Microbicide tetrahydroisoquinoline derivatives

Abstract

Compounds of formula (I) which can be used as fungicides [Formula 1] JPEG2025539452000118.jpg30170 (wherein the substituents are as defined in claim 1) and the agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of these compounds.

Description

[Technical Field]

[0001] The present invention relates to microbicidal tetrahydroisoquinoline derivatives as active ingredients having, for example, microbicidal, particularly fungicidal, activity. The present invention also relates to the preparation of these tetrahydroisoquinoline derivatives, intermediates useful in the preparation of these tetrahydroisoquinoline derivatives, the preparation of these intermediates, pesticide compositions comprising at least one tetrahydroisoquinoline derivative, the preparation of these compositions, and the use of the tetrahydroisoquinoline derivatives or compositions in agriculture or horticulture to control or prevent infestation of plants, harvested food crops, seeds, or non-living materials by phytopathogenic microorganisms, particularly fungi. Summary of the Invention [Means for solving the problem]

[0002] According to a first aspect of the present invention, a compound of formula (I) [ka] (In the formula, Q is selected from 5- or 6-membered heteroaryls, any of said 5- or 6-membered heteroaryls containing 1, 2, 3, or 4 heteroatoms independently selected from N, O, or S, provided that not more than one is O or S, any of said heteroaryls being unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C3-C6 cycloalkyl; R 1 is 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 4is selected from hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimidoyl, 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 said 5- or 6-membered heteroaryl is 1, 2, 3 or 4 independently selected from N, O or S. containing four heteroatoms, provided that not more than one is O or S, wherein said phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with one, two or three substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, carboxy or C1-C4 alkoxy, and said C3-C6 cycloalkyl is unsubstituted or substituted with one, two or three substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl or C1-C4 alkoxy; B 1 is CR 7 or N, B 2 is CR 8 or N, R 5 , R 6 , R 7 and R 8are independently hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, N-C1-C4 alkylamino, N,N-di(C1-C4 alkyl)amino, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C1-C4 alkyl-carbonyl wherein the phenyl, 5- or 6-membered heteroaryl, and C3-C6 cycloalkyl are selected from phenyl, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, amino, phenyl, 5- or 6-membered heteroaryl, and 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 not more than one is O or S; and wherein any of the phenyl, 5- or 6-membered heteroaryl, and C3-C6 cycloalkyl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy; A 1 , A 2 , A 4 are independently methine, N, NR 10 , O or S, with the proviso that A 1 , A 2 and A 4 At least one of is selected from N, O or S, and A 1 , A 2 and A 4 is O or S, and R 10 is selected from hydrogen or C1-C4 alkyl, A 3 is C or N, except that A 3 When N, A 1 , A 2 and A 4 is methine, N or NR 10 and R 10 is selected from hydrogen or C1-C4 alkyl, and Z 1 is 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 not more than one is O or S, and any of said phenyl and 5- or 6-membered heteroaryl is unsubstituted or is selected from halogen, cyano, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, C1-C4 alkoxy , C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, or C2-C4 alkynyl, and 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 alkynyl. or an agrochemically acceptable salt, stereoisomer, or N-oxide thereof, with the proviso that the compound of formula (I) is not the following or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof:

[0003] [Table 1-1]

[0004] [Table 1-2]

[0005] [Table 1-3]

[0006] The PubChem Compound IDs assigned to the compounds excluded from the above claims refer to the compound identification numbers of each compound on the PubChem website https: / / pubchem.ncbi.nlm.nih.gov / .

[0007] Surprisingly, it has been found that the compounds of formula (I) have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases caused by fungi.

[0008] According to a second aspect of the present invention there is provided an agricultural composition comprising a fungicidally effective amount of a compound of formula (I) according to the present invention. Such agricultural compositions may further comprise at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

[0009] According to a third aspect of the present invention there is provided a method for controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I) according to the present invention or a composition comprising a compound of formula (I) is applied to the plant, its part or its habitat.

[0010] According to a fourth aspect of the present invention, there is provided, as a fungicide, a compound of formula (I) [ka] (In the formula, Q is selected from 5- or 6-membered heteroaryls, any of said 5- or 6-membered heteroaryls containing 1, 2, 3, or 4 heteroatoms independently selected from N, O, or S, provided that not more than one is O or S, any of said heteroaryls being unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C3-C6 cycloalkyl; R 1 is selected from hydrogen, halogen, C1-C4 haloalkyl, C3-C6 cycloalkyl, or C1-C4 alkyl; R 2and R 3 are independently selected from hydrogen or C1-C4 alkyl; R 4 is selected from hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimidoyl, 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 said 5- or 6-membered heteroaryl is 1, 2, 3 or 4 independently selected from N, O or S. containing four heteroatoms, provided that not more than one is O or S, wherein said phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with one, two or three substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, carboxy or C1-C4 alkoxy, and said C3-C6 cycloalkyl is unsubstituted or substituted with one, two or three substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl or C1-C4 alkoxy; B 1 is CR 7 or N, B 2 is CR 8 or N, R 5 , R 6 , R 7 and R 8are independently hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, N-C1-C4 alkylamino, N,N-di(C1-C4 alkyl)amino, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C1-C4 alkyl-carbonyl wherein the phenyl, 5- or 6-membered heteroaryl, and C3-C6 cycloalkyl are selected from phenyl, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, amino, phenyl, 5- or 6-membered heteroaryl, and 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 not more than one is O or S; and wherein any of the phenyl, 5- or 6-membered heteroaryl, and C3-C6 cycloalkyl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy; A 1 , A 2 , A 4 are independently methine, N, NR 10 , O or S, with the proviso that A 1 , A 2 and A 4 At least one of N, NR 10 , O or S, and A 1 , A 2 and A 4 is O or S, and R 10 is selected from hydrogen or C1-C4 alkyl, A 3 is C or N, except that A 3 When N, A 1 , A 2 and A 4 is methine, N or NR 10 and R 10is selected from hydrogen or C1-C4 alkyl, and Z 1 is selected from C1-C4 alkyl, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein 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 any of said phenyl, 5- or 6-membered heteroaryl is unsubstituted or is selected from halogen, cyano, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1 substituted by one, two or three substituents independently selected from C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl or C2-C4 alkynyl, and said C3-C6 cycloalkyl is unsubstituted or substituted by one, two or three substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl or C1-C4 alkoxy); or an agrochemically acceptable salt, stereoisomer or N-oxide thereof.

[0011] According to this particular aspect of the invention, this use may exclude methods involving the treatment of the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body. DETAILED DESCRIPTION OF THE INVENTION

[0012] The compounds of formula (I) having at least one basic centre can 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, or strong organic carboxylic acids, for example C1-C4 alkanecarboxylic acids which are unsubstituted or substituted, for example, by halogens, such as acetic acid, for example saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, for example hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid or for example benzoic acid, or organic sulfonic acids, for example C1-C4 alkane or arylsulfonic acids which are unsubstituted or substituted, for example, by halogens, such as methane- or p-toluenesulfonic acid. Compounds of formula (I) having at least one acidic group can, for example, form salts with bases, mineral salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or with ammonia or organic amines, for example morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, for example ethyl, diethyl, triethyl or dimethylpropylamine, or mono-, di- or trihydroxy-lower alkylamines, for example mono-, di- or triethanolamine.

[0013] In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form as N-oxides or in salt form, for example in agriculturally useful salt form.

[0014] N-oxides are the oxidized forms of tertiary amines or nitrogen-containing heteroaromatic compounds, as described, for example, in A. Albini and S. Pietra, "Heterocyclic N-oxides," CRC Press, Boca Raton (1991).

[0015] The compounds of formula (I) according to the invention also include the hydrates which may be formed during salt formation.

[0016] When substituents are indicated as "optionally substituted," this means that they may be substituted with one or more of the same or different substituents, for example, one, two, or three R x It means that it may or may not have a substituent. For example, C1-C6 alkyl substituted with 1, 2 or 3 halogens includes -CH2Cl, -CHCl2, -CCl 3、 Examples include, but are not limited to, -CHF, -CHF, -CF, -CHCF, or -CFCH groups. As another example, C1-C6 alkoxy substituted with 1, 2, or 3 halogens includes, but is not limited to, CH2ClO-, CHCl2O-, CCl3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O-, or CH3CF2O- groups.

[0017] As used herein, the term "halogen" or "halo" refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine. This also applies correspondingly to halogen in combination with other meanings, such as haloalkyl, haloalkenyl, haloalkynyl, haloalkoxy and halocycloalkyl.

[0018] As used herein, amino refers to the group —NH 2 .

[0019] As used herein, cyano refers to a -CN group.

[0020] As used herein, the term "hydroxyl" or "hydroxy" refers to an --OH group.

[0021] As used herein, the term "carboxylic acid" refers to a -COOH group.

[0022] As used herein, "C1-C nThe term "alkyl" refers to a saturated straight or branched hydrocarbon group having 1 to n carbon atoms attached via any of the carbon atoms, such as any one 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.

[0023] As used herein, "C2-C n The term "alkenyl" refers to a straight or branched alkenyl chain moiety having 2 to n carbon atoms and one or two double bonds, for example ethenyl, prop-1-enyl, but-2-enyl.

[0024] As used herein, "C2-C n The term "alkynyl" refers to a straight or branched alkynyl chain moiety having 2 to n carbon atoms and one triple bond, for example ethynyl, prop-2-ynyl, but-3-ynyl.

[0025] As used herein, "C3-C n The term "cycloalkyl" refers to 3 to n-membered cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0026] As used herein, "C1-C nThe term "alkoxy" refers to any one of a linear or branched saturated alkyl group having 1 to n carbon atoms (as defined above) attached through an oxygen atom, i.e., for example, methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy, and 1,1-dimethylethoxy groups. As used herein, "C2-C n The term "alkenyloxy" refers to a straight or branched saturated alkenyl chain having 2 to n carbon atoms (as defined above) attached through an oxygen atom.

[0027] As used herein, "C1-C n Alkoxy-C1~C n The term "alkyl" refers to C1-C n It refers to an alkyl group (as defined above) substituted with an alkoxy group. Examples include methoxymethyl, methoxyethyl, ethoxymethyl, and propoxymethyl.

[0028] As used herein, "C3-C n Cycloalkyl-C1~C n The term "alkyl" refers to C3-C n It refers to an alkyl group (as described above) substituted with a cycloalkyl group. Examples are cyclopropylmethyl and cyclopropylethyl. Similarly, "C3-C n Halocycloalkyl-C1~C n The term "alkyl" refers to an alkyl group substituted with a cycloalkyl group, where the cycloalkyl group is substituted with one or more of the same or different halogen atoms. Examples are 3,3-difluorobutylmethyl and 1-chlorocyclopropylmethyl.

[0029] As used herein, "C1-C nThe term "haloalkyl" refers to a linear or branched saturated alkyl group having 1 to n carbon atoms bonded via any of the carbon atoms (as defined above), in which some or all of the hydrogen atoms in these groups may be replaced by fluorine, chlorine, bromine and / or iodine, i.e., for example, 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-difluoroethyl, 2,2-difluoroethyl. and any one of chloro-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, and nonafluorobutyl. Thus, the term "C1-C2 fluoroalkyl" refers to any one of a C1-C2 alkyl group having 1, 2, 3, 4 or 5 fluorine atoms, such as difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl or pentafluoroethyl. Similarly, as used herein, "C2-C n Haloalkenyl" or "C2-C n The term "haloalkynyl" refers to C-C alkyl groups each substituted with one or more halogen atoms, which may be the same or different. n Alkenyl or C2-C nSimilarly, as used herein, "C3-C" refers to an alkynyl group. n Halocycloalkyl" or "C1-C n The term "haloalkoxy" refers to C-C alkyl groups each substituted with one or more halo atoms, which may be the same or different. n Cycloalkyl group or C1-C n Refers to an alkoxy group.

[0030] As used herein, "C1-C n Alkylthio" or "C1-C n The term "alkylsulfanyl" refers to a C1-C alkyl group linked through a sulfur atom. n Refers to an alkyl group.

[0031] As used herein, "C1-C n Haloalkylthio" or "C1-C n The term "haloalkylsulfanyl" refers to a C1-C alkyl group linked through a sulfur atom. n Refers to haloalkyl groups.

[0032] As used herein, "C1-C n The term "alkylsulfinyl" refers to a C1-C alkyl group linked through the sulfur atom of the sulfinyl (or S(=O)-) group. n Refers to an alkyl group.

[0033] As used herein, "C1-C n The term "alkylsulfonyl" refers to a C1-C alkyl group linked through the sulfur atom of the sulfonyl (or S(=O)2-) group. n Refers to an alkyl group.

[0034] As used herein, "C1-C n Alkylsulfonyl-C1~C n The term "alkyl" refers to C1-C n C1-C substituted with alkylsulfonyl groups n Refers to an alkyl group.

[0035] As used herein, "C1-C n The term "alkylcarbonyl" refers to a C1-C alkyl group linked through the carbon atom of the carbonyl (C=O) group. n Refers to an alkyl group.

[0036] As used herein, "C1-C n The term "alkoxycarbonyl" refers to a C1-C alkyl group linked through the carbon atom of a carbonyl (or C=O) group. n Refers to the alkoxy moiety.

[0037] As used herein, "C1-C n Alkoxycarbonyl-C1~C n The term "alkyl" refers to C1-C n C1-C substituted with alkoxycarbonyl groups n Refers to an alkyl group.

[0038] As used herein, the term "benzoyl" refers to a phenyl group attached through the carbon atom of a carbonyl (C=O) group.

[0039] As used herein, "C1-C n The term "haloalkoxycarbonyl" refers to a C1-C alkoxy group linked through the carbon atom of a carbonyl (C=O) group. n It refers to a haloalkoxy group.

[0040] As used herein, "C2-C n The term "alkenyloxycarbonyl" refers to a C-C alkyl group linked through the carbon atom of a carbonyl (C=O) group. n It refers to an alkenyloxycarbonyl group.

[0041] As used herein, "C1-C n The term "alkylaminocarbonyl" refers to a group of the formula R linked through the carbon atom of a carbonyl (C=O) group. a NHC(=O)-(wherein, R a are the C1 to C2 defined generally above. nIt refers to the group (which is an alkyl group).

[0042] As used herein, "di(C1-C n The term "(alkyl)aminocarbonyl" refers to a group of the formula R linked through the carbon atom of the carbonyl (C=O) group. a NR b C(=O) (in the formula, R a are the C1 to C2 defined generally above. n is an alkyl group, and R b are the C1 to C2 defined generally above. n It refers to the group (which is an alkyl group).

[0043] As used herein, "N-C1 to C n The term "alkylamino" refers to a group of the formula -NH-R a where R a are the C1 to C defined above. n It refers to an alkyl group.

[0044] As used herein, "N,N-diC n The term "alkylamino" refers to a group of the formula -N(R a )R a wherein each R a are C1 to C2, which may be the same or different, as defined above. n It refers to an alkyl group.

[0045] As used herein, "C1-C n Alkylcarbonyloxy-C1~C n The term "alkyl" refers to C1-C n Alkylcarbonyloxy (or R a C(=O)O-) group (in the formula, R a is C1~C n C1-C substituted with haloalkyl groups n Refers to an alkyl group.

[0046] As used herein, "C1-C n Alkoxycarbonyloxy C1-C nThe term "alkyl" refers to C1-C n Alkoxycarbonyloxy (or R c C(=O)O-) group (in the formula, R c is C1~C n C1-C substituted by an alkoxy group n Refers to alkyl groups C1-C connected to nitrogen. n An alkoxy group can be substituted.

[0047] As used herein, the term “N—C1-C4 alkoxy-C—C1-C4 alkyl-carbonimidoyl” refers to a group of the formula —C(R a )=NO(R b )(wherein, R a is a C1-C4 alkyl group as generally defined above, and R b refers to a group of which the alkyl group is a C1-C4 alkyl group as generally defined above.

[0048] As used herein, the term “N-hydroxy-C—Ci-C4 alkyl-carbonimidoyl” refers to a group of the formula —C(R a )=NOH(where R a refers to a group of which the alkyl group is a C1-C4 alkyl group as generally defined above.

[0049] As used herein, "aminocarbonyl-C1-C n The term "alkyl" refers to a C1-C alkyl group substituted with an aminocarbonyl (or NHC(=O)-) group. n Refers to an alkyl group.

[0050] As used herein, "C1-C n Alkylaminocarbonyl-C1~C n The term "alkyl" refers to C1-C n Alkylaminocarbonyl (or R a NHC(=O)-) group (wherein R a is C1~C n C1-C substituted with alkyl groups nRefers to alkyl groups C1-C connected to nitrogen. n The alkyl group can be substituted.

[0051] As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic ring group containing 1, 2, 3, or 4 heteroatoms independently selected from N, O, or S. Examples of heteroaryl include, but are not limited to, furanyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidyl, or pyridyl. "Heteroaryl-C1-C n "Alkyl" or "Heteroaryl-C3-C n The term "cycloalkyl" refers to any C1-C6 alkyl group substituted with a heteroaryl group. n Alkyl or C3-C n Refers to cycloalkyl groups. Heteroaryl-C1-C n Alkyl or heteroaryl-C3-C n Cycloalkyl groups can be optionally substituted on the heteroaryl, alkyl and / or cycloalkyl group.

[0052] As used herein, the term "control" refers to reducing the number of pests, eliminating pests, and / or preventing further pest damage such that damage to plants or plant-derived products is reduced.

[0053] As used herein, the term "pest" refers to insects and mollusks found in agriculture, horticulture, forestry, storage of plant-derived products (such as fruit, grain, and lumber), and pests associated with damage to man-made structures. The term pest encompasses all stages in the life cycle of a pest.

[0054] As used herein, the term "effective amount" refers to the amount of a compound or salt thereof that produces a desired effect upon one or more applications.

[0055] An effective amount is readily determined by one skilled in the art using known techniques and by observing results obtained under analogous circumstances. In determining an effective amount, several factors are taken into consideration, including, but not limited to, the type of plant or derived product being applied, the pest being controlled and its life cycle, the particular compound applied, the type of application, and other relevant circumstances.

[0056] As used herein, the terms "room temperature," or "RT," or "rt" refer to a temperature of about 15° C. to about 35° C. For example, rt can refer to a temperature of about 20° C. to about 30° C.

[0057] The following list refers to compounds of formula (I) of the present invention and defines substituent 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. For any one of these substituents, any definition given below may be combined with any definition of any other substituent given below or elsewhere in this specification.

[0058] In one embodiment of the present invention, R 1 is selected 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 1is hydrogen. In another embodiment of the present invention, R 1 is methyl.

[0059] In one embodiment of the present invention, R 2 , R 3 are independently selected from hydrogen or C1-C4 alkyl. Preferably, R 2 , R 3 are independently selected from hydrogen, methyl or ethyl. More preferably, R 2 , R 3 are independently selected from hydrogen or methyl. Even more preferably, R 2 and R 3 is hydrogen.

[0060] 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-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimidoyl, 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 said 5- or 6-membered heteroaryl is 1, 2, 3 or 4 independently selected from N, O or S. and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, carboxy, or C1-C4 alkoxy; and 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.

[0061] In another embodiment of the present invention, R 4is selected from hydrogen, C1-C4 alkyl, C3-C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimidoyl, 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 one heteroatom selected from N, and the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with one to two substituents independently selected from halogen, C1-C4 haloalkyl, cyano, or C1-C4 alkyl, and the C3-C6 cycloalkyl is unsubstituted or substituted with one substituent selected from cyano. Preferably, R 4 is selected from hydrogen, methyl, acetyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methoxycarbonyl, ethoxycarbonyl, N-methoxy-N-methyl-carbonyl, methylaminocarbonyl, dimethylaminocarbonyl, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, [4-(trifluoromethyl)pyrazol-1-yl], [3-(trifluoromethyl)pyrazol-1-yl], 3-cyanopyrazol-1-yl, 4-cyanopyrazol-1-yl, 5-chloropyrazol-1-yl, 5-fluoropyrazol-1-yl, 3,5-dimethylpyrazol-1-yl, 5-methylpyrazol-1-yl, pyrazol-1-yl, cyclopropyl or 1-cyanocyclopropyl. More preferably, R 4 is selected from hydrogen, methyl, acetyl, C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, phenyl, 4-cyanophenyl, pyrazol-1-yl, cyclopropyl or 1-cyanocyclopropyl. Even more preferably, R 4 is selected from hydrogen, methyl, cyclopropyl or 1-cyanocyclopropyl.

[0062] In another embodiment, R4 is 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.

[0063] 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.

[0064] In one embodiment of the present invention, B 1 is CR 7 and B 2 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 is.

[0065] In one embodiment of the present invention, R 5 and R 6are independently hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, N-C1-C4 alkylamino, N,N-di(C1-C4 alkyl)amino, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C1-C4 alkyl-carbonyl and n-methyl-, ...

[0066] 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. 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 is independently selected from hydrogen or methoxy.

[0067] 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.

[0068] In another embodiment, R 6 is hydrogen, halogen, C1-C3 alkyl, C1-C2 haloalkyl, C1-C3 haloalkoxy, C1-C4 alkoxy, C1-C3 alkenyloxy, C1-C3 alkynyloxy, C1-C2 alkylsulfanyl, C1-C2 alkylsulfinyl, C1-C2 alkylsulfonyl, C1-C2 alkoxy-C1-C2 alkyl, C1-C3 alkoxycarbonyl, C1-C2 alkylcarbonyl, N-C1-C2 alkoxy-C-C1-C2 alkyl-carbonimidoyl, N-hydroxy-C-C1-C2 alkyl-carbonimidoyl, 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, chloro, fluoro, bromo, methyl, ethyl, trifluoromethyl, difluoromethyl, difluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, methoxy, ethoxy, propoxy, allyloxy, prop-2-ynoxy, methylsulfanyl, methylsulfinyl, methylsulfonyl, methoxymethyl, ethoxymethyl, 2-methoxyethoxymethyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, acetyl, propanoyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methylaminocarbonyl, di(methylamino)carbonyl, trifluoromethylsulfonyloxy, cyano, carboxy, phenyl, 2-cyanophenoxy phenyl, 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. 6is hydrogen, chloro, bromo, fluoro, 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 cyano 1-cyclopropyl. Even more preferably, R 6 is hydrogen, chloro, bromo, cyano, methyl or methoxy. Most preferably, R 6 is hydrogen or methoxy.

[0069] In one embodiment of the present invention, R 7 and R 8is hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, N-C1-C4 alkylamino, N,N-di(C1-C4 alkyl)amino, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C1-C4 alkyl-carbonimidoyl, and R is independently selected from hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, amino, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein 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 any 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. 7 and R 8is hydrogen, chloro, fluoro, bromo, methyl, ethyl, trifluoromethyl, difluoromethyl, difluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, methoxy, ethoxy, propoxy, allyloxy, prop-2-ynoxy, methylsulfanyl, methylsulfinyl, methylsulfonyl, methoxymethyl, ethoxymethyl, 2-methoxyethoxymethyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, acetyl, propanoyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methylaminocarbonyl, di(methylamino)carbonyl, trifluoromethylsulfonyloxy, cyano, carboxy, phenyl, 2-cyanophenyl, is selected from 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 8are independently hydrogen, chloro, bromo, fluoro, 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 Even more preferably, R is selected from the group consisting of 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, and 1-cyanocyclopropyl. 7 and R 8 is independently selected from hydrogen, chlorine, bromine, or cyano.

[0070] In another embodiment, R 7 and R 8 are independently selected from hydrogen, halogen, C1-C3 alkyl, or C1-C4 alkoxy. 7 and R 8 are independently selected from hydrogen or halogen. More preferably, R 7 and R 8 is hydrogen, bromine or chlorine. Even more preferably, R 7 and R 8 is hydrogen.

[0071] In one embodiment of the present invention, A 1 , A 2 , A 4 are independently selected from methine, N, O, or S, with the proviso that A 1 , A 2 and A 4 At least one of is selected from N, O or S, and A 1 , A2 or A 4 At most one of is O or S.

[0072] In one embodiment of the present invention, A 3 is C or N, except that A 3 When N, A 1 , A 2 and A 4 is methine or N.

[0073] In one embodiment of the present invention, Z 1 is selected from C1-C4 alkyl, phenyl, 5- or 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein 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 any of said phenyl, 5- or 6-membered heteroaryl is unsubstituted or is selected from halogen, cyano, C1-C4 alkyl, C2-C4 alkenyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1 and C1-C4 cycloalkyl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl or C2-C4 alkynyl.

[0074] In another embodiment, Z 1is 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 not more than one is O or S; either the phenyl and the 5- to 6-membered heteroaryl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from fluoro, chloro, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl; and the C3-C6 cycloalkyl is unsubstituted or substituted with 1 or 2 substituents selected from methyl.

[0075] In another embodiment, 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, O, or S, and either the phenyl or the 5- to 6-membered heteroaryl is unsubstituted or substituted with one or two substituents independently selected from fluoro, chloro, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and the C3-C6 cycloalkyl is unsubstituted or substituted with one or two substituents selected from methyl.

[0076] In yet another embodiment, 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 either the phenyl or the 5- to 6-membered heteroaryl is unsubstituted or substituted with one or two substituents independently selected from fluoro, chloro, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and the C3-C6 cycloalkyl is unsubstituted or substituted with one or two substituents selected from methyl.

[0077] Preferably, Z 1is 1-methylpyrazol-4-yl, 2,3,4-trifluorophenyl, 2,3-difluorophenyl, 3,4-difluorophenyl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2-pyridyl, 2-fluoro-4-methoxy-phenyl, 2-fluoro-4-methylsulfonyl-phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3,5-difluoro-2-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-fluoro-phenyl, 4-fluoro-2-methoxy-phenyl, cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, n-propyl or phenyl. More preferably, Z 1 is selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2-chlorophenyl, 2-fluorophenyl, 3,5-difluoro-2-pyridyl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-fluorophenyl, 3-methylphenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, 4-methylphenyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl or phenyl. Even more preferably, Z 1is selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 3,5-difluoro-2-pyridyl, 2,4-difluorophenyl, 2-fluorophenyl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, cyclobutyl, cyclohexyl, cyclopentyl or phenyl. Even more preferably, Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, 4-fluorophenyl or phenyl.

[0078] In another embodiment of the present invention, Z 1 is selected from C1-C4 alkyl, phenyl, 5- to 6-membered heteroaryl, and 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 not more than one is O or S; the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy; and the C3-C6 cycloalkyl is unsubstituted or substituted with 1 substituent selected from halogen or C1-C4 alkyl. Preferably, Z 1 is selected from phenyl or 5- to 6-membered heteroaryl, said 5- to 6-membered heteroaryl containing one heteroatom selected from N or S, said phenyl and 5- to 6-membered heteroaryl being unsubstituted or substituted with one or two substituents independently selected from fluoro, chloro, C1-C4 alkyl or C1-C4 alkoxy. More preferably, Z 1is selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2-pyridyl, 2-fluorophenyl, 3,5-difluoro-2-furyl, 3-fluoro-2-furyl, 5-fluoro-2-furyl, 3,5-difluoro-2-thienyl, 3-fluoro-2-thienyl, 5-fluoro-2-thienyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, cyclobutyl, cyclohexyl, cyclopentyl or methyl. Even more preferably, Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2-pyridyl, 3,5-difluoro-2-furyl, 3-fluoro-2-furyl, 5-fluoro-2-furyl, 3,5-difluoro-2-thienyl, 3-fluoro-2-thienyl, 5-fluoro-2-thienyl, 2-fluorophenyl, 4-fluorophenyl or phenyl.

[0079] In another embodiment of the present invention, Z 1 is selected from phenyl, 5- to 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains one heteroatom selected from N or S, and the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with one or two substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy, or C1-C4 alkoxy, and the C3-C6 cycloalkyl is unsubstituted or substituted with one substituent selected from halogen or C1-C4 alkyl. Preferably, Z 1is selected from phenyl or 5- to 6-membered heteroaryl, said 5- or 6-membered heteroaryl containing one heteroatom selected from N or S, and said phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with one or two substituents independently selected from fluoro, chloro, C1-C4 alkyl or C1-C4 alkoxy.

[0080] In a further embodiment of the invention, Z 1 is selected from phenyl or 5- to 6-membered heteroaryl, said 5- or 6-membered heteroaryl containing one heteroatom selected from N or S, said phenyl and 5- to 6-membered heteroaryl being unsubstituted or substituted with one or two substituents independently selected from fluoro, chloro, C1-C4 alkyl or C1-C4 alkoxy. Preferably, Z 1 is 1-methylpyrazol-4-yl, 2,3,4-trifluorophenyl, 2,3-difluorophenyl, 3,4-difluorophenyl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2-pyridyl, 2-fluoro-4-methoxy-phenyl, 2-fluoro-4-methylsulfonyl-phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3,5-difluoro-2-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-fluoro-phenyl, 4-fluoro-2-methoxy-phenyl, cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, n-propyl or phenyl. More preferably, Z 1is 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-methoxy-phenyl, 4-fluorophenyl, 4-methylphenyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl or phenyl. Even more preferably, Z 1 is selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 3,5-difluoro-2-pyridyl, 2,4-difluorophenyl, 2-fluorophenyl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, cyclobutyl, cyclohexyl, cyclopentyl or phenyl. Even more preferably, Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, 4-fluorophenyl or phenyl.

[0081] In one embodiment of the present invention, Q is selected from a 5- or 6-membered heteroaryl, said 5- or 6-membered heteroaryl containing 1, 2, 3 or 4 heteroatoms independently selected from N, O or S, provided that not more than one is O or S, and said heteroaryl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl or C3-C6 cycloalkyl.

[0082] In another embodiment of the present invention, Q is Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, Q9, Q10, Q11, Q12, Q13, Q14, Q15 or Q16 [ka] wherein any of Q1 to Q16 is unsubstituted or substituted with 1, 2 or 3 substituents selected from C1 to C4 alkyl, halogen, C1 to C4 haloalkyl or C3 to C6 cycloalkyl; R 9 is selected from hydrogen or C1-C4 alkyl, [ka] indicates the position of attachment to the tetrahydroisoquinoline moiety.

[0083] In a preferred embodiment of the present invention, Q is Q1, Q2, Q3, Q4, Q6, Q7, Q9, Q10, Q11, Q12, Q14 or Q16 [ka] wherein any of the Q groups is unsubstituted or substituted with 1, 2 or 3 substituents selected from C1-C4 alkyl, halogen, C1-C4 haloalkyl or C3-C6 cycloalkyl; R 9 is selected from hydrogen or C1-C4 alkyl, [ka] indicates the position of attachment to the tetrahydroisoquinoline moiety.

[0084] In a more preferred embodiment of the present invention, Q is Q1, Q2, Q3, Q4, Q6, Q11, Q12 or Q16 [ka] wherein any of the Q groups is unsubstituted or substituted with 1, 2 or 3 substituents selected from C1-C4 alkyl, halogen, C1-C4 haloalkyl or C3-C6 cycloalkyl; R 9 is selected from hydrogen or methyl; [ka] indicates the position of attachment to the tetrahydroisoquinoline moiety.

[0085] In an even more preferred embodiment of the invention, Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12 or Q16, any of said Q groups being unsubstituted or substituted with 1, 2 or 3 substituents selected from C1-C4 alkyl, halogen, C1-C4 haloalkyl or C3-C6 cycloalkyl; R 9 is methyl, [ka] indicates the position of attachment to the tetrahydroisoquinoline moiety.

[0086] In an even more preferred embodiment of the invention, Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12 or Q16, any of said Q groups being unsubstituted or substituted with one or two substituents selected from fluorine, chlorine, bromine, cyano or methyl; and R 9 is methyl.

[0087] In an even more preferred embodiment of the present invention, Q is selected from Q, Q, Q, Q, Q, Q, Q, or Q, any of said Q groups is unsubstituted or substituted with one or two substituents selected from fluorine, chlorine, bromine, cyano, or methyl; and R 9 is methyl.

[0088] In an even more preferred embodiment of the present invention, Q is selected from Q, Q or Q, any of said Q groups being unsubstituted or substituted with one or two substituents selected from fluorine, chlorine, bromine, cyano or methyl; and R 9 is methyl.

[0089] In an even more preferred embodiment of the present invention, Q is selected from Q1, Q2 or Q3, and any of said Q groups is unsubstituted or substituted with one substituent selected from methyl.

[0090] Preferably, O is [ka] is selected from: [ka] indicates the position of attachment to the tetrahydroisoquinoline moiety.

[0091] More preferably, O is [ka] is selected from: [ka] indicates the position of attachment to the tetrahydroisoquinoline moiety.

[0092] Even more preferably, O is [ka] is selected from: [ka] indicates the position of attachment to the tetrahydroisoquinoline moiety.

[0093] Most preferably, Q is Q1, Q2a, Q3 or Q4 [ka] is selected from: [ka] indicates the position of attachment to the tetrahydroisoquinoline moiety.

[0094] The present invention therefore provides a compound having the formula R as defined above. 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 in all combinations / sequences of the formula (I).

[0095] In one embodiment of the present invention, the compound of formula (I) has the formula (IA) [ka] 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 A1 to A38 [ka] is selected from: [ka] indicates the position of attachment to the C(=O) group, and the arrow indicates Z 1 indicates the position where the group is bonded, and 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 R 10 is selected from hydrogen or C1-C4 alkyl.

[0096] 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, A is selected from A1 to A38, R 10 is selected from methyl.

[0097] In one embodiment of the present invention, in the compound of formula (IA), 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 [ka] is selected from: [ka] indicates the position of attachment to the C(=O) group, and the arrow indicates Z 1 The position at which the group is bonded is indicated.

[0098] In another embodiment of the present invention, in the compound of formula (IA), 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 [ka] is selected from: [ka] indicates the position of attachment to the C(=O) group, and the arrow indicates Z 1 The position at which the group is bonded is indicated.

[0099] In another preferred embodiment of the present invention, in the compound of formula (IA), 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 [ka] is selected from: [ka] indicates the position of attachment to the C(=O) group, and the arrow indicates Z 1 The position at which the group is bonded is indicated.

[0100] The present invention therefore provides a compound having the formula R as defined above. 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q, B 1 , B 2 and Z 1 in all combinations / sequences of the formula (I).

[0101] Embodiments according to the present invention are provided as described below.

[0102] In one embodiment of the present invention, the compound of formula (I) may be a compound of formula (IA), wherein: R 1 is hydrogen or C1-C4 alkyl, R 2 , R 3 is hydrogen, R 4 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; B1 is N or CR 7 and B2 is N or CR 8 and R 7 and R 8 are independently selected from hydrogen or halogen; Q and Z 1 is as defined for compounds of formula (I) and A is as defined for compounds of formula (IA).

[0103] In another embodiment of the present invention, the compound of formula (I) may be a compound of formula (IA), wherein: R 1 is hydrogen or C1-C4 alkyl, R 2 , R 3 is hydrogen, R 4 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; B 1 is N or CR 7 and B 2 is N or CR 8 and R 7 and R 8 are independently selected from hydrogen or halogen; Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12 or Q16, any of the Q groups being unsubstituted or substituted with one or two substituents selected from fluorine, chlorine, bromine, cyano or methyl; R 9 is methyl, A is selected from A4, A6, A7, A9, A10, A37 or A39; Z 1 is as defined for compounds of formula (I).

[0104] In another preferred embodiment of the present invention, the compound of formula (I) may be a compound of formula (IA), wherein: R 1 is hydrogen or C1-C4 alkyl, R 2 , R 3 is hydrogen, R 4 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; B 1 is N or CR 7 and B 2 is N or CR 8 and R 7 and R 8 are independently selected from hydrogen, halogen, C1-C3 alkyl, or C1-C4 alkoxy; Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12 or Q16, any of the Q groups being unsubstituted or substituted with one or two substituents selected from fluorine, chlorine, bromine, cyano or ethyl; R 9 is methyl, A is selected from A4, A6, A7, A9, A10, A37 or A39; Z 1is 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 either the phenyl or the 5- to 6-membered heteroaryl is unsubstituted or substituted with one or two substituents independently selected from fluoro, chloro, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and the C3-C6 cycloalkyl is unsubstituted or substituted with one or two substituents selected from methyl.

[0105] In another preferred embodiment of the present invention, the compound of formula (I) may be a compound of formula (IA), wherein: R 1 is hydrogen or C1-C4 alkyl, R 2 , R 3 is hydrogen, R 4 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; B 1 is CR 7 and B 2 is CR 8 and R 7 and R 8 are independently selected from hydrogen or halogen; Q is selected from Q1, Q2, or Q3, any of the Q groups being unsubstituted or substituted with one or two substituents selected from fluorine, chlorine, bromine, cyano, or methyl; R 9 is methyl, A is selected from A4, A6, A7, A9, A10, A37 or A39; Z 1is 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 either the phenyl or the 5- to 6-membered heteroaryl is unsubstituted or substituted with one or two substituents independently selected from fluoro, chloro, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and the C3-C6 cycloalkyl is unsubstituted or substituted with one or two substituents selected from methyl.

[0106] In a further preferred embodiment of the invention, the compound of formula (I) may be a compound of formula (IA), wherein: R 1 is hydrogen or C1-C4 alkyl, R 2 , R 3 is hydrogen, R 4 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; B 1 is CR 7 and B 2 is CR 8 and R 7 and R 8 are independently selected from hydrogen or halogen; Q is selected from Q2, Q3, or Q4, any of said Q groups being unsubstituted or substituted with one substituent selected from methyl; A is selected from A4, A7, A9, A10, A37 or A39; Z1 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 either the phenyl or the 5- to 6-membered heteroaryl is unsubstituted or substituted with one or two substituents independently selected from fluoro, chloro, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and the C3-C6 cycloalkyl is unsubstituted or substituted with one or two substituents selected from methyl.

[0107] In yet another preferred embodiment of the present invention, the compound of formula (I) may be a compound of formula (IA), wherein: R 1 is hydrogen or C1-C4 alkyl, R 2 , R 3 is hydrogen, R 4 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; B 1 is CR 7 and B 2 is CR 8 and R 7 and R 8 are independently selected from hydrogen or halogen; Q is selected from Q2, Q3, or Q4, any of said Q groups being unsubstituted or substituted with one substituent selected from methyl; A is selected from A4, A7, A9, A10, A37 or A39; 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.

[0108] In yet another preferred embodiment of the present invention, the compound of formula (I) may be a compound of formula (IA), wherein: R 1 is hydrogen or C1-C4 alkyl, R 2 , R 3 is hydrogen, R 4 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; B 1 is CH, and B 2 is CH, Q is selected from Q2, Q3, or Q4, any of said Q groups being unsubstituted or substituted with one substituent selected from methyl; A is selected from A4, A7, A9, A10, A37 or A39; 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.

[0109] In one embodiment of the present invention, the compound of formula (IA) is B 1 is CH and B 2is CH and A is as defined for compound (IA), [ka] 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).

[0110] Preferably, in the compound of formula (I-A1), R 1 is hydrogen or methyl, R 2 , R 3 is hydrogen, R 4 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12 or Q16, any of the Q groups being unsubstituted or substituted with one or two substituents selected from fluorine, chlorine, bromine, cyano or methyl; R 9 is methyl, A is selected from A4, A6, A7, A9, A10, A37 or A39; Z 1 is as defined for compounds of formula (I).

[0111] More preferably, in the compound of formula (I-A1), R 1 is hydrogen or methyl, R 2 , R 3 is hydrogen, R 4is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; Q is selected from Q2, Q3, or Q4, any of said Q groups being unsubstituted or substituted with one substituent selected from methyl; A is selected from A4, A7, A9, A10, A37 or A39; 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 either the phenyl or the 5- to 6-membered heteroaryl is unsubstituted or substituted with one or two substituents independently selected from fluoro, chloro, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and the C3-C6 cycloalkyl is unsubstituted or substituted with one or two substituents selected from methyl.

[0112] In another embodiment of the present invention, the compound of formula (IA) is B 1 is CH and B 2 is CH and A is A4, [ka] 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).

[0113] Preferably, in the compound of formula (I-A2), R 1 is hydrogen or methyl, R 2 , R 3is hydrogen, R 4 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12 or Q16, any of the Q groups being unsubstituted or substituted with one or two substituents selected from fluorine, chlorine, bromine, cyano or methyl; R 9 is methyl, Z 1 is as defined for compounds of formula (I).

[0114] More preferably, in the compound of formula (I-A2), R 1 is hydrogen or methyl, R 2 , R 3 is hydrogen, R 4 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; Q is selected from Q2, Q3, or Q4, any of said Q groups being unsubstituted or substituted with one substituent selected from methyl; 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 either the phenyl or the 5- to 6-membered heteroaryl is unsubstituted or substituted with one or two substituents independently selected from fluoro, chloro, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and the C3-C6 cycloalkyl is unsubstituted or substituted with one or two substituents selected from methyl.

[0115] In another embodiment of the present invention, the compound of formula (IA) is B 1 is CH and B 2 is CH and A is A7, [ka] 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).

[0116] Preferably, in the compound of formula (I-A3), R 1 is hydrogen or methyl, R 2 , R 3 is hydrogen, R 4 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12 or Q16, any of the Q groups being unsubstituted or substituted with one or two substituents selected from fluorine, chlorine, bromine, cyano or methyl; R 9 is methyl, Z 1 is as defined for compounds of formula (I).

[0117] More preferably, in the compound of formula (I-A3), R 1 is hydrogen or methyl, R 2 , R 3 is hydrogen, R4 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; Q is selected from Q2, Q3, or Q4, any of said Q groups being unsubstituted or substituted with one substituent selected from methyl; 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 either the phenyl or the 5- to 6-membered heteroaryl is unsubstituted or substituted with one or two substituents independently selected from fluoro, chloro, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and the C3-C6 cycloalkyl is unsubstituted or substituted with one or two substituents selected from methyl.

[0118] In another embodiment of the present invention, the compound of formula (IA) is B 1 is CH and B 2 is CH and A is A9, [ka] 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).

[0119] Preferably, in the compound of formula (I-A4), R 1 is hydrogen or methyl, R 2 , R 3 is hydrogen, R 4is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12 or Q16, any of the Q groups being unsubstituted or substituted with one or two substituents selected from fluorine, chlorine, bromine, cyano or methyl; R 9 is methyl, Z 1 is as defined for compounds of formula (I).

[0120] More preferably, in the compound of formula (I-A4), R 1 is hydrogen or methyl, R 2 , R 3 is hydrogen, R 4 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; Q is selected from Q2, Q3, or Q4, any of said Q groups being unsubstituted or substituted with one substituent selected from methyl; 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 either the phenyl or the 5- to 6-membered heteroaryl is unsubstituted or substituted with one or two substituents independently selected from fluoro, chloro, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and the C3-C6 cycloalkyl is unsubstituted or substituted with one or two substituents selected from methyl.

[0121] In another embodiment of the present invention, the compound of formula (IA) is B 1 is CH and B 2 is CH and A is A10, [ka] 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).

[0122] Preferably, in the compound of formula (I-A5), R 1 is hydrogen or methyl, R 2 , R 3 is hydrogen, R 4 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12 or Q16, any of the Q groups being unsubstituted or substituted with one or two substituents selected from fluorine, chlorine, bromine, cyano or methyl; R 9 is methyl, Z 1 is as defined for compounds of formula (I).

[0123] More preferably, in the compound of formula (I-A5), R 1 is hydrogen or methyl, R 2 , R 3 is hydrogen, R 4is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; Q is selected from Q2, Q3, or Q4, any of said Q groups being unsubstituted or substituted with one substituent selected from methyl; 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 either the phenyl or the 5- to 6-membered heteroaryl is unsubstituted or substituted with one or two substituents independently selected from fluoro, chloro, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and the C3-C6 cycloalkyl is unsubstituted or substituted with one or two substituents selected from methyl.

[0124] In another embodiment of the present invention, the compound of formula (IA) is B 1 is CH and B 2 is CH and A is A37, [ka] 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).

[0125] Preferably, in the compound of formula (I-A6), R 1 is hydrogen or methyl, R 2 , R 3 is hydrogen, R 4is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12 or Q16, any of the Q groups being unsubstituted or substituted with one or two substituents selected from fluorine, chlorine, bromine, cyano or methyl; R 9 is methyl, Z 1 is as defined for compounds of formula (I).

[0126] More preferably, in the compound of formula (I-A6), R 1 is hydrogen or methyl, R 2 , R 3 is hydrogen, R 4 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; Q is selected from Q2, Q3, or Q4, any of said Q groups being unsubstituted or substituted with one substituent selected from methyl; 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 either the phenyl or the 5- to 6-membered heteroaryl is unsubstituted or substituted with one or two substituents independently selected from fluoro, chloro, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and the C3-C6 cycloalkyl is unsubstituted or substituted with one or two substituents selected from methyl.

[0127] In another embodiment of the present invention, the compound of formula (IA) is R 1 , B 1 is CH and B 2 is CH and A is A38, [ka] 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).

[0128] Preferably, in the compound of formula (I-A7), R 1 is hydrogen or methyl, R 2 , R 3 is hydrogen, R 4 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; Q is selected from Q1, Q2, Q3, Q4, Q6, Q11, Q12 or Q16, any of the Q groups being unsubstituted or substituted with one or two substituents selected from fluorine, chlorine, bromine, cyano or methyl; R 9 is methyl, Z 1 is as defined for compounds of formula (I).

[0129] More preferably, in the compound of formula (I-A7), R 1 is hydrogen or methyl, R 2 , R 3 is hydrogen, R 4is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl, R 5 , R 6 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy; Q is selected from Q2, Q3, or Q4, any of said Q groups being unsubstituted or substituted with one substituent selected from methyl; 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 either the phenyl or the 5- to 6-membered heteroaryl is unsubstituted or substituted with one or two substituents independently selected from fluoro, chloro, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and the C3-C6 cycloalkyl is unsubstituted or substituted with one or two substituents selected from methyl.

[0130] The presence of one or more possible asymmetric carbon atoms in any of the compounds selected from the compounds of formula (I), (IA), (I-A1), (I-A2), (I-A3), (I-A4), (I-A5), (I-A6) or (I-A7) according to the present invention or the compounds listed in Tables C-1 to C-36 or the compounds listed in Table P (below) means that the compounds may exist in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms.

[0131] In one embodiment, the compound of formula (I) according to the present invention is selected from the compounds listed in any one of Tables C-1 to C-36.

[0132] In another embodiment, the compound of formula (I) according to the present invention is selected from the compounds listed in Table P (below).

[0133] Compounds of formula (I) according to the present invention can be formed as shown in the following schemes, where, unless otherwise specified, the definition of each variable is as defined above for compounds of formula (I).

[0134] In any of the following schemes, the possible presence of one or more asymmetric carbon atoms in the compounds of formula (I) according to the invention means that the compounds can occur in chiral isomeric, i.e. enantiomeric or diastereomeric forms.

[0135] The compound of formula (I) can be prepared by a person skilled in the art according to known methods. More specifically, the compound of formula (I) can be prepared by reacting 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 is as defined for compounds of formula (I)) to compounds of formula (II) 1 , A 2 , A 3 , A 4 and Z 1 can be prepared by reaction of a compound of formula (I) with a carboxylic acid, which is as defined for the compound of formula (I). This reaction is shown in Scheme 1. [ka] Scheme 1

[0136] In Scheme 1, a compound of formula (II) 1 , A 2 , A 3 , A 4 and Z 1 is as defined for compounds of formula (I), can be activated to compounds 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, compounds of formula (IIa) (wherein X 0Compounds of formula (IIa) are formed by treating compounds 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 temperatures between 20°C and 100°C, preferably 25°C. Compounds of formula (IIa) can be converted to compounds 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), optionally in the presence of a base such as triethylamine or pyridine, to give compounds of formula (I). Alternatively, compounds of formula (I) may be prepared by treatment of 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), where X 0 is represented by Scheme 2, 1 , G 2 or G 3 Finally, compounds of formula (II) can be activated by reaction with a coupling reagent such as propanephosphonic anhydride (T3P), as described, for example, in Synthesis 2013, 45, 1569, to give compounds of formula (IIa), where X 0 is G as shown in Scheme 2 4 Further reaction of the compound of formula (III) with an amine (or a salt thereof) provides the compound of formula (I). [ka] Scheme 2

[0137] The compound of formula (II) can be converted by ester hydrolysis to 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 0 is a C1-C4 alkyl). Various conditions can be used, such as aqueous sodium hydroxide or lithium hydroxide and a water-miscible organic solvent such as 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 compounds of formula (IIb) with compounds of formula (III) in the presence of trimethylaluminum or trimethylaluminum-DABCO complex in an inert solvent such as toluene or DCM. Such reactions have been reported in the literature (see Tetrahedron Lett. 1977, 4171-4174, Tetrahedron Lett. 2006, 5767-5769 and references cited therein). Compounds of formula (II) and (IIb) are commercially available or can be synthesized as described below.

[0138] A compound of formula (IIIa) 1 and R 2 is hydrogen and R 3 is hydrogen or methyl, and R 4 , R 5 , R 6 , B 1 and B 2 is as defined for compounds of formula (I)) can be converted into compounds of formula (IV) 3 is hydrogen or methyl, and R 4 , R 5 , R 3 , R 6 , B 1 and B 2can be prepared from compounds of formula (I) (as defined for compounds of formula (I)) by treatment with a reducing agent such as NaBHCN and an acid such as hydrochloric acid or acetic acid in a protic solvent such as methanol or ethanol. Such reactions are well known in the literature, and similar reactions are described, for example, in Deng, Zeping et al., China Patent No. 103772278 and Synthesis 1979, 4, 281-283. Alternatively, compounds of formula (IIIa) can be prepared from compounds of formula (IV) by reduction with hydrogen in the presence of a suitable metal catalyst such as Pd, Ir, or Rh, with a suitable ligand, for example, a diphosphine [1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), or 1,4-bis(diphenylphosphino)butane (dppb)]. A similar reaction is reported, for example, in React. Kinet. Cat. Lett. 2007, 92, 99-104. This reaction is shown in Scheme 3. [ka] Scheme 3

[0139] Further synthesis of compounds of formula (III) can be achieved by directed metallation techniques, as shown in Scheme 4, thus providing compounds of formula (IIIb), where R 3 is hydrogen or methyl, and R 5 , R 6 , Q, B 1 and B 2 is as defined for compounds of formula (I), can be prepared by the synthesis of compounds of formula (VI) (wherein X 0 is a leaving group such as a halogen, and R 0 is C1-C6 alkyl) to give a compound of formula (V), 3 is hydrogen or methyl, and R 5 , R 6 , Q, B 1 and B 2is as defined for compounds of formula (I). Alternatively, compounds of formula (V) can be converted to compounds of formula (R 0 CO)2O(wherein, R 0 is a C1-C6 alkyl) 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 temperatures between 0°C and 60°C. Compounds of formula (V) are then metallated with a base, for example an alkyl metal base such as tert-butyllithium, and an additive such as N,N,N',N'-tetramethylethylenediamine (TMEDA), in an inert polar solvent such as THF or 2-methyl-THF, at low temperatures, for example -78°C to room temperature. 4 -X 0 an electrophile of formula X 0 is as already 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, 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, to give a compound of formula (Va), wherein R 0 is a C1-C6 alkyl, and R 3 is a halogen and R 4 , R 5 , R 6 , Q, B 1 and B 2 is as defined for compounds of formula (I)) is obtained (Scheme 4). [ka] Scheme 4

[0140] Compounds of formula (Va) can be prepared by methods known to those skilled in the art from compounds of formula (IIIa) (wherein R 3 is hydrogen or methyl, and R 4 , R 5 , R 6 , Q, B 1 and B 2 is as defined for compounds of formula (I). For example, a compound of formula (Va) 0 (wherein is tert-butyl) can be treated with an organic or inorganic acid such as trifluoroacetic acid or HCl to provide a compound of formula (IIIa). This reaction is shown in Scheme 5. [ka] Scheme 5

[0141] A compound of formula (IV) 3 is hydrogen or methyl, and R 4 , R 5 , R 6 , Q, B 1 and B 2 is as defined for compounds of formula (I), can be converted to compounds of formula (VIII), where Q is as defined for compounds of formula (I) and X is as defined for compounds of formula (I), typically by a C—C bond forming reaction under palladium catalyzed (alternatively nickel catalyzed) cross coupling conditions. 0 is a halogen, preferably chlorine, bromine or iodine, with a compound of formula (VII) 3 is hydrogen or methyl, and R 4 , R 5 , R 6 , Q, B 1 and B 2 can be prepared by reacting (as defined for compounds of formula (I)) with (as defined for compounds of formula (I)). This reaction is shown in Scheme 6. [ka] Scheme 6

[0142] The Suzuki-Miyaura cross-coupling reaction of a compound of formula (VIII) with 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]palladium(II) dichloride 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 are reviewed, for example, in J. Organomet. Chem. 1999, 576, 147-168. Those skilled in the art will appreciate that the reaction is reversible, i.e., the reaction of a compound of formula (X) (where Q is as defined for a compound of formula (I)) with a compound of formula (IX) (where R 3 is hydrogen or methyl, and R 4 , R 5 , R 6 , Q, B 1 and B 2 is as defined for compounds of formula (I), and X 0 is a halogen, preferably chlorine, bromine or iodine, to give a compound of formula (IV), 5は , hydrogen or methyl, and R 4 , R 5 , R 6 , Q, B 1 and B 2 It will also be appreciated that the reaction can result in the reaction of the compound of formula (I) being as defined for the compound of formula (I). This reaction is shown in Scheme 7. [ka] Scheme 7

[0143] Further cross-coupling chemistry, i.e., C—H activation, can be used to give compounds of formula (IV), where R 3 is hydrogen or methyl, and R 4 , R 5 , R 6 , Q, B 1 and B2 is as defined for compounds of formula (I) and the Q group has at least one aromatic CH group) can also be prepared (Scheme 8). [ka] Scheme 8

[0144] As shown in Scheme 8, a compound of formula (IX) (wherein R 3 is hydrogen or methyl, and R 4 , R 5 , R 6 , B 1 and B 2 is as defined for 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 compounds of formula (I) and the Q group has at least one aryl CH group) in the presence of a palladium catalyst, typically palladium acetate Pd(OAc)2, a suitable ligand, for example 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. 2013, 4, 2374-2379.

[0145] Compounds of formula (III) can also be prepared from compounds of formula (Vc) (Scheme 9). [ka] Scheme 9

[0146] As shown in Scheme 9, compounds of formula (III) can be prepared by condensing compounds of formula (Vc) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , Q, B 1 and B2 is as defined for compounds of formula (I), and R 01 can be prepared by one skilled in the art by carbamate deprotection of a common carbamate protecting group substituent (which may be a component of a methyl, tert-butyl, allyl, 2,2,2-trichloroethyl, or benzyl group). 01 When is methyl, the product can be obtained by heating at a temperature between room temperature and 200°C, preferably between 20°C and the boiling point of the reaction mixture, using a suitable solvent such as DCM and a suitable reagent such as iodotrimethylsilane, as described in, for example, J. Am. Chem. Soc. 1992, 114, 5959. The compound of formula (III) thus obtained is converted to a compound of formula (I) as described in Scheme 1.

[0147] A compound of formula (Vc) 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), and R 01 is as defined above) can be converted to an aldehyde of formula (XIII) (including formaldehyde in its various forms) (wherein R 4 is as defined for compounds of formula (I)) and a compound of formula (XII) 1 , R 2 , R 3 , R 5 , R 6 , Q, B 1 and B 2 is as defined for compounds of formula (I), and R 01 can be formed by the Pictet-Spengler reaction with (as described above) (Scheme 10). [ka] Scheme 10

[0148] A compound of formula (XII) 1 , R 2 , R 3 , R 5 , R 6 , Q, B 1 and B 2 is as defined for compounds of formula (I), and R 01 is as defined above) can be reacted with an amine of formula (XIII) (wherein R 1 , R 2 , R 3 , R 5 , R 6 , Q, B 1 and B 2 can be prepared by the reaction between a methyl chloroformate (as defined for compounds of formula (I)) and a suitable protecting reagent such as methyl chloroformate. This reaction is shown in Scheme 11. [ka] Scheme 11

[0149] 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 reacted with a nitrile of formula (XIV) (wherein R 1 , R 2 , R 3 , R 4 , Q, B 1 and B 2can be prepared by reaction of a nitrile of formula (XIV) with a suitable nucleophile such as (dimethylsulfide)dihydroboron (BMS), where R 2 and R 3 is hydrogen). Alternatively, the Grignard reagent R 5 MgBr or R 6 MgBr (wherein, R 5 and R 6 (wherein X is as defined for compounds of formula (I)) may be added sequentially or simultaneously as nucleophiles to compounds of formula (XIV) to allow the preparation of more highly substituted amines of formula (XIII). Such Grignard additions to nitriles can be carried out by reaction with Ti(O- i The reaction is carried out in the presence of a Lewis acid such as Pr)4 (see Synlett 2007, (4), 652-654). This reaction is shown in Scheme 12. [ka] Scheme 12

[0150] Alternatively, a compound of formula (XIII) 1 , R 5 , R 6 , Q, B 1 and B 2 is as defined for compounds of formula (I), and R 2 , R 3 is hydrogen) can be prepared by reacting an unsaturated nitro compound of formula (XV) 1 , R 5 , R 6 , B 1 and B 2 is as defined for compounds of formula (I)) with a Grignard reagent of formula (XVI) 0 is a halogen, preferably iodine), followed by reaction with a compound of formula (XVII),1 , R 5 , R 6 , Q, B 1 and B 2 can be prepared by one skilled in the art by reacting a compound of formula (XIIIa) (which is as defined for compounds of formula (I)) to a compound of formula (XIIIa). This reaction is shown in Scheme 13. [ka] Scheme 13

[0151] Such conjugate additions of heteroaryl Grignard reagents to α,β-unsaturated nitroolefins have been reported in the literature (see Synthesis, 1988, (5), 379-81), and there are numerous 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. Grignards of formula (XVI) are readily prepared from compounds of formula (VIII) by methods known to those skilled in the art.

[0152] A compound of formula (XIV) 1 , R 2 , R 3 , R 4 , R 8 , R 9 , B 1 and B 2 is as defined for compounds of formula (I), can be prepared by one skilled in the art according to known methods. More specifically, compounds of formula (XIV) and intermediates thereto can be prepared from compounds of formula (XVII) as shown in Scheme 14. [ka] Scheme 13

[0153] For example, a compound of formula (XIV) 1 , R 2 , R 3 , R 8, Q, B 1 and B 2 is as defined for compounds of formula (I), and R 1 is different from hydrogen) can be prepared by the reaction of a compound of formula (XIVa) (wherein R 1 is hydrogen and R 5 , R 6 , Q, B 1 and B 2 is as defined for compounds of formula (I), followed by deprotonation of a suitable alkylating agent R, such as iodomethane. 1 -X 0 (In the formula, R 1 is a C1-C4 alkyl, and X 0 is a halogen).

[0154] A compound of formula (XIVa) 5 , R 6 , Q, B 1 and B 2 (wherein is as defined for compounds of formula (I)) can be prepared from alcohols of formula (XVIII) by treatment with cyanotrimethylsilane (TMSCN) in the presence of a base such as lithium carbonate in a nonpolar solvent such as DCM at temperatures between 0°C and the boiling point of the reaction mixture. Such transformations are well known in the literature under a variety of conditions, as described, for example, in Org. Lett. 2008, 10, 4570 and references therein. Compounds of formula (XVIII) are readily prepared by Grignard reaction of compounds of formula (XVI) with aldehydes of formula (XIX) or Grignard compounds of formula (XXI) with aldehydes of formula (XXII), usually in ethereal solvents such as THF, 2.Me-THF, TBME, or diethyl ether. Such reactions are well known to those skilled in the art. This is summarized in Scheme 15. [ka] Scheme 15

[0155] A compound of formula (II) 1 is N and A 2 is O and A 4 is CH and A 3 is C and Z 1 is as defined for compounds of formula (I), i.e. compounds of formula (IId), may be prepared as shown in Scheme 16. [ka] Scheme 16

[0156] As shown in Scheme 16, a compound of formula (IId) (wherein Z 1 is as defined for compounds of formula (I), and X 01 is C1-C4 alkyl) can be prepared by hydrolyzing a compound of formula (IIc) by treatment with, for example, an alkaline earth metal hydroxide in water or a water-miscible organic solvent such as THF, methanol, ethanol, etc. Such ester hydrolysis is well known to those skilled in the art. Compounds of formula (IIc) can be prepared by hydrolyzing a compound of formula (XXV) (wherein Z 1 is as defined for compounds of formula (I), and X 01 is a C1-C4 alkyl) with hydroxylamine hydrochloride in a polar solvent such as ethanol, and optionally in the presence of, for example, triethylamine, K2CO3, or the like.

[0157] Compounds of formula (XXV) can be prepared by reacting compounds of formula (XXIII) (wherein Z 1 is as defined for compounds of formula (I), a compound of formula (XXIV) or a compound of formula (XXIVa) (wherein X 01is C1-C4 alkyl). Similar reaction sequences to those described in Scheme 15 for preparing compounds of formula (IIc) and (IId) are described, for example, in CN 111072582, WO 2019 / 195810 and WO 2018 / 019929. Further reaction conditions for preparing compounds of formula (XXV) are described, for example, in Bioorg.Med.Chem. 2016, 109, 350-359.

[0158] A compound of formula (II) 1 is O and A 2 and A 4 is N and A 3 is C and Z 1 is as defined for compounds of formula (I), i.e. compounds of formula (IIf), may be prepared as shown in Scheme 17. [ka] Scheme 17

[0159] As shown in Scheme 17, compounds of formula (IIf) are obtained by ester hydrolysis of compounds of formula (IIe) previously described in Scheme 15. Compounds of formula (IIe) (wherein Z 1 is as defined for compounds of formula (I), and X 01 is C1-C4 alkyl) can be prepared by reacting a compound of formula (XXIVa) with a compound of formula (XXVI), optionally in the presence of a base, for example, pyridine or triethylamine, in a solvent such as acetonitrile, chloroform or THF. Similar reactions have been reported, for example, in Bioorg.Med.Chem.2016,24(22),5693-5701 and Chinese Patent No. 114933573. Compounds of formula (XXVI) (wherein Z 1Compounds of formula (XXVII) (wherein R is as defined for compounds of formula (I)) can be obtained by treating compounds of formula (XXVII) with hydroxylamine hydrochloride in the presence of a base such as KCO or NaCO in a polar solvent, such as ethanol. The reaction can also be carried out without a base using a hydroxylamine solution. Such reactions are described, for example, in Med. Chem. Lett. 2020, 30(21), 127508 and Bioorg. Med. Chem. Lett. 2016, 26(23), 5679-5684.

[0160] A compound of formula (XXVI) 1 is as defined for compounds of formula (I), can be prepared by Pd-catalyzed reaction of compounds of formula (XXVIII) (wherein Z is as defined for compounds of formula (I)) using potassium ferricyanide trihydrate and hydroxylamine hydrochloride, as described, for example, in Org. Biomol. Chem. 2015, 13(9), 2541-2545. 1 may also be prepared by a "one-spot" synthesis by cyanation and amidoximation of (as defined for compounds of formula (I)).

[0161] A compound of formula (II) 1 and A 2 is N and A 4 is O and A 3 is C and Z 1 is as described above (i.e., a compound of formula (IIh)), and A 1 and A 2 is N and A 4 is S and A 3 is C and Z 1 is as defined for compounds of formula (I) (i.e. compounds of formula (IIj)) may be prepared as shown in Scheme 18. [ka] Scheme 18

[0162] As shown in Scheme 18, compounds of formula (IIh) and (IIj) are accessible by ester hydrolysis of (IIg) and (IIi), respectively. In the latter compounds, X 01 and Z 1 are as described above. Compounds of formula (IIg) are obtained by dehydration of compounds of formula (XXXI). Compounds of formula (XXXI) are obtained by acylation of hydrazides of formula (XXXII) with compounds of formula (XXIVa). Such reaction sequences for producing oxadiazoles are well known to those skilled in the art. Similar reactions are described in Bioorg. Med. Chem. Lett. 2005, 15, 1423-1428 and WO 2006 / 044617. Compounds of formula (XXXI) can be obtained by acylation of activated carboxylic acids of formula (XXIXa) (wherein Z 1 is as defined for compounds of formula (I), and X 0 can also be prepared by reaction of a compound of formula (XXX) with a compound of formula (XXXa) (as described in Scheme 1 and Scheme 2, respectively). Compounds of formula (XXIXa) can be prepared from the corresponding acid of formula (XXIX) as described in Scheme 1. Such a reaction is described, for example, in J. Prakt. Chem. 1985, 327, 109-116. Compounds of formula (IIi) can be prepared by reaction of a general intermediate of formula (XXXI) (wherein Z 1 is as defined for compounds of formula (I), and X 01 (as previously described) can also be prepared by treatment with Lawesson's reagent or neat phosphoric 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. 1961, 26, 4410-12).

[0163] A compound of formula (II) 1 is O and A 2 is N and A 4 is a methine, and A 3 is C and Z 1is as defined for compounds of formula (I), i.e. compounds of formula (IIl), can be prepared as shown in Scheme 19. [ka] Scheme 19

[0164] As shown in Scheme 19, compounds of formula (IIl) are readily available by hydrolysis of esters of formula (IIk) by methods well known to those skilled in the art and described above. Compounds of formula (IIj) can be obtained by reaction of compounds of formula (XXXIII) with compounds of 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, respectively. Such reaction sequences are described, for example, in J. Het. Chem. 2013, 50(4), 774-780 and J. Chin. Chem. Soc. 2007, 54(3), 643-652. Compounds of formula (XXXIII) can be converted to compounds of formula (XXXV) (wherein Z is a hydroxylamine-containing amine) by treatment with hydroxylamine under conditions well known to those skilled in the art. 1 is readily prepared from (as defined for compounds of formula (I)).

[0165] A compound of formula (II) 1 , A 2 , A 4 is CH or N, and A 3 is N) is represented by the formula (XXXVI) [ka] and a compound of formula (XXXVII) [ka] (In the formula, Z 1 is as previously described under formula I, and X 0 is a halogen, preferably chlorine, bromine or iodine In an inert aprotic or protic solvent, the alkylation can be carried out in the presence of a base, such as an alkaline earth metal base, for example, NaOH, KOH, LiOH, CsCO, or KCO. Such alkylation is well known to those skilled in the art and has been used in this context to prepare compounds of 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 understand that this can result in a mixture of regioisomeric compounds that can be separated by chromatographic techniques, or that pure isomers can be obtained by a gentle selection of conditions and additives (e.g., palladium catalysts for the so-called Buchwald amination). 1 When is heteroaryl or aryl, the SnAr reaction (with or without copper catalysis) can be used to prepare compounds of formula (IIb) (see, e.g., Polyhedron 2019, 165, 22-30; US Patent Application Publication No. 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 references cited therein).

[0166] Salts of compounds of formula (I) can be prepared in a manner known per se: thus, for example, acid addition salts of compounds of formula (I) can be obtained by treatment with a suitable acid or with a suitable ion exchange reagent, and base salts can be obtained by treatment with a suitable base or with a suitable ion exchange reagent.

[0167] Salts of compounds of formula (I) may be converted in a conventional manner, for example into the free compounds (I) (acid addition salts) by treatment with a suitable basic compound or a suitable ion exchange reagent, or into salts with a base, for example by treatment with a suitable acid or a suitable ion exchange reagent.

[0168] Salts of compounds of formula (I) can be converted into other salts (acid addition salts, e.g. other acid addition salts) of compounds of formula (I) in a manner known per se, for example by treating the salt of an inorganic acid, such as hydrochloric acid, with a suitable metal salt of the acid, such as sodium, barium or silver salt (e.g. silver acetate), in a suitable solvent (in which inorganic salts that form, for example, silver chloride, are insoluble and therefore precipitate from the reaction mixture).

[0169] Depending on the procedure or reaction conditions, compounds of formula (I) that have salt-forming properties may be obtained in the free form or in salt form.

[0170] The compounds of formula (I) and, where appropriate, their tautomers, in each free or salt form, may exist in the form of pure isomers, such as enantiomers and / or diastereomers, or as isomeric mixtures, such as enantiomeric mixtures, e.g. racemates, diastereomeric mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms occurring in the molecule and / or depending on the configuration of non-aromatic double bonds occurring in the molecule, in one of the possible isomers or as mixtures thereof; the invention relates to the pure isomers and also to all possible isomeric mixtures, and is to be understood in this sense above and below, respectively, even if details of the stereochemistry are not specifically stated in each case.

[0171] Diastereomeric or racemic mixtures of compounds of formula (I), in free or salt form, depending on which starting materials and procedures are selected, can be separated in known manner on the basis of the physical chemical differences of the components into pure diastereomers or racemates, for example by fractional crystallization, distillation and / or chromatography.

[0172] Enantiomeric mixtures, such as racemates, obtainable in a similar manner can be resolved into their optical antipodes by known methods, for example by recrystallization from optically active solvents, chromatography on chiral adsorbents, for example by high performance liquid chromatography (HPLC) on acetylcellulose using suitable microorganisms, cleavage by specific immobilized enzymes, in which only one enantiomer is complexed, for example via the formation of inclusion compounds with chiral crown ethers, or by conversion into diastereomeric salts, for example by reacting the basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphoric acid, tartaric acid or malic acid, or a sulfonic acid, for example camphorsulfonic acid, to obtain a diastereomeric mixture, which can then be separated, for example, by fractional crystallization according to their different solubilities, and the desired enantiomer can then be liberated by the action of a suitable agent, for example a basic agent.

[0173] Pure diastereomers or enantiomers can be obtained according to the invention not only by separating the appropriate isomeric mixtures, but also by diastereoselective or enantioselective synthesis, which is a method known in the art, e.g., by carrying out the process according to the invention using starting materials with the appropriate stereochemistry.

[0174] When the individual components have different biological activities, it may be advantageous to isolate or synthesize the respective more biologically active isomer, e.g., enantiomer or diastereomer, or mixture of isomers, e.g., mixture of enantiomers or diastereomers.

[0175] As an example, compounds with two or more asymmetric carbon atoms may exist in diastereoisomeric forms which can optionally be separated using, for example, supercritical fluid chromatography (SFC) chromatography with a chiral column. Although such diastereomers may exhibit different fungicidal activity profiles, all isomers and diastereomers form part of the present invention.

[0176] The compounds of formula (I) have at least three chiral carbon atoms (three stereocenters, the star (*) indicates the chiral carbon atoms), and therefore at least eight stereoisomers are available. These at least eight stereoisomers consist of four sets of enantiomers. [ka]

[0177] A compound of formula (I) 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 is as defined for compounds of formula (I), and R 4 is not hydrogen), the relationship between enantiomers and diastereomers is shown in Scheme 20. [ka] Scheme 20

[0178] Those skilled in the art will recognize that the compounds of formula (I) (as shown in Scheme 21) 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 is as defined for formula (I), and R 4 is not hydrogen) are well understood to be within the scope of the present invention.

[0179] A compound of formula (I)2 , R 3 is hydrogen, and Q, R 1 , R 4 , R 5 , R 6 , B 1 , B 2 and Z 1 is as defined for compounds of formula (I), A is as defined for compounds of formula (IA), and R 4 The relationship between enantiomers and diastereomers for the 2-amino group (where 2 is not hydrogen) is shown in Scheme 21. [ka] Scheme 21

[0180] 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 is as defined for compounds of formula (I), A is as defined for compounds of formula (IA), and R 4 is not hydrogen), Q and R 4 The moieties have a syn relationship to each other.

[0181] The syn 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 is as defined for compounds of formula (I), A is as defined for compounds of formula (IA), and R 4 is not hydrogen) is shown in Scheme 22. [ka] Scheme 22

[0182] Preferably, the compound of formula (I) 2 , R 3 is hydrogen, and Q, R 1 , R 4 , R 5 , R 6 , B 1 , B 2 and Z 1 is as defined for compounds of formula (I), A is as defined for compounds of formula (IA), and R 4 is not hydrogen), Q and R 4 The moieties have a syn relationship to each other.

[0183] The compounds of formula (I) and, where appropriate, their tautomers may each be obtained in free form or in salt form, where appropriate also in the form of a hydrate, and / or may include other solvents, such as those that may have been used for the crystallization of compounds present in solid form.

[0184] As already mentioned, it has now been surprisingly found that the compounds of formula (I) of the present invention have a very advantageous level of biological activity for practical use in protecting plants from diseases caused by fungi.

[0185] The compounds of formula (I) according to the present invention can be used in the agricultural sector and related fields of use, for example, as active ingredients for controlling plant pests or against non-living organisms for the control of damaging microorganisms or organisms potentially harmful to humans. The novel compounds are distinguished by excellent activity at low application rates, being well tolerated by plants, and being environmentally safe. They have very useful curative, preventive, and systemic properties and can be used to protect a large number of cultivated plants. The compounds of formula (I) can be used to suppress or eradicate pests that appear on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of different crops of useful plants, while simultaneously protecting those parts of the plant that grow later, for example, from phytopathogenic microorganisms.

[0186] The present invention further relates to a method for controlling or preventing infestation of susceptible plants or plant propagation material and / or harvested food crops by microorganisms by treating the plants or plant propagation material and / or harvested food crops, wherein an effective amount of a compound of formula (I) according to the invention is applied to the plant, its part or its habitat.

[0187] The compound of formula (I) according to the present invention can also be used as a fungicide.As used herein, the term "fungicide" refers to a compound that controls, modifies or prevents the growth of fungi.The term "fungicidally effective amount", when used, refers to the amount of such a compound or a combination of such compounds that can produce an effect on the growth of fungi.Control or modification effect includes all deviations from natural occurrence, such as killing, delaying, etc., and prevention includes the formation of a barrier or other defense in plants to prevent fungal infection.

[0188] To protect against fungal infections and phytopathogenic fungi occurring in the soil, the compounds of formula (I) according to the present invention may also be used as dressings for treating plant propagation material, such as seeds of fruits, tubers, or grains, or plant cuttings. The propagation material can be treated with a composition containing a compound of formula (I) before planting. For example, seeds can be treated with a dressing before sowing. The active compound of formula (I) can also be applied (coated) to grains by impregnating the seeds with a liquid formulation or coating the seeds with a solid formulation. When the propagation material is planted, the composition can also be applied to the planting site, for example, in the sowing furrow during sowing. The present invention also relates to a method for treating such plant propagation material and to the plant propagation material treated in this way.

[0189] Furthermore, the compounds of formula (I) according to the invention can be used to control fungi in relevant fields, for example in the protection of industrial materials, including wood and wood-related industrial products, food storage, hygiene control.

[0190] In addition, the present invention may be used to protect non-living materials such as timber, wallboard and paint from fungal attack.

[0191] The compounds of formula (I) according to the invention are active, for example, against disease-causing fungi and fungal vectors as well as phytopathogenic bacteria and viruses. Fungi and fungal vectors as well as plant pathogenic bacteria and viruses associated with these diseases are, for example: Absidia corymbifera, Alternaria spp., Aphanomyces spp., Ascochyta spp., Aspergillus spp., including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, Aureobasidium spp., including A. pullulans, Blastomyces dermatitidis, and the like. Botryosphaeria spp. including B. dermatitidis, Blumeria graminis, Bremia lactucae, B. dothidea, and B. obtusa; Botrytis spp. including B. cinerea; Candida spp. including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, and C. tropicalis; Cephaloascus fragrans fragrans, Ceratocystis spp., Cercospora spp. including C. arachidicola, Cercosporidium personatum, Cladosporium spp.), Claviceps purpurea, Coccidioides immitis, Cochliobolus spp., Colletotrichum spp. including C. musae, Cryptococcus neoformans, Diaporthe spp., Didymella spp., Drechslera spp., Elsinoe spp., Epidermophyton spp., Erwinia amylovora amylovora, Erysiphe spp. including E. cichoracearum, Eutypa lata, F. culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, F. solani, Fusarium spp. including Gaeumannomyces graminis, Gibberella fujikuroi, fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium spp., Hemileia spp., H. capsulatumHistoplasma spp. including Histoplasma capsulatum, Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp., Monilinia spp., Mucor spp., M. graminicola, Mycosphaerella spp. including M. pomi, Oncobasidium theobromaeon theobromaeon, Ophiostoma piceae, Paracoccidioides spp., Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp., Peronosclerospora spp. including P. maydis, P. philippinensis and P. sorghi, Peronosclerospora spp., Phaeosphaeria nodorum, Phakopsora pachyrhizi, pachyrhizi, Phellinus igniarus, Phialophora spp., Phoma spp., Phomopsis viticola, Phytophthora spp. including P. infestans, P. halstedii, P. viticolaPlasmopara spp. including P. viticola, Pleospora spp., Podosphaera spp. including P. leucotricha, Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp., Pseudoperonospora spp. including P. cubensis and P. humuli, Pseudoperonospora spp. including P. tracheophila, Pseudoperonospora spp. including P. cubensis and P. humuli, Pseudoperonospora spp. including P. tracheophila, Pseudoperonospora spp. including P. leucotricha ... leucotricha, Pseudoperonospora spp. including P. leucotricha, Pseudoperonospora spp. including P. leucotricha, Pseudoperonospora spp. including P. leucotricha, Pseudoperonospora spp. including P. leucotricha, Pseudoperonospora spp. including P. leucotricha, Puccinia spp. including P. tracheiphila, P. hordei, P. recondita, P. striiformis, and P. triticina, Pyrenopeziza spp., Pyrenophora spp., Pyricularia spp. including P. oryzae, Pythium spp. including P. ultimum, Ramularia spp., Rhizoctonia spp., and Rhizomucor pusillus. pusillus, Rhizopus arrhizus, Rhynchosporium spp., Scedosporium spp. including S. apiospermum and S. prolificans, Schizothyrium pomi, Sclerotinia spp., Sclerotium spp., Sclerotium spp., S. nodorum, S. tritici, S.Septoria spp. including (Septoria tritici), Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix spp., Stagonospora nodorum, Stemphylium spp., Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia spp. Trichoderma spp., including T. harzianum, T. pseudokoningii, and T. viride, Trichophyton spp., Typhula spp., Uncinula necator, Urocystis spp., Ustilago spp., Venturia spp., including V. inaequalis, Verticillium spp., and Xanthomonas spp.

[0192] The compounds of formula (I) according to the present invention may be used on turf, ornamental plants such as flowers, shrubs, broad-leaved or evergreen trees, such as conifers, as well as for trunk injection, pest control, etc.

[0193] Target crops and / or useful plants to be protected within the scope of the present invention typically include berry plants, such as blackberries, blueberries, cranberries, raspberries and strawberries; cereals, such as barley, maize (corn), millet, oats, rice, rye, sorghum, triticale and wheat; fiber plants, such as cotton, flax, hemp, jute and sisal; field crops, such as sugar beet and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugarcane, sunflower, tea and tobacco; fruit trees, such as apple, apricot, avocado, banana, cherry, citrus fruits, nectarine, peach, pear and plum; grasses, such as dactylon, strawberry vine, bean grass, Japanese laurel wort, Japanese fescue, rye, St. Augustine grass. and lawn grass; herbs such as basil, borage, chives, coriander, lavender, lovage, peppermint, oregano, parsley, rosemary, sage and thyme; legumes such as beans, lentils, peas and soybeans; nuts such as almonds, cashews, groundnuts, hazelnuts, peanuts, pecans, pistachios and walnuts; palms such as oil palms; ornamental plants such as flowers, shrubs and trees; other trees such as cocoa, coconut, olive and rubber; vegetables such as asparagus, eggplant, broccoli, cabbage, carrots, cucumber, garlic, lettuce, squash, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and perennial and annual crops such as grapes.

[0194] The term "useful plants" should also be understood to include useful plants that have been rendered tolerant to herbicides such as bromoxynil or to classes of herbicides (e.g., HPPD inhibitors, ALS inhibitors such as primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyroyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen oxidase) inhibitors) by conventional methods of breeding (mutagenesis). An example of a crop that has been rendered tolerant to imidazolinones, such as imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rapeseed (canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-tolerant corn varieties commercially available under the trade names RoundupReady®, Herculex I®, and LibertyLink®.

[0195] It is to be understood that the term "useful plants" also includes useful plants that have been transformed using recombinant DNA techniques so as to be able to synthesize one or more selectively acting toxins, such as those known from toxin-producing bacteria, particularly Bacillus bacteria.

[0196] Examples of such plants are YieldGard® (a corn variety expressing a CryIA(b) toxin); YieldGard Root-Feeding Nematode® (a corn variety expressing a CryIIIB(b1) toxin); YieldGard Plus® (a corn variety expressing a CryIA(b) and a CryIIIB(b1) toxin); Starlink® (a corn variety expressing a Cry9(c) toxin); Herculex I® (a corn variety expressing a CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety expressing a CryIA(c) toxin); Bollgard I® (a cotton variety expressing a CryIA(c) toxin); Bollgard II® (a cotton variety expressing CryIA(c) and CryIIA(b) toxins); VIPCOT® (a cotton variety expressing VIP toxin); NewLeaf® (a potato variety expressing CryIIIA toxin); Nature-Gard® Agrisure® GT Advantage (GA21 glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), Agrisure® RW (corn root nematode trait), and Protecta®.

[0197] The term "crop plant" should also be understood to include crop plants that have been transformed using recombinant DNA techniques so as to be capable of synthesizing one or more selectively acting toxins, such as those known from toxin-producing bacteria, particularly those belonging to the genus Bacillus.

[0198] Toxins that can be expressed by transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as 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; or insecticidal proteins from Photorhabdus luminescens, Xenorhabdus nematophilus, e.g., Photorhabdus spp. or Xenorhabdus insecticidal proteins of nematode-symbiotic bacteria such as nematode toxins; toxins produced by animals such as scorpion toxins, spider toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi such as Streptomycete toxins, plant lectins such as pea lectin, barley lectin or snowdrop lectin; agglutinins; proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin and papain inhibitors; ricin, Ribosome-inactivating proteins (RIPs) such as maize RIP, abrin, rufin, saporin or bryodin; steroid metabolic enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers such as sodium or calcium blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

[0199] Furthermore, in the context of the present invention, delta-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or trophic insecticidal proteins (Vip), such as Vip1, Vip2, Vip3, or Vip3A, are also understood to be, in particular, hybrid toxins, truncated toxins, and modified toxins. Hybrid toxins are produced recombinantly by novel combinations of different domains of these 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 native toxin are replaced. In such amino acid substitutions, a non-naturally occurring protease recognition sequence is preferably 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).

[0200] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP 0 374 753, WO 93 / 07278, WO 95 / 34656, EP 0 427 529, EP 0 451 878 and WO 03 / 052073.

[0201] Methods for the preparation of 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 0 367 474, EP 0 401 979 and WO 90 / 13651.

[0202] The toxins contained in the genetically modified plants confer resistance to harmful insects found in all insect taxa, but particularly in beetles (Coleoptera), two-winged insects (Diptera), and butterflies (Lepidoptera).

[0203] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known, some of which are commercially available. Examples of such plants include YieldGard® (a corn variety expressing the Cry1Ab toxin); YieldGard Rootworm® (a corn variety expressing the Cry3Bb1 toxin); YieldGard Plus® (a corn variety expressing the Cry1Ab and Cry3Bb1 toxins); Starlink® (a corn variety expressing the Cry9C toxin); Herculex I® (a corn variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety expressing the Cry1Ac toxin); Bollgard I® (a cotton variety expressing the Cry1Ac toxin); Bollgard II® (a cotton variety expressing Cry1Ac and Cry2Ab toxins); VipCot® (a cotton variety expressing Vip3A and Cry1Ab toxins); NewLeaf® (a potato variety expressing Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), and Protecta®.

[0204] Further examples of such transgenic crops are: 1. Bt11 maize, registration number C / FR / 96 / 05 / 10, from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France. Genetically modified maize (Zea mays) conferred resistance to European corn borers (Ostrinia nubilalis and Sesamia nonagrioides) through recombinant expression of a truncated Cry1Ab toxin. Bt11 maize also conferred resistance to the herbicide glufosinate-ammonium through recombinant expression of the PAT enzyme.

[0205] 2. Bt176 maize, registration number C / FR / 96 / 05 / 10, from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France. Genetically modified maize (Zea mays) conferred resistance to European corn borers (Ostrinia nubilalis and Sesamia nonagrioides) through recombinant expression of the Cry1Ab toxin. Bt176 maize also conferred resistance to the herbicide glufosinate-ammonium through recombinant expression of the PAT enzyme.

[0206] 3. MIR604 maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Maize conferred insect resistance by recombinantly expressing a modified Cry3A toxin. The toxin is Cry3A055 modified by inserting a cathepsin-G-protease recognition sequence. The generation of such transgenic maize plants is described in WO 2003 / 018810.

[0207] 4. MON 863 maize, registration number C / DE / 02 / 9, from Monsanto Europe SA270-272 Avenue de Tervuren, B-1150 Brussels, Belgium. MON 863 expresses the Cry3Bb1 toxin and confers resistance to certain Coleoptera insects.

[0208] 5. IPC 531 Cotton, registration number C / ES / 96 / 02, from Monsanto Europe SA270-272 Avenue de Tervuren, B-1150 Brussels, Belgium.

[0209] 6. 1507 corn from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Maize genetically modified to express the Cry1F protein for resistance to certain Lepidoptera insects and the PAT protein for tolerance to the glufosinate-ammonium herbicide.

[0210] 7. NK603 x MON 810 maize, registration number C / GB / 02 / M3 / 03, from Monsanto Europe SA270-272 Avenue de Tervuren, B 1150 Brussels, Belgium. This conventionally bred hybrid maize variety was obtained by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 maize recombinantly expresses the CP4 EPSPS protein from Agrobacterium sp. strain CP4, which confers tolerance to Roundup® (containing glyphosate) herbicides, as well as the Cry1Ab toxin from Bacillus thuringiensis subsp. kurstaki, which confers resistance to certain lepidopteran insects, such as the European corn borer.

[0211] The compounds of formula (I) according to the invention are effective against phytopathogenic diseases, in particular phytopathogenic fungi, such as Alternaria species on fruits, vegetables and potatoes; Botrytis cinerea on strawberries, tomatoes, sunflowers, pulses, vegetables and grapes; Rhizoctonia solani on potatoes and vegetables; Uncinula necator on grapes; Cladosporium cucumerinum, Didymella bryoniae, Sphaerotheca fuliginea and Glomerella lagenarium on Cucurbits; Leveillula taurica on Cucurbits and Solanaceae crops. taurica); Fusarium spp. in cereals; Leptosphaeria spp. in cereals; and Zymospetoria spp. in cereals.

[0212] As used herein, the term "habitat" means the field in which the plant is growing or in which the seeds of the plant to be cultivated have been sown or will be sown in the soil. It includes the soil, seeds and seedlings, and established vegetation.

[0213] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves and fruits.

[0214] The term "plant propagation material" is understood to refer to reproductive parts, such as seeds, of plants and vegetative parts, such as cuttings or tubers, for example potatoes, which can be used for their propagation. Examples include seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Also included are germinated plants and seedlings that will be transplanted after germination or emergence from the soil. These seedlings can be protected by a complete or partial immersion treatment before transplanting. Preferably, "plant propagation material" is understood to refer to seeds.

[0215] The compounds of formula (I) according to the present invention can be used in their original form or, preferably, together with adjuvants conventionally used in the field of formulations. For this purpose, they can be formulated in a known manner as emulsifiable concentrates, coatable pastes, ready-to-spray or dilutable solutions or suspensions, diluted emulsions, wettable powders, soluble powders, dusts, granules, or as encapsulated polymeric materials. The application method, such as spraying, atomizing, dusting, granulation, coating, or pouring, as well as the type of composition, is selected according to the intended purpose and the circumstances. The composition can also contain further adjuvants, such as stabilizers, defoamers, viscosity modifiers, binders, or tackifiers, as well as fertilizers, sources of trace elements, or other ingredients for achieving special effects.

[0216] Suitable carriers and adjuvants, for example for agricultural applications, can be solid or liquid and are substances useful in formulation technology, such as natural or regenerated inorganic substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are described, for example, in WO 1997 / 33890.

[0217] Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations contain anti-settling and dispersing agents and may further contain wetting agents to enhance activity, as well as anti-foaming agents and crystal growth inhibitors. For use, these concentrates are diluted with water and typically applied as a spray to the area to be treated. The amount of active ingredient can range from 0.5% to 95% of the concentrate.

[0218] Wettable powders are in the form of finely divided particles that disperse readily in water or other liquid carriers. The particles contain the active ingredient held in a solid matrix. Typical solid matrices include fuller's earth, kaolin clay, silica, and other readily wet organic or inorganic solids. Wettable powders usually contain 5% to 95% of the active ingredient and small amounts of wetting agents, dispersing agents, or emulsifying agents.

[0219] Emulsifiable concentrates are homogeneous liquid compositions that are dispersible in water or other liquids and may consist solely of the active compound and a liquid or solid emulsifier, or may also contain a liquid carrier such as xylene, high-boiling aromatic naphtha, isophorone, and other non-volatile organic solvents. When used, these concentrates are dispersed in water or other liquid and typically applied as a spray to the area to be treated. The amount of active ingredient can range from 0.5% to 95% of the concentrate.

[0220] Granular formulations include both extrudates and relatively coarse particles, and are usually applied undiluted to the area where treatment is required. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clay, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, gypsum, wood flour, crushed corncobs, crushed peanut shells, sugar, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate, and other organic or inorganic materials that can absorb or be coated with the active compound. Granular formulations usually contain 5% to 25% active ingredient, which may include surfactants or vegetable oils such as high-boiling aromatic naphtha, kerosene, and other petroleum fractions, and / or adhesives such as dextrin, glue, or synthetic resins.

[0221] Dusts are free-flowing mixtures of the active ingredient and finely divided solids such as talc, clays, flours and other organic and inorganic solids, which act as dispersants and carriers.

[0222] Microcapsules are typically droplets or granules of an active ingredient enclosed in an inert, porous shell that allows the encapsulated material to be released into the environment at a controlled rate. The encapsulated droplets are typically 1 to 50 microns in diameter. The encapsulated liquid typically constitutes 50 to 95% of the capsule's weight and may contain solvent in addition to the active compound. Encapsulated granules are generally porous granules with a porous membrane that seals the pore openings of the granule, retaining the active species in liquid form within the pores of the granule. Granules typically range in diameter from 1 millimeter to 1 centimeter, preferably 1 to 2 millimeters. Granules are formed by extrusion, agglomeration, or prilling, or are naturally occurring. Examples of such materials are vermiculite, calcined clay, kaolin, attapulgite clay, sawdust, and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes, and starch xanthates.

[0223] Other useful formulations for pesticide applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone, alkylated naphthalenes, xylene, and other organic solvents. Pressurized sprayers can also be used, in which the active ingredient is dispersed in finely divided form as a result of evaporation of the low-boiling dispersant solvent carrier.

[0224] Suitable agricultural adjuvants and carriers useful in formulating the compositions of the present invention in the formulation types described above are well known to those skilled in the art.

[0225] Liquid carriers that can be used include, for example, water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetate, 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, diproxitol, alkylpyrrolidinone, 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, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octyl amine Examples of suitable solvents include ethanol, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG 400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, and octanol, as well as ethylene glycol, propylene glycol, glycerin, and N-methyl-2-pyrrolidinone. Water is generally the carrier of choice for dilution of concentrates.

[0226] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, fuller's earth, cottonseed hulls, wheat flour, soy flour, pumice, wood flour, walnut hulls, and lignin.

[0227] A wide variety of surfactants are advantageously employed in both the liquid and solid compositions, especially those designed to be diluted with a carrier before application. These agents, when used, usually constitute from 0.1% to 15% by weight of the formulation. They may be anionic, cationic, nonionic, or polymeric in nature and may be used as emulsifying agents, wetting agents, suspending agents, or for other purposes. Typical surfactants include alkyl sulfates such as diethanolammonium lauryl sulfate; alkylaryl sulfonates, for example, calcium dodecylbenzene sulfone sulfate; alkylphenol-alkylene oxide adducts, for example, nonylphenol-C.sub.18 ethoxylate; alcohol-alkylene oxide adducts, for example, tridecyl alcohol-C.sub.16 ethoxylate; soaps, such as sodium stearate; alkylnaphthalene sulfonates, for example, sodium dibutylnaphthalene sulfonate; dialkyl esters of sulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, for example, sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride; polyethylene glycol esters of fatty acids, for example, polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and dialkyl phosphate esters.

[0228] Other adjuvants commonly used in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, antifoaming agents, sunscreens, compatibilizers, defoamers, sequestering agents, neutralizing and buffering agents, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, emollients, lubricants and adhesives.

[0229] In addition, other biocidal active ingredients or compositions can be combined with the composition of the present invention, used in the method of the present invention, and applied simultaneously or successively with the composition of the present invention.When applied simultaneously, these additional active ingredients can be formulated together with the composition of the present invention, or can be mixed, for example, in a spray tank.These additional biocidal active ingredients can be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and / or plant growth regulators.

[0230] Pesticides are referred to herein using their common names and are known, for example, from “The Pesticide Manual”, 15th Ed., British Crop Protection Council 2009.

[0231] Additionally, the compositions of the present invention can be applied in conjunction with one or more systemic acquired resistance inducers ("SAR" inducers). SAR inducers are known and are described, for example, in U.S. Patent No. 6,919,298, and include, for example, salicylates and the commercially available SAR inducer acibenzolar-S-methyl.

[0232] The compound of formula (I) according to the present invention is usually used in the form of agrochemical compositions, and can be applied to the cropland or the plants to be treated simultaneously or successively with other compounds.These additional compounds can be, for example, fertilizers or sources of trace elements or other preparations that affect plant growth.They can also be selective or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, and if necessary, also contain additional carriers, surfactants or application-promoting adjuvants that are commonly used in the technical field of formulation.

[0233] The compounds of formula (I) according to the invention may be used in the form of (fungicidal) compositions for the control against or protection against phytopathogenic microorganisms, containing 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 the form of an agrochemically available salt, and at least one of the adjuvants mentioned above.

[0234] Therefore, the present invention provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I) according to the present invention, an agriculturally acceptable carrier, and optionally an adjuvant. An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural carriers are well known in the art. Preferably, the composition may comprise, in addition to the compound of formula (I), at least one or more pesticidal active compounds, for example, additional fungicidal active ingredients.

[0235] The compound of formula (I) according to the present invention may be the only active ingredient of the composition or, if appropriate, may be mixed with one or more additional active ingredients, such as pesticides, fungicides, synergists, herbicides or plant growth regulators, which may in some cases result in unexpected synergistic effects.

[0236] Examples of suitable additional active ingredients include acyl amino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenic fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, Mercury fungicides, morpholine fungicides, organophosphate fungicides, organotin fungicides, oxathiin fungicides, oxazole fungicides, phenylsulfamide fungicides, polysulfide fungicides, pyrazole fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungicides, quinone fungicides, quinoxaline fungicides, strobilurin fungicides, sulfonanilide fungicides, thiadiazole fungicides, thiazole fungicides, thiazolidine fungicides, thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, valinamide fungicides and zinc fungicides.

[0237] Examples of suitable additional active ingredients include: petroleum, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenylbenzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylacetamide, 4-chlorophenylphenylsulfone, acetoprole, aldoxicarb, amidithione, amidothioate, amiton, amiton hydrogen oxalate, amitraz, alamite, arsenic trioxide, azobenzene, azotoate, benomyl, benoxafos, benzoic acid Benzil, bixafen, brofenvalerate, bromocyclen, bromophos, bromopropylate, buprofezin, butocarboxim, butoxycarboxim, butylpyridaben, calcium polysulfide, camphechlor, carbanolate, carbophenothion, cymiazole, chinomethionate, chlorbeneside, chlordimeform, chlordimeform hydrochloride, chlorphenetole, chlorfenson, chlorfen sulfide, chlorobenzilate, chloromebuform, chloromethyluron, chloro Propylate, Chlorthiophos, Cinerin I, Cinerin II, Cinerin, Closantel, Coumaphos, Crotamiton, Crotoxyphos, Kufraneb, Cyanthoate, DCPM, DDT, Demefion, Demefion-O, Demefion-S, Demeton-methyl, Demeton-O, Demeton-O-methyl, Demeton-S, Demeton-S-methyl, Demeton-S-methyl sulfone, Dichlofluanid, Dichlorvos, Dicrifos, Dienochlor, Dimefox, Zinex, Zinex-diclexin, Zinocca CAP-4, Dinocap-6, Dinoctone, Dinopentone, Dinosulfone, Dinotervone, Dioxathion, Diphenylsulfone, Disulfiram, DNOC, Dofenapine, Doramectin, Endothion, Eprinomectin, Ethoate-methyl, Etrimphos, Fenazaflor, Fenbutatin Oxide, Fenothiocarb, Fenpyrad, Fenpyroximate, Fenpyrazamine, Fenson, Fentrifanil, Flubenzimine, Flucycloxuron, Fluenethyl, Fluorobenside, FMC 1137, Formetanate, Formetanate Hydrochloride, Formoparanate, γ-HCH, Gliodin, Halfenprox, Hexadecylcyclopropanecarboxylate, Isocarbophos, Jasmolin I,Jasmolin II, iodofenphos, lindane, malonobene, mecarbam, mefosfolan, mesulfen, methacrifos, methyl bromide, metolcarb, mexacarbate, milbemycin oxime, mipafox, monocrotophos, morphothion, moxidectin, naled, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one, nifururidide, nikkomycin, nitrilacarb, nitrilacarb 1:1 zinc chloride complex, omethoate, oxydeprophos, oxydisulfoton, pp'-DDT, parathion, permethrin, fenkapton, phosalone, phospholane, phosphamidon, polychloroterpenes, polynactin, proclonol, promacyl, propoxar, prothidathion, prothoate, pyrethrin I, pyrethrin II, pyrethrins, pyridaphenthion, pirimitate, quinalphos, quintiox, R-1492, phosglycine, rotenone, schradan, cebufos, selamectin, sofamid, SSI-121, sulfiram, sulfuramide, sulfotep, sulfur, diflobidazin, tau-fluvalinate, TEP P, Terbam, Tetradifon, Tetrasulf, Thiafenox, Thiocarboxim, Thiofanox, Thiometon, Thioquinox, Thuringiensin, Triamiphos, Triatene, Triazophos, Triazuron, Tripenofos, Trinactin, Vamidothion, Vaniliprole, Bethoxazin, Copper dioctanoate, Copper sulfate, Sibutrin, Dichlorn, Dichlorophen, Endothal, Fentin, Slaked lime, Nabam, Quinoclamine, Quinonamide, Simazine, Triphenyltin acetate, Triphenyltin hydroxide, Crufomate, Piperazine, Thiophanate, Chloralose, fenthion, pyridin-4-amine, strychnine, 1-hydroxy-1H-pyridine-2-thione, 4-(quinoxalin-2-ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, copper hydroxide, cresol, dipyrithione, dodisin, fenaminosulf, formaldehyde, hydralgafen, kasugamycin, kasugamycin hydrochloride hydrate, nickel bis(dimethyldithiocarbamate), nitrapyrin, octhilinone, oxolinic acid, oxytetracycline, potassium hydroxyquinoline sulfate,Probenazole, streptomycin, streptomycin sesquisulfate, tecloftalam, thiomersal, Adoxophyes orana GV, Agrobacterium radiobacter, Amblyseius spp., Anagrapha falcifera NPV, Anagrus atomus, Aphelinus abdominalis, Aphidius colemani, Aphidoletes aphidimyza, Autographa californica NPV, Bacillus sphaericus Neide, Beauveria bronniartii brongniartii, Chrysoperla carnea, Cryptolaemus montrouzieri, Cydia pomonella GV, Dacnusa sibirica, Diglyphus isaea, Encarsia formosa, Eretmocerus eremicus, Heterorhabditis bacteriophora and H. megidis, Hippodamia convergens, Leptomastix dactylopii, Macrolophus caliginosus caliginosus), Mamestra brassicae NPV, Metaphycus helvolus, Metarhizium anisopliae var. acridum,Metarhizium anisopliae var. anisopliae, Neodiprion sertifer NPV and N. lecontei NPV, Orius spp., Paecilomyces fumosoroseus, Phytoseiulus persimilis, Steinernema bibionis, Steinernema carpocapsae, Steinernema feltiae, Steinernema glaseri, Steinernema riobrave riobrave, Steinernema riobravis, Steinernema scapterisci, Steinernema spp., Trichogramma spp., Typhlodromus occidentalis, Verticillium lecanii), apholate, visadil, busulfan, dimatif, hemel, hempa, metepa, methiotepa, methyl apholate, molzide, penfluron, tepa, thiohempa, thiotepa, trethamine, 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)-tetradec-4,10-dien-1-yl acetate, (Z)-dodec-7-en-1-yl acetate, (Z)-hexadec-11-enal, (Z)-hexadec-11-en-1-yl acetate, (Z)-hexadec-13-en-11-yn-1-yl acetate, (Z)-icosa-13-en-10-one, (Z)-tetradec-7-en-1-al, (Z)-tetradec-9-en-1-ol,(Z)-Tetradeca-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, α-multistriatin, brevicomin, codrelure, codrel Mon, Cure, Disparlure, Dodec-8-en-1-yl acetate, Dodec-9-en-1-yl acetate, Dodeca-8,10-dien-1-yl acetate, Dominicalure, Ethyl 4-methyloctanoate, Eugenol, Frontalin, Grandolure, Grandolure I, Grandolure II, Grandolure III, Grandolure IV, Hexalure, Ipsdienol, Ipsenol, Japonilure, Lineatin, Littlea, Lupula, Medula, Megatomoic Acid, Methyl Eugenol, Muscalua, Octadeca-2,13-dien-1-yl Acetate, Octadeca-3,13-dien-1-yl Acetate, Olfuralua, Orictalua, Ostramon, Siglua, Soldigin, Sulcatol, Tetradec-11-en-1-yl Acetate, Trimedula, Trimedula A, Trimedula B1, Trimedula B2, Trimedula C, Tranquol, 2-(Octylthio)ethanol, Butopyronoxyl, Butoxy(Polypropylene Glycol), Adipic Acid Dibutyl phosphate, dibutyl phthalate, dibutyl succinate, diethyl toluamide, dimethylcarbate, dimethyl phthalate, ethyl hexanediol, hexamide, methoquin-butyl, methyl neodecaneamide, oxamate, picaridin, 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 dimethyl carbamate, 2-(2-butoxyethoxy)ethyl thiocyanate, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methyl carbamate, 2-(4-chloro-3,5-xylyloxy)ethanol, 2-chlorovinyl diethyl phosphate, 2-imidazolidone, 2-isovalerylindan-1,3-dione, 2-methyl(prop-2-ynyl)aminophenyl methyl carbamate, 2-thiocyanate Ethyl laurate, 3-bromo-1-chloroprop-1-ene, 3-methyl-1-phenylpyrazol-5-yldimethylcarbamate, 4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate, 5,5-dimethyl-3-oxocyclohex-1-enyldimethylcarbamate, acetione, acrylonitrile, aldrin, allosamidin, alixycarb, α-ecdysone, aluminum phosphide, aminocarb, anabasine, atidathion, azamethiphos, Bacillus thuringiensis (Bacillusthuringiensis) delta-endotoxin, barium hexafluorosilicate, barium polysulfide, bartholin, Bayer 22 / 190, Bayer 22408, beta-cyfluthrin, beta-cypermethrin, bioethanomethrin, biopermethrin, bis(2-chloroethyl)ether, borax, bromfenvinphos, bromo-DDT, bufencarb, butacarb, butathiophos, butonate, calcium arsenate, calcium cyanide, carbon disulfide, carbon tetrachloride, cartap hydrochloride, sevadine, chlorbicyclen, chlordane, chlordecone, chloroform, chloropicrin, chlorphoxim, chlorprazophos, cis-resmethrin, cismethrin, clocitrin, copper acetoarsenite, copper arsenate, copper oleate, cumitoate, cryolite, CS 708, cyanofenphos, cyanophos, cyclethrin, cythioate, d-tetramethrin, DAEP, dazomet, decarbofuran, diamidaphos, dikapton, diclofenthion, dicresyl, dicyclanil, dieldrin, diethyl 5-methylpyrazol-3-yl phosphate, dilol, dimefluthrin, dimethane, dimethrin, dimethylvinphos, dimethyllan, dinoprop, dinosam, dinoseb, diofenolan, dioxabenzophos, dicyclophos, DSP, ecdysterone, EI1642, EMPC, EPBP, etaphos, ethiofencarb, ethyl formate, ethylene dibromide, ethylene dichloride, ethylene oxide, EXD, fenchlorphos, fenetacarb, fenitrothion, fenoxacrim, fenpyritrin, fensulfothion, fenthion-ethyl, flucofuron, fosmetiran, fospirate, fostietan, furathiocarb, fretrin, guazatine, guazatine acetate, sodium tetrathiocarbonate , Halfenprox, HCH, HEOD, Heptachlor, Heterofos, HHDN, Hydrogen cyanide, Hikincarb, IPSP, Isazophos, Isobenzane, Isodrin, Isofenphos, Isolane, Isoprothiolane, Isoxathion, Juvenile hormone I, Juvenile hormone II, Juvenile hormone III, Kerevan, Kinoprene, Lead arsenate, Leptophos, Lilimphos, Ritidathion, m-Cumenylmethylcarbamate, Magnesium phosphide, Magnesium phosphide Dox, mecarfone, menasone, mercurous chloride, mesulfenphos, metam, metam-potassium, metam-sodium, methanesulfonyl fluoride, methoclotophos, methoprene, methotrin, methoxychlor, methyl isothiocyanate, methyl chloroform, methylene chloride, methoxadiazone, mirex, naphthalophos, naphthalene, NC-170, nicotine, nicotine sulfate, nithiazine, nornicotine, O-5-dichloro-4- Iodophenyl O-ethyl ethyl phosphonothioate, 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, para-dichlorobenzene, parathion-methyl, pentachlorophenol, pentachlorophenyl laurate, PH60-38, fenkapton, phosniclor, phosphine, phoxim-methyl, pyrimetaphos, polychlorodicyclopentadiene isomers, potassium arsenite, potassium thiocyanate, precocene I, precocene II, precocene III, primidophos, profluthrin, promecarb, prothiofos, pyrazophos, pyresmethrin, quassia, quinalphos-methyl, quinothion, lafoxanide, resmethrin, rotenone, cadethrin, ryania, ryanodine, sabadila, shradha cebufos, SI-0009, tiapronil, sodium arsenite, sodium cyanide, sodium fluoride, sodium hexafluorosilicate, sodium pentachlorophenoxide, sodium selenate, sodium thiocyanate, sulcofuron, sulcofuron-sodium, sulfuryl fluoride, sulproos, tard oil, tazimcarb, TDE, tebupirimfos, temephos, telalethrin, tetrachloroethane, cyclofos, thiocyclam, thiocyclam hydrogen oxalate, thiona Zin, thiosultap, thiosultap-sodium, tralomethrin, transpermethrin, triazamate, trichlormetaphos-3, trichloronate, trimethacarb, tolprocarb, triclopyricarb, triplen, veratridine, veratrine, XMC, ζmethrin, zinc phosphide, zolaprofos, meperfluthrin, tetramethylfluthrin, bis(tributyltin) oxide, bromoacetamide, ferric phosphate, niclosamide-olamine, tributyltin oxide, Pyrimorph, triphenmorph, 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, anicifluprine, benclotiaz, cytokinin, DCIP, furfural, isamidophos, kinetin, mulberry dark spot fungus (Myrothecium verrucaria) compound, tetrachlorothiophene, xylenol, zeatin, potassium ethylxanthate, acibenzolar, acibenzolar-S-methyl, Reynoutriasachalinensis extract, α-chlorohydrin, anth, barium carbonate, bisthiosemi, brodifacoum, bromadiolone, bromethalin, chlorophacinone, cholecalciferol, coumachlor, coumafuryl, coumatetralyl, crimidine, difenacoum, difethialone, diphacinone, ergocalciferol, flocoumafen, fluoroacetamide, flupropazine, flupropazine hydrochloride, norbormide, fosacetim, phosphorus, pindone, pyrinuron, sciliroside, sodium fluoroacetate, thallium sulfate, warfarin, 2-(2-butoxyethoxy)ethyl piperonylate, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, farnesol and nerolidol, verbutin, MGK264, piperonyl butoxide, piprotal, propyl isomers, S421, sesamex, sesamolin, sulfoxide, anthraquinone, copper naphthenate, copper oxychloride, dicyclopentadiene, thiram, zinc naphthenate, ziram, imanin, ribavirin, chlorinconazide, mercuric oxide, thiophanate-methyl, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, furametpyr, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, paclobutrazol, pefurazoate, penconazole, prothioconazole, pyrifenox, prochlor , propiconazole, pyrisoxazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole, ancymidol, fenarimol, nuarimol, bupirimate, dimethirimol, ethirimol, dodemorph, fenpropidin, fenpropimorph, spiroxamine, tridemorph, cyprodinil, mepanipyrim, pyrimethanil, fenpiclonil, fludioxonil, benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, oflactose, oxadixyl, carbendazim, debacarb, fuberidazole, thiabendazole, chlozolinate, dichlozolin, mycozolin, procymidone, vinclozolin, boscalid, carboxin, fenfuram, flutolanil, mepronil, Oxycarboxin, penthiopyrad, thifluzamide, dodine, iminoctadine, azoxystrobin, dimoxystrobin, enesterobrine, phenaminestrobin, flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, oryzastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, ferbam, mancozeb, maneb, metiram, propineb, zineb, captafol, captan, fluoroimide, folpet, tolylflua Nido, Bordeaux mixture, copper oxide, mancopper, oxine-copper, nitrothar-isopropyl, edifenphos, iprobenfos, phosdifen, tolclofos-methyl, anilazine, benthiavalicarb, blasticidin-S, chloroneb, chlorothalonil, cyflufenamid, cymoxanil, cyclobutrifluram, diclocymet, diclomedine, dicloran, diethofencarb, dimethomorph, flumorph, dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, ferimzone, fluazinam, fluazinam methylsulfolim, fluopicolide, fluoxythioconazole, flusulfamide, fluxapyroxad, fenhexamid, fosetyl-aluminum, hymexazole, iprovalicarb, cyazofamid, metasulfocarb, metrafenone, pencycuron, phthalide, polyoxin, propamocarb, pyribencarb, proquinazid, pyroquilon, pyriophenone, quinoxyfen, quintozene, tiadinil, triazoxide, tricyclazole, triforine, validamycin, valifenalate, zoxamide, mandipropamid, fulve Neteram, Isopyrazam, Sedaxane, Benzovindiflupyr, Pydiflumetofen, 3-Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide, Isoflucipram, Isotianil, Dipimethitrone, 6-Ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile, 2-(Difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide, 4-(2,6-Difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, Fluindapyr, Chlorpheniramine Methoxystrobin (Jia Xiangchunzi), rubenmixianan, diclobenthiazox, mandestrobin, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol, oxathiapiproline, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate, pyraziflumide, impil Fluxam, Tolprocarb, Mefentrifluconazole, Ipfentrifluconazole, 2-(Difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl) but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine, pyridaclomethyl, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one, aminopyrifen, amethyst Ctrazin, amisulbrom, penflufen, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide, florylpicoxamide, fenpicoxamide, methallylpicoxamide, tebufloquine, ipflufenoquine, quinofumelin, isofetamide, ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate (described in WO 2020 / 056090)

[0033] ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enoxy]phenyl]methyl]pyrazole-3-carboxylate (which can be prepared from 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 from 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 from 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 from 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 from 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 amide (which can be prepared from the method described in WO 2020 / 109391), N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide, benzothiostrobin, Fenamacril, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1), fluopyram, flufenoxadiazam, flutianil, fluopimomide, pyrapropoin, 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-diflu- Oro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, Methyltetraprole, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidinemethanol, Fluoxapiprolin, Enoxastrobin, Methyl (Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop-2-enoate, Methyl (Z)-3-methoxy-2-[ 2-methyl-5-(4-propyltriazol-2-yl)phenoxy]prop-2-enoate, methyl (Z)-2-[5-(3-isopropylpyrazol-1-yl)-2-methyl-phenoxy]-3-methoxy-prop-2-enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-(3-propylpyrazol-1-yl)phenoxy]prop-2-enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]prop-2-enoate These compounds can be prepared from the methods described in WO 2020 / 079111), methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate, methyl (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate (these compounds can be prepared from the methods described in WO 2020 / 193387), 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile ci]benzonitrile, trinexapac, cumoxystrobin, chungcheongmycin, copper thiodiazole, zinc thiazole, amethotractin, iprodione, seboxylamine, N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine , N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine (these compounds are disclosed in WO 2015 / 15 5075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared by the method described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine (these compounds can be prepared from the method 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)oxetan-2-yl]phenyl]-N-methyl-formamidine 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 from the method 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 from the method described in WO 2017 / 025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline, 4,4-difluoro-1-(5-fluoro-4-methylbenzimidazol-1-yl)isoquinoline,

[0033] 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 N,N-dimethyl-1-[[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 are described in WO 2017 / 055473, 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared from the method described in 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 from 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 from the method described in WO 2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile (this compound can be prepared from the method described in WO 2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile (this compound can be prepared from 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 from the method described in WO 2016 / 156290); (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate (this compound can be prepared from the method described in WO 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone (this compound can be prepared from the method described in WO 2011 / 138281), N-methyl-4-[5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzenecarbothioamide; 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-enamide (this compound can be prepared from the method described in WO 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine;N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared from the method described in WO 2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (this compound can be prepared from the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-2-pyridyl]-4-methyl-2-pyridyl]-5 ... (3-methylisoxazol-5-yl)-[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 from 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 from the method described in WO 2017 / 220485); 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)-methoxyisothiazolinone] N-[(Z)-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-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (these compounds can be prepared from the method described in WO 2018 / 202428);

[0238] The compounds of the present invention may also be used in combination with an antiparasitic agent. Such antiparasitic agents include compounds selected from the macrocyclic lactone class of 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 antiparasitic agents include semisynthetic and biosynthetic avermectin / milbemycin derivatives, such as those described in U.S. Pat. No. 5,015,630, WO 9415944, and WO 9522552. Additional antiparasitic agents include benzimidazoles, such as albendazole, cambandazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of this class. Further anthelmintics include imidazothiazoles and tetrahydropyrimidines, such as tetramisole, levamisole, pyrantel pamoate, oxantel or morantel. Further anthelmintics include flukeicides, such as triclabendazole and clorsulon, and cestoicides, such as praziquantel and epsiprantel.

[0239] The compounds of the present invention may be used in combination with derivatives and analogues of the paraherquamide / marcfortine class of anthelmintics and antiparasitic oxazolines, such as those disclosed in U.S. Pat. No. 5,478,855, U.S. Pat. No. 4,639,771 and German Patent No. 19,520,936.

[0240] The compounds of the invention may be used in combination with derivatives and analogues of the general class of dioxomorpholine antiparasitic agents as described in WO 9615121, and may also be used in combination with anthelmintic effective cyclic depsipeptides such as those described in WO 9611945, WO 9319053, WO 9325543, EP 0626375, EP 0382173, WO 9419334, EP 0382173 and EP 0503538.

[0241] The compounds of the invention may be used in combination with other ectoparasiticides, for example fipronil, pyrethroids, organophosphates, insect growth regulators such as lufenuron, ecdysone agonists such as tebufenozide, neonicotinoids such as imidacloprid.

[0242] The compounds of the present invention may be used in combination with terpene alkaloids such as those described in WO 95 / 19363 or WO 04 / 72086, especially the compounds disclosed therein.

[0243] Other examples of such biologically active compounds that may be used in combination with the compounds of the present invention include, but are not limited to: Organic phosphates: Acephate, Azamethiphos, Azinphos-ethyl, Azinphos-methyl, Bromophos, Bromophos-ethyl, Cadusafos, Chlorethoxyphos, Chlorpyrifos, Chlorfenvinphos, Chlormephos, Demeton, Demeton-S-methyl, Demeton-S-methylsulfone, Dialifos, Diazinon, Dichlorvos, Dicrotophos, Dimethoate, Disulfoton, Ethion, Ethoprophos, Etrimphos, Famfur, Fenamiphos, Fenitrothion, Fensulfothion, Fenthion, Flupyrazophos, Fonofos, Formothion, Fosthiazate, Heptenophos, Isazophos, Isothioate, Isothioate Xathion, malathion, methacrifos, methamidophos, methidathion, methyl parathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton methyl, paraoxon, parathion, parathion methyl, phenthoate, phosalone, phospholane, phosphocarb, phosmet, phosphamidon, phorate, phoxim, pirimiphos, pirimiphos methyl, profenofos, propafos, proethamphos, prothiofos, pyraclofos, pyridapenthione, quinalphos, sulprofos, temephos, terbufos, tebupirimphos, tetrachlorvinphos, timeton, triazophos, trichlorfon, vamidothion.

[0244] Carbamates: alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801, isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl (methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717.

[0245] Pyrethroids: acrinathrin, allethrin, alphamethrin, (E)-(1R)-cis-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate 5-benzyl-3-furylmethyl, bifenthrin, β-cyfluthrin, cyfluthrin, α-cypermethrin, β-cypermethrin, bioallethrin, bioallethrin ((S)-cyclopentyl isomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin, cicithrin, cyphenothrin , deltamethrin, empenthrin, esfenvalerate, etofenprox, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (D-isomer), imiprothrin, cyhalothrin, λ-cyhalothrin, permethrin, fenothrin, prallethrin, pyrethrins (natural products), resmethrin, tetramethrin, transfluthrin, theta-cypermethrin, silafluofen, t-fluvalinate, tefluthrin, tralomethrin, zeta-cypermethrin.

[0246] Arthropod growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole, chlorfentadine; b) ecdysone agonists: halofenozide, methoxyfenozide, tebufenozide; c) juvenile hormone-like substances: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen.

[0247] Other antiparasitic agents: acequinocyl, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, campechlor, cartap, chlorobenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidin, cyromazine, diaclor, diafenthiuron, DBI-3204, dinactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, etofenprox, fenazaquin, flumite, MTI-800, fenpyroximate, fluacrypyrim, flubenzimine, flubrocythrinate, flufenzin, flufenprox, fluproxifen, ha Lofenprox, hydramethylnon, IKI-220, Kanemite, NC-196, Niemgard, Nidinolterfuran, Nitenpyram, SD-35651, WL-108477, pyridalyl, propargite, protrifenbut, pymetrozine, pyridaben, pyrimidifen, NC-1111, R-195, RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601, silafluofen, cyromazine, spinosad, tebufenpyrad, tetradifon, tetranactin, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad, triazamate, triethoxyspinosyn, trinactin, belbutin, Bertalec, YI-5301.

[0248] Biological agents: Bacillus thuringiensis ssp. aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, viruses and fungi.

[0249] Bactericides: chlortetracycline, oxytetracycline, streptomycin.

[0250] Other biological agents: enrofloxacin, febantel, penetamate, meloxicam, cephalexin, kanamycin, pimobendan, clenbuterol, omeprazole, tiamulin, benazepril, pyriprole, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, ceftiofur, carprofen, metaflumizone, praziquantel, triclabendazole.

[0251] The following mixtures of compounds of formula (I) with active ingredients are preferred: The abbreviation "TX" means one compound selected from the compounds of formula (I), (IA), (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 compound selected from the group of substances consisting of: petroleum + TX, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX, 2,4-dichlorophenylbenzenesulfonate + TX, 2-fluoro-N-methyl-N- 1-Naphthylacetamide + TX, 4-Chlorophenyl phenyl sulfone + TX, Acetoprole + TX, Aldoxicarb + TX, Amidithione + TX, Amidothioate + TX, Amiton + TX, Amiton hydrogen oxalate + TX, Amitraz + TX, Aramite + TX, Arsenic trioxide + TX, Azobenzene + TX, Azotoate + TX, Benomyl + TX, Benoxafos + TX, Benzyl benzoate + TX, Bixafen + TX, Brofenvalerate + TX, Bromocyclen + TX, Bromophos + TX, Bromopropylate + TX, Buprofen Zin + TX, Butocarboxim + TX, Butoxycarboxim + TX, Butylpyridaben + TX, Calcium polysulfide + TX, Camphechlor + TX, Carbanolate + TX, Carbophenothion + TX, Cimiazole + TX, Chinomethionate + TX, Chlorbeside + TX, Chlordimeform + TX, Chlordimeform hydrochloride + TX, Chlorphenetole + TX, Chlorfenson + TX, Chlorphenesulfide + TX, Chlorbenzilate + TX, Chlormebform + TX, Chlormethiron + TX, Chlorpropylate + TX, Chlor Thiophos + TX, Cinerin I + TX, Cinerin II + TX, Cinerin + TX, Closantel + TX, Coumaphos + TX, Crotamiton + TX, Crotoxyphos + TX, Kufraneb + ​​TX, Cyanthoate + TX, DCPM + TX, DDT + TX, Demefion + TX, Demefion-O + TX, Demefion-S + TX, Demeton-methyl + TX, Demeton-O + TX, Demeton-O-methyl + TX, Demeton-S + TX, Demeton-S-methyl + TX, Demeton-S-methyl sulfone + TX, Dichlofluanid + TX, Dichlorvos + TX,Dicrifos +TX, Dienochlor +TX, Dimefox +TX, Zinex +TX, Zinex-Diclexin +TX, Dinocap-4 +TX, Dinocap-6 +TX, Dinoctone +TX, Dinopentone +TX, Dinosulfone +TX, Dinotervone +TX, Dioxathion +TX, Diphenylsulfone +TX, Disulfiram +TX, DNOC +TX, Dofenapine +TX, Doramectin +TX, Endothion +TX, Eprinomectin +TX, Ethoate-methyl +TX, Etrimphos +TX, Fenazaflor +TX, Fenbutatin Oxide +TX, Fenothiocarb +TX, Fenpyrad +TX, Fenpyroximate +TX, Fenpyrazamine +TX, Fenson +TX, Fentrifanil +TX, Flubenzimine +TX, Flucycloxuron +TX, Fluenethyl +TX, Fluorbenside +TX, FMC 1137+TX, formetanate+TX, formetanate hydrochloride+TX, formparanate+TX, γ-HCH+TX, gliodin+TX, halfenprox+TX, hexadecylcyclopropanecarboxylate+TX, isocarbophos+TX, jasmolin I+TX, jasmolin II+TX, iodofenphos+TX, lindane+TX, malonoven+TX, mecarbam+TX, mefosphorane+TX, mesulfen+TX, methacrifos+TX, methyl bromide+TX, metolcarb+TX, mexacarbate+TX, milbemycin oxime+TX, mipafox+TX, monocrotophos+TX, morphothion+TX, moxidectin+TX, naled+TX, 4-chloro-2-(2-chloro-2-methylpropional) (6-ethyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, nifururidide + TX, nikkomycin + TX, nitrilacarb + TX, nitrilacarb 1:1 zinc chloride complex + TX, omethoate + TX, oxydeprophos + TX, oxydisulfoton + TX, pp'-DDT + TX, parathion + TX, permethrin + TX, fencapton + TX, phosalone + TX, phospholan + TX, phosphamidon + TX, polychloroterpenes + TX, polynactin + TX, proclonol + TX, promacyl + TX, propoxar + TX, prothidathion + TX, prothoate + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrin + TX, pyridaphenthion + TX,Pirimitate + TX, Quinalphos + TX, Quintiox + TX, R-1492 + TX, Phosglycine + TX, Rotenone + TX, Schrader + TX, Cevufos + TX, Selamectin + TX, Sofamid + TX, SSI-121 + TX, Sulfiram + TX, Sulfuramide + TX, Sulfotep + TX, Sulfur + TX, Diflobidazin + TX, τ-Fluvalinate + TX, TEPP + TX, Thelbam + TX, Tetradifon + TX, Tetrasulf + TX, Thiafenox + TX, Thiocarboxim + TX, Thiofanox +TX, Thiometon +TX, Thioquinox +TX, Thuringiensin +TX, Triamiphos +TX, Triatene +TX, Triazophos +TX, Triazuron +TX, Trifenofos +TX, Trinactin +TX, Vamidothion +TX, Vaniliprole +TX, Bethoxazin +TX, Copper dioctanoate +TX, Copper sulfate +TX, Sibutrin +TX, Dichloren +TX, Dichlorophen +TX, Endothal +TX, Fentin +TX, Slaked lime +TX, Nabam +TX, Quinoclamine +TX, Quinonamide +TX, Simazine +T X, triphenyltin acetate + TX, triphenyltin hydroxide + TX, crufomate + TX, piperazine + TX, thiophanate + TX, chloralose + 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, dodizin + TX, phenaminos ruf +TX, formaldehyde +TX, hydralgafen +TX, kasugamycin +TX, kasugamycin hydrochloride hydrate +TX, nickel bis(dimethyldithiocarbamate) +TX, nitrapyrin +TX, octhilinone +TX, oxolinic acid +TX, oxytetracycline +TX, hydroxyquinoline potassium sulfate +TX, probenazole +TX, streptomycin +TX, streptomycin sesquisulfate +TX, tecloftalam +TX, thiomersal +TX, smaller tea tortrix (Adoxophyes orana) GV +TX, Agrobacterium radiobacter +TX,Amblyseius spp. + TX, Anagrapha falcifera NPV + TX, Anagrus atomus + TX, Aphelinus abdominalis NPV + TX, Aphidius colemani NPV + TX, Aphidoletes aphidimyza NPV + TX, Autographa californica NPV + TX, Bacillus sphaericus Neide NPV + TX, Beauveria brongniartii NPV + TX, Chrysoperla carnea NPV + TX, Cryptolaemus montrouzieri NPV + TX, Codling moth NPV + TX, pomonella GV+TX, Dacnusa sibirica+TX, Diglyphus isaea+TX, Encarsia formosa+TX, Eretmocerus eremicus+TX, Heterorhabditis bacteriophora and H. megidis+TX, Hippodamia convergens+TX, Leptomastix dactylopii+TX, Macrolophus caliginosus+TX, Mamestra brassicae NPV+TX, Metaphycus helvolus) + TX, Metarhizium anisopliae var. acridum (Metarhizium anisopliae var. acridum) + TX, Metarhizium anisopliae var. anisopliae (Metarhizium anisopliae var. anisopliae) + TX,Neodiprion sertifer NPV and N. lecontei NPV + TX, Orius spp. + TX, Paecilomyces fumosoroseus + TX, Phytoseiulus persimilis + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Trichogramma spp.) + TX, Typhlodromus occidentalis + TX, Verticillium lecanii + TX, Apholate + TX, Visadil + TX, Busulfan + TX, Dimatif + TX, Hemel + TX, Hempa + TX, Metepa + TX, Methiotepa + TX, Methyl Apholate + TX, Molzide + TX, Penfluron + TX, Tepa + TX, Thiohempa + TX, Thiotepa + TX, Tretamine + TX, Uredepa + TX, (E)-Deca-5-en-1-yl acetate and (E)-Deca-5-en-1-ol + TX, (E)-Trideca-4-en-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E,Z)-Tetradeca-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)-icos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX,(9Z,11E)-tetradec-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradec-9,12-dien-1-yl acetate + TX, 14-methyloctadec-1-ene + TX, 4-methylnonan-5-ol and 4-methylnonan-5-one + TX, α-multistriatin + TX, Brevicomin + TX, Codrelure + TX, Codlemone + TX, Curure + TX, Disparlure + TX, Dodec-8-en-1-yl acetate + TX, Dodec-9-en-1-yl acetate + TX, Dodec-8,10-dien-1-yl acetate En-1-yl acetate + TX, Dominicalure + TX, Ethyl 4-methyloctanoate + TX, Eugenol + TX, Frontalin + TX, Grandolure + TX, Grandolure I + TX, Grandolure II + TX, Grandolure III + TX, Grandolure IV + TX, Hexalure + TX, Ipsdienol + TX, Ipsenol + TX, Japonilure + TX, Lineatin + TX, Littlea + TX, Louplure + TX, Medulure + TX, Megatomoic acid + TX, Methyleugenol + TX, Muscalure + TX, Octadeca-2,13-diene- 1-yl acetate + TX, Octadeca-3,13-dien-1-yl acetate + TX, Olfural + TX, Orictal + TX, Ostramon + TX, Siglua + TX, Soldigin + TX, Sulcatol + TX, Tetradec-11-en-1-yl acetate + TX, Trimedlure + TX, Trimedlure A + TX, Trimedlure B1 + TX, Trimedlure B2 + TX, Trimedlure C + TX, Trunkol + TX, 2-(octylthio)ethanol + TX, Butopyronoxyl + TX, Butoxy(polypropylene glycol) + TX, A Dibutyl dipicate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, diethyltoluamide + TX, dimethylcarbate + TX, dimethyl phthalate + TX, ethyl hexanediol + TX, hexamide + TX, methoquin-butyl + TX, methyl neodecanoamide + 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)acetic acid ethyl ester + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethyl carbamate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methyl carbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidone + TX, 2-isovalerylindan-1,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenyl methyl carbamate acetone + TX, 2-thiocyanatoethyl laurate + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-methyl-1-phenylpyrazol-5-yldimethylcarbamate + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate + TX, 5,5-dimethyl-3-oxocyclohex-1-enyldimethylcarbamate + TX, acetione + TX, acrylonitrile + TX, aldrin + TX, allosamidin + TX, alixycarb + TX, α-ecdysone + TX, aluminum phosphide + TX, aminocarb + TX, anabasine + TX, atidathion + TX, azamethiphos + TX, Bacillus thuringiensis (Bacillus thuringiensis) Delta Endotoxin +TX, Barium Hexafluorosilicate +TX, Barium Polysulfide +TX, Bartholin +TX, Bayer 22 / 190 +TX, Bayer 22408+TX, β-cyfluthrin+TX, β-cypermethrin+TX, bioethanomethrin+TX, biopermethrin+TX, bis(2-chloroethyl)ether+TX, borax+TX, bromfenvinphos+TX, bromo-DDT+TX, bufencarb+TX, butacarb+TX, butathiophos+TX, butonate+TX, calcium arsenate+TX, calcium cyanide+TX, carbon disulfide+TX, carbon tetrachloride+TX, cartap hydrochloride+TX, sevadin+TX, chlorbicyclen+TX, chlordane+TX, chlordecone+TX, chloroform+TX, chloropicrin+TX, chlorphoxim+TX, chlorprazophos+TX, cis-resmethrin+TX,Cismethrin + TX, Clocitrin + TX, Copper acetoarsenite + TX, Copper arsenate + TX, Copper oleate + TX, Cumitoate + TX, Cryolite + TX, CS 708+TX, cyanofenphos+TX, cyanophos+TX, cyclethrin+TX, cythioate+TX, d-tetramethrin+TX, DAEP+TX, dazomet+TX, decarbofuran+TX, diamidaphos+TX, dikapton+TX, diclofenthion+TX, dicresyl+TX, dicyclanil+TX, dieldrin+TX, diethyl 5-methylpyrazol-3-yl phosphate+TX, dilol+TX, dimefluthrin+TX, dimethane+TX, dimethryn+TX, dimethylvinphos+TX, dimethyllan+TX, dinoprop+TX, dinosam+TX, dinoseb+TX, diofenolan+TX, dioxabenzophos+TX, dicyclophos+TX, DSP+TX, ecdysterone+TX, EI 1642+TX, EMPC+TX, EPBP+TX, Ethiaphos+TX, Ethiofencarb+TX, Ethyl formate+TX, Ethylene dibromide+TX, Ethylene dichloride+TX, Ethylene oxide+TX, EXD+TX, Fenchlorphos+TX, Fenetacarb+TX, Fenitrothion+TX, Fenoxacrim+TX, Fenpyritrin+TX, Fensulfothion+TX, Fenthion-ethyl+TX, Flucofuron+TX, Fosmetilan+TX, Fospirate+TX, Fostietan+TX, Furathiocarb+TX, Frethrin+TX, Guazatine+TX, Guazatine acetate+TX, Sodium tetrathiocarbonate+TX, Halfenprox+TX, HCH+TX, HEOD+T X, heptachlor + TX, heterophos + TX, HHDN + TX, hydrogen cyanide + TX, hikincarb + TX, IPSP + TX, isazofos + TX, isobenzan + TX, isodrin + TX, isofenphos + TX, isolane + TX, isoprothiolane + TX, isoxathion + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, kerevan + TX, kinoprene + TX, lead arsenate + TX, leptophos + TX, lilimphos + TX, ritidathion + TX, m-cumenylmethylcarbamate + TX, magnesium phosphide + TX, magidox + TX, mecarfone + TX, menasone + TX, mercurous chloride + TX, mesulfenphos + TX, metam + TX,Metam-potassium +TX, Metam-sodium +TX, Methanesulfonyl fluoride +TX, Metocrotophos +TX, Methoprene +TX, Methotrin +TX, Methoxychlor +TX, Methyl isothiocyanate +TX, Methyl chloroform +TX, Methylene chloride +TX, Methoxadiazone +TX, Mirex +TX, Naphthalophos +TX, Naphthalene +TX, NC-170 +TX, Nicotine +TX, Nicotine sulfate +TX, Nithiazine +TX, Nornicotine +TX, O-5-Dichloro-4-iodofuran Phenyl O-ethyl ethyl phosphonothioate + 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 dithiopyrophosphate + TX, oleic acid + TX, para-dichlorobenzene + TX, parathion-methyl + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH 60-38+TX, Fenkapton+TX, Fosniclor+TX, Phosphine+TX, Phoxim-methyl+TX, Pyrimetaphos+TX, Polychlorodicyclopentadiene Isomers+TX, Potassium Arsenite+TX, Potassium Thiocyanate+TX, Precocene I+TX, Precocene II+TX, Precocene III+TX, Primidophos+TX, Profluthrin+TX, Promecarb+TX, Prothiofos+TX, Pyrazophos+TX, Pyresmethrin+TX, Quassia+TX, Quinalphos-methyl+TX, Quinothione+TX, Lafoxanide+TX, Resmethrin+TX, Rotenone+TX, Kadethrin+TX, Riania+TX, Ryanodine+TX, Sabadilla+TX Schradan +TX, Cebufos +TX, SI-0009 +TX, Tiapronil +TX, Sodium arsenite +TX, Sodium cyanide +TX, Sodium fluoride +TX, Sodium hexafluorosilicate +TX, Sodium pentachlorophenoxide +TX, Sodium selenate +TX, Sodium thiocyanate +TX, Sulcofuron +TX, Sulcofuron-sodium +TX, Sulfuryl fluoride +TX, Sulproos +TX, Tar oil +TX, Tadimcarb +TX, TDE +TX, Tebupi Limphos + TX, Temephos + TX, Teralethrin + TX, Tetrachloroethane + TX, Cyclophos + TX, Thiocyclam + TX, Thiocyclam Hydrogen Oxalate + TX, Thionazine + TX, Thiosultap + TX, Thiosultap-Sodium + TX, Tralomethrin + TX, Transpermethrin + TX, Triazamate + TX, Trichlormetaphos-3 + TX, Trichloronate + TX, Trimethacarb + TX, Tolprocarb + TX, Triclopyricarb + TX, Triplen + TX, Vera Tolidine + TX, veratrine + TX, XMC + TX, zetamethrin + TX, zinc phosphide + TX, zolaprofos + TX and meperfluthrin + TX, tetramethylfluthrin + TX, bis(tributyltin) oxide + TX, bromoacetamide + TX, ferric phosphate + TX, niclosamide-olamine + TX, tributyltin oxide + TX, pyrimorph + TX, triphenmorph + TX, 1,2-dibromo-3-chloropropane + TX, 1,3-dichloropropene + TX, 3,4-dichlorotetramethyl tetrahydrothiophene 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, benclothiaz + TX, cytokinin + TX, DCIP + TX, furfural + TX, isamidophos + TX, kinetin + TX, mulberry dark spot fungus (Myrothecium verrucaria) composition + TX, tetrachlorothiophene + TX, xylenol + TX, zeatin + TX, potassium ethylxanthate + TX, acibenzolar + TX, acibenzolar-S-methyl + TX,Japanese knotweed (Reynoutria sachalinensis) extract +TX, α-chlorohydrin +TX, Anz +TX, barium carbonate +TX, bisthiosemi +TX, brodifacoum +TX, bromadiolone +TX, bromethalin +TX, chlorophacinone +TX, cholecalciferol +TX, coumachlor +TX, coumafuryl +TX, coumatetralyl +TX, crimidine +TX, difenacoum +TX, difethialone +TX, diphacinone +TX, ergocalciferol +TX, flocoumafen +TX, fluoroa Cetoamide + TX, flupropazine + TX, flupropazine hydrochloride + TX, norbormide + TX, fosacetim + TX, phosphorus + TX, pindone + TX, pyrinuron + TX, sciliroside + TX, sodium fluoroacetate + TX, thallium sulfate + TX, warfarin + TX, 2-(2-butoxyethoxy)ethyl piperonylate + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, farnesol and nerolidol + TX, berubutin + TX, MGK 264+TX, piperonyl butoxide+TX, piprotal+TX, propyl isomers+TX, S421+TX, sesamex+TX, sesamolin+TX, sulfoxide+TX, anthraquinone+TX, copper naphthenate+TX, copper oxychloride+TX, dicyclopentadiene+TX, thiram+TX, zinc naphthenate+TX, ziram+TX, imanin+TX, ribavirin+TX, mercuric oxide+TX, thiophanate-methyl+TX, azaconazole+TX, bitertanol+TX, bromuconazole+TX, cyproconazole+TX, difenoconazole+TX, diniconazole+TX, epoxy Conazole + TX, fenbuconazole + TX, fluquinconazole + TX, flusilazole + TX, flutriafol + TX, furametpyr + TX, hexaconazole + TX, imazalil + TX, imibenconazole + TX, ipconazole + TX, metconazole + TX, myclobutanil + TX, paclobutrazol + TX, pefurazoate + TX, penconazole + TX, prothioconazole + TX, pyrifenox + TX, prochloraz + TX, propiconazole + TX, pyrisoxazole + TX, simeconazole + TX, tebuconazole + TX, tetraconazole + TX,Triadimefon +TX, Triadimenol +TX, Triflumizole +TX, Triticonazole +TX, Ancymidol +TX, Fenarimol +TX, Nuarimol +TX, Bupirimate +TX, Dimethirimol +TX, Ethirimol +TX, Dodemorph +TX, Fenpropidin +TX, Fenpropimorph +TX, Spiroxamine +TX, Tridemorph +TX, Cyprodinil +TX, Mepanipyrim +TX, Pyrimethanil +TX, Fenpiclonil +TX, Fludioxonil +TX, Benalaxyl +TX, Furalaxyl +TX, Metalaxyl +TX, R Metalaxyl + TX, Ofrace + TX, Oxadixyl + TX, Carbendazim + TX, Debacarb + TX, Fuberidazole + TX, Thiabendazole + TX, Chlozolinate + TX, Diclozolin + TX, Mycrozolin + TX, Procymidone + TX, Vinclozolin + TX, Boscalid + TX, Carboxin + TX, Fenfuram + TX, Flutolanil + TX, Mepronil + TX, Oxycarboxin + TX, Penthiopyrad + TX, Thifluzamide + TX, Dodine + TX, Iminoctadine + TX, Azoxystrobin + TX, Dimoxystrobin + TX X, Enesterobrine +TX, Phenaminestrobin +TX, Flufenoxystrobin +TX, Fluoxastrobin +TX, Kresoxim-methyl +TX, Metominostrobin +TX, Trifloxystrobin +TX, Oryzastrobin +TX, Picoxystrobin +TX, Pyraclostrobin +TX, Pyrametstrobin +TX, Pyraoxystrobin +TX, Ferbam +TX, Mancozeb +TX, Maneb +TX, Metiram +TX, Propineb +TX, Zineb +TX, Captafol +TX, Captan +TX, Fluorimide +TX, Folpet + TX, tolylfluanid + TX, Bordeaux mixture + TX, copper oxide + TX, mancopper + TX, oxine-copper + TX, nitrothar-isopropyl + TX, edifenphos + TX, iprobenfos + TX, phosdifen + TX, tolclofos-methyl + TX, anilazine + TX, benthiavalicarb + TX, blasticidin-S + TX, chloroneb + ​​TX, chlorothalonil + TX, cyflufenamid + TX, cymoxanil + TX, cyclobutrifluram + TX, diclocymet + TX, diclomedine + TX, dicloran + TX, diethofencarb + TX,Dimethomorph + TX, Flumorph + TX, Dithianon + TX, Ethaboxam + TX, Etridiazole + TX, Famoxadone + TX, Fenamidone + TX, Fenoxanil + TX, Ferimzone + TX, Fluazinam + TX, Fluopicolide + TX, Flusulfamide + TX, Fluxapyroxad + TX, Fenhexamid + TX, Fosetyl-aluminum + TX, Hymexazole + TX, Iprovalicarb + TX, Cyazofamid + TX X, methasulfocarb + TX, metrafenone + TX, pencycuron + TX, phthalide + TX, polyoxin + TX, propamocarb + TX, pyribencarb + TX, proquinazid + TX, pyroquilon + TX, pyriophenone + TX, quinoxyfen + TX, quintozene + TX, tiadinil + TX, triazoxide + TX, tricyclazole + TX, triforine + TX, validamycin + TX, valifenalate + TX, zoxamide + TX, Mandipropamide + TX, fluveneteram + TX, isopyrazam + TX, sedaxane + TX, benzovindiflupyr + TX, pydiflumetofen + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, isoflucipram + TX, isotianil + TX, dipimethitrone + TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile + TX, 2-(difluo (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine + TX, 4-(2-bromo-4-fluoro-phenyl)-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-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine + TX, (2-Bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine + TX, Fluindapyr + TX, Chmethoxystrobin (Jia Xiangchunzi) + TX, Rubenmixianan + TX, Diclobenthiazox + 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]propanol Indan-2-ol + TX, oxathiapiproline + TX, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, pyraziflumide + TX, inpirfluxam + TX, tolprocarb + TX, mefentrifluconazole + TX, ipfentrifluconazole + TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, N'-(2,5-Dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro- Phenyl]methanesulfonate + TX, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, pyridazine Dacromethyl + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazole Trazol-5-one + TX, aminopyrifen + TX, ametoctrazine + TX, amisulbrom + TX, penflufen + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX, flurylpicoxamide + TX, fenpicoxamide + TX, tebufloquine + TX, ipflufenoquine + TX, quinofumelin + TX, isofetamide + TX, N-[2-[2,4-Dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, benzothiostrobin + TX, fenamacryl + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, fluopyram + TX, flutianil + TX, fluopimomide + TX, pyrapropoin + TX, picarbutrazoc s + TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, Methyltetraprole + TX, α-(1,1-dimethylethyl)- α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidinemethanol + TX, fluoxapiprolin + TX, enoxastrobin + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, trinexapac + TX, cumoxystrobin + TX, chungchongmycin + TX, copper thiodiazole + TX, zinc thiazole + TX, amethotractin + TX, iprodione + TX, N-octyl-N'-[2-(octylamino)ethyl]ethane-1,2-Diamine + TX; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl- 6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropoxy N-isopropyl-N-methyl-formamidine + TX (these compounds can be prepared from the method described in WO 2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared from the method described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine + 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 from the method described in 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 from 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-[(1 S)-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 from the method 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)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-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 were prepared by the method described in WO 2017 / 025510). 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline + TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole + TX (these compounds can be prepared from 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]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 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 + TX (this compound can be prepared from 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 from the method described in WO 2017 / 029179); 3 -[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile + TX (this compound can be prepared from the method described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile + TX (this compound can be prepared from the method described in WO 2016 / 156290); (4-phenoxyphenyl) N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzene (N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzene)methyl 2-amino-6-methyl-pyridine-3-carboxylate + TX (this compound can be prepared from the method described in WO 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone + TX (this compound can be prepared from the method described in WO 2011 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzene 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-enamide + TX (this compound can be prepared from the method described in WO 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX;N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared from the method described in WO 2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX (this compound can be prepared from 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-(trifluoro 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX (these compounds can be prepared from the method described in WO 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX (this compound can be prepared from the method 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 from the method described in WO 2018 / 158365);2,2-Difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benz amide + TX, N-[N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX (these compounds can be prepared from the method described in WO 2018 / 202428), chlorinconazide + TX, flumethylsulfolim + TX, fluoxytioconazole + TX, flufenoxadiazam + TX, methallylpicoxamide + TX;

[0252] A reference in parentheses following an active ingredient, for example, [3878-19-1], refers to the Chemical Abstracts Registry Number. The aforementioned mixing partners are publicly known. When the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: CDS TomLin; The British Crop Protection Council], they are listed therein under the entry number shown in parentheses above for the particular compound; for example, the compound "abamectin" is listed under entry number (1). When a "CCN" is added to a particular compound above, the compound in question is included in the "Compendium of Pesticide Common Names," which is accessible via the Internet at [A. Wood; Compendium of Pesticide Common Names, Copyright 1995-2004]; for example, the compound "acetoprole" is listed at the Internet address http: / / www.alanwood.net / pesticides / acetoprole.html.

[0253] Most of the active ingredients mentioned above are referred to above by so-called "common names", where in each case the relevant "ISO common name" or another "common name" is used. If the name is not a "common name", the nature of the name used instead is given for the particular compound in parentheses. In that case, the IUPAC name, IUPAC / Chemical Abstracts name, "chemical name", "customary name", "compound name" or "development code" is used, or if none of these names and no "common name" is used, an "alternative name" is utilized. "CAS Registry Number" means the Chemical Abstracts Registry Number.

[0254] The active ingredient mixtures of compounds selected from the compounds of formula (I), (IA), (I-A1), (I-A2), (I-A3), (I-A4), (I-A5), (I-A6) or (I-A7) or the compounds listed in Tables C-1 to C-36 or the compounds listed in Table P (below) are preferably mixed in a ratio of 100:1 to 1:100, in particular 50:1 to 1:50, more in particular 20:1 to 1:20, even more in particular 10:1 to 1:10, and even more in particular 5:1 to 1:5, which are by weight.

[0255] The mixture may be used in a method for controlling pests, which method comprises applying a composition comprising the mixture to the pest or its environment, but excludes methods for surgical or therapeutic treatment of the human or animal body and diagnostic methods performed on the human or animal body.

[0256] Mixtures comprising a compound selected from the compounds of formula (I), formula (IA), (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 of the active ingredients above may be applied, for example, in a single "ready-mix" form, in combined spray mixtures made up of separate formulations of a single active ingredient such as a "tank mix", and in combined uses of the single active ingredients when applied sequentially, i.e., one after the other over a fairly short period of time such as a few hours or days. The order in which the compounds selected from the compounds of formula (I), formula (IA), (I-A1), (I-A2), (I-A3), (I-A4), (I-A5), (I-A6) or (I-A7) or the compounds listed in Tables C-1 to C-36 or the compounds listed in Table P (below) and the active ingredients are applied is not essential to practicing the present invention.

[0257] The compositions according to the invention may also comprise further solid or liquid adjuvants, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example epoxidized palm oil, rapeseed oil or soybean oil), antifoaming agents, for example silicone oils, preservatives, viscosity modifiers, binders and / or tackifiers, fertilizers or other active ingredients for achieving specific effects, such as bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0258] The compositions according to the invention can be prepared in a manner known per se in the absence of auxiliaries, for example by grinding, sieving and / or compressing the solid active ingredient, and in the presence of at least one auxiliaries, for example by intimately mixing and / or grinding the active ingredient together with the auxiliaries.These methods for preparing the compositions and the use of compound (I) for preparing these compositions are also the subject of the present invention.

[0259] Another aspect of the present invention relates to the use of a compound of formula (I) according to the present invention or a preferred individual compound as defined herein, a composition comprising at least one compound of formula (I) or at least one preferred individual compound as defined herein or a fungicidal or insecticidal mixture comprising at least one compound of formula (I) or at least one preferred individual compound as defined herein in admixture with other fungicides or insecticides as defined above, for controlling or preventing infestation on plants, e.g. useful plants such as crop plants, their propagation material, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living material by phytopathogenic microorganisms, e.g. insects or preferably fungal organisms.

[0260] A further aspect of the present invention relates to a method for controlling or preventing infestation of plants, for example useful plants such as crop plants, their propagation material, for example seeds, harvested crops, for example harvested food crops or non-living material, by phytopathogenic or spoilage microorganisms or organisms potentially harmful to humans, in particular fungal organisms, which method comprises applying as active ingredient a compound of formula (I) according to the invention or a preferred individual compound as defined herein to the plant, to parts of the plant or its habitat, its propagation material or any part of the non-living material.

[0261] Control or prevention means reducing infestation by insects or plant pathogenic or spoilage microorganisms or organisms potentially harmful to humans, especially fungal organisms, to a level that demonstrates improvement.

[0262] A preferred method for controlling or preventing infestation of crop plants by phytopathogenic microorganisms, particularly fungal organisms or insects, involves the application of a compound of formula (I) according to the present invention or an agrochemical composition containing at least one compound of formula (I), by foliar application. The frequency and rate of application will vary depending on the risk of infestation by the corresponding pathogen or insect. However, the compound of formula (I) according to the present invention can also be introduced into the plant through the roots via the soil (systemic action) by drenching the plant with a liquid formulation or by applying the compound to the soil in solid form, for example, in granular form (soil application). In rice cultivation, such granules can be applied to flooded rice 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.

[0263] Formulations, e.g. compositions, containing a compound of formula (I) according to the present invention and optionally a solid or liquid auxiliary or a monomer encapsulating the compound of formula (I), can typically be prepared in known manner by intimately mixing and / or grinding the compounds together with extenders, e.g. solvents, solid carriers and optionally surface-active compounds (surfactants).

[0264] Advantageous application rates are usually 5g to 2kg of active ingredient (ai) per hectare (ha), preferably 10g to 1kg ai / ha, most preferably 20g to 600g ai / ha. When used as a seed drench, a convenient dosage is 10mg to 1g of active substance per kg of seed.

[0265] As used herein, the term "g ai / ha" refers to the application rate expressed in grams [g] of active ingredient [ai] per unit surface [ha]. The unit hectare (symbol ha) is the area of ​​100m square meters (1hm 2 ) square or 10,000 square meters. The hectare is a commonly used unit of area in the metric system.

[0266] When the combinations of the invention are used for seed treatment, an amount of 0.001 to 50 g of compound of formula (I) per kg of seed, preferably 0.01 to 10 g per kg of seed, will generally be sufficient.

[0267] Preferably, the compositions containing the compounds of formula (I) according to the invention are applied either preventively, ie before the onset of disease, or curatively, ie after the onset of disease.

[0268] The compositions of the present invention may be in any conventional form, such as a two-part system, dry seed treatment powder (DS), seed treatment emulsion (ES), seed treatment flowable concentrate (FS), seed treatment solution (LS), seed treatment water dispersible powder (WS), seed treatment capsule suspension (CF), seed treatment gel (GF), emulsion concentrate (EC), suspension concentrate (SC), suspoemulsion (SE), capsule suspension (CS), water dispersible granules (WG), emulsifiable granules, etc. It may be employed in the form of granules (EG), emulsions, water-in-oil (EO), emulsions, oil-in-water (EW), microemulsions (ME), oil dispersions (OD), oil-miscible flowables (OF), oil-miscible liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), technical concentrates (TK), dispersible concentrates (DC), wettable powders (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0269] Such compositions can be prepared in a conventional manner, for example, by mixing the active ingredient with suitable inert ingredients (diluents, solvents, fillers, and optionally other ingredients, such as surfactants, biocides, antifreeze agents, spreading agents, thickeners, and compounds providing auxiliary effects). Conventional sustained-release formulations can also be employed when long-lasting effectiveness is intended. In particular, formulations 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, as well as other compounds providing auxiliary effects, such as the condensation products of formaldehyde with naphthalenesulfonates, alkylarylsulfonates, ligninsulfonates, fatty alkyl sulfates, and ethoxylated alkylphenols and ethoxylated fatty alcohols.

[0270] The seed dressing formulation is applied to seeds in a manner known per se, using the combination of the present invention and a diluent in a suitable seed dressing formulation form, such as an aqueous suspension or a dry powder form with good adhesion to the seeds. Such seed dressing formulations are known in the art. The seed dressing formulation may contain a single active ingredient or a combination of active ingredients in encapsulated form, for example, as slow-release capsules or microcapsules.

[0271] Generally, the formulations contain 0.01 to 90% by weight of active agent, 0 to 20% by weight of agriculturally acceptable surfactant, and 10 to 99.99% by weight of solid or liquid inert compounding agents and adjuvants, where the active agent is composed of at least a compound of formula (I) according to the present invention, optionally together with other active agents, more particularly microbicides, preservatives, etc. Concentrate forms of the compositions generally contain about 2 to 80% by weight, preferably about 5 to 70% by weight, of the active agent. The application form of the formulation may contain, for example, 0.01 to 20% by weight, preferably 0.01 to 5% by weight, of the active agent. Commercially available products are preferably formulated as concentrates, but end users will usually use diluted formulations.

[0272] Commercially available products are preferably formulated as concentrates, but end users will typically use diluted formulations.

[0273] The application rates vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pests to be controlled, the prevailing weather conditions and other factors which depend on the method, time of application and target crop. As a general guideline, the compounds may be applied at rates of 1 to 2000 l / ha, in particular 10 to 1000 l / ha.

[0274] A preferred formulation may have the following composition (by weight):

[0275] Emulsifiable concentrate: Active ingredient: 1-95%, preferably 60-90% Surfactant: 1 to 30%, preferably 5 to 20% Liquid carrier: 1 to 80%, preferably 1 to 35%

[0276] Powder: Active ingredient: 0.1 to 10%, preferably 0.1 to 5% Solid carrier: 99.9 to 90%, preferably 99.9 to 99%

[0277] Suspension concentrate: Active ingredient: 5-75%, preferably 10-50% Water: 94-24%, preferably 88-30% Surfactant: 1 to 40%, preferably 2 to 30%

[0278] Wettable powder: Active ingredient: 0.5 to 90%, preferably 1 to 80% Surfactant: 0.5 to 20%, preferably 1 to 15% Solid carrier: 5 to 95%, preferably 15 to 90%

[0279] Granules: Active ingredient: 0.1 to 30%, preferably 0.1 to 15% Solid carrier: 99.5 to 70%, preferably 97 to 85%

[0280] The disclosure in this application provides for any and all combinations of the embodiments disclosed herein.

[0281] The compounds according to the following Tables C-1 to C-36 can be prepared according to the above method. The following examples are intended to illustrate the present invention and show preferred compounds of formula (I). In any of the following Tables C-1 to C-36, the possible presence of one or more asymmetric carbon atoms in the compound of formula (I) according to the present invention means that the compound can occur in chiral isomeric form, i.e., in the form of enantiomers or diastereomers.

[0282] [Table 2]

[0283] [Table 3]

[0284] Tables C-1 to C-36 show the formula (A): [ka] Specific compounds of the formula: 2 , R 4 , R 5 and R 6 is as defined in any of Tables C-1 to C-36, and the G and Q substituents are as defined in Tables A and B, respectively.

[0285] Table C-1: This table lists 22 compounds of formula (A) C-1.01 to C-1.22 (wherein R 1 , R 2 , R 3 , R 4 and R 6 is H and B 1 and B 2 is CH and Q is Q 1 and G is as defined in Table A).

[0286] For example, compound C-1.01 has the following structure: [ka]

[0287] Table C-2: This table lists 22 compounds of formula (A) C-2.01 to C-2.22 (wherein R 1 , R 2 , R 3 , R 4 and R 6 is H and B 1 and B 2 is CH and Q is Q 2 and G is as defined in Table A).

[0288] Table C-3: This table lists 22 compounds of formula (A) C-3.01 to C-3.22 (wherein R 1 , R 2 , R 3 , R 4 and R 6 is H and B 1 and B 2 is CH and Q is Q 3 and G is as defined in Table A).

[0289] Table C-4: This table lists 22 compounds of formula (A) C-4.01 to C-4.22 (wherein R 1 , R 2 , R 3 , R 4 and R 6 is H and B 1 and B 2 is CH and Q is Q 4 and G is as defined in Table A).

[0290] Table C-5: This table lists 22 compounds of formula (A) C-5.01 to C-5.22 (wherein R 1 , R 2 , R 3 , R 4 and R6 is H and B 1 and B 2 is CH and Q is Q 5 and G is as defined in Table A).

[0291] Table C-6: This table lists 22 compounds of formula (A) C-6.01 to C-6.22 (wherein R 1 , R 2 , R 3 , R 4 and R 6 is H and B 1 and B 2 is CH and Q is Q 6 and G is as defined in Table A).

[0292] Table C-7: This table lists 22 compounds of formula (A) C-7.01 to C-7.22 (wherein R 1 , R 2 , R 3 , R 4 and R 6 is H and B 1 and B 2 is CH and Q is Q 7 and G is as defined in Table A).

[0293] For example, compound C-7.22 has the following structure: [ka]

[0294] Table C-8: This table lists 22 compounds of formula (A) C-8.01 to C-8.22 (wherein R 1 , R 2 , R 3 , R 4 and R 6 is H and B 1 and B 2 is CH and Q is Q 8 and G is as defined in Table A).

[0295] Table C-9: This table lists 22 compounds of formula (A) rac-syn-C-9.01 to racemic-syn-C-9.22 (wherein R 1 , R 2 , R 3 and R 6 is H and R 4 is CH3 and B 1 and B 2 is CH and Q is Q 1 and G is as defined in Table A. In these compounds, the Q substituent and R 4 The substituents have a syn-relationship to each other.

[0296] Table C-10: This table lists 22 compounds of formula (A) racemic-syn-C-10.01 to racemic-syn-C-10.22 (wherein R 1 , R 2 , R 3 and R 6 is H and R 4 is CH3 and B 1 and B 2 is CH and Q is Q 2 and G is as defined in Table A. In these compounds, the Q substituent and R 4 The substituents have a syn-relationship to each other.

[0297] For example, the compound racemic-syn.C-10.05 has the following structure: [ka]

[0298] Table C-11: This table lists 22 compounds of formula (A) racemic-syn-C-11.01 to racemic-syn-C-11.22 (wherein R 1 , R 2 , R 3 and R 6 is H and R 4 is CH3 and B 1 and B 2 is CH and Q is Q 3and G is as defined in Table A).

[0299] Table C-12: This table lists 22 compounds of formula (A) racemic-syn-C-12.01 to racemic-syn-C-12.22 (wherein R 1 , R 2 , R 3 and R 6 is H and R 4 is CH3 and B 1 and B 2 is CH and Q is Q 4 and G is as defined in Table A).

[0300] Table C-13: This table lists 22 compounds of formula (A) racemic-syn-C-13.01 to racemic-syn-C-13.22 (wherein R 1 , R 2 , R 3 and R 6 is H and R 4 is CH3 and B 1 and B 2 is CH and Q is Q 5 and G is as defined in Table A).

[0301] Table C-14: This table lists 22 compounds of formula (A) racemic-syn-C-14.01 to racemic-syn-C-14.22 (wherein R 1 , R 2 , R 3 and R 6 is H and R 4 is CH3 and B 1 and B 2 is CH and Q is Q 6 and G is as defined in Table A).

[0302] Table C-15: This table lists 22 compounds of formula (A) racemic-syn-C-15.01 to racemic-syn-C-15.22 (wherein R 1 , R 2 , R 3 and R6 is H and R 4 is CH3 and B 1 and B 2 is CH and Q is Q 7 and G is as defined in Table A).

[0303] Table C-16: This table lists 22 compounds of formula (A) racemic-syn-C-16.01 to racemic-syn-C-16.22 (wherein R 1 , R 2 , R 3 and R 6 is H and R 4 is CH3 and B 1 and B 2 is CH and Q is Q 8 and G is as defined in Table A).

[0304] Table C-17: This table lists 22 compounds of formula (A) C-17.01 to C-17.22 (wherein R 1 is CH3 and R 2 , R 3 , R 4 and R 6 is H and B 1 and B 2 is CH and Q is Q 1 and G is as defined in Table A).

[0305] Table C-18: This table lists 22 compounds of formula (A) C-18.01 to C-18.22 (wherein R 1 is CH3 and R 2 , R 3 , R 4 and R 6 is H and B 1 and B 2 is CH and Q is Q 2 and G is as defined in Table A).

[0306] Table C-19: This table lists 22 compounds of formula (A) C-19.01 to C-19.22 (wherein R1 is CH3 and R 2 , R 3 , R 4 and R 6 is H and B 1 and B 2 is CH and Q is Q 3 and G is as defined in Table A).

[0307] Table C-20: This table lists 22 compounds of formula (A) C-20.01 to C-20.22 (wherein R 1 is CH3 and R 2 , R 3 , R 4 and R 6 is H and B 1 and B 2 is CH and Q is Q 4 and G is as defined in Table A).

[0308] Table C-21: This table lists 22 compounds of formula (A) C-21.01 to C-21.22 (wherein R 1 is CH3 and R 2 , R 3 , R 4 and R 6 is H and B 1 and B 2 is CH and Q is Q 5 and G is as defined in Table A).

[0309] Table C-22: This table lists 22 compounds of formula (A) C-22.01 to C-22.22 (wherein R 1 is CH3 and R 2 , R 3 , R 4 and R 6 is H and B 1 and B 2 is CH and Q is Q 6 and G is as defined in Table A).

[0310] For example, compound C-22.03 has the following structure: [ka]

[0311] Table C-23: This table lists 22 compounds of formula (A) C-23.01 to C-23.22 (wherein R 1 is CH3 and R 2 , R 3 , R 4 and R 6 is H and B 1 and B 2 is CH and Q is Q 7 and G is as defined in Table A).

[0312] Table C-24: This table lists 22 compounds of formula (A) C-24.01 to C-24.22 (wherein R 1 is CH3 and R 2 , R 3 , R 4 and R 6 is H and B 1 and B 2 is CH and Q is Q 8 and G is as defined in Table A).

[0313] Table C-25: This table lists 22 compounds of formula (A) C-25.01 to C-25.22 (wherein R 1 , R 2 , R 3 , R 4 and R 6 is H and B 1 is CH and B 2 is C-Cl and Q is Q 3 and G is as defined in Table A).

[0314] Table C-26: This table lists 22 compounds of formula (A) C-26.01 to C-26.22 (wherein R 1 , R 2 , R 3 , R4 and R 6 is H and B 1 is CH and B 2 is C-Cl and Q is Q 4 and G is as defined in Table A).

[0315] Table C-27: This table lists 22 compounds of formula (A) C-27.01 to C-27.22 (wherein R 1 , R 2 , R 3 , R 4 and R 6 is H and B 1 is CH and B 2 is C-Cl and Q is Q 5 and G is as defined in Table A).

[0316] Table C-28: This table lists 22 compounds of formula (A) C-28.01 to C-28.22 (wherein R 1 , R 2 , R 3 , R 4 and R 6 is H and B 1 is CH and B 2 is C-Cl and Q is Q 6 and G is as defined in Table A).

[0317] Table C-29: This table lists 22 compounds of formula (A) C-29.01 to C-29.22 (wherein R 1 , R 2 , R 3 , R 4 and R 6 is H and B 1 is CH and B 2 is C-CN and Q is Q 3 and G is as defined in Table A).

[0318] Table C-30: This table lists 22 compounds of formula (A) C-30.01 to C-30.22 (wherein R 1 , R2 , R 3 , R 4 and R 6 is H and B 1 is CH and B 2 is C-CN and Q is Q 4 and G is as defined in Table A).

[0319] For example, compound 30.14 has the following structure: [ka]

[0320] Table C-31: This table lists 22 compounds of formula (A) C-31.01 to C-31.22 (wherein R 1 , R 2 , R 3 , R 4 and R 6 is H and B 1 is CH and B 2 is C-CN and Q is Q 5 and G is as defined in Table A).

[0321] Table C-32: This table lists 22 compounds of formula (A), C-32.01 to C-32.22, where R 1 , R 2 , R 3 , R 4 and R 6 is H and B 1 is CH and B 2 is C-CN and Q is Q 6 and G is as defined in Table A).

[0322] Table C-33: This table lists 22 compounds of formula (A), rac-syn-C-33.01 to rac-syn-C-33.22, where R 1 , R 2 , R 3 and R 6 is H and R 4 is CH3 and B 1is CH and B 2 is C-Cl and Q is Q 4 and G is as defined in Table A. In these compounds, the Q substituent and R 4 The substituents have a syn-relationship to each other.

[0323] Table C-34: This table lists 22 compounds of formula (A), rac-syn-C-34.01 to rac-syn-C-34.22, where R 1 , R 2 , R 3 and R 6 is H and R 4 is CH3 and B 1 is CH and 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 R 4 The substituents have a syn-relationship to each other.

[0324] Table C-35: This table lists 22 compounds of formula (A) rac-syn-C-35.01 to rac-syn-C-35.22 (wherein R 1 , R 2 , R 3 and R 6 is H and R 4 is CH3 and B 1 is CH and 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 R 4 The substituents have a syn-relationship to each other.

[0325] For example, rac-syn-C-35.11 has the following structure: [ka]

[0326] Table C-36: This table lists 22 compounds of formula (A), rac-syn-C-36.01 to rac-syn-C-36.22, where R 1 , R 2 , R 3 and R 6 is H and R 4 is CH3 and B 1 is CH and 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 R 4 The substituents have a syn-relationship to each other. [Example]

[0327] The examples presented below serve to illustrate the invention and are not intended to limit it in any way.

[0328] The compounds of the present invention can be distinguished from known compounds by exhibiting higher efficacy at lower application rates, which can be confirmed by one skilled in the art using the experimental procedures outlined in the Examples, using lower application rates, for example 60 ppm, 20 ppm or 2 ppm, as needed.

[0329] Compounds of formula (I) may have many benefits including, inter alia, advantageous levels of biological activity or excellent properties for use as agrochemical active ingredients (e.g., high biological activity, advantageous spectrum of activity, high safety profile (including improved crop tolerance), improved physicochemical properties or high biodegradability) for protecting plants against diseases caused by fungi.

[0330] Throughout this specification, temperatures are given in degrees Celsius and "mp" means melting point. LC / MS means liquid chromatography mass spectrometry, and a description of the equipment and methods follows.

[0331] 1 H NMR and 19F NMR measurements were recorded on a Bruker 400 MHz spectrometer and chemical shifts were expressed in terms of TMS ( 1 H) and CFCl3 ( 19 F) are given in ppm relative to standard. Spectra were taken in deuterated solvents as indicated. Compounds were characterized using one of the following LCMS methods. The characteristic LCMS values ​​obtained for each compound are the retention time ("Rt", recorded in minutes) and the observed molecular ion (M+H). + or (MH) - It was.

[0332] The following HPLC-MS method was used for the analysis of the compounds.

[0333] Method A (LCMS): Spectra were recorded on a Waters mass spectrometer (SQD, SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ions, capillary: 3.00 kV, cone range: 30 V, extractor: 2.00 V, source temperature: 150 °C, desolvation temperature: 350 °C, cone gas flow: 50 l / h, desolvation gas flow: 650 l / h, mass range: 100-900 Da) and a Waters Acquity UPLC: binary pump, heated column compartment, diode array detector, ELSD detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm; Temperature: 60 °C; DAD wavelength range (nm): 210–500; 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.

[0334] Method B: Spectra were recorded on a Waters mass spectrometer (Acquity QDa mass spectrometer) equipped with an electrospray source (polarity: positive and negative polarity switch), capillary voltage: 0.8 kV, cone range: 25 V, extractor voltage: V (no extraction voltage on the QDa detector), source temperature: 120 °C, desolvation temperature: 600 °C, cone gas flow: 50 L / h, desolvation gas flow: 1000 L / h, mass range: 110–850 Da) and a Waters Acquity UPLC with a quaternary solvent manager, heated column compartment, and diode array detector. Column: Acquity UPLC HSS T3 C18, 1.8 μm, 30 × 2.1 mm, temperature: 40 °C, DAD wavelength range (nm): 200–400, solvent gradient: A = water + 5% acetonitrile + 0.05% HCOOH, B = acetonitrile + 0.1% HCOOH. Gradient: 10% B for 0 min; 10–50% B for 0.–0.2 min; 50–100% B for 0.2–0.6 min; 100% B for 0.6–1.3 min; 100–10% B for 1.3–1.4 min; 10% B for 1.4–1.6 min; flow rate (mL / min) 0.6.

[0335] Method C: Instrumentation: Mass spectrometer: Agilent Technologies 6410 triple quadrupole mass spectrometer; HPLC: Agilent 1200 Series HPLC Optimal mass parameters: Ionization method: electrospray (ESI); Polarity: positive and negative polarity switch; Scan type: MS2 scan; Capillary (kV): 4.00; Fragmenter (V): 100.00; Gas temperature (°C): 350; Gas flow rate (L / min): 11; Nebulizer gas (psi): 40; Mass range: 110-1000 Da; Detection (VWD): 254 nm. Optimal chromatographic parameters: Gradient conditions: Solvent A: water with 0.1% formic acid:acetonitrile::95:5 vol / vol; Solvent B: acetonitrile with 0.1% formic acid.

[0336] [Table 4]

[0337] Column: KINETEX EVO C18, column length: 50 mm, column inner diameter: 4.6 mm, particle size: 2.6 μ, column oven temperature: 40°C.

[0338] Example formulation

[0339] [Table 5]

[0340] This combination is thoroughly mixed with adjuvants and the mixture is thoroughly ground in a suitable mill to give a wettable powder which is diluted with water to give a suspension of the desired concentration.

[0341] [Table 6]

[0342] This combination is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to obtain a powder that can be used directly as a seed treatment.

[0343] emulsifiable concentrate Active ingredient 10% Octylphenol polyethylene glycol ether (ethylene oxide 4-5 moles) 3% Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (ethylene oxide 35 moles) 4% Cyclohexanone 30% Xylene mixture 50%

[0344] Emulsions of any desired dilution that can be used for plant protection are obtained from this concentrate by dilution with water.

[0345] [Table 7]

[0346] Ready-to-use dusts are obtained by combining and mixing with a carrier and grinding the mixture in a suitable mill. Such dusts can also be used for dry seed dressing.

[0347] Extruder Granules Active ingredient 15% Sodium lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 82%

[0348] This combination is mixed with an adjuvant, ground, and the mixture is wetted with water. The mixture is extruded and then dried in a stream of air.

[0349] Coated granules Active ingredient 8% Polyethylene glycol (molecular weight 200) 3% Kaolin 89%

[0350] The finely ground combination is applied uniformly in a mixer to kaolin wetted with polyethylene glycol, thus obtaining dust-free coated granules.

[0351] Suspension concentrate Active ingredient 40% Propylene glycol 10% Nonylphenol polyethylene glycol ether (ethylene oxide 15 moles) 6% Sodium lignosulfonate 10% Carboxymethylcellulose 1% Silicone oil (75% emulsion in water) 1% water 32%

[0352] The finely ground combination is thoroughly mixed with adjuvants to obtain a suspension concentrate, which can then be diluted with water to obtain a suspension of any desired dilution, and such dilutions can be used to treat and protect living plants and plant propagation material against microbial infestation by spraying, pouring, or dipping.

[0353] Flowable seed treatment Active ingredient 40% Propylene glycol 5% Butanol PO / EO copolymer 2% Tristyrenephenol with 10-20 moles of EO 2% 1,2-Benzisothiazolin-3-one (20% aqueous solution) 0.5% Monoazo pigment calcium salt 5% Silicone oil (75% emulsion in water) 0.2% Water 45.3%

[0354] The finely ground composite is thoroughly mixed with adjuvants to obtain a flowable concentrate, from which suspensions of any desired dilution can be obtained by dilution with water and used directly for seed treatment. Such dilutions can be used to treat and protect living plants and plant propagation material against microbial infestation by spraying, pouring or dipping.

[0355] extended-release capsule suspension 28 parts of the combination are mixed with 2 parts aromatic solvent and 7 parts toluene diisocyanate / polymethylene-polyphenylisocyanate (8:1) mixture. This mixture is emulsified in a mixture of 1.2 parts polyvinyl alcohol, 0.05 parts antifoaming agent, and 51.6 parts water until the desired particle size is achieved. A mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts water is added to this emulsion. The mixture is stirred until the polymerization reaction is complete. The resulting capsule suspension is stabilized by adding 0.25 parts thickener and 3 parts dispersant. This capsule suspension formulation contains 28% active ingredient. The median capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in equipment suitable for this purpose.

[0356] Formulation types include emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water dispersible granules (WG), emulsifiable granules (EG), emulsions, water-in-oil (EO), emulsions, oil-in-water (EW), microemulsions (ME), oil dispersions (OD), oil-miscible flowables (OF), oil-miscible liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), technical concentrates (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG) or any technically preferred formulation in combination with an agriculturally acceptable adjuvant.

[0357] Abbreviation CDCl3 deuterated chloroform DABCO 1,4-diazabicyclo[2.2.2]octane, also known as triethylenediamine or TEDA DCC dicyclohexylcarbodiimide DCM dichloromethane DMF Dimethylformamide DMSO dimethyl sulfoxide DMSO-d6 Deuterated dimethyl sulfoxide EDC 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Et3N Triethylamine EtOAc ethyl acetate HATU 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium-3-oxide-hexafluorophosphate HCl Hydrochloric acid h / hrs time LC-MS Liquid Chromatography Mass Spectrometry (LC-MS or LCMS) rh relative humidity rt room temperature Rt retention time ssp. subspecies T3P Propanephosphonic Anhydride, also known as 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphorinane-2,4,6-trioxide THF tetrahydrofuran

[0358] Preparation example Compounds of formula (I) according to the invention may be prepared using the synthetic techniques described both above and below.

[0359] "Mp" means melting point (°C). The free radical represents a methyl group. 1 H NMR and 19 F NMR measurements were recorded on a Bruker 400 MHz spectrometer (or 600 MHz spectrometer as indicated) and chemical shifts were expressed in terms of TMS ( 1 H) standard and CFCl3( 19 F) are given in ppm relative to a standard. Spectra were measured in deuterated solvents as indicated. For compound characterization, one of the following LC-MS methods was used: Characteristic LCMS values ​​obtained for each compound were the retention time ("Rt", recorded in minutes) and the observed molecular ion (M+H). + or (MH) - It was.

[0360] Example P1: Synthesis of [4-(5-chloro-1,2-dimethyl-imidazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(5-phenylisoxazol-3-yl)methanone (compound P-31, Table P) [ka] Step A: Preparation of 4-(5-chloro-1,2-dimethyl-imidazol-4-yl)isoquinoline [ka] A solution of 5-chloro-1,2-dimethylimidazole (CAS: 937818-18-3, 2.000 g, 14.55 mmol) and 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) followed by 1,10-phenanthroline (0.2649 g, 1.455 mmol), and the mixture was degassed with argon for 5 minutes. Palladium(II) acetate (0.3333 g, 1.455 mmol) was then added, and the mixture was stirred at 160 °C for 11 days. The reaction mixture was filtered over Celite, and the cake was washed with some EtOAc. The filtrate was concentrated under reduced pressure and the crude product was purified by flash chromatography with EtOAc / cyclohexane to give 4-(5-chloro-1,2-dimethyl-imidazol-4-yl)isoquinoline. LC-MS: 258[M+H], Rt: 0.57 min (Method A) 1 H NMR(400MHz,CDCl3)δ ppm 2.57(s,3H)3.68(s,3H)7.78(td,J=7.63,1.09Hz,1H)7.90(ddd,J=8.54,7.08,1 .45Hz,1H)8.15(d,J=7.99Hz,1H)8.54(d,J=8.72Hz,1H)8.66(s,1H)9.32(s,1H)

[0361] Step B: Preparation of 4-(5-chloro-1,2-dimethyl-imidazol-4-yl)-1,2,3,4-tetrahydroisoquinoline [ka] 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 at room temperature under argon for 15 minutes. 4N hydrogen chloride in dioxane (1.65 mL, 6.60 mmol) was then added dropwise. The resulting brown solution was stirred at room temperature under argon for 1 hour, 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 Na.sub.2SO.sub.4, filtered and concentrated under reduced pressure to give 4-(5-chloro-1,2-dimethyl-imidazol-4-yl)-1,2,3,4-tetrahydroisoquinoline. LC-MS: 262[M+H], Rt: 0.26 min (Method A) 1 H NMR(400MHz,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).

[0362] Step C: Preparation of [4-(5-chloro-1,2-dimethyl-imidazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(5-phenylisoxazol-3-yl)methanone (Compound P-31, Table P) 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 treated with 1-propanephosphonic anhydride (0.25 mL, 0.41 mmol) followed by N,N-diisopropylethylamine (0.12 mL, 0.69 mmol). 5-Phenylisoxazole-3-carboxylic acid (0.050 g, 0.25 mmol) was then added, and the resulting mixture was stirred at room temperature under an argon atmosphere for 1 hour. 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 phase was washed once with brine, dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure. The crude product was purified by flash chromatography on silica gel eluting with EtOAc to give [4-(5-chloro-1,2-dimethyl-imidazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-(5-phenylisoxazol-3-yl)methanone. LC-MS:433[M+H], Rt:0.85min (Method A)

[0363] Example P2: Preparation of (5-phenylisoxazol-3-yl)-[4-(3-pyridyl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (compound P-6, Table P) [ka] Step A: Preparation of 4-(3-pyridyl)isoquinoline [ka] 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-palladium(II) dichloride dichloromethane complex (0.110 g, 0.132 mmol). The resulting suspension was stirred at 100 °C overnight. The reaction was then quenched with water, EtOAc was added, and the aqueous layer was extracted with CHROMABOND® PTL. Isolute® was added to the organic layer, and the solvent was removed under reduced pressure. The crude product was purified by chromatography on silica gel to give 4-(3-pyridyl)isoquinoline. LC-MS: 207[M+H], Rt: 0.48 min (Method A) 1 H NMR(400MHz,CDCl3)δ ppm 9.33(s,1H)8.81(dd,J=2.4,0.9Hz,1H)8.76(dd,J=4.8,1.8Hz,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)

[0364] Step B: Preparation of 4-(3-pyridyl)-1,2,3,4-tetrahydroisoquinoline [ka] 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) at room temperature. To this mixture was slowly added 4 M hydrochloric acid in dioxane (0.5 mL, 2 mmol). The resulting solution was stirred at room temperature for 1 hour, then diluted with water and basified with 2 N NaOH. The MeOH was removed by concentration under reduced pressure, and the remaining aqueous layer was extracted with DCM (three times). The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure to give 4-(3-pyridyl)-1,2,3,4-tetrahydroisoquinoline. LC-MS: 211[M+H], Rt: 0.22 min (Method A) 1 H NMR(400MHz,CDCl3)δ ppm 8.45-8.53(m,2H)7.41(dt,J=7.8,2.0Hz,1H)7.19-7.26(m,2H)7.07-7.17(m,2H)6.88(d ,J=7.3Hz,1H)4.08-4.25(m,3H)3.46(dd,J=13.2,5.5Hz,1H)3.11(dd,J=12.8,6.6Hz,1H)

[0365] Step C: Synthesis of (5-phenylisoxazol-3-yl)-[4-(3-pyridyl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (Compound P-6) 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 under reduced pressure. The crude product was purified by combiflash chromatography on silica gel to give (5-phenylisoxazol-3-yl)-[4-(3-pyridyl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone. LC-MS: 382[M+H], Rt: 0.91 min (Method A) 1 H NMR(400MHz,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)

[0366] 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) [ka] Step A: Preparation of 4-(1-methyl-1,2,4-triazol-3-yl)isoquinoline [ka] A microwave vial was charged with 3-bromo-1-methyl-1,2,4-triazole (0.12 g, 0.74 mmol), 4-isoquinolylboronic 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). The reaction mixture was degassed with nitrogen for 5 minutes and then treated 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). The resulting reaction mixture was stirred under microwave irradiation at 120 °C for 2 hours (it turned dark brown). The reaction progress was monitored by LCMS and TLC. After completion, the reaction mixture was cooled to room temperature and diluted with saturated aqueous NH4Cl (50 mL). The mixture was extracted with EtOAc (2 x 50 mL), and the combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The crude product was purified by combi flash chromatography to give 4-(1-methyl-1,2,4-triazol-3-yl)isoquinoline. LC-MS (Method B) retention time 0.46 min, m / z211(M+H) 1H NMR(400MHz, CDCl3d)δ ppm 9.29(s,1H),9.20(s,1H),9.04(d,J=8.56Hz,1H),8.22(s,1H),8.03(d,J=8.19 Hz,1H),7.80(ddd,J=8.47,7.00,1.28Hz,1H),7.64-7.67(m,1H),4.07(s,3H).

[0367] Step B: Preparation of 4-(1-methyl-1,2,4-triazol-3-yl)-1,2,3,4-tetrahydroisoquinoline [ka] A round-bottom flask equipped with a magnetic stir bar was charged 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, 1.25 M hydrochloric acid in methanol (0.9 mL, 1 mmol) was added dropwise at room temperature (gas evolution), and the mixture was stirred at room temperature for 12 hours. The reaction mixture was poured into water (50 mL) and basified with 2 M NaOH (pH 12). The mixture was extracted with EtOAc (3 × 30 mL), and the combined organic layers were washed with brine, dried over NaSO, and concentrated under reduced pressure. The crude compound 4-(1-methyl-1,2,4-triazol-3-yl)-1,2,3,4-tetrahydroisoquinoline (0.08 g) was used directly in the next step. LC-MS (Method C) retention time 0.16 min, m / z215(M+H)

[0368] Step C: 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) [5-(2,4-Difluorophenyl)isoxazol-3-yl]-[4-(1-methyl-1,2,4-triazol-3-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone was prepared similarly to Example 1, Step C. LC-MS:422[M+H], Rt:1.07min (Method B) 1 H NMR(400MHz,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=17.48Hz,1H)5.12(d,J= 17.36Hz,1H)5.20(d,J=7.82Hz,1H)6.84(d,J=3.91Hz,1H)6.97-7.26(m,8H)7.92-8.03(m,3H)

[0369] Example P4: Preparation of 4-[2-[5-(2,4-difluorophenyl)isoxazole-3-carbonyl]-3,4-dihydro-1H-isoquinolin-4-yl]-1,5-dimethyl-pyrrole-2-carbonitrile (Compound P-20, Table P) [ka] Step A: Preparation of 4-bromo-1,5-dimethyl-pyrrole-2-carbonitrile [ka] To a stirred solution of 1,5-dimethylpyrrole-2-carbonitrile (3.00 g, 25.0 mmol) in acetic acid (30 mL) was added bromine (1.32 mL, 25.5 mmol) dropwise, and the resulting reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was diluted with water and quenched with a saturated aqueous solution of sodium thiosulfate. The mixture was extracted with EtOAc (3 times), and the combined organic layers were washed with sodium bicarbonate solution NaSO and concentrated under reduced pressure. The crude product was further purified on a silica gel column to give 4-bromo-1,5-dimethyl-pyrrole-2-carbonitrile. 1H NMR(400MHz,CDCl3)δ ppm 6.75(s,1H),3.68(s,3H),2.26(s,3H)

[0370] Step B: Preparation of 4-(4-isoquinolyl)-1,5-dimethyl-pyrrole-2-carbonitrile [ka] A microwave vial was charged with 4-bromo-1,5-dimethyl-pyrrole-2-carbonitrile (1.00 g, 5.02 mmol), 4-isoquinolylboronic 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 minutes 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 a microwave oven at 120 °C for 2 hours, and the reaction progress 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 (2×50 mL), and the combined organic layers were washed with brine, dried over Na2SO4, and concentrated under reduced pressure. The crude product was purified by column chromatography to give 4-(4-isoquinolyl)-1,5-dimethyl-pyrrole-2-carbonitrile. LC-MS retention time 1.00 min, m / z248(M+H) (Method C)

[0371] Step C: Preparation of 1,5-dimethyl-4-(1,2,3,4-tetrahydroisoquinolin-4-yl)pyrrole-2-carbonitrile [ka] A round-bottom flask was charged with 4-(4-isoquinolyl)-1,5-dimethyl-pyrrole-2-carbonitrile (0.90 g, 3.64 mmol), methanol (18.20 mL), and sodium cyanoborohydride (2.40 g, 36.4 mmol). Hydrochloric acid (4.0 mol / L) in dioxane (21.8 mL) was then added dropwise at room temperature (gas evolution), and the mixture was stirred at room temperature for 5 hours. 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 under reduced pressure 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. LC-MS retention time 0.91 min, m / z252(M+H); (Method C)

[0372] Step D: Preparation of 4-[2-[5-(2,4-difluorophenyl)isoxazole-3-carbonyl]-3,4-dihydro-1H-isoquinolin-4-yl]-1,5-dimethyl-pyrrole-2-carbonitrile (Compound P-20) The desired product was prepared analogously to Example 1, Step C to give 4-[2-[5-(2,4-difluorophenyl)isoxazole-3-carbonyl]-3,4-dihydro-1H-isoquinolin-4-yl]-1,5-dimethyl-pyrrole-2-carbonitrile. LC-MS: 459[M+H], Rt: 1.22 min (Method B) 1H NMR(400MHz,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=12.84,6.72Hz,1H)4.18-4.27(m,3H)4.37(dd,J=12.65,4.71Hz,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=3.67Hz,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)

[0373] Example P5: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-methyl-4-(3-pyridyl)-1,3-dihydroisoquinolin-2-yl]methanone (compound P-27, Table P) [ka] Step 1: Preparation of 2-phenyl-2-(3-pyridyl)propanenitrile [ka] A sealed tube equipped with a magnetic stir bar was charged with 3-fluoropyridine (1.78 g, 18.37 mmol), 2-phenylpropanenitrile (2.41 g, 18.373 mmol), potassium tert-butoxide (2.10 g, 18.373 mmol), and DMSO (20 mL) under an argon atmosphere. The reaction mixture was stirred at 80 °C for 2 h. The reaction mixture was then poured into an aqueous solution saturated with potassium bicarbonate. The aqueous phase was extracted with EtOAc (2 × 50 mL), and the combined organic layers were dried over Na SO and concentrated under reduced pressure. The crude material was purified by combiflash (silica gel, gradient: EtOAc in cyclohexane) to give the title compound as a yellow liquid. LC-MS (Method A): 209[M+H]+; Retention time: 0.82 min. 1 H NMR(400MHz,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)

[0374] Step 2: Preparation of 2-phenyl-2-(3-pyridyl)propan-1-amine [ka] A 100 mL three-necked flask equipped with a magnetic stir bar was charged with 2-phenyl-2-(3-pyridyl)propanenitrile (1.10 g, 5.76 mmol, prepared as described above in Step 1) and THF (18 mL). To this yellow solution, borane dimethyl sulfide complex (1.74 mL, 17.28 mmol) was added dropwise at room temperature under an argon atmosphere, and the resulting colorless mixture was stirred at 65 °C for 2 h. The reaction mixture was cooled to 0 °C, after which hydrochloric acid (3.86 mL, 23.16 mmol) was added dropwise (strong gas evolution), and the mixture was stirred at 65 °C for 1 h and then cooled to room temperature. The mixture was diluted with water (80 mL), basified with 13 mL of 6 M NaOH (pH 12), and then extracted twice with EtOAc (3 × 50 mL). The combined organic layers were washed with brine, dried over Na2SO4 and concentrated under reduced pressure to give the title compound as an orange gum, which was used in the next step without further purification. LC-MS (Method A): 213[M+H]+; Retention time: 0.21 min.

[0375] Step 3: Preparation of methyl N-[2-phenyl-2-(3-pyridyl)propyl]carbamate [ka] A 250 mL, one-necked, round-bottom flask equipped with a magnetic stir bar was charged with 2-phenyl-2-(3-pyridyl)propan-1-amine (prepared as described above in Step 2, 1.55 g, 7.30 mmol) and DCM (30 mL). Methyl chloroformate (0.68 mL, 8.76 mmol) was added dropwise, followed by triethylamine (3.07 mL, 21.9 mmol) at 0–10 °C under an argon atmosphere. The ice bath was removed, and the mixture was stirred at room temperature for 1 h. The reaction mixture was poured into water, and the organic phase was separated. The aqueous phase was extracted twice with EtOAc, and the combined organic layers were dried over NaSO and concentrated under reduced pressure. The crude material was purified by combiflash (silica gel, gradient: ethyl acetate in cyclohexane) to give the title compound as a colorless gum. LC-MS (Method A): 271[M+H]+; Retention time: 0.58 min.

[0376] Step 4: Preparation of methyl 4-methyl-4-(3-pyridyl)-1,3-dihydroisoquinoline-2-carboxylate [ka] A one-necked round-bottom flask equipped with a magnetic stir bar was charged with methyl N-[2-phenyl-2-(3-pyridyl)propyl]carbamate (prepared as described above in Step 3, 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). The mixture was stirred for 40 min at room temperature, and LC-MS analysis indicated the reaction was complete. The reaction mixture was slowly poured into water (30 mL), neutralized with NaHCO3, and extracted with EtOAc (3 × 20 mL). The combined organic layers were washed with brine, dried over Na2SO4, and concentrated under reduced pressure. The crude material was purified by combiflash (silica gel, gradient: ethyl acetate in cyclohexane) to give the title compound as a colorless gum. LC-MS (Method A): 283[M+H]+; Retention time: 0.67 min.

[0377] Step 5: Preparation of 4-methyl-4-(3-pyridyl)-2,3-dihydro-1H-isoquinoline [ka] A one-necked round-bottom flask equipped with a magnetic stir bar was charged with methyl 4-methyl-4-(3-pyridyl)-1,3-dihydroisoquinoline-2-carboxylate (prepared as described above in Step 4, 120 mg, 0.42 mmol), 1,2-dichloroethane (5.00 mL / mmol, 2.12 mL), and iodotrimethylsilane (263.1 mg, 0.18 mL, 1.27 mmol). The mixture was stirred at 60 °C under an argon atmosphere for 45 min, and LC-MS analysis showed nearly complete conversion. The reaction was then stirred at room temperature overnight. The reaction mixture was slowly poured into water, neutralized with NaHCO and extracted twice with EtOAc. The combined organic layers were washed with brine, dried over NaSO, and concentrated under reduced pressure to afford the title compound as a dark orange gum, which was used in the next step without further purification. LC-MS (Method A): 225[M+H]+; Retention time: 0.16 min.

[0378] Step 6: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-methyl-4-(3-pyridyl)-1,3-dihydroisoquinolin-2-yl]methanone (Compound P-27, Table P) A one-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 above in Step 5, 60 mg, 0.267 mmol), EtOAc (2.675 mL, 27.30 mmol), N-NN-diisopropylethylamine (104 mg, 0.138 mL, 0.8025 mmol), and 5-(2,4-difluorophenyl)isoxazole-3-carboxylic acid (68.30 mg, 0.2942 mmol). T3P (510.70 mg, 0.473 mL, 0.8025 mmol) was then added dropwise at room temperature, and the mixture was stirred at room temperature for 60 minutes. 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 under reduced pressure. The crude material was purified by combiflash (silica gel, gradient: ethyl acetate in cyclohexane) to give the title compound as a white gum. LC-MS (Method A): 432[M+H]+; Retention time: 0.95 min.

[0379] Further examples of compounds of formula (I) that have been synthesized are shown in Table P.

[0380] [Table 8-1]

[0381] [Table 8-2]

[0382] [Table 8-3]

[0383] [Table 8-4]

[0384] [Table 8-5]

[0385] [Table 8-6]

[0386] [Table 8-7]

[0387] [Table 8-8]

[0388] [Table 8-9]

[0389] Biological Examples Example B1: Alternaria solani / Tomato / Leaf disc (summer blight) Tomato leaf discs (cv. Baby) are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compounds diluted in water. Two days after application, the leaf discs are inoculated with a fungal spore suspension. The inoculated leaf discs are incubated in a climate cabinet at 23°C / 21°C (day / night) under a 12 / 12 h light / dark photoperiod and 80% relative humidity. When an appropriate level of disease damage has developed on the untreated test leaf discs (5-7 days after application), the efficacy of the compound is evaluated as the percentage of disease control compared to the untreated ones.

[0390] The following compounds provided at least 80% control of Alternaria solani at 200 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-13, P-35.

[0391] Example B2: Botryotinia fuckeliana (Botrytis cinerea) / liquid culture (gray mold) Fungal conidia from cryogenic storage are mixed directly into nutrient broth medium (Vogels medium). A (DMSO) solution of the test compound is placed in a microtiter plate (96-well format) and then the nutrient medium containing the fungal spores is added. The test plates are incubated at 24°C and growth inhibition is measured photometrically 3-4 days after application.

[0392] The following compounds provided at least 80% control of Botryotinia fuckeliana at 20 ppm when compared to untreated controls, which showed widespread disease development under identical conditions: P-1, P-6.

[0393] Example B3: Glomerella lagenarium (Colletotrichum lagenarium) / liquid culture (anthrax) Fungal conidia from cryogenic storage are mixed directly into nutrient broth (PDB potato dextrose broth). A solution of the test compound (DMSO) is placed in a microtiter plate (96-well format), followed by the addition of the nutrient broth containing the fungal spores. The test plates are incubated at 24°C, and growth inhibition is measured photometrically 3-4 days after application.

[0394] The following compounds provided at least 80% control of Glomerella lagenarium at 20 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-1, P-2, P-3, P-4, and P-5.

[0395] Example B4: Wheat leaf spot fungus (Phaeosphaeria nodorum) (Septoria nodorum) / Wheat / Leaf spot prevention (leaf spot disease) Wheat leaf segments (cv. Kanzler) are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compounds diluted in water. Two days after application, the leaves are inoculated with a fungal spore suspension. The inoculated test leaf segments are incubated in a climate cabinet at 20°C and 75% relative humidity under a 12-hour light / 12-hour dark photoperiod. When an appropriate level of disease damage has developed on the untreated test leaf segments (5-7 days after application), the efficacy of the compound is evaluated as the percentage of disease control compared to the untreated ones.

[0396] The following compounds provided at least 80% control of wheat leaf blight (Phaeosphaeria nodorum) at 200 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-7.

[0397] Example B5: Monographella nivalis (Microdochium nivale) / Liquid Culture (Root Rot of Cereals) Fungal conidia from cryogenic storage are mixed directly into nutrient broth (PDB potato dextrose broth). A solution of the test compound (DMSO) is placed in a microtiter plate (96-well format), followed by the addition of the nutrient broth containing the fungal spores. The test plates are incubated at 24°C, and growth inhibition is measured photometrically 4-5 days after application.

[0398] The following compounds provided at least 80% control of Monographella nivalis at 20 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-1, P-2, P-3, P-4, P-5, P-6, P-7, P-8, P-9, P-12, and P-15.

[0399] Example B6: Mycosphaerella arachidis (Cercospora arachidicola) / liquid culture (early leaf spot) Fungal conidia from cryogenic storage are mixed directly into nutrient broth (PDB potato dextrose broth). A solution of the test compound (DMSO) is placed in a microtiter plate (96-well format), followed by the addition of the nutrient broth containing the fungal spores. The test plates are incubated at 24°C, and growth inhibition is measured photometrically 4-5 days after application.

[0400] The following compounds provided at least 80% control of Mycosphaerella arachidis at 20 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-1, P-3, P-4, P-5, P-6, P-7, P-8, P-9, P-10, P-11, P-13, and P-14.

[0401] Example B7: Puccinia recondita f.sp. tritici / wheat / leaf disk treatment (brown rust) Wheat leaf segments (cv. Kanzler) are placed on agar in multiwell plates (24-well format). The leaf segments are inoculated with a fungal spore suspension. The plates are stored in the dark at 19°C and 75% rh. The formulated test compounds, diluted in water, are applied one day after sowing. The leaf segments are incubated in a climate cabinet at 19°C and 75% relative humidity under a 12-hour light / 12-hour dark photoperiod. The compound efficacy is evaluated as the percentage of disease control compared to the untreated leaf segments (6-8 days after application) when an appropriate level of disease damage appears on the untreated test leaf segments.

[0402] The following compounds, at 200 ppm, provided at least 80% control of Puccinia recondita f.sp. tritici compared to untreated controls, which experienced significant disease development under identical conditions: P-19.

[0403] Example B8: Magnaporthe grisea (Pyricularia oryzae) / Rice / Leaf blight prevention (rice blight) Rice leaf segments (cv. Ballila) placed on agar in multiwell plates (24-well format) are sprayed with the formulated test compounds diluted in water. Two days after application, the leaf segments are inoculated with a fungal spore suspension. The inoculated leaf segments are incubated in a climate cabinet at 22°C and 80% relative humidity under a 24-hour dark followed by 12-hour light / 12-hour dark photoperiod. When an appropriate level of disease damage has developed on the untreated test leaf segments (5-7 days after application), the efficacy of the compound is evaluated as the percentage of disease control compared to the untreated ones.

[0404] The following compounds provided at least 80% control of Magnaporthe grisea at 200 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-13, P-30.

[0405] Example B9: Pyrenophora teres / barley / leaf spot prevention (net blotch) Barley leaf segments (cv. Hasso) are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compounds diluted in water. Two days after application, the leaf segments are inoculated with a fungal spore suspension. The inoculated leaf segments are incubated in a climate cabinet under a 12-hour light / 12-hour dark photoperiod at 20°C and 65% relative humidity until an appropriate level of disease damage has developed on the untreated test leaf segments (5-7 days after application), at which point the efficacy of the compound is evaluated as disease control compared to the untreated ones.

[0406] The following compounds provided at least 80% control of Pyrenophora teres at 200 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-1.

[0407] Example B10: Pythium ultimum / liquid medium (seedling damping-off) Freshly grown liquid culture fungal mycelium fragments and oospores are mixed directly into nutrient medium (PDB potato dextrose medium). A (DMSO) solution of the test compound is placed in a 96-well microtiter plate, followed by the addition of the nutrient medium containing the fungal mycelium / spore mixture. Test plates are incubated at 24°C, and growth inhibition is measured photometrically 2-3 days after application.

[0408] The following compounds provided at least 80% control of Pythium ultimum at 20 ppm when compared under identical conditions to untreated controls that exhibited severe disease infestation: P-2.

[0409] Example B11: Thanatephorus cucumeris (Rhizoctonia solani) / Liquid culture (root rot, damping-off) Mycelial fragments from freshly grown liquid cultures of the fungus are mixed directly into nutrient medium (PDB potato dextrose medium). A solution of the test compound (DMSO) is placed in a 96-well microtiter plate, after which the nutrient medium containing the fungal material is added. The test plates are incubated at 24°C, and growth inhibition is measured photometrically 3-4 days after application.

[0410] The following compounds provided at least 80% control of Thanatephorus cucumeris at 20 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-2;

[0411] Example B12: Wheat leaf blight fungus (Mycosphaerella graminicola) (Septoria tritici) / liquid culture (leaf blight) Fungal conidia from cryogenic storage are mixed directly into nutrient broth (PDB potato dextrose broth). A solution of the test compound (DMSO) is placed in a microtiter plate (96-well format), followed by the addition of the nutrient broth containing the fungal spores. The test plates are incubated at 24°C, and growth inhibition is measured photometrically 4-5 days after application.

[0412] The following compounds provided at least 80% control of wheat leaf blight (Mycosphaerella graminicola) at 20 ppm when compared to untreated controls that showed widespread disease development under identical conditions: 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, and P-39.

Claims

1. Formula (I) 【Chemistry 1】 (In the formula, Q is selected from 5- or 6-membered heteroaryl, wherein either 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 either of said 5- or 6-membered heteroaryl is unsubstituted or is selected from halogen, cyano, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl or C 3 ~C 6 substituted with 1, 2, or 3 substituents independently selected from cycloalkyl; R 1 is hydrogen, halogen, C 1 ~C 4 Haloalkyl, C 3 ~C 6 Cycloalkyl or C 1 ~C 4 alkyl, R 2 and R 3 are independently hydrogen or C 1 ~C 4 alkyl, R 4 is hydrogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Alkylcarbonyl, N—C 1 ~C 4 Alkoxy-C-C 1 ~C 4 Alkyl-carbonimidoyl, N-hydroxy-C-C 1 ~C 4 Alkyl-carbonimidoyl, C 1 ~C 4 Alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C 1 ~C 4 Alkylaminocarbonyl, di(C 1 ~C 4 alkyl)aminocarbonyl, phenyl, 5- to 6-membered heteroaryl or C 3 ~C 6 cycloalkyl, wherein any of said 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; and any of said phenyl and 5- to 6-membered heteroaryls is unsubstituted or selected from halogen, cyano, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, carboxy or C 1 ~C 4 substituted with 1, 2 or 3 substituents independently selected from alkoxy; 3 ~C 6 Cycloalkyl is unsubstituted or substituted with halogen, cyano, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl or C 1 ~C 4 substituted with 1, 2, or 3 substituents independently selected from alkoxy; B 1 is CR 7 or N, B 2 is CR 8 or N, R 5 , R 6 , R 7 and R 8 are independently hydrogen, halogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 1 ~C 4 Alkoxy, C 1 ~C 4 Haloalkoxy, C 2 ~C 4 Alkenyloxy, C 2 ~C 4 Alkynyloxy, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 4 Alkoxy-C 1 ~C 4 Alkyl, N-C 1 ~C 4 Alkylamino, N,N-di(C 1 ~C 4 alkyl)amino, C 1 ~C 4 Alkoxycarbonyl, C 1 ~C 4 Alkylcarbonyl, N—C 1 ~C 4 Alkoxy-C 1 ~C 4 Alkyl-carbonimidoyl, N-hydroxy-C 1 ~C 4 alkyl-carbonimidoyl, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, amino, phenyl, 5- or 6-membered heteroaryl or C 3 ~C 6 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 not more than one is O or S; and wherein said phenyl, 5- or 6-membered heteroaryl, and C 3 ~C 6 Any of the cycloalkyls may be unsubstituted or may be substituted with halogen, cyano, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl or C 1 ~C 4 substituted with 1, 2, or 3 substituents independently selected from alkoxy; A 1 , A 2 , A 4 are independently a methine, N, NR 10 , O or S, with the proviso that A 1 , A 2 and A 4 At least one of N, NR 10 , O or S, and A 1 , A 2 and A 4 is O or S, and R 10 is hydrogen or C 1 ~C 4 alkyl, A 3 is C or N, provided that A 3 When is N, A 1 , A 2 and A 4 is methine, N or NR 10 and R 10 is hydrogen or C 1 ~C 4 alkyl, and Z 1 is C 1 ~C 4 alkyl, phenyl, 5- or 6-membered heteroaryl or C 3 ~C 6 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 not more than one is O or S; and any of said phenyl and 5- or 6-membered heteroaryl is unsubstituted or selected from halogen, cyano, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl, C 1 ~C 4 Haloalkyl, C 1 ~C 4 Alkoxy, C 1 ~C 4 Haloalkoxy, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl or C 2 ~C 4 alkynyl, wherein the C 3 ~C 6 Cycloalkyl is unsubstituted or substituted with halogen, cyano, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl or C 1 ~C 4 substituted by 1, 2, or 3 substituents independently selected from alkoxy; or an agrochemically acceptable salt, stereoisomer or N-oxide thereof, provided that said compound of formula (I) is Table 1-1 Table 1-2 Table 1-3 or an agrochemically acceptable salt, stereoisomer, or N-oxide thereof, which is not an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof.

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

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

4. R 4 is hydrogen or C 1 ~C 4 A compound of formula (I) according to any one of claims 1 to 3, wherein the aryl group is selected from alkyl.

5. R 5 and R 6 A compound of formula (I) according to any one of claims 1 to 4, wherein:

6. Q is, 【Chemistry 2】 wherein any of the Q groups is unsubstituted or substituted with one or two substituents selected from fluorine, chlorine, bromine, cyano, or methyl; and R 9 is methyl, 【Transformation 3】 indicates the position of attachment to the tetrahydroisoquinoline moiety) A compound of formula (I) according to any one of claims 1 to 5, selected from:

7. Q is, 【Chemistry 4】 (In the formula, 【Transformation 5】 indicates the position of attachment to the tetrahydroisoquinoline moiety) 7. The compound of formula (I) according to claim 6, selected from:

8. Z 1 is C 1 ~C 4 Alkyl, phenyl, 5- to 6-membered heteroaryl or C 3 ~C 6 cycloalkyl, wherein any of the 5- or 6-membered heteroaryls contains one heteroatom selected from N, and any of the phenyl and 5- to 6-membered heteroaryls is unsubstituted or substituted with one or two substituents independently selected from fluoro, chloro, methyl, ethyl, ethynyl, methoxy, or methylsulfonyl, and wherein the C 3 ~C 6 Compounds of formula (I) according to any one of claims 1 to 7, wherein cycloalkyl is unsubstituted or substituted with one or two substituents selected from methyl.

9. 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. Formula (I-A1) 【Transformation 6】 (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , Q and Z 1 is as defined for compounds of formula (I) according to any one of claims 1 to 9, and A is 【Transformation 7】 (In the formula, 【Transformation 8】 indicates the position where it is bonded to the C(=O) group, and the arrow indicates the Z 1 (indicating the position of the bond to the group) (selected from 10. The compound of formula (I) according to any one of claims 1 to 9, which is a compound of formula (I).

11. A is, 【Chemistry 9】 (In the formula, 【Chemistry 10】 indicates the position where it is bonded to the C(=O) group, and the arrow indicates the Z 1 (indicating the position of the bond to the group) The compound of formula (I-A1) according to claim 10, selected from:

12. Compounds of formula (I) as fungicides 【Chemistry 11】 (In the formula, Q is selected from 5- or 6-membered heteroaryl, wherein either 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 either of said 5- or 6-membered heteroaryl is unsubstituted or is selected from halogen, cyano, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl or C 3 ~C 6 substituted with 1, 2, or 3 substituents independently selected from cycloalkyl; R 1 is hydrogen, halogen, C 1 ~C 4 Haloalkyl, C 3 ~C 6 Cycloalkyl or C 1 ~C 4 alkyl, R 2 and R 3 are independently hydrogen or C 1 ~C 4 alkyl, R 4 is hydrogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Alkylcarbonyl, N—C 1 ~C 4 Alkoxy-C-C 1 ~C 4 Alkyl-carbonimidoyl, N-hydroxy-C-C 1 ~C 4 Alkyl-carbonimidoyl, C 1 ~C 4 Alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C 1 ~C 4 Alkylaminocarbonyl, di(C 1 ~C 4 alkyl)aminocarbonyl, phenyl, 5- to 6-membered heteroaryl or C 3 ~C 6 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 not more than one is O or S; and said phenyl and 5- to 6-membered heteroaryl are unsubstituted or selected from halogen, cyano, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, carboxy or C 1 ~C 4 substituted with 1, 2 or 3 substituents independently selected from alkoxy; 3 ~C 6 Cycloalkyl is unsubstituted or substituted with halogen, cyano, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl or C 1 ~C 4 substituted with 1, 2, or 3 substituents independently selected from alkoxy; B 1 is CR 7 or N, B 2 is CR 8 or N, R 5 , R 6 , R 7 and R 8 are independently hydrogen, halogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 1 ~C 4 Alkoxy, C 1 ~C 4 Haloalkoxy, C 2 ~C 4 Alkenyloxy, C 2 ~C 4 Alkynyloxy, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 4 Alkoxy-C 1 ~C 4 Alkyl, N-C 1 ~C 4 Alkylamino, N,N-diC 1 ~C 4 Alkylamino, C 1 ~C 4 Alkoxycarbonyl, C 1 ~C 4 Alkylcarbonyl, N—C 1 ~C 4 Alkoxy-C 1 ~C 4 Alkyl-carbonimidoyl, N-hydroxy-C 1 ~C 4 alkyl-carbonimidoyl, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, amino, phenyl, 5- or 6-membered heteroaryl or C 3 ~C 6 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 not more than one is O or S; and wherein said phenyl, 5- or 6-membered heteroaryl, and C 3 ~C 6 Any of the cycloalkyls may be unsubstituted or may be substituted with halogen, cyano, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl or C 1 ~C 4 substituted with 1, 2, or 3 substituents independently selected from alkoxy; A 1 , A 2 , A 4 are independently a methine, N, NR 10 , O or S, with the proviso that A 1 , A 2 and A 4 At least one of N, NR 10 , O or S, and A 1 , A 2 and A 4 is O or S, and R 10 is hydrogen or C 1 ~C 4 alkyl, A 3 is C or N, provided that A 3 When is N, A 1 , A 2 and A 4 is methine, N or NR 10 and R 10 is hydrogen or C 1 ~C 4 alkyl, and Z 1 is C 1 ~C 4 alkyl, phenyl, 5- or 6-membered heteroaryl or C 3 ~C 6 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 not more than one is O or S; and any of said phenyl and 5- or 6-membered heteroaryl is unsubstituted or selected from halogen, cyano, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl, C 1 ~C 4 Haloalkyl, C 1 ~C 4 Alkoxy, C 1 ~C 4 Haloalkoxy, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl or C 2 ~C 4 alkynyl, wherein the C 3 ~C 6 Cycloalkyl is unsubstituted or substituted with halogen, cyano, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl or C 1 ~C 4 substituted by 1, 2, or 3 substituents independently selected from alkoxy; or an agrochemically acceptable salt, stereoisomer or N-oxide thereof.

13. A pesticide composition comprising a fungicidally effective amount of a compound of formula (I) according to any one of claims 1 to 12.

14. 14. The pesticide composition of claim 13, further comprising at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

15. 13. A method for controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I) according to any one of claims 1 to 12 or a composition comprising said compound of formula (I) is applied to said plant, its part or its habitat.

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