH;

[0217] Q is selected from Q2, Q3, or Q4, wherein any one of the Q groups is unsubstituted or substituted by 1 substituent selected from methyl;

[0218] A is selected from A4, A7, A9, A10, A37, or A39; and

[0219] Z 1 is 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.

[0220] In one embodiment of the present invention, the compound having the formula (I-A) may be a compound having the formula (I-A1), wherein B 1 is CH, B 2 is CH, and A is as defined for the compound (I-A),

[0221]

[0222] wherein R1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q, A, and Z 1 are as defined for the compounds of formula (I).

[0223] Preferably, in the compounds of formula (I-A1)

[0224] R 1 is hydrogen or methyl;

[0225] R 2 , R 3 is hydrogen;

[0226] R 4 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl;

[0227] R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0228] Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12, or Q16, where any one of the Q groups is unsubstituted or substituted by 1 or 2 substituents selected from fluorine, chlorine, bromine, cyano, or methyl, and where R 9 is methyl;

[0229] A is selected from A4, A6, A7, A9, A10, A37, or A39; and

[0230] Z 1 is as defined for the compounds of formula (I).

[0231] More preferably, in the compounds of formula (I-A1)

[0232] R 1 is hydrogen or methyl;

[0233] R 2 , R 3 is hydrogen;

[0234] R 4 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl;

[0235] R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0236] Q is selected from Q2, Q3, or Q4, wherein any one of said Q groups is unsubstituted or substituted with 1 substituent selected from methyl;

[0237] A is selected from A4, A7, A9, A10, A37 or A39; and

[0238] Z 1 is selected from C1-C4 alkyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl, wherein said 5- or 6-membered heteroaryl contains 1 heteroatom selected from N, and wherein any one of said phenyl and 5- to 6-membered heteroaryl is unsubstituted or substituted with 1 or 2 substituents independently selected from fluorine, chlorine, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and wherein said C3-C6-cycloalkyl is unsubstituted or substituted with 1 or 2 substituents selected from methyl.

[0239] In another embodiment of the present invention, the compound having formula (I-A) can be a compound having formula (I-A2), wherein B 1 is CH, B 2 is CH, and A is A4,

[0240]

[0241] wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、Q, A and Z 1 are as defined for the compound having formula (I).

[0242] Preferably, in the compound having formula (I-A2)

[0243] R 1 is hydrogen, or methyl;

[0244] R 2 、R 3 are hydrogen;

[0245] R 4 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0246] R 5 、R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0247] Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12, or Q16, wherein any one of the Q groups is unsubstituted or substituted with 1 or 2 substituents selected from fluorine, chlorine, bromine, cyano, or methyl, and wherein R 9 is methyl; and

[0248] Z 1 is as defined for the compounds of formula (I).

[0249] More preferably, in the compounds of formula (I-A2)

[0250] R 1 is hydrogen, or methyl;

[0251] R 2 、R 3 is hydrogen;

[0252] R 4 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0253] R 5 、R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0254] Q is selected from Q2, Q3, or Q4, wherein any one of the Q groups is unsubstituted or substituted with 1 substituent selected from methyl; and

[0255] 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 contains 1 heteroatom selected from N, and wherein any one of the phenyl and 5- to 6-membered heteroaryl is unsubstituted or substituted with 1 or 2 substituents independently selected from fluorine, chlorine, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and wherein the C3-C6-cycloalkyl is unsubstituted or substituted with 1 or 2 substituents selected from methyl.

[0256] In another embodiment of the present invention, the compound of formula (I-A) may be a compound of formula (I-A3), wherein B 1 is CH, B 2 is CH, and A is A7,

[0257]

[0258] wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6, Q, A, and Z 1 is as defined for compounds of formula (I).

[0259] Preferably, in a compound of formula (I-A3)

[0260] R 1 is hydrogen or methyl;

[0261] R 2 R 3 is hydrogen;

[0262] R 4 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl;

[0263] R 5 R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0264] Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12, or Q16, wherein any one of said Q groups is unsubstituted or substituted with 1 or 2 substituents selected from fluorine, chlorine, bromine, cyano, or methyl, and wherein R 9 is methyl; and

[0265] Z 1 is as defined for compounds of formula (I).

[0266] More preferably, in a compound of formula (I-A3)

[0267] R 1 is hydrogen or methyl;

[0268] R 2 R 3 is hydrogen;

[0269] R 4 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl;

[0270] R 5 R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0271] Q is selected from Q2, Q3, or Q4, wherein any one of said Q groups is unsubstituted or substituted with 1 substituent selected from methyl; and

[0272] Z 1Selected from C1-C4 alkyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N, 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.

[0273] In another embodiment of the present invention, the compound having formula (I-A) can be a compound having formula (I-A4), wherein B 1 is CH, B 2 is CH, and A is A9,

[0274]

[0275] wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、Q, A and Z 1 are as defined for the compound having formula (I).

[0276] Preferably, in the compound having formula (I-A4)

[0277] R 1 is hydrogen, or methyl;

[0278] R 2 、R 3 are hydrogen;

[0279] R 4 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0280] R 5 、R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0281] Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12, or Q16, wherein any one of the Q groups is unsubstituted or substituted by 1 or 2 substituents selected from fluorine, chlorine, bromine, cyano or methyl, and wherein R 9 is methyl; and

[0282] Z 1 is as defined for the compound having formula (I).

[0283] More preferably, in the compound having formula (I-A4)

[0284] R 1 is hydrogen, or methyl;

[0285] R 2 and R 3 is hydrogen;

[0286] R 4 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0287] R 5 and R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0288] Q is selected from Q2, Q3, or Q4, wherein any one of the Q groups is unsubstituted or substituted by 1 substituent selected from methyl; and

[0289] 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 contains 1 heteroatom selected from N, 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.

[0290] In another embodiment of the present invention, the compound having formula (I-A) can be a compound having formula (I-A5), wherein B 1 is CH, B 2 is CH, and A is A10,

[0291]

[0292] wherein R 1 and R 2 and R 3 and R 4 and R 5 and R 6 and Q and A and Z 1 are as defined for the compound having formula (I).

[0293] Preferably, in the compound having formula (I-A5)

[0294] R 1 is hydrogen, or methyl;

[0295] R 2 and R 3 is hydrogen;

[0296] R 4 is hydrogen, a C1-C4 alkyl group, or a C3-C6 cycloalkyl group;

[0297] R 5 、R 6 are independently selected from hydrogen, halogen, cyano, a C1-C4 alkyl group, or a C1-C4 alkoxy group;

[0298] Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12, or Q16, wherein any one of the Q groups is unsubstituted or substituted by 1 or 2 substituents selected from fluorine, chlorine, bromine, cyano, or methyl, and wherein R 9 is methyl; and

[0299] Z 1 is as defined for the compounds of formula (I).

[0300] More preferably, in the compounds of formula (I-A5)

[0301] R 1 is hydrogen, or methyl;

[0302] R 2 、R 3 is hydrogen;

[0303] R 4 is hydrogen, a C1-C4 alkyl group, or a C3-C6 cycloalkyl group;

[0304] R 5 、R 6 are independently selected from hydrogen, halogen, cyano, a C1-C4 alkyl group, or a C1-C4 alkoxy group;

[0305] Q is selected from Q2, Q3, or Q4, wherein any one of the Q groups is unsubstituted or substituted by 1 substituent selected from methyl; and

[0306] Z 1 is selected from a C1-C4 alkyl group, phenyl, a 5- to 6-membered heteroaryl group, or a C3-C6 cycloalkyl group, wherein the 5- or 6-membered heteroaryl group contains 1 heteroatom selected from N, and wherein any one of the phenyl and 5- to 6-membered heteroaryl groups 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 group is unsubstituted or substituted by 1 or 2 substituents selected from methyl.

[0307] In another embodiment of the present invention, the compound of formula (I-A) can be a compound of formula (I-A6), wherein B 1 is CH, B 2is CH, and A is A37,

[0308]

[0309] wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、Q, A and Z 1 are as defined for the compounds of formula (I).

[0310] Preferably, in the compounds of formula (I-A6)

[0311] R 1 is hydrogen, or methyl;

[0312] R 2 、R 3 is hydrogen;

[0313] R 4 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0314] R 5 、R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0315] Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12, or Q16, wherein any one of the Q groups is unsubstituted or substituted by 1 or 2 substituents selected from fluorine, chlorine, bromine, cyano or methyl, and wherein R 9 is methyl; and

[0316] Z 1 is as defined for the compounds of formula (I).

[0317] More preferably, in the compounds of formula (I-A6)

[0318] R 1 is hydrogen, or methyl;

[0319] R 2 、R 3 is hydrogen;

[0320] R 4 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0321] R 5 、R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0322] Q is selected from Q2, Q3, or Q4, wherein any one of said Q groups is unsubstituted or substituted with 1 substituent selected from methyl; and

[0323] Z 1 is selected from C1-C4 alkyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl, wherein said 5- or 6-membered heteroaryl contains 1 heteroatom selected from N, and wherein any one of said phenyl and 5- to 6-membered heteroaryl is unsubstituted or substituted with 1 or 2 substituents independently selected from fluorine, chlorine, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and wherein said C3-C6-cycloalkyl is unsubstituted or substituted with 1 or 2 substituents selected from methyl.

[0324] In another embodiment of the present invention, the compound having formula (I-A) can be a compound having formula (I-A7), wherein R 1 B 1 is CH, B 2 is CH, and A is A38,

[0325]

[0326] wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、Q, A, and Z 1 are as defined for the compound having formula (I).

[0327] Preferably, in the compound having formula (I-A7)

[0328] R 1 is hydrogen or methyl;

[0329] R 2 、R 3 are hydrogen;

[0330] R 4 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0331] R 5 、R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0332] Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12, or Q16, wherein any one of said Q groups is unsubstituted or substituted with 1 or 2 substituents selected from fluorine, chlorine, bromine, cyano, or methyl, and wherein R 9is methyl; and

[0333] Z 1 is as defined for the compounds of formula (I).

[0334] More preferably, in the compounds of formula (I-A7)

[0335] R 1 is hydrogen, or methyl;

[0336] R 2 , R 3 is hydrogen;

[0337] R 4 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0338] R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy;

[0339] Q is selected from Q2, Q3, or Q4, wherein any one of the Q groups is unsubstituted or substituted by 1 substituent selected from methyl; and

[0340] 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 contains 1 heteroatom selected from N, 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.

[0341] In any one of the compounds selected from the compounds of formula (I), (I-A), (I-A1), (I-A2), (I-A3), (I-A4), (I-A5), (I-A6), or (I-A7) according to the present invention, or the compounds selected from the compounds listed in Tables C-1 to C-36 or the compounds listed in Table P (below), the presence of one or more possible asymmetric carbon atoms in these compounds means that these compounds can exist in chiral isomer forms, i.e., enantiomer or diastereomer forms.

[0342] In one embodiment, the compounds of formula (I) according to the present invention are selected from any one of the compounds listed in Tables C-1 to C-36.

[0343] In another embodiment, the compounds of formula (I) according to the present invention are selected from the compounds listed in Table P (below).

[0344] The compounds of formula (I) according to the invention can be prepared as shown in the following scheme, wherein the definition of each variable is as defined above for the compounds of formula (I), unless otherwise specified.

[0345] In any of the following schemes, 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 chiral isomeric forms, i.e., enantiomeric or diastereomeric forms.

[0346] The compounds of formula (I) can be prepared by those skilled in the art according to known methods. More specifically, the compounds of formula (I) can be prepared from a compound of formula (III) or a salt thereof (wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、Q, B 1 and B 2 are as defined for the compounds of formula (I)) by reaction with a compound of formula (II) (wherein A 1 、A 2 、A 3 、A 4 and Z 1 are as defined for the compounds of formula (I)).

[0347] This reaction is shown in Scheme 1.

[0348]

[0349] In Scheme 1, a compound of formula (II) (wherein A 1 、A 2 、A 3 、A 4 and Z 1 are as defined for the compounds of formula (I)) is activated to a compound of formula (IIa) by methods known to those skilled in the art and described, for example, in Tetrahedron 2005, 61(46), 10827 - 10852. For example, a compound of formula (IIa) (wherein X 0is 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 (DCM) or tetrahydrofuran (THF) at a temperature between 20°C and 100°C, preferably 25°C. Optionally, a compound of formula (III) (wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q, B 1 and B 2 is as defined for compounds of formula (I)) to give compounds of formula (I). Alternatively, compounds of formula (I) may be prepared by treating compounds of formula (II) with dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) or 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU) in an inert solvent such as pyridine, DMF, acetonitrile, DCM 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 G as shown in Scheme 2 1 , G 2 or G 3 Finally, compounds of formula (II) can also be reacted with coupling agents such as propanephosphonic anhydride (T3P) to provide compounds of formula (IIa) (wherein X 0 is G as shown in Scheme 2 4 ) for activation, 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).

[0350]

[0351] The compound of formula (II) can be prepared from a compound of formula (IIb) (wherein A 1 , A 2 , A 3 , A 4 and Z 1 is as described in formula (I), and R 0is prepared by ester hydrolysis with a C1-C4 alkyl). A variety of conditions can be used, such as, for example, aqueous sodium hydroxide or lithium hydroxide, and organic water-miscible solvents like THF or dimethoxyethane, methanol or ethanol. Such ester hydrolysis is well known to those skilled in the art. Compounds of formula (IIb) can also be directly converted to compounds of formula (I) by reacting a compound of formula (IIb) with a compound of formula (III) in an inert solvent (such as toluene or DCM) in the presence of trimethylaluminum or a trimethylaluminum-DABCO complex. Such reactions have been reported in the literature (see Tetrahedron Lett. [Tetrahedron Letters] 1977, 4171-4174; Tetrahedron Lett. [Tetrahedron Letters] 2006, 5767-5769 and the references cited therein). Compounds of formula (II) and (IIb) are commercially available or can be synthesized as described below.

[0352] Compounds of formula (IIIa) wherein R 1 and R 2 is hydrogen, R 3 is hydrogen or methyl and R 4 , R 5 , R 6 , B 1 and B 2 are as defined for compounds of formula (I)) can be prepared from compounds of formula (IV) wherein R 3 is hydrogen or methyl, and R 4 , R 5 , R 3 , R 6 , B 1 and B 2It is prepared by treating in a protic solvent (such as methanol or ethanol, etc.) with a reducing agent (such as NaBH3CN) and an acid (such as hydrochloric acid or acetic acid) as defined for the compound of formula (I). Such reactions are well-known in the literature, and similar reactions have been described, for example, in Deng, Zeping et al., CN 103772278 and Synthesis 1979, 4, 281 - 283. Alternatively, the compound of formula (IIIa) can be prepared by reducing the compound of formula (IV) with hydrogen in the presence of a suitable metal catalyst (such as Pd, Ir, Rh) 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)]). Similar reactions have been reported, for example, in React. Kinet. Cat. Lett. 2007, 92, 99 - 104. This reaction is shown in Scheme 3.

[0353]

[0354] Further synthesis of the compound of formula (III) can be achieved by a directed metallation strategy as shown in Scheme 4. Thus, the compound of formula (IIIb) (where R 3 is hydrogen or methyl and R 5 、R 6 、Q、B 1 and B 2 are as defined for the compound of formula (I)) is converted to the compound of formula (V) (where R 0 is a leaving group, such as a halogen, and R 0 is a C1-C6 alkyl) by treating the compound of formula (IIIb) with a compound of formula (VI) (where X 3 is hydrogen or methyl and R 5 、R 6 、Q、B 1 and B 2 are as defined for the compound of formula (I)) by methods known to those skilled in the art and those described in Scheme 1. Alternatively, the compound of formula (V) can be prepared by using an acid anhydride of formula (R 0 CO)2O (where R 0is prepared by treating in an inert solvent (such as DCM, 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. Then, at low temperature (e.g., -78 °C) to room temperature, in an inert polar solvent (such as THF or 2-methyl-THF), a compound of formula (V) is metallized with a base (such as an alkylmetal base, such as tert-butyllithium) and an additive (such as N,N,N',N'-tetramethylethylenediamine (TMEDA)). Subsequently, an electrophile of formula R 4 -X 0 is used (where X 0 is as previously defined, and R 4 is C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4 alkylaminocarbonyl, di(C1-C4 alkyl)aminocarbonyl, or C3-C6 cycloalkyl, where 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) to treat the anion of formula (V) formed under such conditions, yielding a compound of formula (Va) (where R 0 is C1-C6 alkyl and R 3 is halogen, and R 4 , R 5 , R 6 , Q, B 1 and B 2 are as defined for the compound of formula (I)) (Scheme 4).

[0355]

[0356] The compound of formula (Va) can be converted to a compound of formula (IIIa) (where R 3 is hydrogen or methyl, and R 4 , R 5 , R 6 , Q, B 1 and B 2 are as defined for the compound of formula (I)) by methods known to those skilled in the art. For example, the compound of formula (Va) (where R 0 is tert-butyl) can be treated with an organic or inorganic acid (such as trifluoroacetic acid or HCl) to give a compound of formula (IIIa). This reaction is shown in Scheme 5.

[0357]

[0358] A compound of formula (IV) (where R3 is hydrogen or methyl and R 4 、R 5 、R 6 、Q, B 1 and B 2 is as defined for the compounds of formula (I)) can be prepared by reacting a compound of formula (VIII) in which Q is as defined for the compounds of formula (I) and X 0 is a halogen, preferably chlorine, bromine or iodine) with a compound of formula (VII) in which R 3 is hydrogen or methyl and R 4 、R 5 、R 6 、Q, B 1 and B 2 is as defined for the compounds of formula (I)) by means of a C-C bond forming reaction typically under palladium-catalyzed (alternatively nickel-catalyzed) cross-coupling conditions. This reaction is shown in Scheme 6.

[0359]

[0360] The Suzuki-Miyaura cross-coupling reaction between a compound of formula (VIII) and a compound of formula (VII) is well known to those skilled in the art and is 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 J. Organomet. Chem. 1999, 576, 147-168. Those skilled in the art will also recognize that the reaction can be reversed, i.e., by reacting a compound of formula (X) in which Q is as defined for the compounds of formula (I) with a compound of formula (IX) in which R 3 is hydrogen or methyl, R 4 、R 5 、R 6 、B 1 and B 2 is as defined for the compounds of formula (I) and X 0 is a halogen, preferably chlorine, bromine or iodine) to provide a compound of formula (IV) in which R 5 is hydrogen or methyl and R 4 、R 5 、R6 , Q, B 1 and B 2 is as defined for the compounds of formula (I). This reaction is shown in Scheme 7.

[0361]

[0362] Additional cross-coupling chemistry (i.e., C-H activation) can also be used to prepare compounds of formula (IV) wherein R 3 is hydrogen or methyl, and R 4 , R 5 , R 6 , Q, B 1 and B 2 is as defined for the compounds of formula (I), and wherein the Q group has at least one aromatic C-H group) (Scheme 8).

[0363]

[0364] As shown in Scheme 8, a compound of formula (IX) wherein R 3 is hydrogen or methyl, R 4 , R 5 , R 6 , B 1 and B 2 is as defined for the compounds of formula (I), and X 0 is a halogen, preferably chlorine, bromine or iodine) is reacted with a compound of formula (XI) wherein Q is as defined for the compounds of formula (I), and wherein the Q group has at least one aryl C-H) 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 (such as cesium carbonate or potassium carbonate), in an inert solvent (such as chlorobenzene, toluene or xylene), at a temperature between room temperature and 180 °C, optionally under microwave heating conditions, preferably under an inert atmosphere. Similar reactions have been reported in the literature, for example in Chem. Sci. [Chemical Science] 2013, 4, 2374 - 2379.

[0365] The compound of formula (III) can also be prepared from a compound of formula (Vc) (Scheme 9).

[0366]

[0367] As shown in Scheme 9, the compound of formula (III) can be prepared by one skilled in the art from a compound of formula (Vc) wherein R 1 , R 2 , R 3 , R4 , R 5 , R 6 , Q, B 1 and B 2 are as defined for the compounds of formula (I), and R 01 can be a member of the common carbamate protecting group substituents, such as methyl, tert-butyl, allyl, 2,2,2-trichloroethyl or benzyl) by a carbamate deprotection reaction. For example, when R 01 is methyl, a suitable solvent (such as DCM) and a suitable reagent (such as trimethylsilyl iodide) can be used to obtain the product when heated at a temperature between room temperature and 200 °C, preferably between 20 °C and the boiling point of the reaction mixture, as described, for example, in J. Am. Chem. Soc. 1992, 114, 5959. As discussed in Scheme 1, the compound of formula (III) thus obtained is converted into the compound of formula (I).

[0368] A compound of formula (Vc) in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q, B 1 and B 2 are as defined for the compounds of formula (I), and in which R 01 is as described above) can be formed by reacting an aldehyde of formula (XIII) (including formaldehyde in its different forms) in which R 4 is as defined for the compounds of formula (I) with a compound of formula (XII) in which R 1 , R 2 , R 3 , R 5 , R 6 , Q, B 1 and B 2 are as defined for the compounds of formula (I), and in which R 01 is as described above) by a Pictet-Spengler reaction in the presence of an acid in a suitable solvent, as described, for example, in Tetrahedron 1987, 43, 439 (Scheme 10).

[0369]

[0370] A compound of formula (XII) in which R 1 , R 2 , R3 , R 5 , R 6 , Q, B 1 and B 2 is as defined for compounds of formula (I), and wherein R 01 is as described above) can be prepared by reacting an amine of formula (XIII) wherein R 1 , R 2 , R 3 , R 5 , R 6 , Q, B 1 and B 2 is as defined for compounds of formula (I)) with a suitable protecting reagent such as methyl chloroformate, optionally in the presence of a base such as triethylamine or pyridine, in a suitable solvent such as DCM, at a temperature between -20 °C and the boiling point of the mixture, as described, for example, in Org. Biomol. Chem. [Organic & Biomolecular Chemistry] 2016, 14, 6853. This reaction is shown in Scheme 11.

[0371]

[0372] A compound of formula (XIII) or a salt thereof, wherein R 1 , R 2 , R 3 , R 5 , R 6 , Q, B 1 and B 2 is as defined for compounds of formula (I)) can be prepared by reacting a nitrile of formula (XIV) wherein R 1 , R 2 , R 3 , R 4 , Q, B 1 and B 2 is as defined for compounds of formula (I)) with a suitable nucleophile such as (dimethylsulfide)dihydroboron (BMS) in a suitable aprotic solvent such as THF, for example as described in J. Org Chem. [Journal of Organic Chemistry] 1981, 47, 3153. Such a reaction of the nitrile of formula (XIV) gives a compound of formula (XIII) wherein R 2 and R 3 are hydrogen. Alternatively, a Grignard reagent R 5 MgBr or R 6 MgBr, wherein R 5 and R 6(as defined for compounds of formula (I)) can be added, either sequentially or simultaneously, as a nucleophile to a compound of formula (XIV) to allow the preparation of more highly substituted amines of formula (XIII). Such Grignard additions to nitriles are carried out in an inert solvent (such as diethyl ether, tert-butyl methyl ether, and cyclopentyl methyl ether) in the presence of a Lewis acid (such as Ti(O- i Pr)4) (see Synlett [Synthesis Letters] 2007, (4), 652 - 654). This reaction is shown in Scheme 12.

[0373]

[0374] Alternatively, a compound of formula (XIII) in which R 1 、R 5 、R 6 、Q, B 1 and B 2 are as defined for compounds of formula (I), and in which R 2 、R 3 are hydrogen can be prepared by those skilled in the art by reacting an unsaturated nitro compound of formula (XV) in which R 1 、R 5 、R 6 、B 1 and B 2 are as defined for compounds of formula (I) with a Grignard reagent of formula (XVI) in which Q is as defined for compounds of formula (I) and X 0 is a halogen, preferably iodine), and then subsequently reducing the compound of formula (XVII) in which R 1 、R 5 、R 6 、Q, B 1 and B 2 are as defined for compounds of formula (I) to a compound of formula (XIIIa).

[0375] This reaction is shown in Scheme 13.

[0376]

[0377] Such conjugate addition of a heteroaryl Grignard reagent to an α,β-unsaturated nitroolefin has been reported in the literature (see Synthesis, 1988, (5), 379 - 81), and there are many methods for reducing the nitro group to an amine, some examples of which are reported in "Nitro and Related Groups", J. Chem. Soc. Perkin Trans. I, 2002, 23, 2586 - 2597. The Grignard reagent having the formula (XVI) is readily prepared from the compound having the formula (VIII) by methods known to those skilled in the art.

[0378] The compound having the formula (XIV) in which R 1 , R 2 , R 3 , R 4 , R 8 , R 9 , B 1 and B 2 are as defined for the compound having the formula (I)) can be prepared by those skilled in the art according to known methods. More specifically, the compound having the formula (XIV) and its intermediates can be prepared from the compound having the formula (XVII), as shown in Scheme 14.

[0379]

[0380] For example, the compound having the formula (XIV) in which R 1 , R 2 , R 3 , R 8 , Q, B 1 and B 2 are as defined for the compound having the formula (I), and R 1 is not hydrogen) can be prepared by those skilled in the art by the following method: using a strong base (such as n-butyllithium or sodium hydride) in an inert solvent (such as THF) at cryogenic temperature, followed by the addition of a suitable alkylating agent R 1 -X 0 (where R 1 is a C1 - C4 alkyl and X 0 is a halogen) (such as methyl iodide) to deprotonate the compound having the formula (XIVa) in which R 1 is hydrogen, and R 5 , R 6 , Q, B 1 and B 2 are as defined for the compound having the formula (I).

[0381] A compound having the formula (XIVa), wherein R 5 , R 6 , Q, B 1 and B 2 are as defined for the compound having the formula (I)) can be prepared by treating an alcohol having the formula (XVIII) with trimethylsilyl cyanide (TMSCN) in the presence of a base (such as lithium carbonate) in a non-polar solvent (such as DCM) at a temperature between 0 °C and the boiling point of the reaction mixture. Such transformations are well-known in the literature under various conditions, for example as described in Org. Lett. [Organic Letters] 2008, 10, 4570 and the references therein. The compound having the formula (XVIII) is readily prepared by carrying out a Grignard reaction of a compound having the formula (XVI), an aldehyde having the formula (XIX) or a Grignard compound having the formula (XXI) with an aldehyde having the formula (XXII) generally in an ether-type solvent (such as THF, 2-Me-THF, TBME, diethyl ether, etc.).

[0382] Such reactions are well-known to those skilled in the art. This is summarized in Scheme 15.

[0383]

[0384] A compound having the formula (II), wherein A 1 is N, A 2 is O, A 4 is CH, A 3 is C and Z 1 is as defined for the compound having the formula (I)) (i.e., a compound having the formula (IId)) can be prepared as shown in Scheme 16.

[0385]

[0386] As shown in Scheme 16, a compound having the formula (IId), wherein Z 1 is as defined for the compound having the formula (I), and X 01 is a C1-C4 alkyl group) can be prepared by hydrolyzing a compound having the formula (IIc) with, for example, an alkaline earth metal hydroxide in water or in a water-miscible organic solvent (such as THF, methanol, ethanol, etc.). Such ester hydrolysis is well-known to those skilled in the art. The compound having the formula (IIc) can be obtained by treating a compound having the formula (XXV) (wherein Z 1 is as defined for the compound having the formula (I), and X 01 is a C1-C4 alkyl group) with hydroxylamine hydrochloride in a polar solvent (such as ethanol) and optionally in the presence of a base (such as triethylamine, K2CO3, etc.).

[0387] The compound having the formula (XXV) is prepared by reacting a compound having the formula (XXIII) (wherein Z 1 is as defined for the compound having the formula (I)) with a compound having the formula (XXIV) or a compound having the formula (XXIVa) (wherein X 01 is C1-C4 alkyl) in the presence of a base (such as potassium tert-butoxide, sodium hydride or lithium bis(trimethylsilyl)amide) in a solvent (such as THF or toluene). Reaction sequences similar to those described for the preparation of the compounds having the formula (IIc) and (IId) in Scheme 15 are described in, for example, CN 111072582 and WO 2019 / 195810 and WO 2018 / 019929. Further reaction conditions for the preparation of the compound having the formula (XXV) are described in, for example, Bioorg. Med. Chem. [Bioorganic and Medicinal Chemistry] 2016, 109, 350-359.

[0388] The compound having the formula (II) (wherein A 1 is O, A 2 and A 4 is N, A 3 is C, and Z 1 is as defined for the compound having the formula (I)) (i.e., the compound having the formula (IIf)) can be prepared as shown in Scheme 17.

[0389]

[0390] As shown in Scheme 17, the compound having the formula (IIf) is obtained by ester hydrolysis of the compound having the formula (IIe) as previously described in Scheme 15. The compound having the formula (IIe) (wherein Z 1 is as defined for the compound having the formula (I), and X 01 is C1-C4 alkyl) is prepared by reacting a compound having the formula (XXIVa) with a compound having the formula (XXVI) optionally in the presence of a base (such as pyridine or triethylamine) in a solvent (such as acetonitrile, chloroform or THF). Such reactions have been reported in, for example, Bioorg. Med. Chem. [Bioorganic and Medicinal Chemistry] 2016, 24(22), 5693-5701 and CN 114933573. The compound having the formula (XXVI) (wherein Z 1(as defined for the compounds of formula (I)) can be obtained by treating a compound of formula (XXVII) with hydroxylamine hydrochloride in a polar solvent (such as ethanol) in the presence of a base (such as K2CO3 or Na2CO3). The reaction can also be carried out using a solution of hydroxylamine in the absence of a base. Such reactions have been described, for example, in Bioorg. Med. Chem. Lett. [Bioorganic & Medicinal Chemistry Letters] 2020, 30(21), 127508 and Bioorg. Med. Chem. Lett. [Bioorganic & Medicinal Chemistry Letters] 2016, 26(23), 5679 - 5684.

[0391] A compound of formula (XXVI) wherein Z 1 (as defined for the compounds of formula (I)) can also be prepared by a "one - pot" synthesis via Pd - catalyzed cyanation and amidoximation of a compound of formula (XXVIII) wherein Z 1 (as defined for the compounds of formula (I)), as described, for example, in Org. Biomol. Chem. [Organic & Biomolecular Chemistry] 2015, 13(9), 2541 - 2545.

[0392] A compound of formula (II) wherein A 1 and A 2 is N, and A 4 is O, A 3 is C, and Z 1 is as previously described (i.e., a compound of formula (IIh)), and A 1 and A 2 is N, and A 4 is S, A 3 is C, and Z 1 (as defined for the compounds of formula (I), i.e., a compound of formula (IIj)) can be prepared as shown in Scheme 18.

[0393]

[0394] As shown in Scheme 18, the compounds of formula (IIh) and (IIj) are obtained by ester hydrolysis of (IIg) and (IIi), respectively. In the latter compound, X 01 and Z 1is as described previously. The compound having the formula (IIg) is obtained by dehydration of the compound having the formula (XXXI). The compound having the formula (XXXI) is obtained by acylation of the hydrazide having the formula (XXXII) with the compound having the formula (XXIVa). Such a sequence of reactions for generating oxadiazole is well known to those skilled in the art. Similar reactions are described in Bioorg. Med. Chem. Lett. [Bioorganic and Medicinal Chemistry Letters] 2005, 15, 1423 - 1428 and WO 2006 / 044617. The compound having the formula (XXXI) can also be prepared by reacting the activated carboxylic acid having the formula (XXIXa) (where Z 1 is as defined for the compound having the formula (I), and X 0 is as described in Scheme 1 and Scheme 2, respectively) with the compound having the formula (XXX). The compound having the formula (XXIXa) can be prepared from the corresponding acid having the formula (XXIX) as described in Scheme 1. Such reactions are described, for example, in J. Prakt. Chem. [Journal of Practical Chemistry] 1985, 327, 109 - 116. The compound having the formula (IIi) can also be prepared from the common intermediate having the formula (XXXI) (where Z 1 is as defined for the compound having the formula (I), and X 01 is as described previously) by treatment with Lawesson's reagent or pure phosphorus pentasulfide in an inert solvent such as toluene or xylene. Similar reactions are known in the literature (see, for example, WO 2010 / 006713, WO 2009 / 149858, and J. Org Chem. [Journal of Organic Chemistry] 1961, 26, 4410 - 12).

[0395] The compound having the formula (II) (where A 1 is O, A 2 is N, A 4 is methylene, A 3 is C, and Z 1 is as defined for the compound having the formula (I)) (i.e., the compound having the formula (IIl)) can be prepared, for example, as shown in Scheme 19.

[0396]

[0397] As shown in Scheme 19, the compound having formula (III) is readily obtained by hydrolyzing the ester having formula (IIk) by methods known to those skilled in the art and as described above. The compound having formula (IIj) can be obtained by reacting the compound having formula (XXXIII) with the compound having formula (XXXIV) in the presence of an oxidizing agent (such as (diacetoxyiodo)benzene or N-chlorosuccinimide) in an inert solvent (such as methanol or DMF). Such reaction sequences have been described, for example, in J. Het. Chem. [Journal of Heterocyclic Chemistry] 2013, 50(4), 774 - 780 and J. Chin. Chem. Soc. [Chinese Chemical Society Journal] 2007, 54(3), 643 - 652. The compound having formula (XXXIII) is readily prepared by treating the compound having formula (XXXV) (where Z 1 is as defined for the compound having formula (I)) with hydroxylamine under conditions well known to those skilled in the art.

[0398] The compound having formula (II) (where A 1 、A 2 、A 4 is CH or N, and A 3 is N) can be prepared by reacting the compound having formula (XXXVI)

[0399]

[0400] with the compound having formula (XXXVII)

[0401] Z 1 -X 0 (XXXVII)

[0402] where Z 1 is as previously described under formula I and X 0 is a halogen (preferably chlorine, bromine or iodine) in the presence of a base (such as alkali and alkaline earth metal bases like NaOH, KOH, LiOH, Cs2CO3, K2CO3, etc.) in an inert aprotic or protic solvent. Such alkylation is well known to those skilled in the art and has been used in this context for the preparation of compounds having formula (II), as described, for example, in WO 14 / 168221, 2013; WO 10 / 043000, 2010; and WO 14 / 32498, 2014. Those skilled in the art will recognize that this can result in a mixture of regioisomeric compounds that can be separated by chromatographic techniques, or pure isomers can be obtained by judicious selection of conditions and additives (such as palladium catalysts for so-called Buchwald amination). For those where Z 1In the case of a heteroaryl or aryl, the SnAr reaction (with or without copper catalysis) can be used to prepare compounds having formula (IIb) (see, for example, Polyhedron 2019, 165, 22 - 30; US 18 / 0170909, 2018; Org. Lett. 2022, 24(20), 3620 - 3625; J. Org. Chem. 2017, 82(14), 7420 - 7427; Chem. Comm. 2021, 57(57), 7047 - 7050; ACS Catalysis 2019, 9(12), 10674 - 10679; Synthesis 2017, 49(23), 5120 - 5130; J. Org. Chem. 2019, 84(12), 8160 - 8167; and the references cited therein).

[0403] Salts of the compounds having formula (I) can be prepared in a manner known per se. Thus, for example, acid addition salts of the compounds having 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.

[0404] Salts of the compounds having formula (I) can be converted in a conventional manner into the free compound (I), acid addition salts (e.g., by treatment with a suitable basic compound or with a suitable ion - exchange reagent) and salts with bases (e.g., by treatment with a suitable acid or with a suitable ion - exchange reagent).

[0405] Salts of the compounds having formula (I) can be converted in a manner known per se into other salts of the compounds having formula (I), acid addition salts, for example into other acid addition salts, for example by treatment of a salt of an inorganic acid (such as a hydrochloride) with a suitable metal salt of an acid (such as a salt of sodium, barium or silver, for example silver acetate) in a suitable solvent in which the inorganic salt formed (such as silver chloride) is insoluble and thus precipitates from the reaction mixture.

[0406] Depending on the procedure or reaction conditions, the compounds having formula (I) with salt - forming properties can be obtained in free form or in the form of salts.

[0407] Compounds of formula (I) and, where appropriate, their tautomers (in each case in free form or in salt form) can exist in the form of one of the possible isomers or in the form of a mixture of these isomers, for example in the form of pure isomers (such as enantiomers and / or diastereoisomers) or in the form of an isomer mixture (such as a mixture of enantiomers, for example a racemate; or a mixture of diastereoisomers), depending on the number of asymmetric carbon atoms present in the molecule, the absolute and relative configurations and / or depending on the configuration of the non-aromatic double bonds present in the molecule; the present invention relates to the pure isomers as well as to all possible isomer mixtures, and in each case in the context, even in each case where no stereochemical details are specifically mentioned, should be understood in this sense.

[0408] Mixtures of diastereoisomers or racemate mixtures of compounds of formula (I) in free form or in salt form (the obtaining of which can depend on the starting materials and procedures chosen) can be separated in a known manner into the pure diastereoisomers or racemates on the basis of the physicochemical differences of these components, for example by fractional crystallization, distillation and / or chromatography.

[0409] Mixtures of enantiomers (such as racemates) which can be obtained in a similar manner can be resolved into the optical enantiomers by known methods, for example by recrystallization from an optically active solvent; by chromatography on a chiral adsorbent, for example high performance liquid chromatography (HPLC) on acetylcellulose; by cleavage with a specific immobilized enzyme, by means of a suitable microorganism; via the formation of inclusion compounds, for example using a chiral crown ether in which only one enantiomer is complexed; or by conversion into salts of diastereoisomers, for example by reacting the racemate of the basic end product with an optically active acid (such as a carboxylic acid, for example camphoric acid, tartaric acid or malic acid, or a sulfonic acid, for example camphorsulfonic acid), and separating the mixture of diastereoisomers which can be obtained in this way, for example by fractional crystallization based on their different solubilities, so as to obtain the diastereoisomers, from which the desired enantiomer can be liberated by the action of a suitable reagent (such as a basic reagent).

[0410] Pure diastereoisomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials having suitable stereochemistry.

[0411] If the individual components have different biological activities, it is advantageous in each case to separate or synthesize the biologically more effective isomers, such as enantiomers or diastereoisomers or isomer mixtures, for example mixtures of enantiomers or mixtures of diastereoisomers.

[0412] As an example, a compound having more than one asymmetric carbon atom can exist in diastereoisomeric forms, which can optionally be separated using, for example, supercritical fluid chromatography (SFC) chromatography with a chiral column. Such diastereoisomers can exhibit different fungicidal activity profiles, but all isomers and diastereoisomers form part of the present invention.

[0413] The compound having formula (I) has at least three chiral carbon atoms (three stereocenters, where the asterisk (*) indicates a chiral carbon atom), such that at least eight available stereoisomers exist. These at least eight stereoisomers consist of four sets of enantiomers.

[0414]

[0415] For a compound having formula (I), where R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、B 1 、B 2 、A 1 、A 2 、A 3 、A 4 、Q and Z 1 are as defined for a compound having formula (I), and where R 4 is not hydrogen, the relationship between enantiomers and diastereoisomers is shown in Scheme 20.

[0416]

[0417] These diastereoisomers and enantiomers of formula (I) (as shown in Scheme 21) (where Q, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、B 1 、B 2 、A 1 、A 2 、A 3 、A 4 and Z 1 are as defined for formula (I), and where R 4 is not hydrogen) are within the scope of the present invention.

[0418] For a compound having formula (I), where R 2 、R 3is hydrogen and Q, R 1 , R 4 , R 5 , R 6 , B 1 , B 2 , and Z 1 are as defined for the compounds of formula (I), and wherein A is as defined for the compounds of formula (I-A), and wherein R 4 is not hydrogen, the relationship between the enantiomers and diastereoisomers is shown in Scheme 21.

[0419]

[0420] In one embodiment, a compound of formula (I), wherein R 2 , R 3 is hydrogen and Q, R 1 , R 4 , R 5 , R 6 , B 1 , B 2 , and Z 1 are as defined for the compounds of formula (I), and wherein A is as defined for the compounds of formula (I-A), and wherein R 4 is not hydrogen, Q and R 4 have a cis relationship to each other.

[0421] The cis isomer of the compound of formula (I) (wherein R 2 , R 3 is hydrogen and Q, R 1 , R 4 , R 5 , R 6 , B 1 , B 2 , and Z 1 are as defined for the compounds of formula (I), and wherein A is as defined for the compounds of formula (I-A), and wherein R 4 is not hydrogen) is shown in Scheme 22.

[0422]

[0423] Preferably, a compound of formula (I), wherein R 2 , R 3 is hydrogen and Q, R 1 , R 4 , R 5 , R 6 , B 1 , B 2 , and Z1 is as defined for the compounds of formula (I), and in which A is as defined for the compounds of formula (I-A), and in which R 4 is not hydrogen, Q and R 4 have a cis relationship to each other, as shown in Scheme 22.

[0424] The compounds of formula (I) and, where appropriate, their tautomers (in each case in free form or in salt form) can, if appropriate, also be obtained in the form of hydrates and / or include other solvents, for example those which can be used for crystallizing the compounds present in solid form.

[0425] As already indicated, surprisingly, it has now been found that, for practical purposes, the compounds of formula (I) according to the invention have a very advantageous level of biological activity for protecting plants against diseases caused by fungi.

[0426] The compounds of formula (I) according to the invention can be used in the agricultural sector and related fields of use as, for example, active ingredients for controlling phytopathogenic pests, or on inanimate materials for controlling spoilage microorganisms or organisms potentially harmful to humans. These novel compounds are characterized by excellent activity at low application rates, good plant tolerance and environmental safety. They have very useful therapeutic, prophylactic and systemic properties and can be used to protect a large number of cultivated plants. The compounds of formula (I) can be used to inhibit or destroy pests occurring on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of different useful plant crops, while also protecting those later-growing plant parts from, for example, infestation by phytopathogenic microorganisms.

[0427] The invention further relates to a method for controlling or preventing the infestation of plants or plant propagation materials and / or harvested food crops which are susceptible to microbial attack by treating the plants or plant propagation materials and / or harvested food crops, wherein an effective amount of a compound of formula (I) according to the invention is applied to the plants, their parts or their sites.

[0428] It is also possible to use the compounds of formula (I) according to the invention as fungicides. As used herein, the term "fungicide" means a compound which controls, modifies or prevents fungal growth. The term "fungicidally effective amount" when used means the amount of such a compound or combination of such compounds which can have an effect on fungal growth. The effects of controlling or modifying include all deviations from natural development, such as killing, arresting, etc., and prevention includes forming a barrier or other defense in or on the plant to prevent fungal infestation.

[0429] It is also possible to use the compounds of formula (I) according to the invention as seed dressings for treating plant propagation materials (such as seeds, fruits, tubers or grains) or plant cuttings, for protection against fungal infections and against phytopathogenic fungi present in the soil. The propagation materials can be treated with a composition comprising a compound of formula (I) before planting: for example, seed dressing can be carried out before sowing. The active compounds of formula (I) can also be applied to the grains (coating) by impregnating the seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the planting site when planting the propagation materials, for example to the furrows of the seeds during sowing. The invention also relates to such methods of treating plant propagation materials and to plant propagation materials so treated.

[0430] Furthermore, the compounds of formula (I) according to the invention can be used for controlling fungi in related fields, such as in the protection of industrial materials (including wood and wood-related technical products), in food storage, in hygiene management.

[0431] In addition, the present invention can be used to protect inanimate materials (such as wood, wall panels and coatings) from fungal attack.

[0432] Compounds having formula (I) according to the present invention are effective, for example, against fungal and fungal vectors of diseases, as well as phytopathogenic bacteria and viruses. Such fungal and fungal vectors of diseases, and phytopathogenic bacteria and viruses are, for example: Apophysomyces elegans, Alternaria species, Aphanomyces species, Ascochyta species, Aspergillus species (including Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans, Aspergillus niger, Aspergillus terreus), Aureobasidium species (including Aureobasidium pullulans), Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria species (including Botryosphaeria dothidea, Botryosphaeria obtusa), Botrytis species (including Botrytis cinerea), Candida species (including Candida albicans, Candida glabrata, Candida krusei, Candida lusitaniae, Candida parapsilosis, Candida tropicalis), Cephaloascus fragrans, Ceratocystis species, Cercospora species (including Cercospora arachidicola), Cercosporidium personatum, Cladosporium species, Claviceps purpurea, Coccidioides immitis, Cochliobolus species, Colletotrichum species (including Colletotrichum musae), Cryptococcus neoformans, Diaporthe species, Didymella species, Drechslera species, Elsinoe species, Epidermophyton species, Erwinia amylovora, Erysiphe species (including Erysiphe cichoracearum), Eutypa lata, Fusarium species (including Fusarium culmorum, Fusarium graminearum, Fusarium langsethiae, Fusarium moniliforme, Fusarium oxysporum, Fusarium solani, Fusarium verticillioides), Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulata, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium species, Hemileia species, Histoplasma species (including Histoplasma capsulatum H.capsulatum), red thread blight fungus, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum species, Monilinia species, Mucor species, Mycosphaerella species (including M. graminicola, M. pomi), tree tip blight fungus, spruce fungus, Paracoccidioides species, Penicillium species (including P. digitatum, P. italicum), Myriogenospora species, Sclerospora species (including S. maydis, S. philippinensis, S. sorghi), Peronospora species, Septoria tritici, Phakopsora pachyrhizi, Phellinus igniarus, Torrubiella species, Phoma species, Phomopsis viticola, Phytophthora species (including P. infestans), Plasmopara species (including P. halstedii, P. viticola), Pleospora species, Podosphaera species (including P. leucotricha), Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas species, Pseudoperonospora species (including P. cubensis, P. humuli), Pseudopeziza tracheiphila, Puccinia species (including P. hordei, P. recondita, P. striiformis, P. triticina), Sclerotinia species, Pyrenophora species, Pyricularia species (including P. oryzae), Pythium species (including P. ultimum), Ramularia species, Rhizoctonia species, Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium species, Scytalidium species (including Scedosporium apiospermum, Scedosporium prolificans), Schizothyrium pomi, Sclerotinia species, Sclerotium species, Septoria species (including S. nodorum, S. tritici)Puccinia tritici), Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix species, Stagonosporanodorum, Stemphylium species, Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia species, Trichoderma species (including Trichoderma harzianum, Trichoderma pseudokoningii, Trichoderma viride), Trichophyton species, Typhula species, Uncinula necator, Urocystis spp., Ustilago spp., Venturia species (including Venturia inaequalis), Verticillium species, and Xanthomonas species.

[0433] The compounds of formula (I) according to the invention can be used, for example, for turf, ornamental plants such as flowers, shrubs, broad-leaved trees or evergreens such as conifers, and tree injections, pest management, etc.

[0434] Within the scope of the present invention, the target crops and / or useful plants to be protected typically include perennial and annual crops such as berry plants, for example blackberry, blueberry, cranberry, raspberry and strawberry; 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 beet and fodder beet, coffee bean, hops, mustard, rapeseed (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees, for example apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; grasses, for example bermudagrass, bluegrass, bentgrass, centipedegrass, dallisgrass, ryegrass, St. Augustine grass and zoysiagrass; herbs, such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes, for example kidney bean, lentil, pea and soybean; nuts, for example almond, cashew, groundnut, hazelnut, peanut, pecan, pistachio and walnut; palm plants, for example oil palm; ornamental plants, for example flowers, shrubs and trees; other trees, for example cacao tree, coconut tree, olive tree and rubber tree; vegetables, for example asparagus, eggplant, broccoli, cabbage, carrot, cucumber, garlic, lettuce, zucchini, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and vines, for example grapevine.

[0435] The term "useful plant" should be understood to also include 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 flupyrsulfuron, prosulfuron and tritosulfuron, EPSPS (5-enolpyruvylshikimate-3-phosphate synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen oxidase) inhibitors) by conventional breeding methods or genetic engineering. Examples of crops which have been rendered tolerant to imidazolinones (such as imazamox) by conventional breeding methods (mutation) are summer rape (canola). Examples of crops which have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate-resistant and glufosinate-resistant maize varieties which are commercially available under the Herculex and trade names.

[0436] The term "useful plant" should be understood to also include useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesizing one or more selectively acting toxins such as are known, for example, from toxin-producing bacteria, in particular those of the genus Bacillus.

[0437] Examples of such plants are: (Maize variety expressing the CryIA(b) toxin); YieldGard (Maize variety expressing the CryIIIB(b1) toxin); YieldGard (Maize variety expressing the CryIA(b) and CryIIIB(b1) toxins); (Maize variety expressing the Cry9(c) toxin); Herculex (Maize variety expressing the CryIF(a2) toxin and the enzyme phosphinothricin N - acetyltransferase (PAT) conferring tolerance to the herbicide glufosinate); NuCOTN (Cotton variety expressing the CryIA(c) toxin); Bollgard (Cotton variety expressing the CryIA(c) toxin); Bollgard (Cotton variety expressing the CryIA(c) and CryIIA(b) toxins); (Cotton variety expressing the VIP toxin);

[0438] (Potato variety expressing the CryIIIA toxin); GT Advantage (GA21 glyphosate tolerance trait), CBAdvantage (Bt11 corn borer (CB) trait), RW (corn rootworm trait) and

[0439] The term "crop" shall be understood to also include crop plants that have been so transformed by recombinant DNA technology as to be capable of synthesizing one or more selectively acting toxins, such as those known, for example, from toxin - producing bacteria, in particular bacteria of the genus Bacillus.

[0440] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, for example, Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example, Vip1, Vip2, Vip3 or Vip3A; or insecticidal proteins that colonize nematodes by bacteria, such as Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, spider toxins, bee toxins and other insect-specific neurotoxins; toxins produced by fungi, such as streptomyces toxins, lectins, such as pea lectin, barley lectin or snowdrop lectin; agglutinins; protease inhibitors, such as trypsin inhibitors, serine protease inhibitors, potato protease inhibitor, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolic enzymes, such as 3-hydroxy steroid 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.

[0441] Furthermore, in the context of the present invention, δ-endotoxins (e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C) or vegetative insecticidal proteins (Vip) (e.g., Vip1, Vip2, Vip3 or Vip3A) should be understood to obviously also include hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are recombinantly produced by new combinations of different domains of those proteins (see, for example, WO 02 / 15701). Truncated toxins, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid substitutions, preferably a non-naturally occurring protease recognition sequence is inserted into the toxin, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence is inserted into the Cry3A toxin (see WO 2003 / 018810).

[0442] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-0374753, WO93 / 07278, WO 95 / 34656, EP 0427529, EP 0451878 and WO 03 / 052073.

[0443] Methods for preparing such transgenic plants are generally known to those 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 0367474, EP 0401979 and WO 90 / 13651.

[0444] The toxins contained in transgenic plants render the plants tolerant to harmful insects. Such insects can be present in any insect taxon but are particularly common among beetles (Coleoptera), dipteran insects (Diptera) and moths (Lepidoptera).

[0445] Transgenic plants containing 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: (maize variety expressing the Cry1Ab toxin); YieldGard (maize variety expressing the Cry3Bb1 toxin); YieldGard (maize variety expressing the Cry1Ab and Cry3Bb1 toxins); (maize variety expressing the Cry9C toxin); Herculex (maize variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) conferring tolerance to the herbicide glufosinate); NuCOTN (cotton variety expressing the Cry1Ac toxin); Bollgard (cotton variety expressing the Cry1Ac toxin); Bollgard (cotton variety expressing the Cry1Ac and Cry2Ab toxins); (cotton variety expressing the Vip3A and Cry1Ab toxins); (potato variety expressing the Cry3A toxin); GT Advantage (GA21 glyphosate tolerance trait), CB Advantage (Bt11 corn borer (CB) trait) and

[0446] Additional examples of such genetically modified crops are:

[0447] 1. Bt11 maize, from Syngenta Seeds SAS, Chemindel’Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified maize that expresses a truncated Cry1Ab toxin by transgenesis, making it resistant to the attack of European corn borer (Ostrinia nubilalis and Sesamia nonagrioides). Bt11 maize also expresses the PAT enzyme by transgenesis to obtain tolerance to the herbicide glufosinate.

[0448] 2. Bt176 maize, from Syngenta Seeds, Chemindel’Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified maize that expresses the Cry1Ab toxin by transgenesis, making it resistant to the attack of European corn borer (Ostrinia nubilalis and Sesamia nonagrioides). Bt176 maize also expresses the enzyme PAT by transgenesis to obtain tolerance to the herbicide glufosinate.

[0449] 3. MIR604 maize, from Syngenta Seeds, Chemindel’Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Maize with insect resistance by expressing a modified Cry3A toxin by transgenesis. This toxin is Cry3A055 modified by inserting a cathepsin-G protease recognition sequence. The preparation of such transgenic maize plants is described in WO 2003 / 018810.

[0450] 4. MON 863 maize, from Monsanto Europe S.A., Avenue de Tervuren 270-272, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses the Cry3Bb1 toxin and is resistant to certain Coleoptera insects.

[0451] 5. IPC 531 cotton, from Monsanto Europe, Avenue de Tervuren 270-272, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0452] 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 to obtain resistance to certain Lepidoptera insects, and expressing the PAT protein to obtain tolerance to the herbicide glufosinate.

[0453] 7. NK603×MON 810 maize, from Monsanto Europe S.A., 270 - 272 Avenue de Tervuren, B 1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. A hybrid maize variety constituted by conventional breeding by crossing the genetically modified varieties NK603 and MON 810. NK603×MON 810 maize transgenically expresses the protein CP4 EPSPS obtained from the Agrobacterium strain CP4, making it tolerant to the herbicide (containing glyphosate), and also the Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki, making it tolerant to certain Lepidoptera insects, including the European corn borer.

[0454] The compound having formula (I) according to the present invention can be used to control or prevent phytopathogenic diseases, especially phytopathogenic fungi, such as Alternaria spp. on fruits, vegetables and potatoes; Botrytis cinerea on strawberries, tomatoes, sunflowers, leguminous crops, vegetables and grapes; Rhizoctonia solani on potatoes and vegetables; Uncinula necator on grapes; Cladosporium spp., Erysiphe cichoracearum, Sphaerotheca fuliginea and Glomerella lagenarium on cucurbits; Meloidogyne incognita on cucurbits and solanaceous crops; Fusarium spp. on cereals; Leptosphaeria spp. on cereals; and yeast species on cereals.

[0455] As used herein, the term "site" means the place where a plant grows in or on, or the place where the seeds of a cultivated plant are sown, or the place where the seeds are to be placed in the soil. It includes the soil, seeds and seedlings, together with the established vegetation.

[0456] The term "plant" means all the tangible parts of a plant, including seeds, seedlings, young trees, roots, tubers, stems, stalks, leaves and fruits.

[0457] The term "plant propagation material" shall be understood to mean the reproductive parts of plants, such as seeds, which can be used for plant propagation, as well as vegetative material, such as cuttings or tubers (e.g., potatoes). Mention may be made, for example, of seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Mention may also be made of germinated plants and young plants which are to be transplanted after germination or after emergence. These young plants can be protected before transplantation by being treated completely or partially by drenching. Preferably, "plant propagation material" shall be understood to mean seeds.

[0458] The compounds of formula (I) according to the invention can be used in unmodified form or, preferably, together with auxiliaries conventionally employed in the art of formulation. For this purpose, they can be conveniently formulated in known manner as emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granules and also capsules (e.g., in polymeric substances). For the type of composition, the method of application is selected according to the intended purpose and the circumstances prevailing at the time, such as spraying, atomizing, dusting, broadcasting, spreading or watering. The compositions can also contain additional auxiliaries, such as stabilizers, defoamers, viscosity regulators, binders or tackifiers, together with fertilizers, micronutrient donors or other formulations for obtaining special effects.

[0459] Suitable carriers and auxiliaries, for example for agricultural use, can be solid or liquid and are substances useful in the art of formulation, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are described, for example, in WO 1997 / 33890.

[0460] 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 can further contain wetting agents to enhance activity, as well as defoamers and crystal growth inhibitors. In use, these concentrates are diluted in water and are generally applied as sprays to the area to be treated. The amount of the active ingredient can range from 0.5% to 95% of the concentrate.

[0461] Wettable powders are in the form of finely divided particles which are readily dispersible 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 readily wettable organic or inorganic solids. Wettable powders generally contain from 5% to 95% of the active ingredient plus small amounts of wetting agents, dispersants or emulsifiers.

[0462] An emulsifiable concentrate is a homogeneous liquid composition that is dispersible in water or other liquids and can 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. In use, these concentrates are dispersed in water or other liquids and are typically applied as sprays to the area to be treated. The amount of the active ingredient can range from 0.5% to 95% of the concentrate.

[0463] Granular formulations include both extrudates and coarser granules and are typically applied to the area to be treated without dilution. Typical carriers for granular formulations include sand, bleaching earth, attapulgite clay, bentonite, montmorillonite, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, stucco, wood flour, ground corn cobs, ground peanut hulls, 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 the active compound or can be coated with the active compound. Granular formulations typically contain 5% to 25% of the active ingredient, which can include surfactants such as heavy aromatic naphtha, kerosene, and other petroleum fractions, or vegetable oils; and / or adhesives such as dextrin, gum, or synthetic resins.

[0464] Dusts are free-flowing mixtures of the active ingredient and finely divided solids such as talc, clay, flour, and other organic and inorganic solids that serve as dispersants and carriers.

[0465] Microcapsules are typically droplets or particles of the active ingredient encapsulated within an inert porous shell that permits the encapsulated material to escape into the environment at a controlled rate. The diameter of the encapsulated droplets is typically 1 to 50 micrometers. The encapsulated liquid typically constitutes 50% to 95% of the weight of the capsule and may contain a solvent in addition to the active compound. The encapsulated particles are usually porous particles in which a porous membrane seals the particle orifice, retaining the active species in liquid form within the particle pores. The diameter of the particles typically ranges from 1 millimeter to 1 centimeter and preferably 1 millimeter to 2 millimeters. The particles are formed by extrusion, coagulation, or spheronization, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust, and carbon grains. The shell or membrane materials include natural and synthetic rubbers, fibrous materials, styrene-butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes, and starch xanthate.

[0466] Other useful formulations for agrochemical applications include simple solutions of the active ingredient in solvents such as acetone, alkylated naphthalenes, xylenes, and other organic solvents, in which the active ingredient is completely dissolved at the desired concentration. Pressurized sprays can also be used, in which the active ingredient is dispersed in a finely divided form due to the evaporation of a low-boiling dispersant solvent carrier.

[0467] Suitable agricultural adjuvants and carriers useful for formulating the compositions of the present invention are well known to those skilled in the art in the above types of formulations.

[0468] Liquid carriers that can be employed 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 abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, 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 monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, cumene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isopentanone, methyl isobutyl ketone, methyl laurate, methyl caprylate, methyl oleate, dichloromethane, m-xylene, n-hexane, n-octylamine, stearic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin wax, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropyl alcohol, and higher molecular weight alcohols such as pentanol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerol, and N-methyl-2-pyrrolidone. Water is usually the carrier of choice for diluting concentrates.

[0469] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite, fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, and lignin.

[0470] A wide range of surfactants are advantageously employed in the liquid and solid compositions, especially those designed to be diluted with a carrier prior to application. These agents typically comprise from 0.1% to 15% by weight of the formulation when in use. They can be anionic, cationic, nonionic or polymeric in nature and can be employed as emulsifiers, wetting agents, suspending agents or for other purposes. Typical surfactants include alkyl sulfates such as diethanolammonium lauryl sulfate; alkyl aryl sulfonates such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide adducts such as nonylphenol-C 18 ethoxylates; alcohol-alkylene oxide adducts such as tridecanol-C 16 ethoxylates; soaps such as sodium stearate; alkylnaphthalenesulfonates such as sodium dibutylnaphthalenesulfonate; salts of dialkyl esters of sulfosuccinic acid such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol 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.

[0471] Other adjuvants commonly used in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, defoaming agents, light blockers, compatibilizers, antifoaming agents, masking agents, neutralizing agents and buffers, corrosion inhibitors, dyes, flavorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and sticking agents.

[0472] In addition, further, other biocidal active ingredients or compositions can be combined with the compositions of the invention and used in the methods of the invention and applied simultaneously or sequentially with the compositions of the invention. When applied simultaneously, these additional active ingredients can be formulated together with the compositions of the invention or mixed in, for example, a spray tank. These additional biocidal active ingredients can be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and / or plant growth regulators.

[0473] The pesticidal agents mentioned herein by their common names are known, for example, from "The Pesticide Manual", 15th Edition, British Crop Protection Council 2009.

[0474] In addition, the compositions of the invention can also be applied together with one or more systemic acquired resistance inducers ("SAR" inducers). SAR inducers are known and described, for example, in U.S. Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.

[0475] Compounds of formula (I) according to the invention are generally used in the form of agrochemical compositions and can be applied to the crop area or plant to be treated either simultaneously or sequentially with further compounds. For example, these further compounds can be fertilizers or micronutrient donors or other preparations which influence plant growth. They can also be selective or non-selective herbicides, together with insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or adjuvants which are customarily employed in the field of formulation.

[0476] Compounds of formula (I) according to the invention can be used in the form of (fungicidal) compositions for controlling or protecting against phytopathogenic microorganisms, which compositions comprise as active ingredient at least one compound of formula (I) or at least one preferred individual compound as defined herein (in free form or in agrochemically utilizable salt form) and at least one of the abovementioned adjuvants.

[0477] Accordingly, the invention provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I) according to the invention, an agriculturally acceptable carrier and optionally adjuvants. 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 the compound of formula (I), the composition can also comprise at least one or more pesticidally active compounds, for example further fungicidal active ingredients.

[0478] The compound of formula (I) according to the invention can be the sole active ingredient of the composition, or, as appropriate, it can be mixed with one or more further active ingredients, such as pesticidal agents, fungicides, synergists, herbicides or plant growth regulators. In some cases, the further active ingredients can produce an unexpected synergistic activity.

[0479] 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, furoamide fungicides, furoanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine fungicides, organophosphorus fungicides, organotin fungicides, oxathiin fungicides, oxazole fungicides, phenylthioamide fungicides, polysulfide fungicides, pyrazole fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungicides, quinone fungicides, quinoxaline fungicides, strobulurin fungicides, sulfonanilide fungicides, thiadiazole fungicides, thiazole fungicides, thiazolidine fungicides, thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolo pyrimidine fungicides, urea fungicides, valinamide fungicides, and zinc fungicides.

[0480] Examples of suitable additional active ingredients include the following: mineral oil, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenyl benzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylacetamide, 4-chlorophenyl phenyl sulfone, acetoprole, aldicarb, amidithion, amidothioate, amitron, amitron hydrogen oxalate, amitraz, bromopropylate, arsenic trioxide, azobenzene, azinphos, benomyl, benoxa-fos, benzyl benzoate, bixafen, brofluthrinate, bromocyclen, bromophos, bromopropylate, buprofezin, butocarboxim, butoxycarboxim, butylpyridaben, calcium polysulfide, camphechlor, carbaryl, carbophenothion, cycloheximide, chinomethionat, chlorbenside, chlordimeform, chlordimeform hydrochloride, chlorobenzilate, chlorfenson, chlorfensulfide, chlorobenzilate, chloromebuform, chloromethiuron, chloropropylate, chlorthiophos, cinerin I, cinerin II, cinerins, closantel, coumaphos, crotamiton, crotoxyphos, cyhexatin, cyanthoate, DCPM, DDT, demephion, demephion-O, demephion-S, demeton, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulfon, dichlofluanid, dichlorvos, dicliphos, dicofol, dimefox, dinex, dinex-diclexine, dinocap-4, dinocap-6, dinoseb, dinopenton, dinosulfon, dinoterbon, dioxathion, diphenyl sulfone, disulfiram, DNOC, dofenapyn, doramectin, endothion, eprinomectin, ethion, etrimfos, fenazaflor, fenbutatin oxide, fenothiocarb,fenpyrad, fenpyroximate, fenpyrazamine, fenson, fentrifanil, flubenzimine, flucycloxuron, fluenetil, fluorbenside, FMC 1137, amitraz, amitraz hydrochloride, formparanate, γ-HCH, glyodin, halfenprox, hexadecyl cyclopropanecarboxylate, isocarbophos, jasmolin I, jasmolin II, jodfenphos, lindane, malonoben, mecarbam, mephosfolan, methiirame, methacrifos, methyl bromide, metolcarb, mexacarbate, milbemycin oxime, mipafox, monocrotophos, morphothion, moxidectin, naled, 4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one, nifluridide, nikkomycin, nitrilacarb, nitrilacarb 1:1 zinc chloride complex, omethoate, oxydeprofos, oxydisulfoton, pp'-DDT, parathion, permethrin, phenkapton, phosalone, phosfolan, phosphamidon, polychloroterpenes, polynactins, propachlor, promacyl, propoxur, prothidathion, prothoate, pyrethrin I, pyrethrin II, pyrethrins, pyridaphenthion, pyrimitate, quinalphos, quintiofos, R-1492, phosglycin, rotenone, schradan, sebufos, selamectin, sophamide, SSI-121, sulfenuron, sulfluramid, sulfotepSulfur, diflovidazin, tau-fluvalinate, TEPP, terbam, tetradifon, tetrasul, thiafenox, thiocarboxime, thiofanox, thiometon, chinomethionat, thuringiensin, triamiphos, triarathene, triazophos, triazuron, trifenofos, trinactin, formetanate, vaniliprole, bethoxazin, copper dioctoate, copper sulfate, cybutryne, dichlone, dichlorophen, galic acid, triphenyltin, slaked lime, sodium thiosulfate, quinoclamine, quinonamid, simazine, triphenyltin acetate, triphenyltin hydroxide, crotoxyphos, piperazine, thiophanate-methyl, chlorbufam, fenthion, pyridin-4-amine, strychnine, 1-hydroxy-1H-pyridine-2-thione, 4-(quinoxalin-2-ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, copper hydroxide, cresol, bipyrithione, dodine, fenaminosulf, formaldehyde, mercuric chloride, kasugamycin, kasugamycin hydrochloride hydrate, nickel bis(dimethyldithiocarbamate), nitrapyrin, octhilinone, oxolinic acid, oxytetracycline, potassium 8-hydroxyquinoline sulfate, probenazole, streptomycin, streptomycin sesquisulfate, tecloftalam, thimerosal, Adoxophyes orana granulovirus, Agrobacterium radiobacter, Amblyseius spp., Autographa gamma nucleopolyhedrovirus, Anagrus atomus, Aphelinus abdominalis, Aphidius colemani, Aphidoletes aphidimyza, Autographa californica nucleopolyhedrovirus, Bacillus sphaericus Neide, Beauveria brongniartii, Chrysoperla carnea, Cryptolaemus montrouzieri, Cydia pomonella granulovirus, Dacnusa sibirica, Diglyphus isaea,Encarsia formosa, Eretmocerus eremicus, Heterorhabditis bacteriophora, H. megidis, Hippodamia convergens, Leptomastix dactylopii, Macrolophus caliginosus, Mamestra brassicae NPV, Metaphycus helvolus, Metarhizium anisopliae var. acridum, Metarhizium anisopliae var. anisopliae, Neodiprion sertifer NPV and N. lecontei NPV, Orius species, Paecilomyces fumosoroseus, Phytoseiulus persimilis, Steinernema bibionis, Steinernema carpocapsae, Steinernema feltiae, Steinernema glaseri, Steinernema riobrave, Steinernema riobravis, Steinernema scapterisci, Steinernema spp., Trichogramma spp., Typhlodromus occidentalis, Verticillium lecanii, apholate, bisazir, busulfan, dimatif, hemel, hempa, metepa, methiotepa, methyl apholate, morzid, penfluron, tepa, thiohempa, thiotepa, tretamine, uredepa, (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-ol, (E,Z)-tetradeca-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)-heneicosa-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)-dodeca-7,9-dien-1-yl acetate, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate, 14-methyloctadec-1-ene, 4-methylnonan-5-ol and 4-methylnonan-5-one, alpha-multistriatin, brevicomin, codlelure, codlemone, cuelure, disparlure, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodec-8,10-dien-1-yl acetate, dominicalure, ethyl 4-methyloctanoate, eugenol, frontalin, grandlure, grandlure I, grandlure II, grandlure III, grandlure IV, hexalure, ipsdienol, ipsenol, japonilure, lineatin, litlure, looplure, medlure, megatomoic acid, methyleugenol, muscalure, octadeca-2,13-dien-1-yl acetate, octadeca-3,13-dien-1-yl acetate, orfralure, oryctalure, ostramone, siglure, sordidin, sulcatol, tetradec-11-en-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,Butopyronoxyl, butoxy(polypropylene glycol), dibutyl adipate, dibutyl phthalate, dibutyl succinate, diethyltoluamide, dimethylcarbate, dimethyl phthalate, ethylhexylglycerin, hexamide, methoquin-butyl, methyl neodecanoamide, oxamate, picaridin, 1,1-dichloro-1-nitroethane, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane, 1,2-dichloropropane and 1,3-dichloropropene, 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-dimethylphenoxy)ethanol, 2-chlorovinyl diethyl phosphate, 2-imidazolidinone, 2-isovalerylindan-1,3-dione, 2-methyl(propargyl)aminophenyl methylcarbamate, 2-thiocyanatoethyl laurate, 3-bromo-1-chloropropene, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate, 4-methyl(propargyl)amino-3,5-dimethylphenyl methylcarbamate, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate, fenthion, acrylonitrile, aldrin, allomurin, asana, α-ecdysone, aluminium phosphide, aminocarb, neonicotinoid, ethyl methidathion, pirimiphos-methyl, Bacillus thuringiensis δ-endotoxins, barium hexafluorosilicate, barium polysulfide, d-allethrin, Bayer 22 / 190, Bayer 22408, β-cyfluthrate, β-cypermethrin, bioethanomethrin, bioallethrin, bis(2-chloroethyl) ether, borax, bromfenvinfos, bromo-DDT, bufencarb, butacarb, butathiofos, butonate, calcium arsenate, calcium cyanide, carbon disulfide, carbon tetrachloride, cartap hydrochloride, cevadine, endosulfan, chlordane, kepone, chloroform, chloropicrin, chlorphoxim, chlorprazophos, cis-resmethrin, cismethrin, cyhalothrin, copper acetoarsenite, copper arsenate, copper oleate, chlorthiophos, cryolite, CS 708, cyanofenphos, cyanophos, cycloprothrin, chlorfensulphide, d-tetramethrin, DAEP, dazomet, decarbofuran, diamidafos, isocarbophos, dichlorvos, dicresyl, dicyclanil, dieldrin, diethyl 5-methylpyrazol-3-yl phosphate,Diprophylline (dilor), transfluthrin, dimetan, dimethrin, dimethylvinphos, dimetilan, binapacryl, dinoterb, ethofenprox, dioxabenzofos, dithicrofos, DSP, ecdysone, EI 1642, EMPC, EPBP, etaphos, ethiofencarb, ethyl formate, dibromoethane, dichloroethane, ethylene oxide, EXD, fenthion, fenethacarb, fenitrothion, fenoxacrim, fenpirithrin, fensulfothion, fenthion-ethyl, fipronil, butathiofos, fospirate, fosthietan, furathiocarb, furethrin, biguanide, biguanide acetate, sodium tetrathiocarbonate, halfenprox, HCH, HEOD, heptachlor, phocid thion, HHDN, hydrocyanic acid, hyquincarb, IPSP, chlorpyrifos, carbon chlordane, isodrin, isofenphos, isolane, isoprothiolane, isoxathion, juvenile hormone I, juvenile hormone II, juvenile hormone III, chlorcyclopentane, kinoprene, lead arsenate, bromophos, lirimfos, fosthiazate, mipafox, magnesium phosphide, azinphos, tetramethrin, menazon, mercurous chloride, mesulfenfos, metam, metam potassium, metam sodium, methanesulfonyl fluoride, methocrotophos, methoprene, pyrethrins, methoxychlor, methyl isothiocyanate, methyl chloroform, dichloromethane, metoxadiazone, mirex, naftalofos, naphthalene, NC-170, nicotine, nicotine sulfate, nithiazine, nornicotine, O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate, O,O,O',O'-tetrapropyl dithiopyrophosphate,Oleic acid, p-dichlorobenzene, parathion-methyl, pentachlorophenol, pentachlorophenyl laurate, PH 60-38, fenthion, parathion, phosphine, phoxim-methyl, pirimetaphos, polychlorodicyclopentadiene isomers, potassium arsenite, potassium thiocyanate, precocene I, precocene II, precocene III, primidophos, profluthrin, promecarb, profenofos, pyrazophos, pyresmethrin, quassia, quinalphos-methyl, chlorthiophos, rafoxanide, resmethrin, rotenone, kadethrin, ryania, ryanodine, sabadilla, schradan, sebufos, SI-0009, thiapronil, sodium arsenite, sodium cyanide, sodium fluoride, sodium hexafluorosilicate, sodium pentachlorophenate, sodium selenate, sodium thiocyanate, sulcofuron, sulcofuron-sodium, sulfuryl fluoride, sulprofos, tar, thiodicarb, TDE, butathiofos, temephos, empenthrin, tetrachloroethane, thicrofos, thiocyclam, thiocyclam hydrogen oxalate, thionazin, thiosultap, thiosultap-sodium, tralomethrin, transpermethrin, azidrin, trichlormetaphos-3, trichlorfon, trimethacarb, tolprocarb, triclopyricarb, triprene, veratridine, veratrine, XMC, zetamethrin, zinc phosphide, zolaprofos, meperfluthrin, tetraflumethrin, bis(tributyltin) oxide, bromoacetamide, iron phosphate, niclosamide ethanolamine, tributyltin oxide, pyrimorph, trifenmorph, 1,2-dibromo-3-chloropropane, 1,3-dichloropropene, 3,4-dichlorotetrahydrothiophene 1,1-dioxide, 3-(4-chlorophenyl)-5-methylrhodanine, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid, 6-isopentenylaminopurine, anisiflupurin, benclothiaz,Cytokinins, DCIP, furfural, isamidophos, kinetin, Myrothecium verrucaria composition, tetrachlorothiophene, xylenol, zeatin, potassium ethylxanthate, acibenzolar, acibenzolar-S-methyl, Reynoutria sachalinensis extract, alpha-chlorohydrin, antu, barium carbonate, bithiosemi, brodifacoum, bromadiolone, bromofacitin, chlorofacitin, cholecalciferol, chlorfenac, coumatetralyl, crimidine, difenacoum, difethialone, diphacinone, ergocalciferol, fluoride flocoumafen, fluoroacetamide, flupropadine, flupropadine hydrochloride, flucoumafen, flucoumafen, phosphorus, pindone, pyrinuron, scilla glycoside, sodium fluoroacetate, thallium sulfate, warfarin, 2-(2-butoxyethoxy)ethyl piperonate, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, farnesol with nerolidol, piperonyl butoxide, MGK 264, piperonyl butoxide, pipertal, propyl ester isomer), S421, sesamex, sesasmolin, sulfoxide, anthraquinone, copper cyclohexane, copper oxychloride, dicyclopentadiene, thiram, zinc cyclohexane, zinc zirconia, imanin, ribavirin, chloroindole hydrazide, mercuric oxide, thiophanate-methyl, azaconazole, bifenthrin, oxadiazole, cyproconazole, fenpropimorph, diniconazole, epoxiconazole, nitrobenzene, fluquinconazole, flusilazole, flutriafol, furopyram, hexaconazole, imazalil, imipenem, phyconazole, metconazole, nitrobenzene azole, paclobutrazol, pyrimethanol, penconazole, prothioconazole, pyrifenox, prochloraz, propiconazole, pyrisoxazole, simeconazole, tebuconazole, tetrafluthrin, triadimefon, triadimenol, triflumizole, trichlorfonazole, pyrimidine, chlorfenapyr, flufenapyr, bupirimate, dimethirimol, ethirimol, dodecacyclic morpholine, fenpropidin, fenbutrazol, spiroxaplanol, tridecamorph, cyprodinil, pyrimidine,pyrimethanil, fenpiclonil, fludioxonil, benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl, carbendazim, debacarb, dimethirimol, thiabendazole, chlozolinate, dichlozoline, myclozoline, procymidone, vinclozoline, boscalid, carboxin, mepronil, flutolanil, fenfuram, oxycarboxin, penthiopyrad, thifluzamide, dodine, iminoctadine, azoxystrobin, enestroburin, enoxastrobin, enostamide, flufenoxystrobin, fluoxastrobin, metominostrobin, metconazole, trifloxystrobin, orysastrobin, pyraclostrobin, pyribencarb, pyraoxystrobin, ferbam, mancozeb, maneb, metiram, propineb, zineb, captafol, captan, fluoroimide, chlorothalonil, tolylfluanid, bordeaux mixture, copper oxide, mancopper, oxine-copper, nitrothal-isopropyl, kitazin, iprobenphos, phosdiphen, tolclofos-methyl, anilazine, benthiavalicarb, blasticidin-S, chloroneb, chlorothalonil, cyflufenamid, cymoxanil, cybutryne, diclocymet, diclomezine, dicloran, diethofencarb, dimethomorph, flumorph, dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, ferimzone, fluazinam, flumetylsulforim, fluopicolide, fluoxytioconazole, flusulfamide,fluxapyroxad, fenhexamid, fosetyl-aluminum, hymexazol, propineb, cyazofamid, methasulfocarb, metrafenone, pencycuron, piperalin, polyoxins, propamocarb, pyribencarb, proquinazid, pyroquilon, pyriofenone, quinoxyfen, quintozene, tiadinil, triazoxide, tricyclazole, tridemorph, validamycin, valifenalate, zoxamide, mandipropamid, flubeneteram, isopyrazam, sedaxane, benzovindiflupyr, pydiflumetofen, 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide, isoflucypram, isotianil, dipymetitrone, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithieno[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-trimethyl-indan-4-yl]pyrazole-4-carboxamide, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-2,5-dimethyl-pyrazol-3-amine, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, fluindapyr, coumethoxystrobin (jiaxiangjunzhi), lvbenmixianan, dichlobentiazox, mandestrobin, 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, flutianiliproletert-Butyl N-[6-[[[(1-methyltetrazol-5-yl)phenylmethylene]amino]oxymethyl]-2-pyridinyl]carbamate, pyraziflumid, inpyrfluxam, trolprocarb, fluopyram, ipfentrifluconazole, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethylinden-4-yl]pyridine-3-carboxamide, N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylformamidine, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethylphenyl]-N-ethyl-N-methylformamidine, methyl [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chlorophenyl]sulfonate, but-3-yn-1-yl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)phenylmethylene]amino]oxymethyl]-2-pyridinyl]carbamate, methyl N-[[5-[4-(2,4-dimethylphenyl)-1,2,4-triazol-2-yl]-2-methylphenyl]methyl]carbamate, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine, pyridachlometyl, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylinden-4-yl]pyrazole-4-carboxamide, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methylphenyl]-4-methyl-1H-tetrazol-5-one, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]-1H-tetrazol-5-one, aminopyrifen, ametoctradin, amisulbrom, penflufen, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethylpent-3-enamide, florylpicoxamid, fenpicoxamid, metarylpicoxamid, tebufloquin, ipflufenoquin, quinofumelin, isofetamid,Ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate (which can be prepared by the method described in WO 2020 / 056090), ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enoxy]phenyl]methyl]pyrazole-3-carboxylate (which 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 (which 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 (which 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 (which can be prepared by the method described in WO 2020 / 109391), 6-chloro-N-[2-(2-chloro-4-methyl-phenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide (which can be prepared by the method described in WO 2020 / 109391), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (which can be prepared by the method described in WO 2020 / 109391), N-[2-[2,4-dichlorophenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide, benzothiostrobin, phenamacril, zinc salt of 5-amino-1,3,4-thiadiazole-2-thiol (2:1), fluopyram, flufenoxadiazam, flutianil, fluopimomide, pyrapropoyne, picarbutrazox, 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-pyridinyl]oxy]benzonitrile, metyltetraprole, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidine methanol, fluoxapiprolin, enoxastrobin, methyl (Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)-1,2,4-triazol-2-yl]phenoxy]prop-2-enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-(4-propyl-1,2,4-triazol-2-yl)phenoxy]prop-2-enoate, methyl (Z)-2-[5-(3-isopropyl-1H-pyrazol-1-yl)-2-methylphenoxy]-3-methoxyprop-2-enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-(3-propyl-1H-pyrazol-1-yl)phenoxy]prop-2-enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)-1H-pyrazol-1-yl]phenoxy]prop-2-enoate (these compounds can be prepared by the methods described in WO 2020 / 079111), methyl (Z)-2-(5-cyclohexyl-2-methylphenoxy)-3-methoxyprop-2-enoate, methyl (Z)-2-(5-cyclopentyl-2-methylphenoxy)-3-methoxyprop-2-enoate (these compounds can be prepared by the methods 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-pyridinyl]oxy]benzonitrile, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridinyl]oxy]benzonitrile, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridinyl]oxy]benzonitrile, trinexapac, coumoxystrobin, zhongshengmycin, thiodiazole copper, thiazole zinc, amectotractin, iprodione, seboctylamine, N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxyethoxy]-3-pyridinyl]-N-ethyl-N-methylformamidine,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-(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 can be prepared by the methods described in 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 methods 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 methods described in WO 2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetan-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 methods 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-propyl]-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,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 the methods described in 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 methods 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-isoquinolinyl)-7,8-dihydro-6H-cyclopenta[d]benzimidazole (these compounds can be prepared by the methods described in 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-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, 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, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine (these compounds can be prepared by the methods described in WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 093348 and WO 2017 / 118689); 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared by the method described in WO 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-hydroxypropyl]imidazole-4-carbonitrile (this compound can be prepared by the method described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile (this compound can be prepared by the method described in WO 2016 / 156290); (4-phenoxyphenyl)methyl 2-aminopyridine-3-carboxylate (this compound can be prepared by the method described in WO 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithieno[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone (this compound can be prepared by the method described in WO 2011 / 138281),N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]thiobenzamide; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine (this compound can be prepared by the method described in WO2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methyl-formamidine; N'-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-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); ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate (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, 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-carbimino]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (these compounds can be prepared by the method described in WO 2018 / 202428).、

[0481] The compounds of the present invention can also be used in combination with anthelmintic agents. Such anthelmintic agents include compounds selected from macrolide compounds, such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin, and milbemycin derivatives, as described in EP 0357460, EP 0444964, and EP 0594291. Additional anthelmintic agents include semi-synthetic and biosynthetic avermectin / milbemycin derivatives, such as those described in US 5,015,630, WO 9415944, and WO 9522552. Additional anthelmintic agents include benzimidazoles, such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of this class. Additional anthelmintic agents include imidazothiazoles and tetrahydropyrimidines, such as tetramisole, levamisole, pyrantel pamoate, oxantel, or morantel. Additional anthelmintic agents include trematocides (such as triclabendazole and closantel) and cestocides (such as praziquantel and etisazole).

[0482] The compounds of the present invention can be used in combination with derivatives and analogs of anthelmintic agents of the paraherquamide / marcfortine class, as well as anti-parasitic oxazolines (such as those disclosed in US 5478855, US 4639771, and DE-19520936).

[0483] The compounds of the present invention can be used in combination with derivatives and analogs of dioxolane anti-parasitic agents of the general class described in WO 9615121, as well as cyclic peptides having anthelmintic activity (such as those described in WO 9611945, WO 9319053, WO 9325543, EP 0626375, EP 0382173, WO 9419334, EP 0382173, and EP 0503538).

[0484] The compounds of the present invention can be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as chlorfenapyr; ecdysone agonists such as tebufenozide, etc.; neonicotinoids such as imidacloprid, etc.

[0485] The compounds of the present invention can be used in combination with terpenoid alkaloids, such as those described in WO 95 / 19363 or WO 04 / 72086, especially the compounds disclosed therein.

[0486] Other examples of such bioactive compounds that can be used in combination with the compounds of the present invention include, but are not limited to, the following:

[0487] 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.

[0488] Carbamates: aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, chlorpyrifos, carbofuran, butylthiocarb, diflubenzuron, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801, isoprocarb, indoxacarb, methiocarb, methomyl, (methyl)carbamic acid 5-methyl-m-isopropylphenylbutynyl ester, cypermethrin, pirimicarb, propoxur, thiodicarb, long-lasting carb, triazolam, UC-51717.

[0489] 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.

[0490] Arthropod growth regulators: a) Chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, flucarazone, flufenoxuron, flubendiamide, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, ethofenprox, hexythiazox, etoxazole, clofentezine; b) Ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) Juvenile hormone analogs: pyriproxyfen, methoprene (including S-methoprene), phenoxycarb; d) Lipid biosynthesis inhibitors: spirodiclofen.

[0491] Other antiparasitic drugs: acequinocyl, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorbenside, chlordimeform, chlorfenapyr, chromafenozide, clothianidin, cinmethionat, diacloden, diafenthiuron, DBI-3204, diomycin, dihydroxymethyl dihydroxypyrrolidine, dicofol, dienochlor, endosulfan, ethiprole, etofenprox, fenazaquin, flumite, MTI-800, fenpyroximate, fluacrypyrim, flubenzimine, flucythrinate, flufenerim, flutriafol, fluproxyfen, halofenprox, hydramethylnon, IKI-220, hydrocerussite, NC-196, neem guard, nidinorterfuran, nitenpyram, SD-35651, WL-108477, pyridalyl, propargite, protrifenbute, pymetrozine, pyridaben, pyrimidifen, NC-1111, R-195, RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601, silafluofen, silomadine, spinosad, pyridaben, tetradifon, tetraantibiotic, thiacloprid, thiosultap, thiamethoxam, tolfenpyrad, triazamate, triactinomycin, synergistic piperonyl ether, vertalec, YI-5301.

[0492] Biological agents: Bacillus thuringiensis ssp. aizawai, Bacillus thuringiensis ssp. kurstaki, Bacillus thuringiensis δ-endotoxin, baculovirus, entomopathogenic bacteria, viruses, and fungi.

[0493] Bactericides: chlortetracycline, oxytetracycline, streptomycin.

[0494] Other biological agents: enrofloxacin, febantel, penethamate hydriodide, meloxicam, cefalexin, kanamycin, pimobendan, clenbuterol, omeprazole, thiomurin, benazepril, pyriprole, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, ceftiofur, carprofen, mefronil, praziquantel, triclabendazole.

[0495] 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), (I-A), (I-A1), (I-A2), (I-A3), (I-A4), (I-A5), (I-A6), or (I-A7), or a compound selected from the compounds listed in Tables C-1 to C-36 or the compounds listed in Table P (below), and compounds selected from the group consisting of: mineral oil + TX, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX, 2,4-dichlorophenyl benzenesulfonate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 4-chlorophenyl phenyl sulfone + TX, acetoprole + TX, aldicarb + TX, cythioate + TX, dimethoate + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, chlorbenside + TX, arsenic trioxide + TX, azobenzene + TX, azinphos + TX, benomyl + TX, benoxaphos + TX, benzyl benzoate + TX, bixafen + TX, brodifacoum + TX, broxacillin + TX, bromophos + TX, bromopropylate + TX, buprofezin + TX, butocarboxim + TX, butoxycarboxim + TX, butylpyridaben + TX, lime sulfur + TX, toxaphene + TX, carbaryl + TX, carbophenothion + TX, cycloheximide + TX, chinomethionat + TX, chlorfenson + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorobenzilate + TX, chlorfenson + TX, dicofol + TX, ethylanilide + TX, etoxazole + TX, fenazaquin + TX, fenpyroximate + TX, fluacrypyrim + TX, fluazuron + TX, flufenzin + TX,Flubenzimine + TX, FMC 1137 + TX, Amitraz + TX, Amitraz hydrochloride + TX, Carbaryl + TX, γ-HCH + TX, Chlorophthalim + TX, Bifenazate + TX, Hexadecyl cyclopropanecarboxylate + TX, Isocarbophos + TX, Pyrethrins I + TX, Pyrethrins II + TX, Iodofenphos + TX, Lindane + TX, Propargite + TX, Aphox + TX, Phosamidon + TX, Methiophanate + TX, Methacrifos + TX, Methyl bromide + TX, MTMC + TX, Carbofuran + TX, Milbemycin + TX, Mipafox + TX, Monocrotophos + TX, Salithion + TX, Moxidectin + TX, Naled + TX, 4-Chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, Flucythrinate + TX, Nikkomycin + TX, Phenothrin + TX, Phenothrin 1:1 zinc chloride complex + TX, Omethoate + TX, Isofenphos-methyl + TX, Sulfotep + TX, pp'-DDT + TX, Parathion + TX, Permethrin + TX, Fenthion + TX, Phosalone + TX, Phosfolan + TX, Phosphamidon + TX, Turpentine chloride + TX, Tetranactin + TX, Proclonol + TX, Pyridalyl + TX, Propoxur + TX, Ethoprophos + TX, Prothiofos + TX, Pyrethrins I + TX, Pyrethrins II + TX, Pyrethrum + TX, Pyridaphenthion + TX, Pyrimiphos-methyl + TX, Quinalphos + TX, Quinalphos + TX, R-1492 + TX, Glyphosate + TX, Rotenone + TX, Schradan + TX, Cadusafos + TX, Selamectin + TX, Sulprofos + TX, SSI-121 + TX, Sufentanil + TX, Flufenoxuron + TX, Sulfotep + TX, Sulfur + TX, Flufenzine + TX, τ-Fluvalinate + TX, TEPP + TX, BPMC + TX, Tetradifon + TX, Sulofenphos + TX, Thiafenox + TX, Aldicarb + TX, Thiofanox + TX, Dimethoate + TX, Chlofenethol + TX, Bt + TX, Triazophos + TX, Triazamate + TX, Chlorfenvinphos + TX, Trivalent actinomycetes + TX, Formetanate + TX, Flupyradifurone + TX, Baythroid + TX, Copper dicaprylate + TX, Copper sulfate + TX, Cyclobutanecarbonitrile + TX, Dichlone + TX, Dichlorophen + TX, Myclobutanil + TX, Triphenyltin + TX, Slaked lime + TX, Sodium thiram + TX, Flumequin + TX, Quinonamid + TX, Simazine + TX, Triphenyltin acetate + TX, Triphenyltin hydroxide + TX, Crotxyphos + TX, Piperazine + TX, Thiophanate-methyl + TX, Chlorozolinate + TX, Fenthion + TX, Pyridin-4-amine + TX, Strychnine + TX, 1-Hydroxy-1H-pyridine-2-thione + TX, 4-(Quinoxalin-2-ylamino)benzenesulfonamide + TX, 8-Hydroxyquinoline sulfate + TX, Bronopol + TX, Copper hydroxide + TX, Cresol + TX,Dipyrithione + TX, dodixin + TX, sodium sulfamethoxazole + TX, formaldehyde + TX, mercury plus phenanthene + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel bis(dimethyldithiocarbamate) + TX, trichloromethylpyridine + TX, octhiothionine + TX, oxolinic acid + TX, oxytetracycline + TX, potassium hydroxyquinoline sulfate + TX, thiabendazole + TX, streptomycin + TX, streptomycin sesquisulfate + TX, chlorothiazide + TX, thimerosal + TX, cotton brown-banded tornado GV ​​+ TX, radiobacterium + TX, blunt mite species + TX, celery armyworm NPV + TX, original cherry-winged tassel wasp + TX, short-spurred aphid wasp + TX, cotton aphid parasitic wasp + TX, aphid-eating gall midge + TX, lucerne armyworm NPV + TX, Bacillus sphaeroides + TX, Beauveria bassiana + TX, common lacewings + TX, Cryptochilus monticola + TX, Codling moth GV + TX, Siberian jawed braconid + TX, Pea leafminer + TX, Aphididae + TX, Aphididae + TX, Bacteriophora heterorhabditis and Heterorhabditis spp. + TX, Long-legged ladybird + TX, citrus mealybug parasitic wasp + TX, Blight bug + TX, Cabbage armyworm NPV + TX, Yellow-stalked jumping wasp + TX, Yellow-green Metarhizium + TX, Metarhizium anisopliae microspore variant + TX, European new pine sawfly NPV and red-headed new pine sawfly NPV + TX, species of the genus Microsporum + TX, Penicillium fumosorum + TX, Chilean phytoseiid mite + TX, mosquito nematode + TX, Steinernema carinella +TX, Steinernema araneus +TX, Gnaphalium nematode +TX, Steinernema rapis +TX, Steinernema rapis +TX, Steinernema mole cricket +TX, Steinernema species +TX, Trichogramma spp. +TX, Western blind mite +TX, Verticillium lecanii +TX, oxazolidinone +TX, bis(aziridine)methylaminophosphonium sulfide +TX, busulfan +TX, dimethivin +TX, hexamethylmelamine +TX, hexamethylphosphonium +TX, methyl thio ... 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)-dodeca-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate + TX, 14-methyloctadec-1-ene + TX, 4-methylnon-5-ol and 4-methylnon-5-one + TX, α-multistriatin + TX, western pine beetle aggregation pheromone + TX, dodecadienol + TX, geraniol + TX, cue-lure + TX, epoxy nonadecane + TX, dodec-8-en-1-yl acetate + TX, dodec-9-en-1-yl acetate + TX, dodec-8,10-dien-1-yl acetate + TX, domcryl + TX, ethyl 4-methylcaprylate + TX, eugenol + TX, southern pine beetle aggregation pheromone + TX, methyl eugenol mixture + TX, methyl eugenol mixture I + TX, methyl eugenol mixture II + TX, methyl eugenol mixture III + TX, methyl eugenol mixture IV + TX, hexalure + TX, ipsdienol + TX, picrodendrol + TX, chafer sex pheromone + TX, trimethyldioxatricyclononane + TX, litural + TX, pink bollworm sex pheromone + TX, methacrilep + TX, maggotomic acid + TX, cucumerin + TX, cucurbitene + TX, octadeca-2,13-dien-1-yl acetate + TX, octadeca-3,13-dien-1-yl acetate + TX, helcopene + TX, rhinotrogus longulus aggregation pheromone + TX, nonylacar + TX, cucurbitacin + TX, sodiine + TX, mycetophagol + TX, tetradec-11-en-1-yl acetate + TX, medfly attractant + TX, medfly attractant A + TX, medfly attractant B1 + TX, medfly attractant B2 + TX, medfly attractant C + TX, tricoc + TX, 2-(octylthio)-ethanol + TX, butopyronoxyl + TX, butoxy(polypropylene glycol) + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, diethyltoluamide + TX, dimethyl phthalate + TX, ethylhexylglycerin + TX, hexanamide + TX, mequitazine + TX, methyl neodecanoate + TX, oxamate + TX, picaridin + TX, 1-dichloro-1-nitroethane + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane + TX, 1,2-dichloropropane and 1,3-dichloropropene + TX, 1-bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, O-ethyl S-[2-(2-chloroethenyl)-2-ethylsulfinylethyl]methylphosphonothioate + 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)phenyl methylcarbamate +2-(4-chloro-3,5-dimethylphenoxy)ethanol + TX, 2-chloroethenyl diethyl phosphate + TX, 2-imidazolidinone + TX, 2-isovalerylindan-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-dimethylphenyl methylcarbamate + TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate + TX, Muscatox + TX, acrylonitrile + TX, aldrin + TX, allomurin + TX, asana + TX, α-ecdysone + TX, aluminium phosphide + TX, aminocarb + TX, neonicotin + TX, ethion + TX, pirimiphos-methyl + TX, Bacillus thuringiensis delta-endotoxins + TX, barium hexafluorosilicate + TX, barium polysulphide + TX, resmethrin + TX, Bayer 22 / 190 + TX, Bayer 22408 + TX, beta-cyfluthrin + TX, beta-cypermethrin + TX, empenthrin + TX, bioallethrin + TX, bis(2-chloroethyl)ether + TX, borax + TX, bromfenvinfos + TX, bromo-DDT + TX, dimecron + TX, bendiocarb + TX, demethylbutapyrimfos + TX, butonate + TX, calcium arsenate + TX, calcium cyanide + TX, carbon disulphide + TX, carbon tetrachloride + TX, cartap hydrochloride + TX, cevadine + TX, endosulfan + TX, chlordane + TX, kepone + TX, chloroform + TX, trichloronitromethane + TX, chlorphoxim + TX, chlorprazophos + TX, cis-resmethrin + TX, cis-resmethrin + TX, lambda-cyhalothrin + TX, cupric acetoarsenite + TX, cupric arsenate + TX, copper oleate + TX, cyanofenphos + TX, cryolite + TX, CS 708 + TX, cyanofenphos + TX, cyanophos + TX, cycloprothrin + TX, cythioate + TX, d-tetramethrin + TX, DAEP + TX, dazomet + TX, carbofuran + TX, ethoprophos + TX, isothioate + TX, dichlorvos + TX, dicresyl + TX, dicyclanil + TX, dieldrin + TX, diethyl 5-methylpyrazol-3-yl phosphate + TX, diprophylline + TX, transfluthrin + TX, dimefox + TX, pyrethrins + TX, methyldichlorvos + TX, methiocarb + TX, binapacryl + TX, dinocap + TX, dinoseb + TX, phenthoate + TX, phosmet + TX, phenthoate + TX, DSP + TX, ecdysone + TX, EI 1642 + TX, EMPC + TX, EPBP + TX, oxydeprofos + TX, ethiofencarb + TX, ethyl formate + TX, ethylene dibromide + TX, ethylene dichloride + TX, ethylene oxide + TX, EXD + TX, fenthion + TX, ethiocarb + TX,Fenitrothion + TX, Ethirimol + TX, Cyfluthrin + TX, Fensulfothion + TX, Fenthion - ethyl + TX, Fipronil + TX, EPN + TX, Fosthiazate + TX, Cadusafos + TX, Furathiocarb + TX, Resmethrin + TX, Guazatine + TX, Guazatine acetate + TX, Sodium tetrathiocarbonate + TX, Bifenazate + TX, HCH + TX, HEOD + TX, Heptachlor + TX, Sumithion + TX, HHDN + TX, Hydrocyanic acid + TX, Pirimicarb + TX, IPSP + TX, Isazofos + TX, Carbophenothion + TX, Isodrin + TX, Isofenphos + TX, Imazalil + TX, Isoprothiolane + TX, Oxamyl + TX, Juvenile hormone I + TX, Juvenile hormone II + TX, Juvenile hormone III + TX, Chlorprene + TX, Kinoprene + TX, Lead arsenate + TX, Bromophos + TX, Propazine + TX, Tefluthrin + TX, MIPC + TX, Magnesium phosphide + TX, Azinphos - methyl + TX, Dimethoate + TX, Calomel + TX, Fenthion sulfoxide + TX, Metam + TX, Metam potassium + TX, Metam sodium + TX, Methanesulfonyl fluoride + TX, Butenochlor + TX, Methoprene + TX, Pyrethrins, type II + TX, Methoxychlor + TX, Methyl isothiocyanate + TX, Methyl chloroform + TX, Methylene chloride + TX, Acetoprole + TX, Mirex + TX, Naftalofos + TX, Naphthalene + TX, NC - 170 + TX, Nicotine + TX, Nicotine sulfate + TX, Nitrothal - isopropyl + TX, Nornicotine + TX, O - 5 - dichloro - 4 - iodophenyl O - ethyl ethylphosphonothioate + TX, O,O - diethyl O - 4 - methyl - 2 - oxo - 2H - chromen - 7 - yl phosphorothioate + TX, O,O - diethyl O - 6 - methyl - 2 - propylpyrimidin - 4 - yl phosphorothioate + TX, O,O,O',O' - tetrapropyl pyrophosphorodithioate + TX, Oleic acid + TX, p - dichlorobenzene + TX, Parathion - methyl + TX, Pentachlorophenol + TX, Pentachlorophenyl laurate + TX, PH 60 - 38 + TX, Phenthoate + TX, Parathion - p + TX, Phosphine + TX, Phoxim - methyl + TX, Methamidophos + TX, Polyisobutene succinic anhydride + TX, Potassium arsenite + TX, Potassium thiocyanate + TX, Precocene I + TX, Precocene II + TX, Precocene III + TX, Acephate + TX, Profluthrin + TX, BPMC + TX, Prothiofos + TX, Triflumizole + TX, Resmethrin + TX, Quassia amara extract + TX, Quinalphos - methyl + TX, Chlorthiophos + TX, Rafoxanide + TX, Resmethrin + TX, Rotenone + TX, Thienylpyrethrin + TX, Ryania + TX, Ryanodine + TX, Veratrum sabadilla + TX, Schradan + TX, Cartap + TX, SI - 0009 + TX, Etoxazole + TX, Sodium arsenite + TX, Sodium cyanide + TX, Sodium fluoride + TX, Sodium hexafluorosilicate + TX, Sodium pentachlorophenate + TXSodium selenate + TX, Sodium thiocyanate + TX, Salkafuron + TX, Salkafuron sodium + TX, Sulfuryl fluoride + TX, Profenofos + TX, Tar + TX, Pyridaben + TX, TDE + TX, Butylpyrimiphos + TX, Abate + TX, Allethrin + TX, 1,1,2,2-Tetrachloroethane + TX, EPN + TX, Thiosultap + TX, Thiosultap hydrogen oxalate + TX, Sulfotep + TX, Monosultap + TX, Bisultap + TX, Tralomethrin + TX, Transfluthrin + TX, Triazamate + TX, Trichlorometaphosphate-3 + TX, Chlorbufam + TX, BPMC + TX, Trimethacarb + TX, Tefluthrin + TX, Chlorothalonil + TX, Teflubenzuron + TX, Veratridine + TX, Veratrine + TX, XMC + TX, Zeta-cypermethrin + TX, Zinc phosphide + TX, Zolaprofos + TX, and Chloroflurane + TX, Tetramethrin + TX, Bis(tributyltin) oxide + TX, Bromoacetamide + TX, Iron phosphate + TX, Niclosamide ethanolamine + TX, Tributyltin oxide + TX, Pyrimorph + TX, Melubrin + TX, 1,2-Dibromo-3-chloropropane + TX, 1,3-Dichloropropene + TX, 3,4-Dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-(4-Chlorophenyl)-5-methylrhodanine + TX, 5-Methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid + TX, 6-Isopentenylaminopurine + TX, 2-Fluoro-N-(3-methoxyphenyl)-9H-purin-6-amine + TX, Benzyl chloride + TX, Cytokinin + TX, DCIP + TX, Furfural + TX, Isamidofos + TX, Kinetin + TX, Myrothecium verrucaria composition + TX, Tetrachlorothiophene + TX, Xylenol + TX, Zeatin + TX, Potassium ethylxanthate + TX, Benalaxyl + TX, Benalaxyl-M + TX, Polygonum cuspidatum extract + TX, α-Chloroalcohol + TX, Antu + TX, Barium carbonate + TX, Diphacinone + TX, Bromadiolone + TX, Bromethalin + TX, Chlorophacinone + TX, Cholecalciferol + TX, Chlorophacinone + TX, Coumatetralyl + TX, Coumatetralyl + TX, Difenacoum + TX, Tiacumicarb + TX, Warfarin + TX, Warfarin + TX, 2-(2-Butoxyethoxy)ethyl piperate + TX, 5-(1,3-Benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, Farnesol with nerolidol + TX, PBO + TX, MGK 264 + TX, Piperonyl butoxide + TX, Safroxan + TX, Octachlorodipropyl ether + TX, S421 + TX, Synergistic powder + TX, Sesamin + TX, Sulfoxide + TX, Anthraquinone + TX, Copper naphthenate + TX, Copper oxychloride + TX,Dicyclopentadiene + TX, Thiram + TX, Zinc naphthenate + TX, Ziram + TX, Imanine + TX, Ribavirin + TX, Mercuric oxide + TX, Thiophanate-methyl + TX, Azaconazole + TX, Bitertanol + TX, Bromuconazole + TX, Cyproconazole + TX, Difenoconazole + TX, Diniconazole + TX, Epoxiconazole + TX, Fenbuconazole + TX, Fluopyram + TX, Hexaconazole + TX, Imazalil + TX, Imibenconazole + TX, Ipconazole + TX, Metconazole + TX, Myclobutanil + TX, Paclobutrazol + TX, Pyributicarb + TX, Tebuconazole + TX, Prothioconazole + TX, Pyrifenox + TX, Prochloraz + TX, Propiconazole + TX, Pyriofenone + TX, Simeconazole + TX, Tebuconazole + TX, Tetraconazole + TX, Triadimefon + TX, Triadimenol + TX, Triflumizole + TX, Tricyclazole + TX, Ancymidol + TX, Fenarimol + TX, Fluoromide + TX, Ethirimol + TX, Dimethirimol + TX, Dodemorph + TX, Fenpropidin + TX, Fenpropimorph + TX, Spiroxamine + TX, Tridemorph + TX, Cyprodinil + TX, Fenoxanil + TX, Pyrimethanil + TX, Fentrazamide + TX, Fludioxonil + TX, Benalaxyl + TX, Furalaxyl + TX, Metalaxyl + TX, R-Metalaxyl + TX, Furophanate + TX, Oxadixyl + TX, Carbendazim + TX, Imibenconazole + TX, Fuberidazole + TX, thiabendazole + TX, Chlorothalonil + TX, Procymidone + TX, Vinclozolin + TX, Iprodione + TX, Procymidone + TX, Vinclozolin + TX, Iprodione + TX, Boscalid + TX, Carboxin + TX, Methfuroxam + TX, Tricyclazole + TX, oxycarboxin + TX, Pyrisoxazole + TX, Tifluzamide + TX, dodine + TX, guazatine + TX, Azoxystrobin + TX, Dimoxystrobin + TX, Enestroburin + TX, Enostrobin + TX, Fluopyram + TX, Fluoxastrobin + TX, Kresoxim-methyl + TX, Metominostrobin + TX, Trifloxystrobin + TX, Trifloxystrobin + TX, Zoxamide + TX, Ferbam + TX, Mancozeb + TX, Manganese ethylenebisdithiocarbamate + TX, Metiram + TX, Metazam + TX, Zinc manganese ethylenebisdithiocarbamate + TX, Zineb + TX, Captafol + TX, Captan + TX, Pyrazolate + TX, Chlorothalonil + TX, Tolylfluanid + TX, Bordeaux mixture + TX, Copper oxide + TX, Copper manganese ethylenebisdithiocarbamate + TX, Oxine copper + TX, Phthalide + TX, Kitazin + TX, IBP + TX, Chlorpyrifos-methyl + TX, TPN + TX, Chlorothalonil + TX, Cyflufenamid + TX, Cymoxanil + TX, Cyflufenamid + TX, Clopyralid + TX, Dichlofluanid + TX, Ethirimol + TX, Dimethirimol + TX, Fluazinam + TX, Flumorph + TX, Flumorph + TX, Dithianon + TX, Thiazoleamine + TX,etridiazole + TX, oxadixyl + TX, fenamidone + TX, picoxystrobin + TX, ferimzone + TX, fluazinam + TX, fluopicolide + TX, sulfluramid + TX, fluxapyroxad + TX, fenhexamid + TX, fosetyl-aluminum + TX, hymexazol + TX, propineb + TX, cyazofamid + TX, sulcofuron + TX, metrafenone + TX, tebuconazole + TX, pyroquilon + TX, polyoxin + TX, propamocarb + TX, pyribencarb + TX, iodocarb + TX, pyroquilon + TX, metrafenone + TX, quinoxyfen + TX, quintozene + TX, tiadinil + TX, imazalil + TX, tricyclazole + TX, tridemorph + TX, validamycin + TX, dimethomorph + TX, zoxamide + TX, mandipropamid + TX, fluopyram + TX, pyraclostrobin + TX, fluxapyroxad + TX, fluopyram + TX, benzovindiflupyr + TX, fluxapyroxad + TX, 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, isoflucypram + TX, isofetamid + TX, dipicamid + TX, 6-ethyl-5,7-dioxopyrrolo[4,5][1,4]dithieno[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-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-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, fluindapyr + TX, methyl ethyl carbamate + TX, ribetazine + TX, dichlobenil + TX, mandestrobin + 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, flutianil + TX, N-[6-[[[(1-methyltetrazol-5-yl)phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamic acid tert-butyl ester + TX, bixafen + TX, inpyrfluxam + TX, toclofos-methyl + TX, chlorfluzuron + TX, ipfentrifluconazole + TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylformamidine + TX,N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + TX, methylsulfonic acid [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] ester + TX, N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]but-3-ynyl carbamate + TX, N-[[5-[4-(2,4-dimethylphenyl)-1,2,3-triazol-2-yl]-2-methyl-phenyl]methyl]methyl carbamate + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, Pydar + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylinden-4-yl]pyrazole-4-carboxamide + TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-1H-tetrazol-5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]-1H-tetrazol-5-one + TX, Amiphenazole + TX, Zoxamide + TX, Indaziflam + TX, Fenpyrazamine + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX, Pyrimethanil + TX, Bupirimate + TX, Ibutamiprid + TX, Fluopicolide + TX, Chinomethionat + TX, Isotianil + TX, N-[2-[2,4-dichlorophenoxy]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, Benzothiazole + TX, Cyenopyrac + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, Fluopyram + TX, Fluopyram + TX, Fluopyram + TX, Fluopyram + TX, Tetraconazole + TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethylinden-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylinden-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-pyridinyl]oxy]benzonitrile + TX, Metconazole + TX, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidine methanol + TX,Flufenoxypyr + TX, Enestroburin + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridinyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioalkyl-1,2,4-triazol-1-yl)propyl]-3-pyridinyl]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-pyridinyl]oxy]benzonitrile + TX, Trinexapac-ethyl + TX, Cercosporamide + TX, Zhongshengmycin + TX, Thiodiazole copper + TX, Thiazole zinc + TX, Amitrole + TX, Iprodione + TX, N-octyl-N'-[2-(octylamino)methyl]ethane-1,2-diamine + TX; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-isopropyl-N-methyl-formamidine + TX (These compounds can be prepared by the methods described in 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 methods described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenylethyl)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 the methods described in WO 2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[2-(trifluoromethyl)oxetan-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 the methods described in 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 the methods described in 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 the methods described in WO2017 / 025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX,1-(4,5-Dimethyl-1H-benzo[d]imidazol-1-yl)-4,4-difluoro-3,3-dimethylisoquinoline + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methyl-1H-benzo[d]imidazol-1-yl)isoquinoline + TX, 4,4-difluoro-1-(5-fluoro-4-methyl-1H-benzo[d]imidazol-1-yl)-3,3-dimethylisoquinoline + TX, 3-(4,4-difluoro-3,3-dimethylisoquinolin-1-yl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole + TX (these compounds can be prepared by the methods described in WO 2016 / 156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]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, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate + 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 WO 2017 / 055473, WO 2017 / 055469,Prepared by the methods described in WO2017 / 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-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate + TX (this compound can be prepared by the method described in WO 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithieno[2,3-c:5,6-c']bipyrrole-1,3,5,7(2H,6H)-tetrone + TX (this compound can be prepared by the method described in WO 2011 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]thiobenzamide + TX; 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 the method described in WO 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methyl-formamidine + TX; N'-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methyl-formamidine + TX (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 + 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 methods 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 methods described in WO 2018 / 065414); Ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate + TX (This compound can be prepared by the methods described in WO2018 / 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-C-methyl-carbamimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX (These compounds can be prepared by the methods described in WO 2018 / 202428), Chlorodiflubenzuron + TX, Fluoxastrobin + TX, Fluopyram + TX, Fluazaindolizine + TX, Picolinafen + TX.

[0496] References in brackets after the active ingredient, e.g., [3878-19-1], refer to Chemical Abstracts Registry Numbers. The mixing combinations described above are known. Where the active ingredient is included in "The Pesticide Manual", [The Pesticide Manual - A World Compendium]; 13th Edition; Editor: C.D.S. Tomlin; The British Crop Protection Council], they are described therein by the entry numbers given in parentheses above for the particular compound; for example, the compound "Abamectin" is described by the entry number (1). Where "[CCN]" is added above to a particular compound, the said compound is included in "Compendium of Pesticide Common Names", which is available on the Internet [A. Wood; Compendiumof PesticideCommon Names , Copyright obtained in the period from 1995 to 2004; for example, the compound "acetoprole" is described at the Internet address http: / / www.alanwood.net / pesticides / acetoprole.html.

[0497] Most of the above active ingredients are mentioned above by means of the so-called "common name", using the corresponding "ISO common name" or another "common name" in a single case. If the name is not a "common name", the type of name used is replaced by the name given in parentheses for the particular compound; in this case, the IUPAC name, the IUPAC / Chemical Abstracts name, the "chemical name", the "trivial name", the "compound name" or the "development code" is used, or, if neither one of those names nor the "common name" is used, the "alias" is adopted. "CAS Registry Number" means the Chemical Abstracts Registry Number.

[0498] A mixture of active ingredients of compounds selected from the compounds of formula (I), (I-A), (I-A1), (I-A2), (I-A3), (I-A4), (I-A5), (I-A6), or (I-A7), or from the compounds listed in Tables C-1 to C-36 or in Table P (below) is preferably in a mixing ratio of from 100:1 to 1:100, in particular from 50:1 to 1:50, more particularly from 20:1 to 1:20, even more particularly from 10:1 to 1:10 and still more particularly from 5:1 to 1:5. Those mixing ratios are by weight.

[0499] A mixture as described above can be used in a method for controlling pests, which method comprises applying a composition comprising the mixture as described above to the pests or their environment, with the exception of methods for treating the human or animal body by surgery or therapy and diagnostic methods carried out on the human or animal body.

[0500] Compounds comprising a compound selected from compounds having formula (I), (I-A), (I-A1), (I-A2), (I-A3), (I-A4), (I-A5), (I-A6), or (I-A7), or a compound selected from the compounds listed in Tables C-1 to C-36 or the compounds listed in Table P (below) and a mixture of one or more active ingredients as described above can be applied, for example, in a single "ready-to-use" form, in a combined spray mixture consisting of separate formulations of the individual active ingredient components, such as "tank mixing", and when applied in a sequential manner, i.e., one after the other within a reasonably short period of time (such as a few hours or days), the individual active ingredients are used in combination. The order of application of a compound selected from compounds having formula (I), (I-A), (I-A1), (I-A2), (I-A3), (I-A4), (I-A5), (I-A6), or (I-A7), or a compound selected from the compounds listed in Tables C-1 to C-36 or the compounds listed in Table P (below) and one or more active ingredients as described above is not critical for carrying out the present invention.

[0501] The compositions according to the invention can also contain further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (such as epoxidized coconut oil, rapeseed oil or soybean oil), defoamers (such as silicone oils), preservatives, viscosity regulators, binders and / or tackifiers, fertilizers or other active ingredients for obtaining specific effects, such as bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0502] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries, for example by grinding, sieving and / or compressing the solid active ingredients; and in the presence of at least one auxiliary, for example by intimately mixing the active ingredient with one or more auxiliaries and / or grinding the active ingredient together with one or more auxiliaries. These methods for preparing the compositions and the use of the compound (I) for preparing these compositions are also the subject of the present invention.

[0503] Another aspect of the invention relates to the use of a fungicidal or insecticidal mixture comprising a compound of formula (I) according to the invention or preferably an individual compound as defined herein, or a composition comprising at least one compound of formula (I) or at least one individual compound as defined herein, or at least one compound of formula (I) or at least one individual compound as defined herein (mixed with other fungicides or insecticides as described above) for controlling or preventing plants (such as useful plants, e.g., crop plants), their propagation materials (such as seeds), harvested crops (such as harvested food crops), or inanimate materials from being infested by insects or phytopathogenic microorganisms (preferably fungal organisms).

[0504] Another aspect of the invention relates to a method for controlling or preventing plants (such as useful plants, e.g., crop plants), their propagation materials (such as seeds), harvested crops (such as harvested food crops), or inanimate materials from being infested by phytopathogenic microorganisms or spoilage microorganisms or organisms potentially harmful to humans (especially fungal organisms), which method comprises applying a compound of formula (I) according to the invention or preferably an individual compound as defined herein as an active ingredient to these plants, parts of these plants or their sites, their propagation materials, or any part of these inanimate materials.

[0505] Controlling or preventing means reducing the infestation by insects or phytopathogenic microorganisms or spoilage microorganisms or organisms potentially harmful to humans (especially fungal organisms) to a proven improved level.

[0506] A preferred method for controlling or preventing crop plants from being infested by phytopathogenic microorganisms (especially fungal organisms) or insects is foliar application, which method comprises applying a compound of formula (I) according to the invention or an agrochemical composition containing at least one compound of formula (I). The frequency and rate of application will depend on the risk of infestation by the respective pathogen or insect. However, the compound of formula (I) according to the invention can also penetrate plants via the roots (systemic action) through the soil by soaking the sites of the plants with a liquid formulation or by applying the compound in solid form, for example in granular form, to the soil (soil application). In rice crops, such granules can be applied to flooded paddy fields. The compound of formula (I) can also be applied to seeds (coating) by impregnating the seeds or tubers with a liquid formulation of the fungicide or coating them with a solid formulation.

[0507] 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 (such as solvents, solid carriers and optionally surface-active compounds (surfactants)).

[0508] Advantageous application rates are generally 5 g to 2 kg of active ingredient (a.i.) / hectare (ha), preferably 10 g to 1 kg a.i. / ha, most preferably 20 g to 600 g a.i. / ha. When used as a seed soaking agent, a suitable dose is 10 mg to 1 g of active substance / kg of seeds.

[0509] As used herein, the term "g a.i. / ha" refers to the application rate given in grams [g] of active ingredient [a.i.] / unit surface [ha]. The unit hectare (symbol ha) is a metric unit equal to the area of a square with a side length of 100 m (1 hm 2 ) or 10,000 square meters. The hectare is a commonly used area unit in the metric system.

[0510] When the combinations of the invention are used for treating seeds, application rates of 0.001 to 50 g of the compound of formula (I) / kg of seeds, preferably 0.01 to 10 g / kg of seeds, are generally sufficient.

[0511] Suitably, the compositions comprising a compound of formula (I) according to the invention are applied prophylactically (i.e., before the development of the disease) or therapeutically (i.e., after the development of the disease).

[0512] The compositions of the invention can be employed in any conventional form, for example in the form of a two-pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an oil-in-water emulsion (EO), a water-in-oil emulsion (EW), a microemulsion (ME), an oil dispersion (OD), an oil suspension (OF), an oil-soluble liquid formulation (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid formulation (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP) or in the form of any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0513] Such compositions can be produced in a conventional manner, for example by mixing the active ingredient with suitable formulation inert agents (diluents, solvents, fillers and optionally other formulation ingredients such as surfactants, biocides, antifreeze agents, adhesives, thickeners and compounds providing auxiliary effects). Conventional sustained-release formulations aimed at long-term sustained efficacy can also be used. In particular, formulations to be applied in spray form, such as water-dispersible concentrates (e.g., EC, SC, DC, OD, SE, EW, EO, etc.), wettable powders and granules, can 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.

[0514] The combination according to the invention and a diluent are used to apply the seed dressing formulation to the seeds in a suitable seed dressing formulation form (e.g., in the form of an aqueous suspension or a dry powder having good adhesion to the seeds) in a manner known per se. Such seed dressing formulations are known in the art. The seed dressing formulation can contain a single active ingredient or a combination of active ingredients in encapsulated form, such as in the form of sustained-release capsules or microcapsules.

[0515] Generally, these formulations contain 0.01% to 90% by weight of the active agent, 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 of at least a compound of formula (I) according to the invention together with other active agents (especially microbicides or preservatives, etc.). The concentrated form of the composition usually contains 2% to 80% by weight, preferably 5% to 70% by weight of the active agent. The application form of the formulation can contain, for example, 0.01% to 20% by weight, preferably 0.01% to 5% by weight of the active agent. However, commercial products will preferably be formulated as concentrates and the end user will generally use diluted formulations.

[0516] However, it is preferred to formulate commercial products as concentrates and the end user will generally use diluted formulations.

[0517] The application rates vary within a wide range and depend on the nature of the soil, the application method, the crop plants, the pests to be controlled, the prevailing climatic conditions, and other factors governed by the application method, the application time and the target crop. Generally speaking, the compounds can be applied at a rate of 1 to 2000 l / ha, especially 10 to 1000 l / ha.

[0518] Preferred formulations can have the following composition (% by weight):

[0519] Emulsifiable Concentrate :

[0520] Active ingredient: 1% to 95%, preferably 60% to 90%

[0521] Surfactant: 1% to 30%, preferably 5% to 20%

[0522] Liquid carrier: 1% to 80%, preferably 1% to 35%

[0523] Dust :

[0524] Active ingredient: 0.1% to 10%, preferably 0.1% to 5%

[0525] Solid carrier: 99.9% to 90%, preferably 99.9% to 99%

[0526] Suspension Concentrate:

[0527] Active ingredient: 5% to 75%, preferably 10% to 50%

[0528] Water: 94% to 24%, preferably 88% to 30%

[0529] Surfactant: 1% to 40%, preferably 2% to 30%

[0530] Wettable Powder :

[0531] Active ingredient: 0.5% to 90%, preferably 1% to 80%

[0532] Surfactant: 0.5% to 20%, preferably 1% to 15%

[0533] Solid carrier: 5% to 95%, preferably 15% to 90%

[0534] Granule:

[0535] Active ingredient: 0.1% to 30%, preferably 0.1% to 15%

[0536] Solid carrier: 99.5% to 70%, preferably 97% to 85%

[0537] The disclosure of the present application enables each combination of the embodiments disclosed herein to be obtained.

[0538] The compounds according to Tables C-1 to C-36 below can be prepared according to the above method. The following examples are intended to illustrate the present invention and to show the preferred compounds of formula (I). In any of the following Tables C-1 to C-36, the presence of one or more possible asymmetric carbon atoms in the compounds of formula (I) according to the present invention means that these compounds can exist in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms.

[0539] Table A

[0540] This table discloses 22 compounds of formula (A):

[0541]

[0542] wherein R 1 、R 2 、R 3 、R 4 、R 6 、B 1 、B 2 and Q are as defined above for the compounds of formula (I), and G has the formula as defined below

[0543]

[0544]

[0545] Table B

[0546] This table discloses 8 compounds of formula (A):

[0547]

[0548] wherein R 1 、R 2 、R 3 、R 4 、R 6 、B 1 、and B 2 are as defined above for the compounds of formula (I), and Q is as defined below:

[0549]

[0550]

[0551] Tables C-1 to C-36 disclose specific compounds of formula (A):

[0552]

[0553] wherein R 2 、R 4 、R 5 and R 6 are each defined as in any one of Tables C-1 to C-36, and the G and Q substituents are defined as in Tables A and B, respectively.

[0554] Table C-1: This table provides 22 compounds C-1.01 to C-1.22 having formula (A), wherein R 1 、R 2 、R 3 、R 4 and R 6 are H, B 1 and B 2 are C-H, Q is Q 1 and G is defined as in Table A.

[0555] For example, compound C-1.01 has the following structure:

[0556]

[0557] Table C-2: This table provides 22 compounds C-2.01 to C-2.22 having formula (A), wherein R 1 、R 2 、R 3 、R 4 and R 6 are H, B 1 and B 2 are C-H, Q is Q 2 and G is defined as in Table A.

[0558] Table C-3: This table provides 22 compounds C-3.01 to C-3.22 having formula (A), wherein R 1 、R 2 、R 3 、R 4 and R 6 are H, B 1 and B 2 are C-H, Q is Q 3 and G is defined as in Table A.

[0559] Table C-4: This table provides 22 compounds C-4.01 to C-4.22 having formula (A), wherein R 1 、R 2 、R 3 、R 4 and R 6 are H, B1 and B 2 is C-H, Q is Q 4 , and G is defined as in Table A.

[0560] Table C-5: This table provides 22 compounds of formula (A), C-5.01 to C-5.22, where R 1 , R 2 , R 3 , R 4 and R 6 are H, B 1 and B 2 is C-H, Q is Q 5 , and G is defined as in Table A.

[0561] Table C-6: This table provides 22 compounds of formula (A), C-6.01 to C-6.22, where R 1 , R 2 , R 3 , R 4 and R 6 are H, B 1 and B 2 is C-H, Q is Q 6 , and G is defined as in Table A.

[0562] Table C-7: This table provides 22 compounds of formula (A), C-7.01 to C-7.22, where R 1 , R 2 , R 3 , R 4 and R 6 are H, B 1 and B 2 is C-H, Q is Q 7 , and G is defined as in Table A.

[0563] For example, compound C-7.22 has the following structure:

[0564]

[0565] Table C-8: This table provides 22 compounds of formula (A), C-8.01 to C-8.22, where R 1 , R 2 , R 3 , R 4 and R 6 are H, B 1 and B 2 is C-H, Q is Q 8 , and G is defined as in Table A.

[0566] Table C-9: This table provides 22 compounds of formula (A) from racemic-cis-C-9.01 to racemic-cis-C-9.22, where R 1 、R 2 、R 3 、and R 6 is H, R 4 is CH3, B 1 and B 2 are C-H, Q is Q 1 ,and G is as defined in Table A. Among these compounds, the Q substituent and the R 4 substituent have a cis relationship with each other.

[0567] Table C-10: This table provides 22 compounds of formula (A) from racemic-cis-C-10.01 to racemic-cis-C-10.22, where R 1 、R 2 、R 3 、and R 6 are H, R 4 is CH3, B 1 and B 2 are C-H, Q is Q 2 ,and G is as defined in Table A. Among these compounds, the Q substituent and the R 4 substituent have a cis relationship with each other.

[0568] For example, the compound racemic-cis.C-10.05 has the following structure:

[0569]

[0570] Table C-11: This table provides 22 compounds of formula (A) from racemic-cis-C-11.01 to racemic-cis-C-11.22, where R 1 、R 2 、R 3 、and R 6 are H, R 4 is CH3, B 1 and B 2 are C-H, Q is Q 3 ,and G is as defined in Table A.

[0571] Table C-12: This table provides 22 compounds of formula (A) from racemic-cis-C-12.01 to racemic-cis-C-12.22, where R 1 、R 2 、R3 and R 6 is H, R 4 is CH3, B 1 and B 2 is C-H, Q is Q 4 , and G is defined as in Table A.

[0572] Table C-13: This table provides 22 compounds of formula (A) from racemic-cis-C-13.01 to racemic-cis-C-13.22, where R 1 、R 2 、R 3 、and R 6 is H, R 4 is CH3, B 1 and B 2 is C-H, Q is Q 5 , and G is defined as in Table A.

[0573] Table C-14: This table provides 22 compounds of formula (A) from racemic-cis-C-14.01 to racemic-cis.C-14.22, where R 1 、R 2 、R 3 、and R 6 is H, R 4 is CH3, B 1 and B 2 is C-H, Q is Q 6 , and G is defined as in Table A.

[0574] Table C-15: This table provides 22 compounds of formula (A) from racemic-cis-C-15.01 to racemic-cis-C-15.22, where R 1 、R 2 、R 3 、and R 6 is H, R 4 is CH3, B 1 and B 2 is C-H, Q is Q 7 , and G is defined as in Table A.

[0575] Table C-16: This table provides 22 compounds of formula (A) from racemic-cis-C-16.01 to racemic-cis-C-16.22, where R 1 、R 2 、R 3 、and R 6 is H, R 4 is CH3, B 1and B 2 is C-H, Q is Q 8 and G is defined as in Table A.

[0576] Table C-17: This table provides 22 compounds of formula (A), C-17.01 to C-17.22, where R 1 is CH3, R 2 , R 3 , R 4 and R 6 are H, B 1 and B 2 is C-H, Q is Q 1 and G is defined as in Table A.

[0577] Table C-18: This table provides 22 compounds of formula (A), C-18.01 to C-18.22, where R 1 is CH3, R 2 , R 3 , R 4 and R 6 are H, B 1 and B 2 is C-H, Q is Q 2 and G is defined as in Table A.

[0578] Table C-19: This table provides 22 compounds of formula (A), C-19.01 to C-19.22, where R 1 is CH3, R 2 , R 3 , R 4 and R 6 are H, B 1 and B 2 is C-H, Q is Q 3 and G is defined as in Table A.

[0579] Table C-20: This table provides 22 compounds of formula (A), C-20.01 to C-20.22, where R 1 is CH3, R 2 , R 3 , R 4 and R 6 are H, B 1 and B 2 is C-H, Q is Q 4 and G is defined as in Table A.

[0580] Table C-21:This table provides 22 compounds of formula (A), C-21.01 to C-21.22, where R 1 is CH3, R 2 , R 3 , R 4 and R 6 are H, B 1 and B 2 are C-H, Q is Q 5 , and G is as defined in Table A.

[0581] Table C-22: This table provides 22 compounds of formula (A), C-22.01 to C-21.22, where R 1 is CH3, R 2 , R 3 , R 4 and R 6 are H, B 1 and B 2 are C-H, Q is Q 6 , and G is as defined in Table A.

[0582] For example, compound C-22.03 has the following structure:

[0583]

[0584] Table C-23: This table provides 22 compounds of formula (A), C-23.01 to C-23.22, where R 1 is CH3, R 2 , R 3 , R 4 and R 6 are H, B 1 and B 2 are C-H, Q is Q 7 , and G is as defined in Table A.

[0585] Table C-24: This table provides 22 compounds of formula (A), C-24.01 to C-24.22, where R 1 is CH3, R 2 , R 3 , R 4 and R 6 are H, B 1 and B 2 are C-H, Q is Q 8 , and G is as defined in Table A.

[0586] Table C-25:This table provides 22 compounds C-25.01 to C-25.22 having formula (A), wherein R 1 , R 2 , R 3 , R 4 and R 6 Yes H, B 1 Yes CH, B 2 is C-Cl, Q is Q 3 , and G is as defined in Table A.

[0587] Table C-26: This table provides 22 compounds C-26.01 to C-26.22 having formula (A), wherein R 1 , R 2 , R 3 , R 4 and R 6 Yes H, B 1 Yes CH, B 2 is C-Cl, Q is Q 4 , and G is as defined in Table A.

[0588] Table C-27: This table provides 22 compounds C-27.01 to C-27.22 having formula (A), wherein R 1 , R 2 , R 3 , R 4 and R 6 Yes H, B 1 Yes CH, B 2 is C-Cl, Q is Q 5 , and G is as defined in Table A.

[0589] Table C-28: This table provides 22 compounds C-28.01 to C-28.22 having formula (A), wherein R 1 , R 2 , R 3 , R 4 and R 6 Yes H, B 1 Yes CH, B 2 is C-Cl, Q is Q 6 , and G is as defined in Table A.

[0590] Table C-29: This table provides 22 compounds C-29.01 to C-29.22 having formula (A), wherein R 1 , R 2 , R 3 , R 4 and R 6 Yes H, B1 is CH, B 2 is C-CN, and Q is Q 3 , and G is as defined in Table A.

[0591] Table C-30: This table provides 22 compounds of formula (A), C-30.01 to C-30.22, where R 1 , R 2 , R 3 , R 4 , and R 6 are H, B 1 is CH, B 2 is C-CN, and Q is Q 4 , and G is as defined in Table A.

[0592]

[0593]

[0594] Table C-31: For example, compound 30.14 has the following structure: 1 , R 2 , R 3 , R 4 , and R 6 are H, B 1 is CH, B 2 is C-CN, and Q is Q 5 , and G is as defined in Table A.

[0595] Table C-32: This table provides 22 compounds of formula (A), C-31.01 to C-31.22, where R 1 , R 2 , R 3 , R 4 , and R 6 are H, B 1 is CH, B 2 is C-CN, and Q is Q 6 1 , and G is as defined in Table A.

[0596] Table C-33: This table provides 22 compounds of formula (A), racemic-cis-C-33.01 to racemic-cis-C-33.22, where R 1 , R 2 , R 3 , and R 6 are H, R 4 is CH3, B 1 is CH, B2 is C-Cl, and Q is Q 4 , and G is as defined in Table A. In these compounds, the Q substituent and the R 4 substituent have a cis relationship to each other.

[0597] Table C-34: This table provides 22 compounds of formula (A) from racemic-cis-C-34.01 to racemic-cis-C-34.22, where R 1 , R 2 , R 3 , and R 6 are H, R 4 is CH3, B 1 is CH, B 2 is C-Cl, and Q is Q 6 , and G is as defined in Table A. In these compounds, the Q substituent and the R 4 substituent have a cis relationship to each other.

[0598] Table C-35: This table provides 22 compounds of formula (A) from racemic-cis-C-35.01 to racemic-cis-C-35.22, where R 1 , R 2 , R 3 , and R 6 are H, R 4 is CH3, B 1 is CH, B 2 is C-CN, and Q is Q 4 , and G is as defined in Table A. In these compounds, the Q substituent and the R 4 substituent have a cis relationship to each other.

[0599] For example, the compound racemic-cis-C-35.11 has the following structure:

[0600]

[0601] Table C-36: This table provides 22 compounds of formula (A) from racemic-cis-C-36.01 to racemic-cis-C-36.22, where R 1 , R 2 , R 3 , and R 6 are H, R 4 is CH3, B 1 is CH, B 2 is C-CN, and Q is Q 6 , and G is as defined in Table A. In these compounds, the Q substituent and the R 4The substituents have a cis relationship to each other.

[0602] Examples

[0603] The following examples are used to illustrate the invention and are not meant to limit the invention in any way.

[0604] The compounds of the invention may differ from known compounds in greater efficacy at low application rates, which can be confirmed by a person of ordinary skill in the art using the experimental procedures outlined in the examples, using lower application rates (if necessary), for example, 60 ppm, 20 ppm, or 2 ppm.

[0605] Compounds having the formula (I) can have any number of benefits, including, inter alia, a favorable level of biological activity for protecting plants against diseases caused by fungi or superior properties for use as an active ingredient in agrochemicals (e.g., higher biological activity, favorable activity spectrum, increased safety (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).

[0606] Throughout this specification, temperatures are given in degrees Celsius and "m.p." means melting point. LC / MS means liquid chromatography mass spectrometry, and the apparatus and methods are described below.

[0607] Recorded on a Bruker 400 MHz spectrometer 1 1H NMR and 19 19F NMR measurements, chemical shifts relative to TMS ([[]]END]] 1 1H) and CFCl3 ([[]]END]] 19 19F) standards are given in ppm. The spectra are measured in the deuterated solvents as indicated. These compounds are characterized using any of the following LCMS methods. The characteristic LCMS values obtained for each compound are the retention time ("Rt", recorded in minutes) and the measured molecular ion (M + H) + or (M - H) - .

[0608] The following HPLC-MS methods are used for the analysis of the compounds:

[0609] Method A (LCMS):Spectra were recorded on a mass spectrometer (SQD, SQDII single quadrupole mass spectrometer) from Waters, equipped with an electrospray source (polarity: positive and negative ions, capillary: 3.00 kV, cone voltage range: 30 V, extractor: 2.00 V, source temperature: 150 °C, desolvation temperature: 350 °C, cone gas flow rate: 50 l / h, desolvation gas flow rate: 650 l / h, mass range: 100 to 900 Da) and an Acquity UPLC from Waters: binary pump, heated column compartment, diode array detector and ELSD detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 x 2.1 mm, temperature: 60 °C, DAD wavelength range (nm): 210 to 500, solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; gradient: 10% - 100% B in 1.2 min; flow rate (ml / min): 0.85.

[0610] Method B: Spectra were recorded on a mass spectrometer (Acquity QDa mass spectrometer) from Waters, equipped with an electrospray source (polarity: positive and negative polarity switching), capillary: 0.8 kV, cone voltage range: 25 V, extractor: V (no extractor voltage for Qda detector), source temperature: 120 °C, desolvation temperature: 600 °C, cone gas flow rate: 50 L / h, desolvation gas flow rate: 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, 30 x 2.1 mm, temperature: 40 °C, DAD wavelength range (nm): 200 to 400, solvent gradient: A = water + 5% acetonitrile + 0.1% HCOOH, B = acetonitrile + 0.05% HCOOH; gradient: 0 min 10% B; 0. - 0.2 min 10% - 50% B; 0.2 - 0.6 min 50% - 100% B; 0.6 - 1.3 min 100% B; 1.3 - 1.4 min 100% - 10% B; 1.4 - 1.6 min 10% B; flow rate (mL / min) 0.6.

[0611] Method C: Instrument: Mass spectrometer: 6410 triple quadrupole mass spectrometer from Agilent Technologies; HPLC: Agilent 1200 series HPLC

[0612] Optimized quality parameters: Ionization method: Electrospray ionization (ESI); Polarity: Positive and negative polarity switching; Scan type: MS2 scan; Capillary (kV): 4.00; Fragmentation voltage (V): 100.00; Gas temperature (°C): 350; Gas flow rate (L / min): 11; Nebulizer gas (psi): 40; Mass range: 110 to 1000 Da; Detection (VWD): 254 nm. Optimized chromatographic parameters: Gradient conditions: Solvent A: Water containing 0.1% formic acid: Acetonitrile: 95:5 v / v; Solvent B: Acetonitrile containing 0.1% formic acid

[0613]

[0614] Column: KINETEX EVO C18, Column length: 50 mm, Column inner diameter: 4.6 mm; Particle size: 2.6 μm. Column oven temperature: 40 °C

[0615] Formulation Examples

[0616]

[0617] The combination is thoroughly mixed with adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a wettable powder that can be diluted with water to give a suspension of the desired concentration.

[0618]

[0619] The combination is thoroughly mixed with adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a powder that can be directly used for seed treatment.

[0620] Emulsifiable Concentrate

[0621]

[0622]

[0623] An emulsion of any required dilution that can be used in plant protection can be obtained by diluting this concentrate with water.

[0624]

[0625] A ready-to-use dust is obtained by mixing the combination with a carrier and grinding the mixture in a suitable grinder. Such dusts can also be used for dry seed dressing.

[0626] Extruded Granule

[0627]

[0628] The combination is mixed with adjuvants and ground, and the mixture is moistened with water. The mixture is extruded and then dried in an air stream.

[0629] Coated Granule

[0630] 8% active ingredient

[0631] 3% polyethylene glycol (molecular weight 200)

[0632] 89% kaolin

[0633] The finely ground combination is evenly applied in a mixer to kaolin moistened with polyethylene glycol. Dust-free coated granules are obtained in this way.

[0634] Suspension Concentrate

[0635]

[0636]

[0637] The finely ground combination is intimately mixed with adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants together with plant propagation materials can be treated and protected against microbial infestation by spraying, watering or dipping.

[0638] Flowable Concentrate for Seed Treatment

[0639]

[0640] The finely ground combination is intimately mixed with adjuvants, giving a flowable concentrate from which suspensions of any desired dilution can be obtained by dilution with water and which can be used directly for seed treatment. Using such dilutions, living plants together with plant propagation materials can be treated and protected against microbial infestation by spraying, watering or dipping.

[0641] Sustained Release Capsule Suspension

[0642] Mix a combination of 28 parts with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate-mixture (8:1). Emulsify this mixture in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 part of an antifoaming agent, and 51.6 parts of water until the desired particle size is reached. Add to this emulsion a mixture of 2.8 parts of 1,6-hexanediamine in 5.3 parts of water. Stir the mixture until the polymerization reaction is complete. Stabilize the obtained capsule suspension by adding 0.25 part of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% of the active ingredient. The diameter of the medium capsules is 8 - 15 microns. Apply the obtained formulation as an aqueous suspension in a device suitable for this purpose to the seeds.

[0643] Formulation types include emulsion concentrate (EC), suspension concentrate (SC), suspoemulsion (SE), capsule suspension (CS), water dispersible granule (WG), emulsifiable granule (EG), emulsion, water-in-oil emulsion (EO), oil-in-water emulsion (EW), microemulsion (ME), oil dispersion (OD), oil suspension (OF), oil-soluble solution (OL), soluble concentrate (SL), ultra-low volume suspension (SU), ultra-low volume solution (UL), technical material (TK), dispersible concentrate (DC), wettable powder (WP), soluble granule (SG), or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0644] Abbreviations

[0645] CDCl3 deuterated chloroform

[0646] DABCO 1,4-diazabicyclo[2.2.2]octane, also known as triethylenediamine or TEDA

[0647] DCC dicyclohexylcarbodiimide

[0648] DCM dichloromethane

[0649] DMF dimethylformamide

[0650] DMSO dimethyl sulfoxide

[0651] DMSO-d6 deuterated dimethyl sulfoxide

[0652] EDC 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide

[0653] Et3N triethylamine

[0654] EtOAc ethyl acetate

[0655] HATU 1-[Bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium-3- oxide hexafluorophosphate

[0656] HCl Hydrochloric acid

[0657] h / hrs hour / hours

[0658] LC-MS Liquid chromatography mass spectrometry (LC-MS or LCMS)

[0659] rh Relative humidity

[0660] rt Room temperature

[0661] Rt Retention time

[0662] ssp. Subspecies

[0663] T3P Propane phosphonic anhydride, also known as 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane 2,4,6-trioxide

[0664] THF Tetrahydrofuran

[0665] Preparation Examples

[0666] The compounds of formula (I) according to the present invention can be prepared using the synthetic techniques described above and below.

[0667] “Mp” means melting point in °C. The radical represents a methyl group. Recorded on a Bruker 400 MHz spectrometer (or 600 MHz as indicated) 1 H NMR and 19 F NMR measurements, chemical shifts relative to TMS ( 1 H) and CFCl3 ( 19 F) standards are given in ppm. The spectra are measured in the deuterated solvent as indicated. These compounds are characterized using any of the following LC-MS methods. The characteristic LCMS values obtained for each compound are the retention time (“Rt”, recorded in minutes) and the measured molecular ion (M+H) + or (M-H) - .

[0668] Example P1: Synthesis of [4-(5-chloro-1,2-dimethyl-imidazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(5-phenyl isoxazol-3-yl)methanone (Compound P-31, Table P)

[0669]

[0670] Step A: Preparation of 4-(5-chloro-1,2-dimethyl-imidazol-4-yl)isoquinoline

[0671]

[0672] A solution of 5-chloro-1,2-dimethyl-imidazole (CAS: 937818-18-3, 2.000 g, 14.55 mmol), 4-bromoisoquinoline (CAS: 1532-97-4, 3.277 g, 15.28 mmol) in toluene (58 mL) was treated with cesium carbonate (4.76 g, 14.55 mmol), then treated with 1,10-phenanthroline (0.2649 g, 1.455 mmol), and the mixture was degassed with argon for 5 minutes. Then palladium(II) acetate (0.3333 g, 1.455 mmol) was added, and the mixture was stirred at 160 °C for 11 days. The reaction mixture was filtered through celite, and the cake was washed with some EtOAc. The filtrate was concentrated in vacuo, and the obtained crude product was purified by flash chromatography using EtOAc / cyclohexane to give 4-(5-chloro-1,2-dimethyl-imidazol-4-yl)isoquinoline.

[0673] LC-MS: 258 [M+H], Rt: 0.57 min (Method A)

[0674] 1 H NMR (400 MHz, CDCl3) δ ppm 2.57 (s, 3H) 3.68 (s, 3H) 7.78 (td, J = 7.63, 1.09 Hz, 1H) 7.90 (ddd, J = 8.54, 7.08, 1.45 Hz, 1H) 8.15 (d, J = 7.99 Hz, 1H) 8.54 (d, J = 8.72 Hz, 1H) 8.66 (s, 1H) 9.32 (s, 1H)

[0675] Step B: Preparation of 4-(5-chloro-1,2-dimethyl-imidazol-4-yl)-1,2,3,4-tetrahydroisoquinoline

[0676]

[0677] Sodium cyanoborohydride (0.429 g, 6.60 mmol) was added portionwise to a pale yellow solution of 4-(5-chloro-1,2-dimethyl-imidazol-4-yl)isoquinoline (0.425 g, 1.65 mmol) in methanol (16.5 mL). The resulting pale yellow solution was stirred for 15 minutes at room temperature under argon. Then 4N hydrogen chloride in dioxane (1.65 mL, 6.60 mmol) was added dropwise. The resulting brown solution was stirred for 1 hour at room temperature under argon and then the mixture was diluted with water and basified with 2 mL of 4N aqueous NaOH. The reaction mixture was diluted with water and then extracted three times with EtOAc. The combined organic layers were washed once with brine, dried over anhydrous Na2SO4, filtered and concentrated in vacuo to give 4-(5-chloro-1,2-dimethyl-imidazol-4-yl)-1,2,3,4-tetrahydroisoquinoline.

[0678] LC-MS: 262 [M+H], Rt: 0.26 min (Method A)

[0679] 1 1H NMR (400 MHz, DMSO d-6) δ ppm 6.98 - 7.11 (m, 3H) 6.76 - 6.83 (m, 1H) 3.82 - 3.99 (m, 3H) 3.47 (s, 3H) 3.01 - 3.11 (m, 2H) 2.23 (s, 3H).

[0680] Step C: Preparation of [4-(5-chloro-1,2-dimethyl-imidazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(5-phenyl isoxazol-3-yl)methanone (Compound P-31, Table P)

[0681] 4-(5-Chloro-1,2-dimethyl-imidazol-4-yl)-1,2,3,4-tetrahydroisoquinoline (0.060 g, 0.23 mmol) was dissolved in EtOAc (2.3 mL) and then treated with 1-propane phosphonic anhydride (0.25 mL, 0.41 mmol), followed by treatment with N,N-diisopropylethylamine (0.12 mL, 0.69 mmol), and then 5-phenylisoxazole-3-carboxylic acid (0.050 g, 0.25 mmol) was added and the resulting mixture was stirred for 1 hour at room temperature under an argon atmosphere. The reaction mixture was diluted with water and EtOAc, the aqueous phase was separated, and the aqueous phase was back-extracted with EtOAc. The combined organic phases were washed once with brine, dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The crude product was purified by flash chromatography on silica gel (eluting with EtOAc) to afford [4-(5-chloro-1,2-dimethyl-imidazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(5-phenylisoxazol-3-yl)methanone.

[0682] LC-MS: 433 [M+H], Rt: 0.85 min (Method A)

[0683] Example P2: Preparation of (5-phenylisoxazol-3-yl)-[4-(3-pyridyl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-6, Table P)

[0684]

[0685] Step A: Preparation of 4-(3-pyridyl)isoquinoline

[0686]

[0687] Under an argon atmosphere, 4-bromoisoquinoline (CAS 1532-97-4, 0.550 g, 2.64 mmol) was dissolved in 1,4-dioxane (8 mL) and water (1.32 mL), and then treated with pyridine-3-boronic acid (CAS: 1692-25-7, 0.502 g, 3.97 mmol), cesium carbonate (2.59 g, 7.93 mmol), and 1,1'-bis(diphenylphosphino)ferrocene-dichloropalladium(II) dichloromethane complex (0.110 g, 0.132 mmol). The resulting suspension was stirred overnight at 100 °C. The reaction was then quenched with water, EtOAc was added, and the aqueous layer was extracted with PTL. was added to the organic layer, and the solvent was removed in vacuo. The crude product was purified by silica gel chromatography to give 4-(3-pyridyl)isoquinoline.

[0688] LC-MS: 207 [M+H], Rt: 0.48 min (Method A)

[0689] 1 1H NMR (400 MHz, CDCl3) δ ppm 9.33 (s, 1H) 8.81 (dd, J = 2.4, 0.9 Hz, 1H) 8.76 (dd, J = 4.8, 1.8 Hz, 1H) 8.51 (s, 1H) 8.06 - 8.14 (m, 1H) 7.83 - 7.94 (m, 2H) 7.65 - 7.79 (m, 2H) 7.45 - 7.55 (m, 1H)

[0690] Step B: Preparation of 4-(3-pyridyl)-1,2,3,4-tetrahydroisoquinoline

[0691]

[0692] At room temperature, a solution of 4-(3-pyridyl)isoquinoline (0.154 g, 0.7468 mmol) in methanol (7.5 mL) was treated with sodium cyanoborohydride (0.2964 g, 4.481 mmol). 4M Hydrochloric acid (0.5 mL, 2 mmol) in dioxane was slowly added to this mixture. The resulting solution was stirred at room temperature for 1 hour and then diluted with water and basified with 2N NaOH. MeOH was removed by vacuum concentration, and the resulting aqueous layer was extracted with DCM (three times). The combined organic layers were dried over Na2SO4, filtered, and concentrated in vacuo to afford 4-(3-pyridyl)-1,2,3,4-tetrahydroisoquinoline.

[0693] LC-MS: 211 [M+H], Rt: 0.22 min (Method A)

[0694] 1 H NMR (400 MHz, CDCl3) δ ppm 8.45 - 8.53 (m, 2H) 7.41 (dt, J = 7.8, 2.0 Hz, 1H) 7.19 - 7.26 (m, 2H) 7.07 - 7.17 (m, 2H) 6.88 (d, J = 7.3 Hz, 1H) 4.08 - 4.25 (m, 3H) 3.46 (dd, J = 13.2, 5.5 Hz, 1H) 3.11 (dd, J = 12.8, 6.6 Hz, 1H)

[0695] Step C: Preparation of (5-phenylisoxazol-3-yl)-[4-(3-pyridyl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-6)

[0696] A suspension of 4-(3-pyridyl)-1,2,3,4-tetrahydroisoquinoline (0.161 g, 0.7656 mmol) in DCM (11.4 mL) was cooled to 0 °C and treated with 5-phenylisoxazole-3-carbonyl chloride (0.1621 g, 0.7809 mmol) and triethylamine (0.427 mL, 3.062 mmol). The resulting solution was stirred at room temperature overnight and then concentrated in vacuo. The crude product was purified by silica gel combiflash chromatography to afford (5-phenylisoxazol-3-yl)-[4-(3-pyridyl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone.

[0697] LC-MS: 382 [M+H], Rt: 0.91 min (Method A)

[0698] 11H NMR (400 MHz, CDCl3) δ ppm 8.37 - 8.60 (m, 2H) 7.69 - 7.88 (m, 2H) 7.12 - 7.57 (m, 8H) 6.88 - 7.02 (m, 1H) 6.32 - 6.86 (m, 1H) 4.86 - 5.30 (m, 2H) 3.92 - 4.47 (m, 3H)

[0699] Example P3: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-(1-methyl-1,2,4-triazol-3-yl)-3,4- dihydro-1H-isoquinolin-2-yl]methanone (Compound P-33, Table P)

[0700]

[0701] Step A: Preparation of 4-(1-methyl-1,2,4-triazol-3-yl)isoquinoline

[0702]

[0703] Charge a microwave vial with 3 - bromo - 1 - methyl - 1,2,4 - triazole (0.12 g, 0.74 mmol), 4 - isoquinolinylboronic acid (0.19 g, 1.1 mmol), sodium carbonate (0.24 g, 2.2 mmol), 1,4 - dioxane (2.2 mL) and water (0.74 mL). Degas the reaction mixture with nitrogen for 5 min and then treat with chloro(2 - dicyclohexylphosphino - 2',4',6' - triisopropyl - 1,1' - biphenyl)[2 - (2' - amino - 1,1' - biphenyl)]palladium(II) (0.030 g, 0.037 mmol). Stir the resulting reaction mixture under microwave irradiation at 120 °C for 2 h (which turns dark brown). Monitor the reaction progress by LCMS and TLC. After completion, cool the reaction mixture to room temperature and dilute with saturated aqueous NH4Cl (50 mL). Extract the mixture with EtOAc (2 X 50 mL), wash the combined organic layers with brine, dry over sodium sulfate and concentrate in vacuo. Purify the crude product by combi flash chromatography to afford 4 - (1 - methyl - 1,2,4 - triazol - 3 - yl)isoquinoline.

[0704] LC - MS (method B) retention time 0.46 min m / z 211 (M + H)

[0705] 1H NMR (400 MHz, CDCl3d) δ ppm 9.29 (s, 1H), 9.20 (s, 1H), 9.04 (d, J = 8.56 Hz, 1H), 8.22 (s, 1H), 8.03 (d, J = 8.19 Hz, 1H), 7.80 (ddd, J = 8.47, 7.00, 1.28 Hz, 1H), 7.64 - 7.67 (m, 1H), 4.07 (s, 3H).

[0706] Step B: Preparation of 4-(1-methyl-1,2,4-triazol-3-yl)-1,2,3,4-tetrahydroisoquinoline

[0707]

[0708] Charge a round-bottom flask equipped with a magnetic stir bar with 4-(1-methyl-1,2,4-triazol-3-yl)isoquinoline (0.09 g, 0.4 mmol), methanol (5 mL), and sodium cyanoborohydride (0.2 g, 3 mmol). Then, add dropwise 1.25 M hydrochloric acid in methanol (0.9 mL, 1 mmol) (gas evolution) at room temperature, and stir the mixture at room temperature for 12 h. Pour the reaction mixture into water (50 mL) and basify with 2 M NaOH (pH 12). Extract the mixture with EtOAc (3 X 30 mL), and then wash the combined organic layers with brine, dry over Na2SO4, and concentrate in vacuo. Use the crude compound 4-(1-methyl-1,2,4-triazol-3-yl)-1,2,3,4-tetrahydroisoquinoline (0.08 g) as such for the next step.

[0709] LC-MS (Method C) retention time 0.16 min, m / z 215 (M+H)

[0710] Step C: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-(1-methyl-1,2,4-triazol-3-yl)-3,4- Preparation of [2,3-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-33, Table P)

[0711] Prepare [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-(1-methyl-1,2,4-triazol-3-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone analogously to Step C of Example 1.

[0712] LC-MS: 422 [M+H], Rt: 1.07 min (Method B)

[0713] 1 H NMR (400 MHz, CDCl3) δ ppm 3.85 (s, 3H) 3.91 (s, 1H) 4.30 - 4.37 (m, 2H) 4.48 - 4.60 (m, 3H) 4.99 (d, J = 17.48 Hz, 1H) 5.12 (d, J = 17.36 Hz, 1H) 5.20 (d, J = 7.82 Hz, 1H) 6.84 (d, J = 3.91 Hz, 1H) 6.97 - 7.26 (m, 8H) 7.92 - 8.03 (m, 3H)

[0714] Example P4: Preparation of 4-[2-[5-(2,4-difluorophenyl)isoxazole-3-carbonyl]-3,4-dihydro-1H-isoquinolin-4-yl]- 1,5-dimethyl-1H-pyrrole-2-carbonitrile (Compound P-20, Table P)

[0715]

[0716] Step A: Preparation of 4-bromo-1,5-dimethyl-1H-pyrrole-2-carbonitrile

[0717]

[0718] To a stirred solution of 1,5-dimethylpyrrole-2-carbonitrile (3.00 g, 25.0 mmol) in acetic acid (30 mL) was added dropwise bromine (1.32 mL, 25.5 mmol), and the resulting reaction mixture was stirred at room temperature for 16 h. The reaction mixture was diluted with water and quenched with saturated aqueous sodium thiosulfate. The mixture was extracted with EtOAc (three times), and the combined organic layers were washed with sodium bicarbonate solution and Na2SO4 and concentrated in vacuo. The crude product was further purified by silica gel column chromatography to give 4-bromo-1,5-dimethyl-pyrrole-2-carbonitrile.

[0719] 1 1H NMR (400 MHz, CDCl3) δ ppm 6.75 (s, 1H), 3.68 (s, 3H), 2.26 (s, 3H)

[0720] Step B: Preparation of 4-(isoquinolin-4-yl)-1,5-dimethyl-1H-pyrrole-2-carbonitrile

[0721]

[0722] A microwave vial was charged with 4-bromo-1,5-dimethyl-pyrrole-2-carbonitrile (1.00 g, 5.02 mmol), 4-isoquinolinylboronic acid (1.30 g, 7.54 mmol), sodium carbonate (1.60 g, 15.1 mmol), 1,4-dioxane (15.1 mL) and water (5 mL). The reaction mixture was degassed with nitrogen for 5.0 min and then treated with chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (0.20 g, 0.251 mmol). The resulting reaction mixture was stirred in the MW at 120 °C for 2 h and the progress of the reaction was monitored by LCMS and TLC. After completion of the reaction, the mixture was cooled to room temperature and diluted with saturated NH4Cl (50 mL). The mixture was extracted with EtOAc (2 X 50 mL), and the combined organic layers were washed with brine, dried over Na2SO4 and concentrated in vacuo. The crude product was purified by column chromatography to give 4-(4-isoquinolinyl)-1,5-dimethyl-pyrrole-2-carbonitrile.

[0723] LC-MS retention time 1.00 min m / z 248 (M+H) (Method C)

[0724] Step C: Preparation of 1,5-dimethyl-4-(1,2,3,4-tetrahydroisoquinolin-4-yl)pyrrole-2-carbonitrile

[0725]

[0726] Charge a round-bottom flask with 4-(4-isoquinolyl)-1,5-dimethyl-pyrrole-2-carbonitrile (0.90 gm, 3.64 mmol), methanol (18.20 mL) and sodium cyanoborohydride (2.40 g, 36.4 mmol). Then, hydrochloric acid (4.0 mol / L) in dioxane (21.8 mL) was added dropwise at room temperature (gas evolution), and the mixture was stirred at room temperature for 5 h. The reaction was monitored by LCMS. After completion of the reaction, the reaction mixture was basified by adding saturated NaHCO3 solution and then extracted with EtOAc (three times). The combined organic layers were concentrated in vacuo to give 1,5-dimethyl-4-(1,2,3,4-tetrahydroisoquinolin-4-yl)pyrrole-2-carbonitrile, which was used in the next step without further purification.

[0727] LC-MS retention time 0.91 min m / z 252 (M+H); (Method C)

[0728] Step D: Preparation of 4-[2-[5-(2,4-difluorophenyl)isoxazole-3-carbonyl]-3,4-dihydro-1H-isoquinolin-4-yl]- 1,5-dimethyl-1H-pyrrole-2-carbonitrile (Compound P-20)

[0729] The desired product was prepared analogously to Step C of Example 1 to give 4-[2-[5-(2,4-difluorophenyl)isoxazole-3-carbonyl]-3,4-dihydro-1H-isoquinolin-4-yl]-1,5-dimethyl-pyrrole-2-carbonitrile.

[0730] LC-MS: 459 [M+H], Rt: 1.22 min (Method B)

[0731] 1 H NMR (400 MHz, CDCl3) δ ppm 0.86 - 0.91 (m, 1H) 1.18 - 1.36 (m, 3H) 1.23 - 1.32 (m, 2H) 2.16 (s, 3H) 2.31 (s, 1H) 3.54 (s, 3H) 3.63 - 3.67 (m, 1H) 3.69 (s, 1H) 3.97 (dd, J = 12.84, 6.72 Hz, 1H) 4.18 - 4.27 (m, 3H) 4.37 (dd, J = 12.65, 4.71 Hz, 1H) 4.97 - 5.03 (m, 1H) 5.06 - 5.12 (m, 1H) 5.24 (s, 1H) 5.27 - 5.29 (m, 1H) 5.30 - 5.32 (m, 1H) 6.24 (s, 1H) 6.36 (s, 1H) 6.71 (d, J = 3.67 Hz, 1H) 6.97 - 7.09 (m, 5H) 7.12 - 7.25 (m, 3H) 7.28 - 7.31 (m, 1H) 7.92 - 8.01 (m, 1H)

[0732] Example P5: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-methyl-4-(pyridin-3-yl)-1,3-dihydroiso quinolin-2-yl]methanone (Compound P-27, Table P)

[0733]

[0734] Step 1: Preparation of 2-phenyl-2-(pyridin-3-yl)propanenitrile

[0735]

[0736] Under an argon atmosphere, 3-fluoropyridine (1.78 g, 18.37 mmol), 2-phenylpropionitrile (2.41 g, 18.373 mmol), potassium tert-butoxide (2.10 g, 18.373 mmol) and DMSO (20 mL) were charged into a sealed tube equipped with a magnetic stir bar. The reaction mixture was stirred at 80 °C for 2 hours. Then the reaction mixture was poured into an aqueous solution saturated with potassium bicarbonate. The aqueous phase was extracted with EtOAc (2 x 50 mL), and 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 yellow liquid.

[0737] LC-MS (Method A): 209 [M+H]+; retention time: 0.82 min.

[0738] 1 1H NMR (400 MHz, CDCl3) δ ppm 2.17 (s, 3H) 7.26 - 7.5 (m, 6H) 7.72 (d, 1H) 8.6 (d, 1H) 8.68 (d, 1H)

[0739] Step 2: Preparation of 2-phenyl-2-(pyridin-3-yl)propan-1-amine

[0740]

[0741] Charge a 100 mL three-necked flask equipped with a magnetic stir bar with 2-phenyl-2-(3-pyridyl)propanenitrile (prepared as described in Step 1 above, 1.10 g, 5.76 mmol) and THF (18 mL). Under an argon atmosphere at room temperature, add borane dimethyl sulfide complex (1.74 mL, 17.28 mmol) dropwise to this yellow solution, and stir the resulting colorless mixture at 65 °C for 2 h. Cool the reaction mixture to 0 °C, then add hydrochloric acid (3.86 mL, 23.16 mmol) dropwise (strong gas evolution), and stir the mixture at 65 °C for 1 h and then cool it to room temperature. Dilute the mixture with water (80 mL), basify with 13 mL of 6 M NaOH (pH 12), and then extract twice with EtOAc (3 × 50 mL). Wash the combined organic layers with brine, dry over Na2SO4, and concentrate in vacuo to give the title compound as an orange gum, which is used in the next step without further purification.

[0742] LC-MS (Method A): 213 [M+H]+; retention time: 0.21 min.

[0743] Step 3: Preparation of methyl N-[2-phenyl-2-(3-pyridyl)propyl]carbamate

[0744]

[0745] Charge a 250 mL single-necked round-bottom flask equipped with a magnetic stir bar with 2-phenyl-2-(3-pyridyl)propan-1-amine (prepared as described in Step 2 above, 1.55 g, 7.30 mmol) and DCM (30 mL). Add methyl chloroformate (0.68 mL, 8.76 mmol) dropwise under an argon atmosphere at 0 °C - 10 °C, followed by triethylamine (3.07 mL, 21.9 mmol). Remove the ice bath and stir the mixture at room temperature for 1 h. Pour the reaction mixture into water and separate the organic phase. Extract the aqueous phase twice with EtOAc, dry the combined organic layers over Na2SO4, and concentrate in vacuo. Purify the crude material by combiflash (silica gel, gradient: ethyl acetate in cyclohexane) to give the title compound as a colorless gum.

[0746] LC-MS (Method A): 271 [M+H]+; retention time: 0.58 min.

[0747] Step 4: Preparation of methyl 4-methyl-4-(3-pyridyl)-1,3-dihydroisoquinoline-2-carboxylate

[0748]

[0749] Charge a single-neck round-bottom flask equipped with a magnetic stir bar with methyl N-[2-phenyl-2-(3-pyridyl)propyl]carbamate (prepared as described in step 3 above, 180 mg, 0.665 mmol), hydrochloric acid (5.00 mL / mmol, 4.00 g, 3.33 mL, 40.50 mmol), and paraformaldehyde (39.96 mg, 0.42 mmol). Stir the mixture at room temperature for 40 minutes, where LC-MS analysis shows completion of the reaction. Slowly pour the reaction mixture into water (30 mL), neutralize with NaHCO3, and extract with EtOAc (3 x 20 mL). Wash the combined organic layers with brine, dry over Na2SO4, and concentrate in vacuo. Purify the crude material by combiflash (silica gel, gradient: ethyl acetate in cyclohexane) to afford the title compound as a colorless gum.

[0750] LC-MS (Method A): 283 [M+H]+; retention time: 0.67 min.

[0751] Step 5: Preparation of 4-methyl-4-(pyridin-3-yl)-2,3-dihydro-1H-isoquinoline

[0752]

[0753] Charge a single-neck round-bottom flask equipped with a magnetic stir bar with methyl 4-methyl-4-(3-pyridyl)-1,3-dihydroisoquinoline-2-carboxylate (prepared as described in step 4 above, 120 mg, 0.42 mmol), 1,2-dichloroethane (5.00 mL / mmol, 2.12 ml), and trimethylsilyl iodide (263.1 mg, 0.18 mL, 1.27 mmol). Stir the mixture at 60 °C under an argon atmosphere for 45 min, where LC-MS analysis shows almost complete conversion. Then allow the reaction to stir at room temperature overnight. Slowly pour the reaction mixture into water, neutralize with NaHCO3, and extract twice with EtOAc. Wash the combined organic layers with brine, dry over Na2SO4, and concentrate in vacuo to afford the title compound as a dark orange gum, which is used in the next step without further purification.

[0754] LC-MS (Method A): 225 [M+H]+; retention time: 0.16 min.

[0755] Step 6: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-methyl-4-(pyridin-3-yl)-1,3-dihydroiso quinolin-2-yl]methanone (Compound P-27, Table P)

[0756] A single-necked round-bottom flask equipped with a magnetic stir bar was charged with 4-methyl-4-(3-pyridyl)-2,3-dihydro-1H-isoquinoline (prepared as described in step 5 above, 60 mg, 0.267 mmol), EtOAc (2.675 mL, 27.30 mmol), N,N-diisopropylethylamine (104 mg, 0.138 mL, 0.8025 mmol), and 5-(2,4-difluorophenyl)isoxazole-3-carboxylic acid (68.30 mg, 0.2942 mmol). Then, T3P (510.70 mg, 0.473 mL, 0.8025 mmol) was added dropwise at room temperature, and the mixture was stirred at room temperature for 60 min. The reaction mixture was slowly poured into water, neutralized with NaHCO3, and extracted twice with EtOAc. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated in vacuo. The crude material was purified by combiflash (silica gel, gradient: ethyl acetate in cyclohexane) to afford the title compound as a white gum.

[0757] LC-MS (method A): 432 [M+H]+; retention time: 0.95 min.

[0758] Additional examples of the synthesized compounds of formula (I) are shown in Table P.

[0759] Table P: Synthesized compounds and spectroscopic and physicochemical data.

[0760]

[0761]

[0762]

[0763]

[0764]

[0765]

[0766]

[0767]

[0768] Biological Examples

[0769] Example B1: Alternaria solani / Tomato / Leaf disc (Early blight)

[0770] Tomato leaf discs of the cultivar Baby were placed on agar in a multi-well plate (24-well format) and sprayed with the formulated test compounds diluted in water. Two days after application, the leaf discs were inoculated with a spore suspension of the fungus. The inoculated leaf discs were incubated in a climatic chamber under a light regime of 12 / 12 h (light / dark), at 23 °C / 21 °C (day / night) and 80% rh, and the activity of the compounds was evaluated as the percentage of disease control compared to untreated controls when an appropriate level of disease damage appeared on the untreated test leaf discs (5 to 7 days after application).

[0771] When compared to untreated controls showing extensive disease development under the same conditions, the following compounds gave at least 80% control of Alternaria solani at 200 ppm: P-13, P-35

[0772] Example B2: Botryotinia fuckeliana (Botrytis cinerea) / Liquid culture (Grey mould) Example B3: Colletotrichum lagenarium / Liquid culture (Anthracnose)

[0773] 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 to 4 days after application.

[0774] When compared to untreated controls showing extensive disease development under the same conditions, the following compounds gave at least 80% control of Botryotinia fuckeliana at 20 ppm: P-1, P-6

[0775] Example B4: Septoria nodorum / Wheat / Leaf disc prophylaxis (Glume blotch)

[0776] Fungal conidia from frozen storage were directly mixed into nutrient broth (PDB potato dextrose 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 measured photometrically 3 to 4 days after application.

[0777] When compared to untreated controls showing extensive disease development under the same conditions, the following compounds gave at least 80% control of Glomerella cingulata at 20 ppm: P-1, P-2, P-3, P-4, P-5

[0778] Example B5: Monographella nivalis / Liquid culture (Cereal root rot) (Snow mould)

[0779] The wheat leaf segment cultivar Kanzler was placed on agar in a multi-well plate (24-well format) and sprayed with the formulated test compound diluted in water. Two days after application, the leaf discs were inoculated with a spore suspension of the fungus. The inoculated test leaf discs were incubated in a climate chamber under a light regime of 12 h light / 12 h dark at 20 °C and 75% rh, and the activity of the compound was evaluated as the percentage of disease control compared to the untreated, when an appropriate level of disease damage appeared on the untreated test leaf discs (5 to 7 days after application).

[0780] When compared to an untreated control that showed extensive disease development under the same conditions, the following compounds gave at least 80% control of Pyrenophora tritici-repentis at 200 ppm: P-7

[0781] Example B6: Mycosphaerella arachidis (Cercospora arachidicola) / Liquid culture (Early leaf spot) Example B7: Puccinia recondita f. sp. tritici / Wheat / Leaf disc treatment

[0782] Fungal conidia from frozen storage were directly mixed into nutrient broth (PDB potato dextrose 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 4 to 5 days after application.

[0783] When compared to an untreated control that showed extensive disease development under the same conditions, the following compounds gave at least 80% control of Cladosporium nivalem at 20 ppm: P-1, P-2, P-3, P-4, P-5, P-6, P-7, P-8, P-9, P-12, P-15

[0784] (Brown rust) Example B8: Magnaporthe grisea (Pyricularia oryzae) / Rice / Leaf

[0785] Fungal conidia from frozen storage were directly mixed into nutrient broth (PDB potato dextrose 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 4 to 5 days after application.

[0786] When compared to an untreated control that showed extensive disease development under the same conditions, the following compounds gave at least 80% control of Mycosphaerella arachidicola at 20 ppm: P-1, P-3, P-4, P-5, P-6, P-7, P-8, P-9, P-10, P-11, P-13, P-14

[0787] ​ ​

[0788] The wheat leaf segments of the cultivar Chancellor were placed on agar in a multiwell plate (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 12 h light / 12 h dark, and the activity of the compound was evaluated as the percentage of disease control compared to the untreated control when an appropriate level of disease damage appeared on the untreated test leaf segments (6 to 8 days after application).

[0789] When compared to an untreated control showing extensive disease development under the same conditions, the following compounds gave at least 80% control of Puccinia recondita f. sp. tritici at 200 ppm:

[0790] P-19

[0791] ​ ​ Disc prophylactic (rice blast)

[0792] The rice leaf segments of the cultivar Ballila were placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. Two days after application, the leaf segments were inoculated with a spore suspension of the fungus. The inoculated leaf segments were incubated at 22 °C and 80% 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 compound was evaluated as the percentage of disease control compared to the untreated control when an appropriate level of disease damage appeared in the untreated test leaf segments (5 to 7 days after application).

[0793] When compared to an untreated control showing extensive disease development under the same conditions, the following compounds gave at least 80% control of Magnaporthe oryzae at 200 ppm: P-13, P-30

[0794] Example B9: Pyrenophora teres / barley / leaf disc prophylactic (net blotch)

[0795] The barley leaf segments of the cultivar Hasso were placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. Two days after application, the leaf segments were inoculated with a spore suspension of the fungus. The inoculated leaf segments were incubated at 20 °C and 65% rh in a climate chamber under a light regime of 12 h light / 12 h dark, and the activity of the compound was evaluated as the disease control compared to the untreated control when an appropriate level of disease damage appeared on the untreated control leaf segments (5 to 7 days after application).

[0796] When compared to untreated controls that showed extensive disease development under the same conditions, the following compounds gave at least 80% control of Pyrenophora teres at 200 ppm: P-1

[0797] Example B10: Pythium ultimum / liquid culture (damping-off at seedling stage)

[0798] Mycelial fragments and oospores of a fresh growth liquid culture of the fungus were directly mixed into nutrient broth (PDB potato dextrose broth). After placing the (DMSO) solution of the test compound into a microtiter plate (96-well format), nutrient broth containing the fungal mycelium / spore mixture was added. The test plates were incubated at 24 °C and growth inhibition was determined photometrically 2 to 3 days after application.

[0799] When compared to untreated controls that showed extensive disease development under the same conditions, the following compounds gave at least 80% control of Pythium ultimum at 20 ppm: P-2

[0800] Example B11: Rhizoctonia solani / liquid culture (root rot, damping-off)

[0801] Mycelial fragments of a fresh growth liquid culture of the fungus were directly mixed into nutrient broth (PDB potato dextrose broth). After placing the (DMSO) solution of the test compound into a microtiter plate (96-well format), nutrient broth containing the fungal material was added. The test plates were incubated at 24 °C and growth inhibition was determined photometrically 3 to 4 days after application.

[0802] When compared to untreated controls that showed extensive disease development under the same conditions, the following compounds gave at least 80% control of Rhizoctonia solani at 20 ppm: P-2

[0803] Example B12: Mycosphaerella graminicola (Septoria tritici) / liquid culture (Septoria blotch) Example B12: Mycosphaerella graminicola (Septoria tritici) / liquid culture (Septoria blotch)

[0804] Conidia of the fungus from frozen storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing the (DMSO) solution of the test compound into a microtiter plate (96-well format), nutrient broth containing the fungal spores was added. The test plates were incubated at 24 °C and growth inhibition was determined photometrically 4 to 5 days after application.

[0805] When compared to untreated controls that showed extensive disease development under the same conditions, the following compounds gave at least 80% control of Mycosphaerella graminicola at 20 ppm:

[0806] P-1, P-2, P-3, P-4, P-5, P-6, P-7, P-8, P-9, P-10, P-11, P-12, P-13, P-14, P-15, P-16, P-17, P-18, P-19, P-20, P-21, P-22, P-23, P-24, P-25, P-26, P-27, P-28, P-29, P-30, P-31, P-32, P-33, P-34, P-35, P-36, P-39

Claims

1. A compound of formula (I) or an agrochemically acceptable salt, stereoisomer, or N-oxide thereof, wherein, Q is selected from 5- or 6-membered heteroaryl; wherein any one of the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that no more than one is O or S; and wherein any one of the 5- or 6-membered heteroaryl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C 4- alkyl, C1-C4-haloalkyl, or C3-C6 cycloalkyl; R 1 selected from hydrogen, a halogen, a C1-C4 haloalkyl group, a C3-C6 cycloalkyl group, or a C1-C4 alkyl group; R 2 and R 3 are independently selected from hydrogen, or C1-C4-alkyl; R 4 selected from hydrogen, C1-C4-alkyl, C1-C4-alkylcarbonyl, N-C1-C4-alkoxy-C-C1-C4-alkyl-carbodiimide, N-hydroxy-C-C1-C 4- alkyl-carbodiimide, C1-C4-alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4-alkylaminocarbonyl, di(C1-C4-alkyl)aminocarbonyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein any one of said 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that not more than one is O or S; wherein any one of said phenyl and 5- to 6-membered heteroaryl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, carboxyl, or C1-C4-alkoxy; and wherein said C3-C6-cycloalkyl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, or C1-C4-alkoxy; B 1 selected from CR 7 or N; B 2 selected from CR 8 or N; R 5 、R 6 、R 7 and R 8 are 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 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, N-C1-C4 alkylamino, N,N-bis(C1-C4 alkyl)amino, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbodiimide, N-hydroxy-C1-C4 alkyl-carbodiimide, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, amino, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl; wherein any one of said 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that not more than one is O or S; and wherein any one of said 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; A 1 、A 2 、A 4 are independently selected from methylene, N, NR 10 , O, or S, provided that A 1 、A 2 and A 4 at least one of which is selected from N, NR 10 , O or S, and A 1 、A 2 and A 4 no more than one of which is O or S, where R 10 is selected from hydrogen or C1-C4 alkyl; A 3 is C or N, provided that when A 3 is N, A 1 , A 2 and A 4 are methylene, N or NR 10 , where R 10 is selected from hydrogen or C1-C4 alkyl; and Z 1 selected from C1-C4 alkyl, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl; wherein any one of said 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that no more than one is O or S; wherein any one of said phenyl and 5- or 6-membered heteroaryl is unsubstituted or substituted by 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 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, or C2-C4 alkynyl; and wherein said C3-C6 cycloalkyl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy provided that the compound of formula (I) is not or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof.

2. The compound of formula (I) according to claim 1, wherein, B 1 and B 2 is CH.

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

4. A compound of formula (I) according to any one of claims 1 to 3, wherein, R 4 Selected from hydrogen, or C1-C4 alkyl groups.

5. A compound of formula (I) according to any one of claims 1 to 4, wherein, R 5 and R 6 is 6. A compound having the formula (I) according to any one of claims 1 to 5, wherein, Q is selected from Any one of the Q groups is unsubstituted or substituted with 1 or 2 substituents selected from fluorine, chlorine, bromine, cyano or methyl, and wherein R 9 is methyl, and wherein denotes the position attached to the tetrahydroisoquinoline moiety.

7. The compound of formula (I) according to claim 6, wherein, Q is selected from wherein denotes the position attached to the tetrahydroisoquinoline moiety.

8. A compound having the formula (I) according to any one of claims 1 to 7, wherein, Z 1 selected from C1-C4 alkyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein any one of the 5- or 6-membered heteroaryl contains 1 heteroatom selected from N, 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.

9. The compound of formula (I) according to claim 8, wherein, Z 1 is 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.

10. A compound having the formula (I) according to any one of claims 1 to 9, wherein, The compound of formula (I) is a compound of formula (I-A1), wherein R 1 , R 2 , R 3 , R 4 , R 5 , Q and Z 1 are as defined for a compound of formula (I) according to any one of claims 1 to 9, and A is selected from Among them represents the position attached to the C(=O) group and the arrow represents the position attached to the 1 Z group.

11. The compound having the formula (I-A1) according to claim 10, wherein, A is selected from: wherein indicates the position attached to the C(=O) group and the arrow indicates the position attached to the 1 Z group.

12. Use of a compound of formula (I) or an agrochemically acceptable salt, stereoisomer, or N-oxide thereof as a fungicide, wherein, Q is selected from 5- or 6-membered heteroaryl, wherein any one of the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that not more than one is O or S; and wherein any one of the 5- or 6-membered heteroaryl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C 4- alkyl, C1-C4-haloalkyl, or C3-C6 cycloalkyl; R 1 selected from hydrogen, halogen, C1-C4 haloalkyl, C3-C6 cycloalkyl, or C1-C4 alkyl; R 2 and R 3 are independently selected from hydrogen, or C1-C4-alkyl; R 4 selected from hydrogen, C1-C4-alkyl, C1-C4-alkylcarbonyl, N-C1-C4-alkoxy-C-C1-C4-alkyl-carbodiimide, N-hydroxy-C-C1-C 4- alkyl-carbodiimide, C1-C4-alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4-alkylaminocarbonyl, di(C1-C4-alkyl)aminocarbonyl, phenyl, a 5- to 6-membered heteroaryl, or a C3-C6-cycloalkyl; wherein any one of the 5- or 6-membered heteroaryls contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that not more than one is O or S; wherein the phenyl and the 5- to 6-membered heteroaryl are unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, carboxyl, or C1-C4-alkoxy; and wherein the C3-C6-cycloalkyl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, or C1-C4-alkoxy; B 1 selected from CR 7 or N; B 2 selected from CR 8 , or N; R 5 、R 6 、R 7 and R 8 are 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 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, N-C1-C4 alkylamino, N,N-di-C1-C4 alkylamino, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbodiimide, N-hydroxy-C1-C4 alkyl-carbodiimide, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, amino, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl; wherein any one of said 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that not more than one is O or S; and wherein any one of said 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; A 1 、A 2 、A 4 are independently selected from methylene, N, NR 10 , O, or S, provided that A 1 , A 2 and A 4 at least one of which is selected from N, NR 10 , O or S, and A 1 , A 2 and A 4 no more than one of which is O or S, where R 10 is selected from hydrogen or C1-C4 alkyl; A 3 is C or N, provided that when A 3 is N, A 1 , A 2 and A 4 are methylene, N or NR 10 , where R 10 is selected from hydrogen or C1-C4 alkyl; and Z 1 selected from C1-C4 alkyl, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein any of said 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that no more than one is O or S; wherein any of said phenyl, and 5- or 6-membered heteroaryl is unsubstituted or substituted by 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 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, or C2-C4 alkynyl; and wherein said C3-C6 cycloalkyl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy.

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

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

15. A method for controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I) as claimed in any one of claims 1 to 12 or a composition comprising the compound of formula (I) is applied to the plants, parts thereof, or the locus thereof.

Images