Microbiocidal tetrahydroisoquinoline derivatives

Abstract

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

Description

[0001] The present invention relates to microbicidal tetrahydroisoquinoline derivatives, for example as active ingredients, which have microbicidal activity, especially fungicidal activity. The invention also relates to the preparation of these tetrahydroisoquinoline derivatives, to intermediates useful in the preparation of these tetrahydroisoquinoline derivatives, to the preparation of these intermediates, to agrochemical compositions comprising at least one of these tetrahydroisoquinoline derivatives, to the preparation of these compositions and to the use of these tetrahydroisoquinoline derivatives or compositions in agriculture or horticulture for controlling or preventing infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, especially fungi.

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

[0003]

[0004] wherein,

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

[0006] R 2 is selected from hydrogen, halogen, C1-C 4- alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, C1-C 4- alkylcarbonyl, N-C1-C4-alkoxy-C-C1-C4-alkyl-carbimino, N-hydroxy-C-C1-C4-alkyl-carbimino, or C1-C 4- alkoxycarbonyl;

[0007] R 3 is selected from hydrogen, halogen, C1-C4-haloalkyl, or C1-C4-alkyl;

[0008] R 4 is selected from hydrogen, halogen, C1-C4-haloalkyl, C3-C6-cycloalkyl, or C1-C4-alkyl;

[0009] R 5 and R 6 are independently selected from hydrogen, or C1-C4-alkyl;

[0010] R 7Selected from hydrogen, C1-C4-alkyl, C1-C4-alkylcarbonyl, N-C1-C4-alkoxy-C-C1-C4-alkyl-carbodiimide, N-hydroxy-C-C1-C 4- alkyl-carbodiimide, C1-C4-alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4-alkylaminocarbonyl, bis(C1-C4-alkylamino)carbonyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- to 6-membered heteroaryl contains 1, 2, 3 or 4 identical or different heteroatoms selected from N, O or S, provided that no more than one is O or S; and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with 1, 2 or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4-haloalkyl, cyano, carboxyl, C1-C4-alkyl and C1-C4-alkoxy; and wherein the C3-C6-cycloalkyl is unsubstituted or substituted with 1, 2 or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4-haloalkyl, cyano, C1-C4-alkyl, or C1-C4-alkoxy;

[0011] B 1 Selected from CR 10 、 or N;

[0012] B 2 Selected from CR 11 、 or N;

[0013] R 8 、 R 9 、 R 10 and R 11 independently selected from hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C2-C4-alkenyloxy, C2-C4-alkynyloxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-alkoxy-C1-C4-alkyl, N-C 1- C4-alkylamino, N,N-bis(C 1-(C4-alkyl)amino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, N-C1-C4-alkoxy-C1-C4-alkyl-carbodiimide, N-hydroxy-C1-C4-alkyl-carbodiimide, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, amino, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- to 6-membered heteroaryl contains 1, 2, 3 or 4 identical or different heteroatoms selected from N, O or S, provided that not more than one is O or S; and wherein any one of the phenyl, 5- to 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted with 1, 2, 3 or up to the maximum possible number of identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, and C1-C4-alkoxy;

[0014] W is selected from O, N, S, *-CH2O- # , *-CH2NH- # , *-CH2S- # , or a bond, wherein the asterisk (*) represents the position attached to the carbonyl, and # represents the position attached to Z 1 attached; and

[0015] Z 1Selected from C1-C6 alkyl, phenyl, or 6-membered heteroaryl, wherein the C1-C6-alkyl is unsubstituted or substituted with 1, 2 or 3 identical or different substituents selected from the following: halogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C2-C4-alkenyloxy, C2-C4-alkynyloxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, N-C1-C4-alkoxy-C-C1-C4-alkyl-carbodiimide, N-hydroxy-C-C1-C4-alkyl-carbodiimide, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxyl, phenyl, 5- to 6-membered saturated or partially saturated heterocycle, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein any one of the 6-membered heteroaryl and the 5- to 6-membered heteroaryl contains 1, 2 or 3 identical or different heteroatoms selected from N, O or S, provided that not more than one is O or S; wherein any one of the 5- to 6-membered saturated or partially saturated heterocycles contains 1, 2 or 3 identical or different heteroatoms selected from N, O or S, provided that not more than one is O or S; wherein any one of the phenyl, any one of the 6-membered heteroaryl, any one of the 5- to 6-membered heteroaryl and any one of the 5- to 6-membered saturated or partially saturated heterocycles is unsubstituted or substituted with 1, 2, 3 or up to the maximum possible number of identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, and C1-C4-alkoxy; and wherein any one of the C3-C6-cycloalkyl is unsubstituted or substituted with 1, 2, 3 or up to the maximum possible number of identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, and C1-C4-alkoxy,

[0016] provided that the compound of formula (I) is not

[0017] PubChem CID 121198298 / CAS No.: 2309773-83-7

[0018] PubChem CID / CAS No.: 2034366-76-0

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

[0020] The PubChem Compound CID (which is the PubChem unique identifier (Compound Identifier CID)) given for the above-excluded compounds refers to the identifier of each compound in the PubChem website https: / / pubchem.ncbi.nlm.nih.gov / for each compound.

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

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

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

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

[0025]

[0026] wherein

[0027] R 1 is selected from hydrogen, C1-C 4- alkyl, C2-C 4- alkenyl, C2-C 4- alkynyl, or C3-C 6- cycloalkyl;

[0028] R 2 is selected from hydrogen, halogen, C1-C 4- alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, C1-C 4- alkylcarbonyl, N-C1-C4-alkoxy-C-C1-C4-alkyl-carbimino, N-hydroxy-C-C1-C4-alkyl-carbimino, or C1-C 4- alkoxycarbonyl;

[0029] R 3 is selected from hydrogen, halogen, C1-C4-haloalkyl, or C1-C4-alkyl;

[0030] R 4Selected from hydrogen, halogen, C1-C4-haloalkyl, C3-C6-cycloalkyl, or C1-C4-alkyl;

[0031] R 5 and R 6 are independently selected from hydrogen, or C1-C4-alkyl;

[0032] R 7 is selected from hydrogen, C1-C4-alkyl, C1-C4-alkylcarbonyl, N-C1-C4-alkoxy-C-C1-C4-alkyl-carbodiimido, N-hydroxy-C-C1-C 4- alkyl-carbodiimido, C1-C4-alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4-alkylaminocarbonyl, bis(C1-C4-alkylamino)carbonyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- to 6-membered heteroaryl contains 1, 2, 3 or 4 identical or different heteroatoms selected from N, O or S, provided that no more than one is O or S; wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted by 1, 2 or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4-haloalkyl, cyano, carboxyl, C1-C4-alkyl and C1-C4-alkoxy; and wherein the C3-C6-cycloalkyl is unsubstituted or substituted by 1, 2 or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4-haloalkyl, cyano, C1-C4-alkyl, or C1-C4-alkoxy;

[0033] B 1 is selected from CR 10 、or N;

[0034] B 2 is selected from CR 11 、or N;

[0035] R 8 、R 9 、R 10 and R 11 are independently selected from hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C2-C4-alkenyloxy, C2-C4-alkynyloxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-alkoxy-C1-C4-alkyl, N-C 1- C4-alkylamino, N,N-bis(C 1-(C4-alkyl)amino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, N-C1-C4-alkoxy-C1-C4-alkyl-carbodiimide, N-hydroxy-C1-C4-alkyl-carbodiimide, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, amino, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- to 6-membered heteroaryl contains 1, 2, 3 or 4 identical or different heteroatoms selected from N, O or S, provided that not more than one is O or S; and wherein any one of the phenyl, 5- to 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted by 1, 2, 3 or up to the maximum possible number of identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, and C1-C4-alkoxy;

[0036] W is selected from O, N, S, *-CH2O- # , *-CH2NH- # , *-CH2S- # , or *-CH2- # , where the asterisk (*) represents the position attached to the carbonyl, and # represents the position attached to Z 1 ; and

[0037] Z 1Selected from C1-C6 alkyl, phenyl, or 5- to 6-membered heteroaryl, wherein the C1-C6-alkyl is unsubstituted or substituted with 1, 2 or 3 identical or different substituents selected from the following: halogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C2-C4-alkenyloxy, C2-C4-alkynyloxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, N-C1-C4-alkoxy-C-C1-C4-alkyl-carbodiimide, N-hydroxy-C-C1-C4-alkyl-carbodiimide, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxyl, phenyl, 5- to 6-membered saturated or partially saturated heterocycle, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein any one of the 5- to 6-membered heteroaryl contains 1, 2 or 3 identical or different heteroatoms selected from N, O or S, provided that no more than one is O or S; wherein any one of the 5- to 6-membered saturated or partially saturated heterocycles contains 1, 2 or 3 identical or different heteroatoms selected from N, O or S, provided that no more than one is O or S; wherein any one of the phenyl, any one of the 5- to 6-membered heteroaryl and any one of the 5- to 6-membered saturated or partially saturated heterocycles is unsubstituted or substituted with 1, 2, 3 or up to the maximum possible number of identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, and C1-C4-alkoxy; and wherein any one of the C3-C6-cycloalkyl is unsubstituted or substituted with 1, 2, 3 or up to the maximum possible number of identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, and C1-C4-alkoxy,

[0038] provided that the compound of formula (I) is not

[0039] PubChem CID 121198298 / CAS No.: 2309773-83-7

[0040] PubChem CID / CAS No.: 2034366-76-0

[0041] or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.

[0042] According to another aspect of the present invention, there is provided a compound of formula (I) or an agrochemically acceptable salt, stereoisomer, or N-oxide thereof,

[0043]

[0044] wherein,

[0045] R 1 is selected from hydrogen, C1-C 4- alkyl, C2-C 4- alkenyl, C2-C4-alkynyl, or C3-C 6- cycloalkyl;

[0046] R 2 is selected from hydrogen, halogen, C1-C 4- alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, C1-C 4- alkylcarbonyl, N-C1-C4-alkoxy-C-C1-C4-alkyl-carbimino, N-hydroxy-C-C1-C4-alkyl-carbimino, or C1-C 4- alkoxycarbonyl;

[0047] R 3 is selected from hydrogen, halogen, C1-C4-haloalkyl, or C1-C4-alkyl;

[0048] R 4 is selected from hydrogen, halogen, C1-C4-haloalkyl, C3-C6-cycloalkyl, or C1-C4-alkyl;

[0049] R 5 and R 6 are independently selected from hydrogen, or C1-C4-alkyl;

[0050] R 7 is selected from hydrogen, C1-C4-alkyl, C1-C4-alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbimino, N-hydroxy-C-C1-C 4-alkyl-carbonimino, C1-C4-alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4-alkylaminocarbonyl, di(C1-C4alkylamino)carbonyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- to 6-membered heteroaryl contains 1, 2, 3 or 4 identical or different heteroatoms selected from N, O or S, provided that not more than one is O or S; wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted by 1, 2 or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4-haloalkyl, cyano, carboxyl, C1-C4-alkyl and C1-C4-alkoxy; and wherein the C3-C6-cycloalkyl is unsubstituted or substituted by 1, 2 or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4-haloalkyl, cyano, C1-C4-alkyl, or C1-C4-alkoxy;

[0051] B 1 selected from CR 10 , or N;

[0052] B 2 selected from CR 11 , or N;

[0053] R 8 、R 9 、R 10 and R 11 are independently selected from hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C2-C4-alkenyloxy, C2-C4-alkynyloxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-alkoxy-C1-C4-alkyl, N-C 1- C4-alkylamino, N,N-di(C 1- C4-alkyl)amino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, N-C1-C4-alkoxy-C1-C4-alkyl-carbonimino, N-hydroxy-C1-C4-alkyl-carbonimino, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxyl, amino, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- to 6-membered heteroaryl contains 1, 2, 3 or 4 identical or different heteroatoms selected from N, O or S, provided that not more than one is O or S; and wherein any one of the phenyl, 5- to 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted by 1, 2, 3 or up to the maximum possible number of identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, and C1-C4-alkoxy;

[0054] W is selected from O, N, S, *-CH2O- # , *-CH2NH- # , *-CH2S- # , or a bond, where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 ; and

[0055] Z 1 is selected from C1-C6 alkyl, phenyl, or 5- to 6-membered heteroaryl, where the C1-C6-alkyl is unsubstituted or substituted with 1, 2, or 3 identical or different substituents selected from the following: halogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C2-C4-alkenyloxy, C2-C4-alkynyloxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, N-C1-C4-alkoxy-C-C1-C4-alkyl-carbodiimide, N-hydroxy-C-C1-C4-alkyl-carbodiimide, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, phenyl, 5- to 6-membered saturated or partially saturated heterocycle, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; where any one of the 5- to 6-membered heteroaryl contains 1, 2, or 3 identical or different heteroatoms selected from N, O, or S, provided that no more than one is O or S; where any one of the 5- to 6-membered saturated or partially saturated heterocycles contains 1, 2, or 3 identical or different heteroatoms selected from N, O, or S, provided that no more than one is O or S; where any one of the phenyls, any one of the 5- to 6-membered heteroaryls, and any one of the 5- to 6-membered saturated or partially saturated heterocycles is unsubstituted or substituted with 1, 2, 3, or up to the maximum possible number of identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, and C1-C4-alkoxy; and where any one of the C3-C6-cycloalkyls is unsubstituted or substituted with 1, 2, 3, or up to the maximum possible number of identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, and C1-C4-alkoxy,

[0056] provided that the compound of formula (I) is not

[0057] PubChem CID 121198298 / CAS No.: 2309773-83-7

[0058] PubChem CID / CAS No.: 2034366-76-0

[0059] or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.

[0060] According to this particular aspect of the invention, the use may exclude methods for treating the human or animal body by surgery or therapy and diagnostic methods practiced on the human or animal body.

[0061] Compounds of formula (I) having at least one basic center may, for example, form acid addition salts with, for example: strong inorganic acids (such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrohalic acids), strong organic carboxylic acids (such as unsubstituted or halogen-substituted C1-C4 alkanoic acids, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid), or organic sulfonic acids (such as unsubstituted or halogen-substituted C1-C4 alkanesulfonic acids or arylsulfonic acids, for example methanesulfonic acid or p-toluenesulfonic acid). Compounds of formula (I) having at least one acidic group may, for example, form salts with bases, for example mineral salts, such as alkali metal or alkaline earth metal salts, for example sodium salts, potassium salts or magnesium salts; or with ammonia or organic amines (such as morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, for example ethylamine, diethylamine, triethylamine or dimethylpropylamine, or mono-, di- or tri-hydroxy-lower alkylamines, for example monoethanolamine, diethanolamine or triethanolamine).

[0062] In each case, the compounds of formula (I) according to the invention are in free form, oxidized form (such as N-oxide), or salt form (for example in the form of an agronomically available salt).

[0063] N-oxides are the oxidized forms of tertiary amines or of nitrogen-containing heteroaromatic compounds. They are described, for example, in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.

[0064] The compounds of formula (I) according to the invention also include the hydrates that may form during salt formation.

[0065] When a substituent is indicated as “optionally substituted”, this means that they may or may not carry one or more identical or different substituents, for example, one, two or three Rs xSubstituents. For example, C1-C6 alkyl groups substituted with 1, 2, or 3 halogens may include, but are not limited to, -CH2Cl, -CHCl2, -CCl3, -CH2F, -CHF2, -CF3, -CH2CF3, or -CF2CH3 groups. As another example, C1-C6 alkoxy groups substituted with 1, 2, or 3 halogens may include, but are not limited to, CH2ClO-, CHCl2O-, CCl3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O-, or CH3CF2O- groups. Additionally, as used herein, the term "optionally substituted" may be used interchangeably with the term "unsubstituted or substituted".

[0066] As used herein, the term "halogen" or "halo" refers to fluorine, chlorine, bromine, or iodine, preferably fluorine, chlorine, or bromine. This also correspondingly applies to halogens in combination with other meanings, such as haloalkyl, haloalkenyl, haloalkynyl, haloalkoxy, and halocycloalkyl.

[0067] As used herein, amino means the -NH2 group.

[0068] As used herein, cyano means the -CN group.

[0069] As used herein, the term "hydroxyl" or "hydroxy" means the -OH group.

[0070] As used herein, the term "carboxylic acid" means the -COOH group.

[0071] As used herein, the term "C1-C n -alkyl" refers to a saturated straight-chain or branched hydrocarbon group having 1 to n carbon atoms and attached via any one of the carbon atoms, such as any of the following groups: methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n-pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, or 1-ethyl-2-methylpropyl.

[0072] As used herein, the term "C2-C n"-enyl" means a straight or branched alkenyl chain moiety having from two to n carbon atoms and one or two double bonds, such as vinyl, prop-1-enyl, but-2-enyl.

[0073] As used herein, the term "C2-C n -ynyl" means a straight or branched alkynyl chain moiety having from two to n carbon atoms and one triple bond, such as ethynyl, prop-2-ynyl, but-3-ynyl.

[0074] As used herein, the term "C3-C n -cycloalkyl" means a three (3)-to n-membered cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0075] As used herein, the term "C1-C n -alkoxy" means a straight or branched saturated alkyl (as mentioned above) having from one (1) to n carbon atoms attached via an oxygen atom, i.e., for example, any of the following groups: methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy, and 1,1-dimethylethoxy. As used herein, the term "C2-C n -alkenyloxy" means a straight or branched alkenyl chain (as mentioned above) having from two (2) to n carbon atoms attached via an oxygen atom.

[0076] As used herein, the term "C 2- C n -alkynyloxy" means a group having the formula -OR a wherein R a is a C 2- C n -alkynyl as generally defined above.

[0077] As used herein, the term "C1-C n -alkoxy-C1-C n -alkyl" means an alkyl (as mentioned above) substituted with a C1-C n -alkoxy. Examples are methoxymethyl, methoxyethyl, ethoxymethyl, and propoxymethyl.

[0078] As used herein, the term "C3-C n -cycloalkyl-C1-C n -alkyl" means an alkyl (as mentioned above) substituted with a C3-C n -cycloalkyl. Examples are cyclopropylmethyl, cyclopropylethyl. Similarly, the term "C3-C n -halocycloalkyl-C1-C n"-alkyl" means an alkyl group substituted by a cycloalkyl group, wherein the cycloalkyl group is substituted by one or more identical or different halogen atoms. Examples are 3,3-difluorobutylmethyl and 1-chlorocyclopropylmethyl.

[0079] As used herein, the term "C1-C n -haloalkyl" means a straight-chain or branched-chain saturated alkyl group having 1 to n carbon atoms attached via any of the carbon atoms (as mentioned above), wherein some or all of the hydrogen atoms in these groups may be replaced by fluorine, chlorine, bromine, and / or iodine, i.e., for example, any of the following groups: chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl, or nonafluorobutyl. Accordingly, the term "C1-C2 fluoroalkyl" will mean a C1-C2 alkyl group bearing 1, 2, 3, 4, or 5 fluorine atoms, such as any of the following groups: difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, or pentafluoroethyl. Similarly, as used herein, the term "C2-C n -haloalkenyl" or "C2-C n -haloalkynyl" means a C2-C n -alkenyl or C2-C n -alkynyl substituted by one or more halogen atoms which may be the same or different. Similarly, as used herein, the term "C3-C n -halocycloalkyl" or "C1-C n -haloalkoxy" means a C3-C n -cycloalkyl or C1-C n -alkoxy substituted by one or more halogen atoms which may be the same or different.

[0080] As used herein, the term "C1-C n -alkylthio" or "C1-C n -alkylsulfanyl" means a C1-C attached via a sulfur atomn -alkyl

[0081] As used herein, the term "C1-C n -haloalkylthio" or "C1-C n -haloalkylsulfanyl" refers to a C1-C n haloalkyl group linked through a sulfur atom.

[0082] As used herein, the term "C1-C n -alkylsulfinyl" refers to a C1-C n alkyl group linked through the sulfur atom of a sulfinyl (or S(=O)-) group.

[0083] As used herein, the term "C1-C n -alkylsulfonyl" refers to a C1-C n alkyl group linked through the sulfur atom of a sulfonyl (or S(=O)2-) group.

[0084] As used herein, the term "C1-C n -alkylsulfonyl-C1-C n -alkyl" refers to a C1-C n alkyl group substituted by a C1-C n alkylsulfonyl group.

[0085] As used herein, the term "C1-C n -alkylcarbonyl" refers to a C1-C n alkyl group linked through the carbon atom of a carbonyl (C=O) group.

[0086] As used herein, the term "C1-C n -alkoxycarbonyl" refers to a C1-C n alkoxy moiety linked through the carbon atom of a carbonyl (or C=O) group.

[0087] As used herein, the term "C1-C n -alkoxycarbonyl-C1-C n -alkyl" refers to a C1-C n alkyl group substituted by a C1-C n -alkoxycarbonyl group.

[0088] As used herein, the term "benzoyl" refers to a phenyl group linked through the carbon atom of a carbonyl (C=O) group.

[0089] As used herein, the term "C1-C n -haloalkoxycarbonyl" refers to a C1-C n haloalkoxy group linked through the carbon atom of a carbonyl (C=O) group.

[0090] As used herein, the term "C2-C n -alkenyloxycarbonyl" means a C2-C n -alkenyloxycarbonyl group attached through the carbon atom of a carbonyl (C=O) group.

[0091] As used herein, the term "C1-C n -alkylaminocarbonyl" means a C1-C n -alkylamino (or R a NHC(=O)-, where R a is C1-C n -alkyl) attached through the carbon atom of a carbonyl (C=O) group.

[0092] As used herein, the term "aminocarbonyl-C1-C n -alkyl" means a C1-C n -alkyl substituted with an aminocarbonyl (or NH2C(=O)-) group.

[0093] As used herein, the term "C1-C n -alkylaminocarbonyl-C1-C n -alkyl" means a C1-C n -alkyl substituted with a C1-C a -alkylaminocarbonyl (or R n NHC(=O)-) group, where R a is C1-C n -alkyl. The C1-C n -alkyl attached to the nitrogen can be substituted.

[0094] As used herein, the term "N-C1-C n alkylamino" means a group having the formula -NH-R a , where R a is C1-C n alkyl as defined above.

[0095] As used herein, the term "N,N-diC1-C n alkylamino" means a group having the formula -N(R a )R a , where each R a is C1-C n alkyl as defined above, which may be the same or different.

[0096] As used herein, the term "C1-C n -alkylcarbonyloxy-C1-C n -alkyl" means a C1-C n -alkyl substituted with a C1-Ca C(=O)O-) group-substituted C1-C n -alkyl, wherein R a is C1-C n -haloalkyl.

[0097] As used herein, the term "C1-C n -alkoxycarbonyloxy-C1-C n -alkyl" refers to C1-C n -alkoxycarbonyloxy (or R c C(=O)O-) group-substituted C1-C n -alkyl, wherein R c is C1-C n -alkoxy. The C1-C n -alkoxy linked to nitrogen may be substituted.

[0098] As used herein, the term "N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimino" refers to a group having the formula -C(R a )=NO(R b ) wherein R a is C 1- C4 alkyl as generally defined above, and R b is C 1- C4 alkyl as generally defined above.

[0099] As used herein, the term "N-hydroxy-C-C1-C4 alkyl-carbonimino" refers to a group having the formula -C(R a )=NOH, wherein R a is C 1- C4 alkyl as generally defined above.

[0100] As used herein, the term "heterocyclic group" refers to a stable 3-membered, 4-membered, 5-membered to 6-membered non-aromatic monocyclic group containing 1, 2 or 3 heteroatoms / groups individually selected from nitrogen, oxygen, sulfur, S=O and SO2. The heterocyclic group may be bonded to the remainder of the molecule via a carbon atom or a heteroatom. Examples of heterocyclic groups include, but are not limited to, epoxy group, aziridinyl group, pyrrolinyl group, pyrrolidinyl group, tetrahydrofuryl group, tetrahydrothienyl group, tetrahydropyranyl group, piperidinyl group, piperazinyl group, tetrahydropyranyl group, dioxolanyl group, morpholinyl group, oxazinylalkyl group, oxetanyl group, 1,1-dioxothietan-3-yl group, or δ-lactamyl group. The heterocycloalkyl may be substituted on the heteroatom and / or carbon atom. The term "saturated or partially saturated heterocycle" should be understood to mean both monocyclic systems and bicyclic systems, as well as saturated and partially unsaturated heterocycles.

[0101] As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic group containing 1, 2, 3, or 4 heteroatoms independently selected from N, O, and S. Examples of heteroaryl include, but are not limited to, furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidinyl, or pyridyl. The term "heteroaryl-C1-C n -alkyl" or "heteroaryl-C3-C n -cycloalkyl" refers to a C1-C n -alkyl or C3-C n -cycloalkyl substituted by heteroaryl, respectively. Heteroaryl-C1-C n -alkyl or heteroaryl-C3-C n -cycloalkyl may be optionally substituted on the heteroaryl, alkyl, and / or cycloalkyl.

[0102] As used herein, the term "control" means reducing the number of pests, eliminating pests, and / or preventing further pest damage such that damage to the plant or to plant-derived products is reduced.

[0103] As used herein, the term "pest" refers to insects and mollusks present in agriculture, horticulture, forestry, and the storage of plant-derived products (such as fruits, grains, and wood); and those pests associated with the damage of man-made structures. The term pest encompasses all stages of the pest life cycle.

[0104] As used herein, the term "effective amount" means the amount of a compound or its salt that provides the desired effect upon single or multiple applications.

[0105] The effective amount can be readily determined by those skilled in the art using known techniques and by observing the results obtained in similar situations. In determining the effective amount, many factors are considered, including but not limited to the type of plant or derived product to be applied; the pest to be controlled and its life cycle; the particular compound to be applied; the type of application; and other relevant circumstances.

[0106] As used herein, the term "room temperature" or "RT" or "rt" or "ambient temperature" refers 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.

[0107] The following list provides the substituents R of the compounds of formula (I) according to the present invention 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R8 , R 9 , B 1 , B 2 , W and Z 1 definitions, including preferred definitions. For any one of these substituents, any of the definitions given below can be combined with any of the definitions of any other substituent given below or elsewhere in this document.

[0108] In one embodiment of the present invention, R 1 is selected from the group consisting of: hydrogen, C1-C 4- alkyl, C2-C 4- alkenyl, C2-C4-alkynyl, or C3-C6 cycloalkyl. In another embodiment of the present invention, R 1 is C1-C4 alkyl. Preferably, R 1 is methyl, ethyl, or isopropyl. More preferably, R 1 is methyl.

[0109] In one embodiment of the present invention, R 2 is selected from the group consisting of: hydrogen, halogen, C1-C 4- alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C3-C6 cycloalkyl, C1-C 4- alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimino, N-hydroxy-C-C1-C4 alkyl-carbonimino, or C1-C 4- alkoxycarbonyl. In another embodiment of the present invention, R 2 is hydrogen, halogen, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimino, or N-hydroxy-C1-C4 alkyl-carbonimino. Preferably, R 2 is hydrogen, halogen, methyl, ethyl, cyclopropyl, C1-C2 alkylcarbonyl, N-C1-C2 alkoxy-C-C1-C2 alkyl-carbonimino, or N-hydroxy-C-C1-C2 alkyl-carbonimino. More preferably, R 2 is hydrogen, fluorine, chlorine, bromine, methyl, ethyl, cyclopropyl, acetyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, or -C(CH3)=NOH. In a preferred embodiment of the present invention, R 2 is selected from hydrogen, halogen, or C1-C4 alkyl. Most preferably, R 2 is hydrogen, chlorine, or methyl. In a preferred embodiment, R 2 is hydrogen. In another preferred embodiment, R 2 is methyl. In yet another preferred embodiment, R2 is chlorine.

[0110] In one embodiment, R 3 is selected from hydrogen, halogen, C1-C4 haloalkyl, or C1-C4 alkyl. Preferably, R 3 is hydrogen, or C1-C4 alkyl. More preferably, R 3 is hydrogen, or methyl. Most preferably, R 3 is hydrogen.

[0111] In one embodiment of the present invention, R 4 is selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, or C3-C6-cycloalkyl. Preferably, R 4 is hydrogen, chlorine, bromine, fluorine, methyl, ethyl, trifluoromethyl, difluoromethyl, or cyclopropyl. More preferably, R 4 is hydrogen, chlorine, bromine, or methyl. Even more preferably, R 4 is hydrogen, or methyl. Most preferably, R 4 is hydrogen. In one embodiment of the present invention, R 4 is hydrogen. In another embodiment of the present invention, R 4 is methyl.

[0112] In one embodiment of the present invention, R 5 and R 6 are independently selected from hydrogen, or C1-C4-alkyl. Preferably, R 5 and R 6 are independently selected from hydrogen, methyl, or ethyl. More preferably, R 5 and R 6 are independently selected from hydrogen, or methyl. Even more preferably, R 5 and R 6 are hydrogen.

[0113] In one embodiment, R 7 is selected from hydrogen, C1-C4 alkyl, C1-C4-alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbodiimide, N-hydroxy-C-C1-C 4-alkyl-carbimino, C1-C4-alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4-alkylaminocarbonyl, bis(C1-C4-alkylamino)carbonyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- to 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O and S, provided that no more than one is O or S; and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with 1 to 3 substituents independently selected from: halogen, C1-C4-haloalkyl, cyano, carboxyl, C1-C4-alkyl, or C1-C4-alkoxy; and wherein the C3-C6-cycloalkyl is unsubstituted or substituted with 1 to 3 substituents independently selected from: halogen, C1-C4-haloalkyl, cyano, C1-C4-alkyl, or C1-C4-alkoxy.

[0114] In another embodiment of the invention, R 7 is selected from the group consisting of: hydrogen, C1-C4-alkyl, C3-C1-C4-alkylcarbonyl, C1-C4-alkoxycarbonyl, N-C1-C4-alkoxy-C-C1-C4-alkyl-carbimino, N-hydroxy-C-C1-C4-alkyl-carbimino, N-methoxy-N-methyl-carbonyl, C1-C4-alkylaminocarbonyl, bis(C1-C4-alkylamino)carbonyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- to 6-membered heteroaryl contains 1 heteroatom selected from N; and wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted with 1 to 2 substituents independently selected from: halogen, C1-C4-haloalkyl, cyano, or C1-C4-alkyl; and wherein the C3-C6-cycloalkyl is unsubstituted or substituted with 1 substituent selected from cyano. Preferably, R 7 is selected from hydrogen, methyl, acetyl, C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methoxycarbonyl, ethoxycarbonyl, N-methoxy-N-methyl-carbonyl, methylaminocarbonyl, dimethylaminocarbonyl, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, [4-(trifluoromethyl)pyrazol-1-yl], [3-(trifluoromethyl)pyrazol-1-yl], 3-cyanopyrazol-1-yl, 4-cyanopyrazol-1-yl, 5-chloropyrazol-1-yl, 5-fluoropyrazol-1-yl, 3,5-dimethylpyrazol-1-yl, 5-methylpyrazol-1-yl, pyrazol-1-yl, cyclopropyl, or 1-cyanocyclopropyl. More preferably, R 7 is selected from hydrogen, methyl, acetyl, C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, phenyl, 4-cyanophenyl, pyrazol-1-yl, cyclopropyl, or 1-cyanocyclopropyl. Even more preferably, R 7Selected from hydrogen, methyl, cyclopropyl, or 1-cyanocyclopropyl.

[0115] In another embodiment, R 7 is selected from hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl. Preferably, R 7 is hydrogen, methyl, cyclopropyl, or 1-cyanocyclopropyl. Even more preferably, R 7 is hydrogen, methyl, or cyclopropyl.

[0116] In another preferred embodiment, R 7 is C1-C4 alkyl. Preferably, R 7 is methyl or ethyl. More preferably, R 7 is methyl.

[0117] In one embodiment of the present invention, R 8 , R 9 , R 10 and R 11 are independently selected from the group consisting of hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, N-C1-C4-alkylamino, N,N-bis(C 1- C4-alkyl)amino, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbodiimide, N-hydroxy-C1-C4 alkyl-carbodiimide, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, amino, phenyl, 5- to 6-membered heteroaryl, or C3-C6 cycloalkyl, wherein the 5- to 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O and S, provided that not more than one is O or S; and wherein any one of the phenyl, 5- to 6-membered heteroaryl and C3-C6-cycloalkyl may optionally be substituted with 1, 2 or 3 substituents independently selected from the following: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy.

[0118] In one embodiment of the present invention, R 8 and R 9 are independently selected from hydrogen, halogen, cyano, C1-C4 alkyl, or C1-C4 alkoxy. Preferably, R 8 and R 9 are independently selected from hydrogen, halogen, methyl, methoxy, or cyano. More preferably, R 8 and R 9 are independently selected from hydrogen, methyl, chlorine, fluorine, bromine, or methoxy. Even more preferably, R8 and R 9 is independently selected from hydrogen or methoxy group.

[0119] In another embodiment of the present invention, R 8 is hydrogen, halogen or cyano group. Preferably, R 8 is hydrogen, bromine, chlorine or cyano group. More preferably, R 8 is hydrogen, cyano group or bromine. Even more preferably, R 8 is hydrogen.

[0120] In another embodiment, R 9 is selected from hydrogen, halogen, C1-C3 alkyl group, C1-C2 haloalkyl group, C1-C3 haloalkoxy group, C1-C4 alkoxy group, C1-C3 alkenyloxy group, C1-C3 alkynyloxy group, C1-C2 alkylthio group, C1-C2 alkylsulfinyl group, C1-C2 alkylsulfonyl group, C1-C2 alkoxy-C1-C2 alkyl group, C1-C3 alkoxycarbonyl group, C1-C2 alkylcarbonyl group, N-C1-C2 alkoxy-C-C1-C2 alkyl-carbodiimide group, N-hydroxy-C-C1-C2 alkyl-carbodiimide group, hydroxy group, C1-C2 alkylaminocarbonyl group, bis(C1-C2 alkylamino)carbonyl group, trifluoromethylsulfonyloxy group, cyano group, carboxyl group, phenyl group, 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, [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 group or 1-cyanocyclopropyl group. Preferably, R 9is hydrogen, chlorine, fluorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, difluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, methoxy, ethoxy, propoxy, allyloxy, prop-2-ynyloxy, methylthio, methylsulfinyl, methylsulfonyl, methoxymethyl, ethoxymethyl, 2-methoxyethoxymethyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, acetyl, propionyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methylaminocarbonyl, bis(methylamino)carbonyl, trifluoromethylsulfonyloxy, cyano, carboxy, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, [4-(trifluoromethyl)pyrazol-1-yl], [3-(trifluoromethyl)pyrazol-1-yl], 3-cyanopyrazol-1-yl, 4-cyanopyrazol-1-yl, 5-chloropyrazol-1-yl, 4-chloropyrazol-1-yl, 3-chloropyrazol-1-yl, 5-fluoropyrazol-1-yl, 4-fluoropyrazol-1-yl, 3-fluoropyrazol-1-yl, 3,5-dimethylpyrazol-1-yl, 5-methylpyrazol-1-yl, 4-methylpyrazol-1-yl, 3-methylpyrazol-1-yl, pyrazol-1-yl, cyclopropyl, or 1-cyanocyclopropyl. More preferably, R 9 is hydrogen, chlorine, bromine, fluorine, cyano, methyl, methoxy, propoxy, allyloxy, methoxymethyl, 2-methoxyethoxymethyl, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, [4-(trifluoromethyl)pyrazol-1-yl], [3-(trifluoromethyl)pyrazol-1-yl], 3-cyanopyrazol-1-yl, 4-cyanopyrazol-1-yl, 5-chloropyrazol-1-yl, 4-chloropyrazol-1-yl, 3-chloropyrazol-1-yl, 5-fluoropyrazol-1-yl, 4-fluoropyrazol-1-yl, 3-fluoropyrazol-1-yl, 3,5-dimethylpyrazol-1-yl, 5-methylpyrazol-1-yl, 4-methylpyrazol-1-yl, 3-methylpyrazol-1-yl, pyrazol-1-yl, cyclopropyl, or 1-cyanocyclopropyl. Even more preferably, R 9 is hydrogen, chlorine, bromine, cyano, methyl, or methoxy. Most preferably, R 9 is hydrogen, or methoxy.

[0121] In an embodiment of the present invention, B 1 is CR 10 and B 2 is CR 11 , or B 1 is N and B 2 is CR 11 , or B 1 is CR 10 and B 2 is N. Preferably, B1 is CR 10 and B 2 is CR 11 .

[0122] In one embodiment of the present invention, R 10 and R 11 are independently selected from the group consisting of: hydrogen, halogen, hydroxy, cyano, amino, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, N-C1-C4 alkylamino, N,N-bis(C1-C4-alkyl)amino, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbodiimide, N-hydroxy-C1-C4 alkyl-carbodiimide, alkyl-C═N-OR X (X = (CH2)n-CN, hydroxy, trifluoromethylsulfonyloxy, carboxy, phenyl, 5- to 6-membered heteroaryl, and C3-C6 cycloalkyl; wherein the 5- to 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms independently selected from N, O and S, provided that no more than one is O or S; and wherein any one of the phenyl, 5- to 6-membered heteroaryl and C3-C6-cycloalkyl may optionally be substituted by 1, 2 or 3 substituents independently selected from: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy. Preferably, R 10 and R 11Independently selected from hydrogen, chlorine, fluorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, difluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, methoxy, ethoxy, propoxy, allyloxy, prop-2-ynyloxy, methylthio, methylsulfinyl, methylsulfonyl, methoxymethyl, ethoxymethyl, 2-methoxyethoxymethyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, acetyl, propionyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methylaminocarbonyl, bis(methylamino)carbonyl, trifluoromethylsulfonyloxy, cyano, carboxyl, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, [4-(trifluoromethyl)pyrazol-1-yl], [3-(trifluoromethyl)pyrazol-1-yl], 3-cyanopyrazol-1-yl, 4-cyanopyrazol-1-yl, 5-chloropyrazol-1-yl, 4-chloropyrazol-1-yl, 3-chloropyrazol-1-yl, 5-fluoropyrazol-1-yl, 4-fluoropyrazol-1-yl, 3-fluoropyrazol-1-yl, 3,5-dimethylpyrazol-1-yl, 5-methylpyrazol-1-yl, 4-methylpyrazol-1-yl, 3-methylpyrazol-1-yl, pyrazol-1-yl, cyclopropyl, or 1-cyanocyclopropyl. More preferably, R 10 and R 11 Independently selected from hydrogen, chlorine, bromine, fluorine, cyano, methyl, methoxy, propoxy, allyloxy, methoxymethyl, 2-methoxyethoxymethyl, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, [4-(trifluoromethyl)pyrazol-1-yl], [3-(trifluoromethyl)pyrazol-1-yl], 3-cyanopyrazol-1-yl, 4-cyanopyrazol-1-yl, 5-chloropyrazol-1-yl, 4-chloropyrazol-1-yl, 3-chloropyrazol-1-yl, 5-fluoropyrazol-1-yl, 4-fluoropyrazol-1-yl, 3-fluoropyrazol-1-yl, 3,5-dimethylpyrazol-1-yl, 5-methylpyrazol-1-yl, 4-methylpyrazol-1-yl, 3-methylpyrazol-1-yl, pyrazol-1-yl, C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, cyclopropyl, or 1-cyanocyclopropyl. Even more preferably, R 10 and R 11 Independently selected from hydrogen, chlorine, bromine, or cyano.

[0123] In another embodiment, R 10 and R 11 Independently selected from hydrogen, halogen, C1-C3 alkyl, or C1-C4 alkoxy. Preferably, R 10 and R 11 Independently selected from hydrogen, or halogen. More preferably, R 10 and R11 is hydrogen, bromine, or chlorine. Even more preferably, R 10 and R 11 are hydrogen.

[0124] In one embodiment of the present invention, W is selected from O, N, S, *-CH2O- # , *-CH2NH- # , *-CH2S- # , or *-CH2- # , where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 Preferably, W is selected from O, N, *-CH2O- # , *-CH2NH- # , *-CH2S- # , or *-CH2- # , where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 More preferably, W is selected from O, N, *-CH2O- # , *-CH2NH- # , or *-CH2- # , where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 Preferably, W is selected from O, N, or *-CH2- # , - # , where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 attached position.

[0125] In another embodiment, W is selected from O. In yet another embodiment, W is selected from N. In yet another embodiment, W is *-CH2- # , - # , where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 attached position.

[0126] In one embodiment of the present invention, W is selected from O, N, S, *-CH2O- # , *-CH2NH- # , *-CH2S- # , or a bond, where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 attached position. Preferably, W is selected from O, N, *-CH2O- # , *-CH2NH- # , *-CH2S- # , or a bond, where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z1 The attached position. More preferably, W is selected from O, N, *-CH2O- # , *-CH2NH- # , or a bond, where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 Preferably, W is selected from O, N, or a bond.

[0127] In another embodiment, W is selected from O. In still another embodiment, W is selected from N. In still another embodiment, W is a bond.

[0128] In one embodiment, Z 1 is selected from C1-C6 alkyl, phenyl, or 5- to 6-membered heteroaryl; where the C1-C6 alkyl is unsubstituted or substituted with 1, 2, or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbodiimide, N-hydroxy-C-C1-C4 alkyl-carbodiimide, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxyl, phenyl, 5- to 6-membered saturated or partially saturated heterocycle, 5- to 6-membered heteroaryl, and C3-C6-cycloalkyl; where any one of the 5- to 6-membered heteroaryl contains 1, 2, or 3 identical or different heteroatoms selected from N, O, or S, provided that no more than one is O or S; where any one of the 5- to 6-membered saturated or partially saturated heterocycles contains 1, 2, or 3 identical or different heteroatoms selected from N, O, or S, provided that no more than one is O or S; where any one of the phenyl, any one of the 5- to 6-membered heteroaryl, and any one of the 5- to 6-membered saturated or partially saturated heterocycles is unsubstituted or substituted with 1, 2, 3, or up to the maximum possible number of identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, and C1-C4 alkoxy; and where any one of the C3-C6-cycloalkyl is unsubstituted or substituted with 1, 2, 3, or up to the maximum possible number of identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, and C1-C4 alkoxy.

[0129] Preferably, Z 1Selected from C1-C6 alkyl, phenyl, or 5- to 6-membered heteroaryl; wherein the C1-C6 alkyl is unsubstituted or substituted by 1, 2, or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4 alkyl, C1-C4 haloalkyl, phenyl, 5- to 6-membered heteroaryl, and C3-C6-cycloalkyl; wherein any of the 5- to 6-membered heteroaryls contains 1 or 2 identical or different heteroatoms selected from N or O; and wherein any of the phenyls and any of the 5- to 6-membered heteroaryls are unsubstituted or substituted by 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, and C3-C6-cycloalkyl.

[0130] More preferably, Z 1 Selected from C1-C6 alkyl, phenyl, or 5- to 6-membered heteroaryl; wherein the C1-C6 alkyl is unsubstituted or substituted by 1, 2, or 3 identical or different substituents selected from the group consisting of: chlorine, fluorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, and 5- to 6-membered heteroaryl; wherein any of the 5- to 6-membered heteroaryls contains 1 or 2 identical or different heteroatoms selected from N or O; and wherein any of the phenyls and any of the 5- to 6-membered heteroaryls are unsubstituted or substituted by 1 or 2 identical or different substituents selected from the group consisting of: chlorine, bromine, fluorine, cyano, methyl, ethyl, and cyclopropyl.

[0131] More preferably, Z 1 Selected from C1-C6 alkyl, phenyl, or 5- to 6-membered heteroaryl; wherein the C1-C6 alkyl is unsubstituted or substituted by 1, 2, or 3 identical or different substituents selected from the group consisting of: chlorine, fluorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, cyclopropyl, cyclohexyl, phenyl, and 6-membered heteroaryl; wherein the 5- to 6-membered heteroaryl and the 6-membered heteroaryl contain 1 heteroatom selected from N; and wherein any of the phenyl, the 5- to 6-membered heteroaryl, and the 6-membered heteroaryl are unsubstituted or substituted by 1 or 2 identical or different substituents selected from the group consisting of: chlorine, bromine, fluorine, cyano, methyl, ethyl, and cyclopropyl.

[0132] More preferably, Z 1Selected from C1-C6 alkyl, phenyl, 2,4-difluorophenyl, 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, 3-fluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3,4-difluoro-2-pyridyl, 3,5-difluoro-2-pyridyl, 4-fluoropyridazin-3-yl, 4,5-difluoropyridazin-3-yl, or 5-fluoropyridazin-4-yl; wherein the C1-C6 alkyl is unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: chlorine, fluorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, cyclopropyl, cyclohexyl, phenyl, and 6-membered heteroaryl; wherein the 6-membered heteroaryl contains 1 heteroatom selected from N; and wherein the phenyl and the 6-membered heteroaryl are unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: chlorine, bromine, fluorine, cyano, methyl, ethyl, and cyclopropyl.

[0133] In another embodiment, Z 1 Selected from C1-C6 alkyl, phenyl, 2,4-difluorophenyl, 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, 3-fluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3,4-difluoro-2-pyridyl, 3,5-difluoro-2-pyridyl, 4-fluoropyridazin-3-yl, 4,5-difluoropyridazin-3-yl, or 5-fluoropyridazin-4-yl; wherein the C1-C6 alkyl is unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: chlorine, fluorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, cyclopropyl, cyclohexyl, phenyl, and 6-membered heteroaryl; wherein the 6-membered heteroaryl contains 1 heteroatom selected from N; and wherein the phenyl and the 6-membered heteroaryl are unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: chlorine, bromine, fluorine, cyano, methyl, ethyl, and cyclopropyl.

[0134] In another preferred embodiment, Z 1Selected from C1-C6 alkyl, phenyl, 2,4-difluorophenyl, 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, 3-fluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3,4-difluoro-2-pyridyl, 3,5-difluoro-2-pyridyl, 4-fluoropyridazin-3-yl, 4,5-difluoropyridazin-3-yl, or 5-fluoropyridazin-4-yl; wherein said C1-C6 alkyl is unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: chlorine, fluorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, cyclopropyl, cyclohexyl, phenyl, 2,4-difluorophenyl, 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, 3-fluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3,4-difluoro-2-pyridyl, 3,5-difluoro-2-pyridyl, 4-fluoropyridazin-3-yl, 4,5-difluoropyridazin-3-yl, and 5-fluoropyridazin-4-yl.

[0135] In one embodiment of the present invention, Z 1Selected from C1-C6 alkyl, phenyl, or 6-membered heteroaryl; wherein the C1-C6 alkyl is unsubstituted or substituted by 1, 2, or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbodiimide, N-hydroxy-C-C1-C4 alkyl-carbodiimide, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxyl, phenyl, 5- to 6-membered saturated or partially saturated heterocycle, 5- to 6-membered heteroaryl, and C3-C6-cycloalkyl; wherein any one of the 6-membered heteroaryl and 5- to 6-membered heteroaryl contains 1, 2, or 3 identical or different heteroatoms selected from N, O, or S, provided that no more than one is O or S; wherein any one of the 5- to 6-membered saturated or partially saturated heterocycles contains 1, 2, or 3 identical or different heteroatoms selected from N, O, or S, provided that no more than one is O or S; wherein any one of the phenyl, any one of the 6-membered heteroaryl, any one of the 5- to 6-membered heteroaryl, and any one of the 5- to 6-membered saturated or partially saturated heterocycles is unsubstituted or substituted by 1, 2, 3, or up to the maximum possible number of identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6-cycloalkyl, and C1-C4 alkoxy; and wherein any one of the C3-C6-cycloalkyl is unsubstituted or substituted by 1, 2, 3, or up to the maximum possible number of identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, and C1-C4 alkoxy.

[0136] Preferably, Z 1 Selected from C1-C6 alkyl, phenyl, or 6-membered heteroaryl; wherein the C1-C6 alkyl is unsubstituted or substituted by 1, 2, or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4 alkyl, C1-C4 haloalkyl, phenyl, 5- to 6-membered heteroaryl, and C3-C6-cycloalkyl; wherein any one of the 6-membered heteroaryl and 5- to 6-membered heteroaryl contains 1 or 2 identical or different heteroatoms selected from N or O; and wherein any one of the phenyl, any one of the 6-membered heteroaryl, and any one of the 5- to 6-membered heteroaryl is unsubstituted or substituted by 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, and C3-C6-cycloalkyl.

[0137] More preferably, Z 1 is selected from C1-C6 alkyl, phenyl, or 6-membered heteroaryl; wherein said C1-C6 alkyl is unsubstituted or substituted with 1, 2, or 3 identical or different substituents selected from the group consisting of: chlorine, fluorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, cyclopropyl, cyclohexyl, phenyl, and 6-membered heteroaryl; wherein any one of said 6-membered heteroaryls contains 1 heteroatom selected from N; and wherein any one of said phenyl and said 6-membered heteroaryl is unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: chlorine, bromine, fluorine, cyano, methyl, ethyl, and cyclopropyl.

[0138] In one embodiment of the present invention, Z 1 is selected from C1-C 6- alkyl; wherein said C1-C6-alkyl is unsubstituted or substituted with 1, 2, or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C2-C4-alkenyloxy, C2-C4-alkynyloxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbodiimide, N-hydroxy-C-C1-C4 alkyl-carbodiimide, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxyl, phenyl, 5- to 6-membered saturated or partially saturated heterocycle, 5- to 6-membered heteroaryl, and C3-C6-cycloalkyl; wherein any one of said 5- to 6-membered heteroaryls contains 1, 2, or 3 identical or different heteroatoms selected from N, O, or S, provided that no more than one is O or S; wherein any one of said 5- to 6-membered saturated or partially saturated heterocycles contains 1, 2, or 3 identical or different heteroatoms selected from N, O, or S, provided that no more than one is O or S; wherein any one of said phenyl, any one of said 5- to 6-membered heteroaryls, and any one of said 5- to 6-membered saturated or partially saturated heterocycles is unsubstituted or substituted with 1, 2, 3, or up to the maximum possible number of identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, and C1-C4 alkoxy; and wherein any one of said C3-C6-cycloalkyl is unsubstituted or substituted with 1, 2, 3, or up to the maximum possible number of identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, and C1-C4 alkoxy.

[0139] Preferably, Z 1 is selected from C1-C6 alkyl; wherein the C1-C6 alkyl is unsubstituted or substituted with 1, 2 or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4 alkyl, C1-C4 haloalkyl, phenyl, 5- to 6-membered heteroaryl and C3-C6-cycloalkyl; wherein any one of the 5- to 6-membered heteroaryls contains 1 or 2 identical or different heteroatoms selected from N or O; and wherein any one of the phenyls and any one of the 5- to 6-membered heteroaryls is unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl and C3-C6-cycloalkyl.

[0140] More preferably, Z 1 is selected from C1-C6 alkyl; wherein the C1-C6 alkyl is unsubstituted or substituted with 1, 2 or 3 identical or different substituents selected from the group consisting of: chlorine, fluorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, cyclopropyl, cyclohexyl, phenyl and 6-membered heteroaryl; wherein any one of the 6-membered heteroaryls contains 1 heteroatom selected from N; and wherein any one of the phenyl and the 6-membered heteroaryl is unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: chlorine, bromine, fluorine, cyano, methyl, ethyl and cyclopropyl.

[0141] Accordingly, the present invention makes it possible to obtain compounds of formula (I) which have Rs in all combinations / each permutation as defined above 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、B 1 、B 2 、W and Z 1 。

[0142] Embodiments according to the present invention are provided, as listed below.

[0143] Preferably, in the compound of formula (I)

[0144] R 1 is methyl;

[0145] R 2 is hydrogen, chlorine, or methyl;

[0146] R 3 is hydrogen;

[0147] R 4is hydrogen, or a methyl group;

[0148] R 5 and R 6 is hydrogen;

[0149] R 7 is hydrogen, a C1-C4 alkyl group, or a C3-C6 cycloalkyl group;

[0150] R 8 is hydrogen, bromine, chlorine, or a cyano group;

[0151] R 9 is hydrogen, bromine, chlorine, a cyano group, a methyl group, or a methoxy group;

[0152] B 1 is N, or CR 10 wherein R 10 is hydrogen, bromine, chlorine, or a cyano group;

[0153] B 2 is N, or CR 11 wherein R 11 is hydrogen, bromine, chlorine, or a cyano group; and

[0154] W and Z 1 are as defined for the compounds of formula (I) according to the present invention.

[0155] Preferably, in the compounds of formula (I)

[0156] R 1 is a methyl group;

[0157] R 2 is hydrogen, chlorine, or a methyl group;

[0158] R 3 is hydrogen;

[0159] R 4 is hydrogen, or a methyl group;

[0160] R 5 and R 6 is hydrogen;

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

[0162] R 8 is hydrogen, bromine, chlorine, or a cyano group;

[0163] R 9 is hydrogen, bromine, chlorine, a cyano group, a methyl group, or a methoxy group;

[0164] B 1 is N, or CR 10 wherein R10 is hydrogen, bromine, chlorine, or cyano;

[0165] B 2 is N, or CR 11 , where R 11 is hydrogen, bromine, chlorine, or cyano;

[0166] W is O, N, *-CH2O- # , *-CH2NH- # , or a bond, where the asterisk (*) indicates the position attached to the carbonyl group, and # indicates the position attached to Z 1 ; and

[0167] Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0168] Preferably, in the compounds of formula (I)

[0169] R 1 is methyl;

[0170] R 2 is hydrogen, chlorine, or methyl;

[0171] R 3 is hydrogen;

[0172] R 4 is hydrogen, or methyl;

[0173] R 5 and R 6 are hydrogen;

[0174] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0175] R 8 is hydrogen, bromine, chlorine, or cyano;

[0176] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0177] B 1 is N, or CR 10 , where R 10 is hydrogen, bromine, chlorine, or cyano;

[0178] B 2 is N, or CR 11 , where R 11 is hydrogen, bromine, chlorine, or cyano;

[0179] W is O, N, *-CH2O- # , *-CH2NH- #、 or *-CH2- # , where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 ; and

[0180] Z 1 is as defined for the compound of formula (I) according to the present invention.

[0181] Preferably, in the compound of formula (I)

[0182] R 1 is methyl;

[0183] R 2 is hydrogen, chlorine, or methyl;

[0184] R 3 is hydrogen;

[0185] R 4 is hydrogen, or methyl;

[0186] R 5 and R 6 are hydrogen;

[0187] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0188] R 8 is hydrogen, bromine, chlorine, or cyano;

[0189] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0190] B 1 is N, or CR 10 , where R 10 is hydrogen, bromine, chlorine, or cyano;

[0191] B 2 is N, or CR 11 , where R 11 is hydrogen, bromine, chlorine, or cyano;

[0192] W is O, N, *-CH2O- # , *-CH2NH- # , *-CH2S- # , or a bond, where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 ; and

[0193] Z 1is a C1-C6 alkyl group, phenyl group, or 5- to 6-membered heteroaryl group; wherein said C1-C6 alkyl group is unsubstituted or substituted with 1, 2, or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4 alkyl group, C1-C4 haloalkyl group, phenyl group, 5- to 6-membered heteroaryl group, and C3-C6 cycloalkyl group; wherein any one of said 5- to 6-membered heteroaryl groups contains 1 or 2 identical or different heteroatoms selected from N or O; and wherein any one of said phenyl groups and any one of said 5- to 6-membered heteroaryl groups are unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano group, C1-C4 alkyl group, and C3-C6 cycloalkyl group.

[0194] Preferably, in the compound having formula (I)

[0195] R 1 is methyl;

[0196] R 2 is hydrogen, chlorine, or methyl;

[0197] R 3 is hydrogen;

[0198] R 4 is hydrogen, or methyl;

[0199] R 5 and R 6 are hydrogen;

[0200] R 7 is hydrogen, C1-C4 alkyl group, or C3-C6 cycloalkyl group;

[0201] R 8 is hydrogen, bromine, chlorine, or cyano group;

[0202] R 9 is hydrogen, bromine, chlorine, cyano group, methyl, or methoxy group;

[0203] B 1 is N, or CR 10 wherein R 10 is hydrogen, bromine, chlorine, or cyano group;

[0204] B 2 is N, or CR 11 wherein R 11 is hydrogen, bromine, chlorine, or cyano group;

[0205] W is O, N, *-CH2O- # 、*-CH2NH- # 、*-CH2S- # 、or a bond, wherein the asterisk (*) represents the position attached to the carbonyl group, and # represents the attachment to Z 1Attached position; and

[0206] Z 1 is selected from C1-C6-alkyl, phenyl, or 6-membered heteroaryl; wherein said C1-C6-alkyl is unsubstituted or substituted with 1, 2 or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4-alkyl, C1-C4-haloalkyl, phenyl, 5- to 6-membered heteroaryl, and C3-C6-cycloalkyl; and wherein any one of said 6-membered heteroaryl and said 5- to 6-membered heteroaryl contains 1 or 2 identical or different heteroatoms selected from N or O, and wherein any one of said phenyl, said 6-membered heteroaryl and said 5- to 6-membered heteroaryl is unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4-alkyl, and C3-C6-cycloalkyl.

[0207] Preferably, in the compound of formula (I)

[0208] R 1 is methyl;

[0209] R 2 is hydrogen, chlorine, or methyl;

[0210] R 3 is hydrogen;

[0211] R 4 is hydrogen, or methyl;

[0212] R 5 and R 6 are hydrogen;

[0213] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0214] R 8 is hydrogen, bromine, chlorine, or cyano;

[0215] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0216] B 1 is N, or CR 10 wherein R 10 is hydrogen, bromine, chlorine, or cyano;

[0217] B 2 is N, or CR 11 wherein R 11 is hydrogen, bromine, chlorine, or cyano;

[0218] W is O, N, *-CH2O- # 、*-CH2NH-# 、 or a key, where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 ; and

[0219] Z 1 is C1-C6 alkyl, phenyl, or 5- to 6-membered heteroaryl; wherein the C1-C6 alkyl is unsubstituted or substituted by 1, 2, or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4 alkyl, C1-C4 haloalkyl, phenyl, 5- to 6-membered heteroaryl, and C3-C6-cycloalkyl; wherein any one of the 5- to 6-membered heteroaryls contains 1 or 2 identical or different heteroatoms selected from N or O; and wherein any one of the phenyls and any one of the 5- to 6-membered heteroaryls is unsubstituted or substituted by 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, and C3-C6-cycloalkyl.

[0220] Preferably, in the compound having formula (I)

[0221] R 1 is methyl;

[0222] R 2 is hydrogen, chlorine, or methyl;

[0223] R 3 is hydrogen;

[0224] R 4 is hydrogen, or methyl;

[0225] R 5 and R 6 are hydrogen;

[0226] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0227] R 8 is hydrogen, bromine, chlorine, or cyano;

[0228] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0229] B 1 is N, or CR 10 , where R 10 is hydrogen, bromine, chlorine, or cyano;

[0230] B 2 is N, or CR 11 , where R 11 is hydrogen, bromine, chlorine, or cyano;

[0231] W is O, N, *-CH2O- # , *-CH2NH- # , or a bond, where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 ; and

[0232] Z 1 is selected from C1-C6-alkyl, phenyl, or 6-membered heteroaryl; wherein the C1-C6-alkyl is unsubstituted or substituted with 1, 2 or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4-alkyl, C1-C4-haloalkyl, phenyl, 5- to 6-membered heteroaryl, and C3-C6-cycloalkyl; and wherein any one of the 6-membered heteroaryl and the 5- to 6-membered heteroaryl contains 1 or 2 identical or different heteroatoms selected from N or O, and wherein any one of the phenyl, the 6-membered heteroaryl and the 5- to 6-membered heteroaryl is unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4-alkyl, and C3-C6-cycloalkyl.

[0233] In one embodiment of the present invention, the compound having formula (I) can be a compound having formula (I-A), wherein R 1 is methyl, R 3 , R 5 , R 6 is hydrogen, and B 1 is CR 10 ; and

[0234]

[0235] wherein R 2 , R 4 , R 7 , R 8 , R 9 , R 10 , R 11 , B 2 , W and Z 1 are as defined for the compound having formula (I) according to the present invention.

[0236] Preferably, in the compound having formula (I-A), B 2 is N; and R 2 , R 4 , R 7 , R 8 , R 9 , R 10 , W and Z 1 are as defined for the compound having formula (I) according to the present invention.

[0237] Preferably, in the compound of formula (I-A), B 2 is CR 11 ; and R 2 、R 4 、R 7 、R 8 、R 9 、R 10 、R 11 、W and Z 1 are as defined for the compound of formula (I) according to the present invention.

[0238] Preferably, in the compound of formula (I-A), W is O, N, *-CH2O- # 、*-CH2NH- # 、*-CH2S- # 、or a bond, where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 ; and R 2 、R 4 、R 7 、R 8 、R 9 、R 10 、R 11 、B 2 and Z 1 are as defined for the compound of formula (I) according to the present invention.

[0239] Preferably, in the compound of formula (I-A), W is O, N, *-CH2O- # 、*-CH2NH- # 、*-CH2S- # 、or *-CH2- # ,where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 ; and R 2 、R 4 、R 7 、R 8 、R 9 、R 10 、R 11 、B 2 and Z 1 are as defined for the compound of formula (I) according to the present invention.

[0240] Preferably, in the compound of formula (I-A), W is O, N, *-CH2O- # 、*-CH2NH- # 、or *-CH2S- #or a bond, where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 attached position; Z 1 is selected from C1-C6-alkyl, phenyl, or 5- to 6-membered heteroaryl; wherein the C1-C6-alkyl is unsubstituted or substituted with 1, 2 or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4-alkyl, C1-C4-haloalkyl, phenyl, 5- to 6-membered heteroaryl, and C3-C6-cycloalkyl; and wherein any one of the 5- to 6-membered heteroaryls contains 1 or 2 identical or different heteroatoms selected from N or O, and wherein any one of the phenyls and any one of the 5- to 6-membered heteroaryls is unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4-alkyl, and C3-C6-cycloalkyl; and R 2 , R 4 、R 7 、R 8 、R 9 、R 10 、R 11 and B 2 are as defined for the compounds of formula (I) according to the present invention.

[0241] Preferably, in the compounds of formula (I-A), W is O, N, *-CH2O- # 、*-CH2NH- # 、or *-CH2S- # 、or a bond, where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 attached position; Z 1 is selected from C1-C6-alkyl, phenyl, or 6-membered heteroaryl; wherein the C1-C6-alkyl is unsubstituted or substituted with 1, 2 or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4-alkyl, C1-C4-haloalkyl, phenyl, 5- to 6-membered heteroaryl, and C3-C6-cycloalkyl; and wherein any one of the 6-membered heteroaryls and any one of the 5- to 6-membered heteroaryls contains 1 or 2 identical or different heteroatoms selected from N or O, and wherein any one of the phenyls, any one of the 6-membered heteroaryls and any one of the 5- to 6-membered heteroaryls is unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4-alkyl, and C3-C6-cycloalkyl; and R 2 、R 4 、R 7 、R 8 、R 9 、R 10 、R 11 and B2 is as defined for a compound of formula (I) according to the present invention.

[0242] Preferably, in a compound of formula (I-A)

[0243] R 2 is hydrogen, chlorine, or methyl;

[0244] R 4 is hydrogen, or methyl;

[0245] R 7 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl;

[0246] R 8 is hydrogen, bromine, chlorine, or cyano;

[0247] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0248] R 10 is hydrogen, bromine, chlorine, or cyano;

[0249] B 2 is N; and

[0250] W and Z 1 are as defined for a compound of formula (I) according to the present invention.

[0251] Preferably, in a compound of formula (I-A)

[0252] R 2 is hydrogen, chlorine, or methyl;

[0253] R 4 is hydrogen, or methyl;

[0254] R 7 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl;

[0255] R 8 is hydrogen, bromine, chlorine, or cyano;

[0256] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0257] R 10 is hydrogen, bromine, chlorine, or cyano;

[0258] B 2 is CR 11 wherein R 11 is hydrogen, bromine, chlorine, or cyano; and

[0259] W and Z 1is as defined for a compound of formula (I) according to the present invention.

[0260] Preferably, in a compound of formula (I-A)

[0261] R 2 is hydrogen, chlorine, or methyl;

[0262] R 4 is hydrogen, or methyl;

[0263] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0264] R 8 is hydrogen, bromine, chlorine, or cyano;

[0265] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0266] R 10 is hydrogen, bromine, chlorine, or cyano;

[0267] B 2 is CR 11 wherein R 11 is hydrogen, bromine, chlorine, or cyano; and

[0268] W is O, N, *-CH2O- # *-CH2NH- # *-CH2S- # or a bond, where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 attached; and

[0269] Z 1 is C1-C6 alkyl, phenyl, or a 5- to 6-membered heteroaryl; wherein the C1-C6 alkyl is unsubstituted or substituted with 1, 2, or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4 alkyl, C1-C4 haloalkyl, phenyl, 5- to 6-membered heteroaryl, and C3-C6-cycloalkyl; wherein any one of the 5- to 6-membered heteroaryls contains 1 or 2 identical or different heteroatoms selected from N or O; and wherein any one of the phenyls and any one of the 5- to 6-membered heteroaryls are unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, and C3-C6-cycloalkyl.

[0270] Preferably, in a compound of formula (I-A)

[0271] R 2 is hydrogen, chlorine, or methyl;

[0272] R 4 is hydrogen, or methyl;

[0273] R 7 is hydrogen, a C1-C4 alkyl group, or a C3-C6-cycloalkyl group;

[0274] R 8 is hydrogen, bromine, chlorine, or cyano;

[0275] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0276] R 10 is hydrogen, bromine, chlorine, or cyano;

[0277] B 2 is CR 11 wherein R 11 is hydrogen, bromine, chlorine, or cyano; and

[0278] W is O, N, *-CH2O- # 、*-CH2NH- # 、*-CH2S- # 、or a bond, where the asterisk (*) indicates the position attached to the carbonyl group, and # indicates the position attached to Z 1 ; and

[0279] Z 1 is a C1-C6 alkyl group, phenyl, or a 6-membered heteroaryl group; wherein the C1-C6 alkyl group is unsubstituted or substituted with 1, 2, or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4 alkyl groups, C1-C4 haloalkyl groups, phenyl, 5- to 6-membered heteroaryl groups, and C3-C6-cycloalkyl groups; wherein any of the 6-membered heteroaryl group and the 5- to 6-membered heteroaryl group contains 1 or 2 identical or different heteroatoms selected from N or O; and wherein any of the phenyl, the 6-membered heteroaryl group, and the 5- to 6-membered heteroaryl group is unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl groups, and C3-C6-cycloalkyl groups.

[0280] Preferably, in the compound having the formula (I-A)

[0281] R 2 is hydrogen, chlorine, or methyl;

[0282] R 4 is hydrogen, or methyl;

[0283] R 7 is hydrogen, a C1-C4 alkyl group, or a C3-C6-cycloalkyl group;

[0284] R8 is hydrogen, bromine, chlorine, or cyano;

[0285] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0286] R 10 is hydrogen, bromine, chlorine, or cyano;

[0287] B 2 is CR 11 wherein R 11 is hydrogen, bromine, chlorine, or cyano; and

[0288] W is O, N, or a bond; and

[0289] Z 1 is as defined for the compounds of formula (I) according to the invention.

[0290] Preferably, in the compounds of formula (I-A)

[0291] R 2 is hydrogen, chlorine, or methyl;

[0292] R 4 is hydrogen, or methyl;

[0293] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0294] R 8 is hydrogen, bromine, chlorine, or cyano;

[0295] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0296] R 10 is hydrogen, bromine, chlorine, or cyano;

[0297] B 2 is CR 11 wherein R 11 is hydrogen, bromine, chlorine, or cyano; and

[0298] W is O, N, or a bond; and

[0299] Z 1is a C1-C6 alkyl group, a phenyl group, or a 5- to 6-membered heteroaryl group; wherein the C1-C6 alkyl group is unsubstituted or substituted with 1, 2, or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4 alkyl, C1-C4 haloalkyl, phenyl, 5- to 6-membered heteroaryl, and C3-C6 cycloalkyl; wherein any one of the 5- to 6-membered heteroaryl groups contains 1 or 2 identical or different heteroatoms selected from N or O; and wherein any one of the phenyl groups and any one of the 5- to 6-membered heteroaryl groups is unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, and C3-C6 cycloalkyl.

[0300] Preferably, in the compound having formula (I-A)

[0301] R 2 is hydrogen, chlorine, or methyl;

[0302] R 4 is hydrogen, or methyl;

[0303] R 7 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl;

[0304] R 8 is hydrogen, bromine, chlorine, or cyano;

[0305] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0306] R 10 is hydrogen, bromine, chlorine, or cyano;

[0307] B 2 is CR 11 wherein R 11 is hydrogen, bromine, chlorine, or cyano; and

[0308] W is O, N, or a bond; and

[0309] Z 1is a C1-C6 alkyl group, phenyl group, or 6-membered heteroaryl group; wherein the C1-C6 alkyl group is unsubstituted or substituted with 1, 2, or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4 alkyl group, C1-C4 haloalkyl group, phenyl group, 5- to 6-membered heteroaryl group, and C3-C6 cycloalkyl group; wherein any one of the 6-membered heteroaryl group and the 5- to 6-membered heteroaryl group contains 1 or 2 identical or different heteroatoms selected from N or O; and wherein any one of the phenyl groups, the 6-membered heteroaryl group, and the 5- to 6-membered heteroaryl group is unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano group, C1-C4 alkyl group, and C3-C6 cycloalkyl group.

[0310] In one embodiment of the present invention, the compound having formula (I-A) can be a compound having formula (I-A1), wherein B 2 is CR 11 ; W is a bond; and

[0311]

[0312] wherein R 2 、R 4 、R 7 、R 8 、R 9 、R 10 、R 11 、W, and Z 1 are as defined for the compound having formula (I) according to the present invention.

[0313] Preferably, in the compound having formula (I-A1)

[0314] R 2 is hydrogen, chlorine, or methyl;

[0315] R 4 is hydrogen, or methyl;

[0316] R 7 is hydrogen, a C1-C4 alkyl group, or a C3-C6 cycloalkyl group;

[0317] R 8 is hydrogen, bromine, chlorine, or cyano group;

[0318] R 9 is hydrogen, bromine, chlorine, cyano group, methyl, or methoxy group;

[0319] R 10 is hydrogen, bromine, chlorine, or cyano group;

[0320] R 11 is hydrogen, bromine, chlorine, or cyano group; and

[0321] Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0322] Preferably, in the compounds of formula (I-A1)

[0323] R 2 is hydrogen, chlorine, or methyl;

[0324] R 4 is hydrogen, or methyl;

[0325] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0326] R 8 is hydrogen, bromine, chlorine, or cyano;

[0327] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0328] R 10 is hydrogen, bromine, chlorine, or cyano;

[0329] R 11 is hydrogen, bromine, chlorine, or cyano; and

[0330] Z 1 is selected from C1-C6 alkyl; wherein the C1-C6 alkyl is unsubstituted or substituted with 1, 2 or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4 alkyl, C1-C4 haloalkyl, phenyl, 5- to 6-membered heteroaryl, and C3-C6-cycloalkyl; wherein the 5- to 6-membered heteroaryl contains 1 or 2 identical or different heteroatoms selected from N or O; and wherein the phenyl and the 5- to 6-membered heteroaryl are unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl and C3-C6-cycloalkyl.

[0331] More preferably, in the compounds of formula (I-A1)

[0332] R 2 is hydrogen, chlorine, or methyl;

[0333] R 4 is hydrogen, or methyl;

[0334] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0335] R 8 is hydrogen, bromine, chlorine, or cyano;

[0336] R9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0337] R 10 is hydrogen, bromine, chlorine, or cyano;

[0338] R 11 is hydrogen, bromine, chlorine, or cyano; and

[0339] Z 1 is selected from C1-C6 alkyl; wherein the C1-C6 alkyl is unsubstituted or substituted with 1, 2 or 3 identical or different substituents selected from the group consisting of: chlorine, fluorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, cyclopropyl, phenyl and 6-membered heteroaryl; wherein the 6-membered heteroaryl contains 1 heteroatom selected from N; and wherein the phenyl and the 6-membered heteroaryl are unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: chlorine, bromine, fluorine, cyano, methyl, ethyl and cyclopropyl.

[0340] In another embodiment of the present invention, the compound having the formula (I-A) may be a compound having the formula (I-A2), wherein B 2 is CR 11 ; W is O; and

[0341]

[0342] wherein R 2 , R 4 , R 7 , R 8 , R 9 , R 10 , R 11 , W and Z 1 are as defined for the compound having the formula (I) according to the present invention.

[0343] Preferably, in the compound having the formula (I-A2)

[0344] R 2 is hydrogen, chlorine, or methyl;

[0345] R 4 is hydrogen, or methyl;

[0346] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0347] R 8 is hydrogen, bromine, chlorine, or cyano;

[0348] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0349] R 10 is hydrogen, bromine, chlorine, or cyano;

[0350] R 11 is hydrogen, bromine, chlorine, or cyano; and

[0351] Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0352] Preferably, in the compounds of formula (I-A2)

[0353] R 2 is hydrogen, chlorine, or methyl;

[0354] R 4 is hydrogen, or methyl;

[0355] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0356] R 8 is hydrogen, bromine, chlorine, or cyano;

[0357] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0358] R 10 is hydrogen, bromine, chlorine, or cyano;

[0359] R 11 is hydrogen, bromine, chlorine, or cyano; and

[0360] Z 1 is selected from C1-C6 alkyl, phenyl, or 5- to 6-membered heteroaryl; wherein the C1-C6 alkyl is unsubstituted or substituted with 1, 2 or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4 alkyl, C1-C4 haloalkyl, phenyl, 5- to 6-membered heteroaryl and C3-C6-cycloalkyl; wherein any of the 5- to 6-membered heteroaryls contains 1 or 2 identical or different heteroatoms selected from N or O; and wherein any of the phenyls, any of the 5- to 6-membered heteroaryls is unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl and C3-C6-cycloalkyl.

[0361] In yet another embodiment of the present invention, the compound of formula (I-A) may be a compound of formula (I-A3), wherein B 2 is CR 11 ; W is N; and

[0362]

[0363] wherein R 2 、R 4 、R 7 、R 8 、R 9 、R 10 、R 11 、W, and Z 1 are as defined for the compounds of formula (I) according to the invention.

[0364] Preferably, in the compounds of formula (I-A3)

[0365] R 2 is hydrogen, chlorine, or methyl;

[0366] R 4 is hydrogen, or methyl;

[0367] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0368] R 8 is hydrogen, bromine, chlorine, or cyano;

[0369] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0370] R 10 is hydrogen, bromine, chlorine, or cyano;

[0371] R 11 is hydrogen, bromine, chlorine, or cyano; and

[0372] Z 1 is as defined for the compounds of formula (I) according to the invention.

[0373] Preferably, in the compounds of formula (I-A3)

[0374] R 2 is hydrogen, chlorine, or methyl;

[0375] R 4 is hydrogen, or methyl;

[0376] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0377] R 8 is hydrogen, bromine, chlorine, or cyano;

[0378] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0379] R10 is hydrogen, bromine, chlorine, or cyano;

[0380] R 11 is hydrogen, bromine, chlorine, or cyano; and

[0381] Z 1 is C1-C6 alkyl, phenyl, or 5- to 6-membered heteroaryl; wherein the C1-C6 alkyl is unsubstituted or substituted with 1, 2, or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4 alkyl, C1-C4 haloalkyl, phenyl, 5- to 6-membered heteroaryl, and C3-C6 cycloalkyl; wherein any of the 5- to 6-membered heteroaryls contains 1 or 2 identical or different heteroatoms selected from N or O; wherein any of the phenyls, any of the 5- to 6-membered heteroaryls is unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, and C3-C6 cycloalkyl.

[0382] In a further embodiment of the invention, the compound having formula (I-A) can be a compound having formula (I-A4), wherein B 2 is CR 11 ; W is *-CH2O- # ; wherein the asterisk (*) represents the position attached to the carbonyl, and # represents the position attached to Z 1 ; and

[0383]

[0384] wherein R 2 , R 4 , R 7 , R 8 , R 9 , R 10 , R 11 , W, and Z 1 are as defined for the compound having formula (I) according to the invention.

[0385] Preferably, in the compound having formula (I-A4)

[0386] R 2 is hydrogen, chlorine, or methyl;

[0387] R 4 is hydrogen, or methyl;

[0388] R 7 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl;

[0389] R 8 is hydrogen, bromine, chlorine, or cyano;

[0390] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0391] R 10 is hydrogen, bromine, chlorine, or cyano;

[0392] R 11 is hydrogen, bromine, chlorine, or cyano; and

[0393] Z 1 is as defined for the compounds of formula (I) according to the invention.

[0394] Preferably, in the compounds of formula (I-A4)

[0395] R 2 is hydrogen, chlorine, or methyl;

[0396] R 4 is hydrogen, or methyl;

[0397] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0398] R 8 is hydrogen, bromine, chlorine, or cyano;

[0399] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0400] R 10 is hydrogen, bromine, chlorine, or cyano;

[0401] R 11 is hydrogen, bromine, chlorine, or cyano; and

[0402] Z 1 is selected from C1-C6 alkyl, phenyl, or 5- to 6-membered heteroaryl; where the C1-C6 alkyl is unsubstituted or substituted with 1, 2 or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4 alkyl, C1-C4 haloalkyl, phenyl, 5- to 6-membered heteroaryl and C3-C6-cycloalkyl; where any of the 5- to 6-membered heteroaryls contains 1 or 2 identical or different heteroatoms selected from N or O; and where any of the phenyls, any of the 5- to 6-membered heteroaryls is unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl and C3-C6-cycloalkyl.

[0403] Preferably, in the compounds of formula (I-A4)

[0404] R 2 is hydrogen, chlorine, or methyl;

[0405] R 4 is hydrogen, or methyl;

[0406] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0407] R 8 is hydrogen, bromine, chlorine, or cyano;

[0408] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0409] R 10 is hydrogen, bromine, chlorine, or cyano;

[0410] R 11 is hydrogen, bromine, chlorine, or cyano; and

[0411] Z 1 is phenyl, or a 5- to 6-membered heteroaryl; wherein the 5- to 6-membered heteroaryl contains 1 or 2 identical or different heteroatoms selected from N or O; and wherein the phenyl and the 5- to 6-membered heteroaryl are unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, and C3-C6-cycloalkyl.

[0412] In a further embodiment of the invention, the compound having formula (I-A) can be a compound having formula (I-A4), wherein B 2 is CR 11 ; W is *-CH2S- # ; wherein the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 ; and

[0413]

[0414] wherein R 2 , R 4 , R 7 , R 8 , R 9 , R 10 , R 11 , W, and Z 1 are as defined for the compound having formula (I) according to the invention.

[0415] Preferably, in the compound having formula (I-A5)

[0416] R 2 is hydrogen, chlorine, or methyl;

[0417] R 4is hydrogen, or methyl;

[0418] R 7 is hydrogen, a C1-C4 alkyl group, or a C3-C6-cycloalkyl group;

[0419] R 8 is hydrogen, bromine, chlorine, or a cyano group;

[0420] R 9 is hydrogen, bromine, chlorine, a cyano group, methyl, or a methoxy group;

[0421] R 10 is hydrogen, bromine, chlorine, or a cyano group;

[0422] R 11 is hydrogen, bromine, chlorine, or a cyano group; and

[0423] Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0424] Preferably, in the compounds of formula (I-A5)

[0425] R 2 is hydrogen, chlorine, or methyl;

[0426] R 4 is hydrogen, or methyl;

[0427] R 7 is hydrogen, a C1-C4 alkyl group, or a C3-C6-cycloalkyl group;

[0428] R 8 is hydrogen, bromine, chlorine, or a cyano group;

[0429] R 9 is hydrogen, bromine, chlorine, a cyano group, methyl, or a methoxy group;

[0430] R 10 is hydrogen, bromine, chlorine, or a cyano group;

[0431] R 11 is hydrogen, bromine, chlorine, or a cyano group; and

[0432] Z 1Selected from C1-C6 alkyl, phenyl, or 5- to 6-membered heteroaryl; wherein said C1-C6 alkyl is unsubstituted or substituted with 1, 2 or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4 alkyl, C1-C4 haloalkyl, phenyl, 5- to 6-membered heteroaryl and C3-C6-cycloalkyl; wherein any one of said 5- to 6-membered heteroaryls contains 1 or 2 identical or different heteroatoms selected from N or O; and wherein any one of said phenyls, any one of said 5- to 6-membered heteroaryls is unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl and C3-C6-cycloalkyl.

[0433] Preferably, in the compound of formula (I-A5)

[0434] R 2 is hydrogen, chlorine, or methyl;

[0435] R 4 is hydrogen, or methyl;

[0436] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0437] R 8 is hydrogen, bromine, chlorine, or cyano;

[0438] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0439] R 10 is hydrogen, bromine, chlorine, or cyano;

[0440] R 11 is hydrogen, bromine, chlorine, or cyano; and

[0441] Z 1 is phenyl, or 5- to 6-membered heteroaryl; wherein said 5- to 6-membered heteroaryl contains 1 or 2 identical or different heteroatoms selected from N or O; and wherein said phenyl and said 5- to 6-membered heteroaryl are unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl and C3-C6-cycloalkyl.

[0442] In a further embodiment of the present invention, the compound of formula (I-A) can be a compound of formula (I-A4), wherein B 2 is CR 11 ; W is *-CH2NH- # ; wherein the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 attached; and

[0443]

[0444] wherein R 2 、R 4 、R 7 、R 8 、R 9 、R 10 、R 11 、W and Z 1 are as defined for the compounds of formula (I) according to the present invention.

[0445] Preferably, in the compounds of formula (I-A6)

[0446] R 2 is hydrogen, chlorine, or methyl;

[0447] R 4 is hydrogen, or methyl;

[0448] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0449] R 8 is hydrogen, bromine, chlorine, or cyano;

[0450] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0451] R 10 is hydrogen, bromine, chlorine, or cyano;

[0452] R 11 is hydrogen, bromine, chlorine, or cyano; and

[0453] Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0454] Preferably, in the compounds of formula (I-A6)

[0455] R 2 is hydrogen, chlorine, or methyl;

[0456] R 4 is hydrogen, or methyl;

[0457] R 7 is hydrogen, C1-C4 alkyl, or C3-C6-cycloalkyl;

[0458] R 8 is hydrogen, bromine, chlorine, or cyano;

[0459] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0460] R 10 is hydrogen, bromine, chlorine, or cyano;

[0461] R 11 is hydrogen, bromine, chlorine, or cyano; and

[0462] Z 1 is selected from C1-C6 alkyl, phenyl, or 5- to 6-membered heteroaryl; wherein the C1-C6 alkyl is unsubstituted or substituted with 1, 2, or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4 alkyl, C1-C4 haloalkyl, phenyl, 5- to 6-membered heteroaryl, and C3-C6 cycloalkyl; wherein any one of the 5- to 6-membered heteroaryls contains 1 or 2 identical or different heteroatoms selected from N or O; and wherein any one of the phenyls and any one of the 5- to 6-membered heteroaryls are unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, and C3-C6 cycloalkyl.

[0463] Preferably, in the compound having formula (I-A6)

[0464] R 2 is hydrogen, chlorine, or methyl;

[0465] R 4 is hydrogen, or methyl;

[0466] R 7 is hydrogen, C1-C4 alkyl, or C3-C6 cycloalkyl;

[0467] R 8 is hydrogen, bromine, chlorine, or cyano;

[0468] R 9 is hydrogen, bromine, chlorine, cyano, methyl, or methoxy;

[0469] R 10 is hydrogen, bromine, chlorine, or cyano;

[0470] R 11 is hydrogen, bromine, chlorine, or cyano; and

[0471] Z 1 is phenyl, or 5- to 6-membered heteroaryl; wherein the 5- to 6-membered heteroaryl contains 1 or 2 identical or different heteroatoms selected from N or O; and wherein the phenyl and the 5- to 6-membered heteroaryl are unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4 alkyl, and C3-C6 cycloalkyl.

[0472] In any one of the compounds according to the invention selected from compounds having formula (I), (I-A), (I-A1), (I-A2), (I-A3), (I-A4), (I-A5), or (I-A6), or selected from the compounds listed in Tables B-1 to B-27 or the compounds listed in Table P (below), the presence of one or more possible asymmetric carbon atoms means that these compounds can exist in chiral isomer forms, i.e., enantiomer or diastereomer forms.

[0473] More preferably, the compounds having formula (I) according to the invention are selected from the compounds listed in any one of Tables B-1 to B-27.

[0474] Even more preferably, the compounds having formula (I) according to the invention are selected from the compounds listed in Table P (below).

[0475] Even still more preferably, the compounds having formula (I) according to the invention are selected from

[0476] 3-(2,4-difluorophenyl)-1-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]propan-1-one,

[0477] ethyl 2-cyclohexylethyl 4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxylate,

[0478] ethyl 2-cyclopropylethyl 4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxylate,

[0479] 1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]heptan-1-one,

[0480] 1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]hexan-1-one,

[0481] 3-(2,4-difluorophenyl)-1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]propan-1-one,

[0482] 1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-3-(4-fluorophenyl)propan-1-one,

[0483] 1-[4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]heptan-1-one,

[0484] 1-[4-(1,5-Dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]decan-1-one,

[0485] 1-[4-(1,5-Dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]octan-1-one,

[0486] 1-[racemic-(1S,4S)-4-(1,5-Dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]heptan-1-one,

[0487] Ethyl 2-cyclohexyl 4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinoline-2-carboxylate,

[0488] 2-(2,4-Difluorophenoxy)-1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]ethanone,

[0489] 2-(2,4-Difluorophenyl)sulfanyl-1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]ethanone,

[0490] 2-[(2,4-Difluorophenyl)methoxy]-1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]ethanone,

[0491] Ethyl 2-cyclohexyl racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxylate,

[0492] 3-Cyclopentyl-1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]propan-1-one,

[0493] 1-[4-(1,5-Dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-5-(dithiolan-3-yl)pentan-1-one,

[0494] 1-[4-(1,5-Dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-5-methyl-hexan-1-one,

[0495] 3-(4-Bromophenyl)-1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]propan-1-one,

[0496] 1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]oct-7-yn-1-one,

[0497] 3-(4-chlorophenyl)-1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]propan-1-one,

[0498] 3-(3,4-dichlorophenyl)-1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]propan-1-one,

[0499] 1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-6,6-difluoro-hex-5-en-1-one,

[0500] Ethyl 2-(4-fluorophenyl) 4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxylate,

[0501] 6,6-difluoro-1-[racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]hex-5-en-1-one,

[0502] 6,6-difluoro-1-[racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]hexan-1-one,

[0503] Racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxylic acid pentyl ester,

[0504] 7,7,7-trifluoro-1-[racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]heptan-1-one,

[0505] 1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-7,7,7-trifluoro-heptan-1-one,

[0506] 4-(1,5-dimethylpyrazol-4-yl)-N-pentyl-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0507] N-(2-cycloheptylethyl)-4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0508] N-(1,3-Benzothiazol-2-yl)-4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0509] N-(5-tert-Butylisoxazol-3-yl)-4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0510] N-(5-Chloro-6-methyl-2-pyridinyl)-4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0511] N-(Cyclohexylmethyl)-4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0512] 4-(1,5-Dimethylpyrazol-4-yl)-N-(m-tolyl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0513] N-(3-Cyclopentylpropyl)-4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0514] N-(3-Cyclopropyl-3-methyl-butyl)-4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0515] N-(4-Chlorophenyl)-4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0516] N-(4-Cyclopropylphenyl)-4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0517] N-(2-Cyclohexylethyl)-4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0518] Racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-N-pentyl-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0519] Racemic-(1S,4S)-N-[(2,4-difluorophenyl)methyl]-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0520] 3-(2,4-difluorophenyl)-1-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]propan-1-one,

[0521] 1-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]-7,7-difluoroheptan-1-one,

[0522] 5-cyclopropyl-1-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]pentan-1-one,

[0523] 5-cyclopropyl-1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]pentan-1-one,

[0524] 4-(1,5-dimethylpyrazol-4-yl)-N-(5-fluoropentyl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0525] N-(5,5-difluoropentyl)-4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0526] (1S,4S)-N-(3-cyclopropylpropyl)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0527] (1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-N-(5-fluoropentyl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0528] (1S,4S)-N-(5,5-difluoropentyl)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0529] 5,5-difluoropentyl 4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxylate, or

[0530] 5-fluoropentyl 4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxylate.

[0531] In a preferred embodiment of the present invention, the compound having formula (I) according to the present invention is selected from:

[0532] 3-(2,4-Difluorophenyl)-1-[4-(1-methyl-1H-pyrazol-4-yl)-3,4-dihydroisoquinolin-2-yl]propan-1-one,

[0533] Ethyl 2-cyclohexyl 4-(1,5-dimethyl-1H-pyrazol-4-yl)-3,4-dihydroisoquinoline-2-carboxylate,

[0534] Ethyl 2-cyclopropyl 4-(1,5-dimethyl-1H-pyrazol-4-yl)-3,4-dihydroisoquinoline-2-carboxylate,

[0535] 1-[4-(1,5-Dimethyl-1H-pyrazol-4-yl)-3,4-dihydroisoquinolin-2-yl]heptan-1-one,

[0536] 1-[4-(1,5-Dimethyl-1H-pyrazol-4-yl)-3,4-dihydroisoquinolin-2-yl]hexan-1-one,

[0537] 3-(2,4-Difluorophenyl)-1-[4-(1,5-dimethyl-1H-pyrazol-4-yl)-3,4-dihydroisoquinolin-2-yl]propan-1-one,

[0538] 1-[4-(1,5-Dimethyl-1H-pyrazol-4-yl)-3,4-dihydroisoquinolin-2-yl]-3-(4-fluorophenyl)propan-1-one,

[0539] 1-[4-Methyl-4-(1-methyl-1H-pyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]heptan-1-one,

[0540] 1-[4-(1,5-Dimethyl-1H-pyrazol-4-yl)-3,4-dihydroisoquinolin-2-yl]decan-1-one,

[0541] 1-[4-(1,5-Dimethyl-1H-pyrazol-4-yl)-3,4-dihydroisoquinolin-2-yl]octan-1-one,

[0542] 1-[rac-(1S,4S)-4-(1,5-Dimethyl-1H-pyrazol-4-yl)-1-methyl-3,4-dihydroisoquinolin-2-yl]heptan-1-one,

[0543] Ethyl 2-cyclohexyl 4-methyl-4-(1-methyl-1H-pyrazol-4-yl)-1,3-dihydroisoquinoline-2-carboxylate,

[0544] 2-(2,4-Difluorophenoxy)-1-[4-(1,5-dimethyl-1H-pyrazol-4-yl)-3,4-dihydroisoquinolin-2-yl]ethanone,

[0545] 2-(2,4-Difluorophenyl)thio-1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]ethanone,

[0546] 2-[(2,4-Difluorophenyl)methoxy]-1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]ethanone,

[0547] (1S,4S)-4-(1,5-Dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxylic acid 2-cyclohexylethyl ester,

[0548] 3-Cyclopentyl-1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]propan-1-one,

[0549] 1-[4-(1,5-Dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-5-(dithiolan-3-yl)pentan-1-one,

[0550] 1-[4-(1,5-Dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-5-methyl-hexan-1-one,

[0551] 3-(4-Bromophenyl)-1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]propan-1-one,

[0552] 1-[4-(1,5-Dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]oct-7-yn-1-one,

[0553] 3-(4-Chlorophenyl)-1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]propan-1-one,

[0554] 3-(3,4-Dichlorophenyl)-1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]propan-1-one,

[0555] 1-[4-(1,5-Dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-6,6-difluoro-hex-5-en-1-one,

[0556] 4-(1,5-Dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxylic acid 2-(4-fluorophenyl)ethyl ester,

[0557] 6,6-Difluoro-1-[racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]hex-5-en-1-one,

[0558] 6,6-Difluoro-1-[racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]hex-1-one,

[0559] Racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxylic acid pentyl ester,

[0560] 7,7,7-Trifluoro-1-[racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]hept-1-one,

[0561] 1-[4-(1,5-Dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]-7,7,7-trifluoro-hept-1-one,

[0562] 4-(1,5-Dimethylpyrazol-4-yl)-N-pentyl-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0563] N-(5-Chloro-6-methyl-2-pyridyl)-4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0564] N-(Cyclohexylmethyl)-4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0565] 4-(1,5-Dimethylpyrazol-4-yl)-N-(m-tolyl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0566] N-(3-Cyclopentylpropyl)-4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0567] N-(3-Cyclopropyl-3-methyl-butyl)-4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0568] N-(4-Chlorophenyl)-4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0569] N-(4-Cyclopropylphenyl)-4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0570] N-(2-Cyclohexylethyl)-4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0571] Racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-N-pentyl-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0572] Racemic-(1S,4S)-N-[(2,4-difluorophenyl)methyl]-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0573] 3-(2,4-Difluorophenyl)-1-[racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-yl]propan-1-one,

[0574] 1-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-yl]-7,7-difluoro-heptan-1-one,

[0575] 5-Cyclopropyl-1-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-yl]pentan-1-one,

[0576] 5-Cyclopropyl-1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-yl]pentan-1-one,

[0577] 4-(1,5-Dimethylpyrazol-4-yl)-N-(5-fluoropentyl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0578] N-(5,5-Difluoropentyl)-4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0579] (1S,4S)-N-(3-Cyclopropylpropyl)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0580] (1S,4S)-4-(1,5-Dimethylpyrazol-4-yl)-N-(5-fluoropentyl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0581] (1S,4S)-N-(5,5-difluoropentyl)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxamide,

[0582] 5,5-difluoropentyl 4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxylate, or

[0583] 5-fluoropentyl 4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxylate.

[0584] The compounds of formula (I) according to the invention can be prepared as shown in Schemes 1 to 20 below, wherein the definition of each variable is as defined above for the compounds of formula (I), unless otherwise specified.

[0585] In particular, the compounds of formula (I) in which R 4 and R 6 are hydrogen and R 5 is hydrogen or methyl can be prepared as shown in Schemes 1 to 7 below, wherein the definition of each variable is as defined above for the compounds of formula (I), unless otherwise specified.

[0586] In any of the following schemes, the presence of one or more possible asymmetric carbon atoms in the compounds of formula (I) according to the invention means that these compounds can exist in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms.

[0587] The compounds of formula (I) can be prepared by those skilled in the art according to known methods. More specifically, the compounds of formula (I) can be prepared from a compound of formula (III) or a salt thereof (wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B 2 are as defined for the compounds of formula (I)) by reaction with a compound of formula (II) (wherein Z 1 and W are as defined for the compounds of formula (I)). This reaction is shown in Scheme 1.

[0588]

[0589] In Scheme 1, the compound of formula (II) (wherein Z 1 is as defined for the compound of formula (I)) is activated to a compound of formula (Iia) by methods known to those skilled in the art and described, for example, in Tetrahedron 2005, 61(46), 10827-10852. For example, a compound of formula (Iia) (wherein X 0 is halogen) is formed by treating the compound of formula (II) with, for example, oxalyl chloride or thionyl chloride in an inert solvent such as dichloromethane (DCM) or tetrahydrofuran (THF) in the presence of a catalytic amount of N,N-dimethylformamide (DMF) at a temperature between 20 °C and 100 °C, preferably at 25 °C. Optionally in the presence of a base (such as triethylamine or pyridine), the compound of formula (Iia) is treated with a compound of formula (III) (wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B 2 are as defined for the compound of formula (I)) to give a compound of formula (I). Alternatively, the compound of formula (I) can be prepared by treating the compound of formula (II) 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 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) to give an activated compound of formula (Iia) (wherein X 0 is G 1 , G 2 or G 3 ) as described in Scheme 1a. Finally, the compound of formula (II) can also be activated by reaction with a coupling reagent (such as propanephosphonic anhydride (T3P)) to provide a compound of formula (Iia) (wherein X 0 is G 4 ) as described, for example, in Synthesis 2013, 45, 1569. Further reaction with an amine (or its salt) of the compound of formula (III) gives a compound of formula (I).

[0590]

[0591] The compound having formula (II) can be prepared from the compound having formula (Iib), where Z 1 is as described in formula (I), W is a bond, and R 0 is C1-C4 alkyl) by ester hydrolysis. Various conditions can be used, such as, for example, aqueous sodium hydroxide or lithium hydroxide and an organic water-miscible solvent like THF or dimethoxyethane or methanol or ethanol. Such ester hydrolysis is well known to those skilled in the art. The compound having formula (Iib) can also be directly converted to the compound having formula (I) by reacting the compound having formula (Iib) with the compound having formula (III) in an inert solvent (such as toluene or DCM) in the presence of trimethylaluminum or a trimethylaluminum-DABCO complex. Such reactions have been reported in the literature (see Tetrahedron Lett. 1977, 4171-4174; Tetrahedron Lett. 2006, 5767-5769 and the references cited therein). The compounds having formula (II) and (Iib) are commercially available.

[0592] More preferably, the compound having formula (I) where W is O, S, or NH (i.e., the compounds having formula (Ia), (Ib), and (Ic) respectively) are prepared as shown in Scheme 1b:

[0593]

[0594] As shown in Scheme 1b, the activated carbonyl compound having formula (IIId) is prepared from the compound having formula (III) by optionally treating with a compound having formula Lg 1 COLg 1 or Lg 1 COLg 2 in the presence of a base (such as pyridine, triethylamine, etc.). Examples of the compounds having formula Lg 1 COLg 1 and Lg 1 (C=O)Lg 2 are, but not limited to, phosgene (COCl2), diphosgene (Cl3CO(CO)Cl), triphosgene (Cl3CO(CO)OCCl3), carbonyldiimidazole (CDI), methyl chloroformate (CH3O(C=O)Cl), etc. This yields the activated carbonyl compound having formula (IIId), where Lg 1 is a leaving group such as halogen, N-imidazole, methoxy, etc., and R 1 、R2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B 2 are as defined for compounds of formula (I). Then the compound of formula (IIId) can optionally be treated with an amine of formula Z 1 -NH2 in the presence of a base in an inert solvent (such as Me-THF, toluene, dichloromethane (DCM), etc.) to give a compound of formula (Ia). Examples of such reactions are well known to those skilled in the art (see, for example, J. Org. Chem. [Journal of Organic Chemistry], 2014, 79(15), 6913 - 6938). The compound of formula (IIId) can be reacted with an alcohol of formula Z 1 -OH, or a thiol of formula Z 1 -SH under similar conditions as above to give compounds of (Ib) and (Ic), respectively. Examples of such reactions in the literature are Angew. Chem. Int. Ed. [Angewandte Chemie International Edition], 2012, 51(17), 4166 - 4170; Eu. J. Med. Chem. [European Journal of Medicinal Chemistry] 2019, 176, 187 - 194; J. Med. Chem. [Journal of Medicinal Chemistry] 2010, 53(5), 2010 - 2037; JP 57032260, 1982.

[0595] The amine (Z 1 -NH2), the alcohol (Z 1 -OH), and the thiol (Z 1 -SH) are generally commercially available.

[0596] The compound of formula (III) wherein R 4 and R 6 are hydrogen, R 5 is hydrogen or methyl and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B 2 are as defined for compounds of formula (I) (i.e., the compound of formula (IIIa)) can be prepared from a compound of formula (Iva) wherein R 4 and R 6 are hydrogen, R 5is hydrogen or methyl and R 1 、R 2 、R 3 、R 7 、R 8 、R 9 、B 1 and B 2 is prepared by treatment in a protic solvent (such as methanol or ethanol etc.) with a reducing agent (such as NaBH3CN) and an acid (such as hydrochloric acid, or acetic acid) as defined for the compounds of formula (I). Such reactions are well-known in the literature and similar reactions have been described, for example, in Deng, Zeping et al., CN 103772278 and Synthesis [Synthesis] 1979, 4, 281 - 283. Alternatively, the compounds of formula (IIIa) can be prepared by reduction of the compounds of formula (Iva) with hydrogen in the presence of a suitable metal catalyst (such as Pd, Ir, Rh) and a suitable ligand (such as diphosphine [1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp) or 1,4-bis(diphenylphosphino)butane (dppb)]). Similar reactions have been reported, for example, in React. Kinet. Cat. Lett. [Reaction Kinetics and Catalysis Letters] 2007, 92, 99 - 104. This reaction is shown in Scheme 2.

[0597]

[0598] As shown in Scheme 3, by methods known to those skilled in the art and by those methods described in Scheme 1, by treating a compound of formula (IIIb) (wherein R 0 is a leaving group, such as a halogen, and R 0 is a C1 - C6 alkyl) with a compound of formula (VI), a compound of formula (IIIb) (wherein R 4 、R 6 and R 7 are hydrogen, R 5 is hydrogen or methyl and R 1 、R 2 、R 3 、R 8 、R 9 、B 1 and B 2 is as defined for the compounds of formula (I)) can be converted into a compound of formula (V) (wherein R 4 、R 6 and R 7 are hydrogen, R 5 is hydrogen or methyl and R 1 、R2 , R 3 , R 8 , R 9 , B 1 and B 2 is as defined for compounds of formula (I)). Alternatively, a compound of formula (V) can be prepared by treating, in an inert solvent (such as DCM, THF or 2-methyl-THF), optionally in the presence of a base (such as triethylamine or dimethylaminopyridine), at a temperature between 0 °C and 60 °C, with an acid anhydride of formula (R 0 CO)2O, wherein R 0 is C1-C6 alkyl). Then, at low temperature (e.g., -78 °C) to room temperature, in an inert polar solvent (such as THF or 2-methyl-THF), the compound of formula (V) is metallated with a base (such as an alkylmetal base, such as tert-butyllithium) and an additive (such as N,N,N',N'-tetramethylethylenediamine (TMEDA)). Subsequently, the anion of formula (V) formed under such conditions is treated with an electrophile of formula R 7 -X 0 , wherein X 0 is as previously defined, and R 7 is C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4 alkylaminocarbonyl, di(C1-C4 alkylamino)carbonyl, or C3-C6 cycloalkyl, wherein the C3-C6-cycloalkyl is optionally substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy), to yield a compound of formula (Va), wherein R 4 and R 6 are hydrogen, R 5 is hydrogen or methyl, R 0 is C1-C6 alkyl and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B 2 is as defined for compounds of formula (I)). This reaction is shown in Scheme 3.

[0599]

[0600] The compound of formula (Va) can be converted to a compound of formula (IIIa) (wherein R 4 and R 6 are hydrogen, R5 is hydrogen or methyl and R 1 、R 2 、R 3 、R 7 、R 8 、R 9 、B 1 and B 2 are as defined for the compounds of formula (I). For example, a compound of formula (Va) in which R 0 is tert-butyl) can be treated with an organic or inorganic acid (such as trifluoroacetic acid or HCl) to give a compound of formula (IIIa). This reaction is shown in Scheme 4.

[0601]

[0602] A compound of formula (Iva) in which R 4 and R 6 are hydrogen, R 5 is hydrogen or methyl and R 1 、R 2 、R 3 、R 7 、R 8 、R 9 、B 1 and B 2 are as defined for the compounds of formula (I) can be prepared by reacting a compound of formula (VIII) in which R 1 、R 2 and R 3 are as defined for the compounds of formula (I), and X 0 is a halogen, preferably chlorine, bromine or iodine) with a compound of formula (VII) in which R 5 is hydrogen or methyl and R 7 、R 8 、R 9 、B 1 and B 2 are as defined for the compounds of formula (I) typically under palladium-catalyzed (alternatively nickel-catalyzed) cross-coupling conditions by means of a C-C bond forming reaction. This reaction is shown in Scheme 5.

[0603]

[0604] The Suzuki-Miyaura cross-coupling reaction between a compound of formula (VIII) and a compound of formula (VII) is well known to those skilled in the art and is generally carried out in the presence of a palladium catalyst (such as tetrakis(triphenylphosphine)palladium(0) or [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex) and a base (such as sodium carbonate or potassium carbonate) in a solvent (such as N,N-dimethylformamide, dioxane or a dioxane-water mixture) at a temperature between room temperature and 160 °C, optionally under microwave heating conditions, and preferably under an inert atmosphere. Such reactions have been reviewed, for example, in J. Organomet. Chem. 1999, 576, 147-168. Those skilled in the art will also recognize that the reaction can be reversed, i.e., by reacting a compound of formula (X) (wherein R 1 , R 2 and R 3 are as defined for the compound of formula (I)) with a compound of formula (IX) (wherein R 5 is hydrogen or methyl, R 7 , R 8 , R 9 , B 1 and B 2 are as defined for the compound of formula (I), and X 0 is a halogen, preferably chlorine, bromine or iodine) to provide a compound of formula (Iva) (wherein R 4 and R 6 are hydrogen, R 5 is hydrogen or methyl and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B 2 are as defined for the compound of formula (I)). This reaction is shown in Scheme 6.

[0605]

[0606] Additional cross-coupling chemistries (i.e., C-H activation) can also be used to prepare a compound of formula (Iva) (wherein R 4 and R 6 are hydrogen, R 5 is hydrogen or methyl and R 1 , R 2 , R 3 , R 7 , R 8 , R 9, B 1 and B 2 is as defined for the compounds of formula (I) (Scheme 7).

[0607]

[0608] As shown in Scheme 7, a compound of formula (IX) wherein R 5 is hydrogen or methyl, R 7 , R 8 , R 9 , B 1 and B 2 is as defined for the compounds of formula (I), and X 0 is halogen, preferably chlorine, bromine or iodine) is reacted with a compound of formula (XI) wherein R 1 , R 2 and R 3 is as defined for the compounds of formula (I)) in the presence of a palladium catalyst (typically palladium acetate Pd(OAc)₂), a suitable ligand (such as 1,10-phenanthroline), in the presence of a base (such as cesium carbonate or potassium carbonate), in an inert solvent (such as chlorobenzene, toluene or xylene), at a temperature between room temperature and 180 °C, optionally under microwave heating conditions, preferably under an inert atmosphere. Similar reactions have been reported in the literature, for example in Chem. Sci. [Chemical Science] 2013, 4, 2374 - 2379.

[0609] In addition, the compound of formula (III) can be prepared from the compound of formula (XVI) (Scheme 8).

[0610]

[0611] As shown in Scheme 8, the compound of formula (III) can be prepared by a person skilled in the art from a compound of formula (XVI) wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B 2 is as defined for the compounds of formula (I), and R 01 can be a member of common carbamate protecting group substituents, such as methyl, tert-butyl, allyl, 2,2,2-trichloroethyl or benzyl) by a carbamate deprotection reaction. For example, when R 01When R is methyl, a suitable solvent (such as DCM) and a suitable reagent (such as trimethylsilyl iodide) can be used to obtain the product by heating at a temperature between room temperature and 200 °C, preferably between 20 °C and the boiling point of the reaction mixture, as described, for example, in J. Am. Chem. Soc. 1992, 114, 5959. The compound of formula (III) thus obtained is converted to a compound of formula (I) (Scheme 1).

[0612] A compound of formula (XVI) in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B 2 are as defined for the compound of formula (I) and in which R 01 is as described above) can be formed by reacting an aldehyde of formula (XV) (including formaldehyde in its different forms) in which R 7 is as defined for the compound of formula (I) with a compound of formula (XIV) in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , B 1 and B 2 are as defined for the compound of formula (I) and in which R 01 is as described above) by a Pictet - Spengler reaction in a suitable solvent in combination with an acid, as described, for example, in Tetrahedron 1987, 43, 439 (Scheme 9).

[0613]

[0614] A compound of formula (XIV) in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , B 1 and B2 is as defined for the compounds of formula (I) and wherein R 01 is as described above) can be prepared by reacting an amine of formula (XIII) wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , B 1 and B 2 is as defined for the compounds of formula (I)) with a suitable protecting reagent such as methyl chloroformate, optionally in the presence of a base such as triethylamine or pyridine, in a suitable solvent such as DCM, at a temperature between -20 °C and the boiling point of the mixture, as described, for example, in Org. Biomol. Chem. [Organic & Biomolecular Chemistry] 2016, 14, 6853. This reaction is shown in Scheme 10.

[0615]

[0616] A compound of formula (XIII) or a salt thereof, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , B 1 and B 2 is as defined for the compounds of formula (I)) can be prepared by those skilled in the art by reacting a nitrile of formula (XII) wherein R 1 , R 2 , R 3 , R 4 , R 8 , R 9 , B 1 and B 2 is as defined for the compounds of formula (I)) with a suitable nucleophile such as (dimethylsulfide)dihydroboron (BMS) in a suitable aprotic solvent such as THF, for example as described in J. Org Chem. [Journal of Organic Chemistry] 1981, 47, 3153. Alternatively, a Grignard reagent R 5 MgBr or R 6 MgBr wherein R 5 and R 6(as defined for compounds of formula (I)) can be added, either sequentially or simultaneously, as a nucleophile to a compound of formula (XII) to allow the preparation of a more highly substituted amine of formula (XIII). Such a Grignard addition to a nitrile is carried out in an inert solvent (such as diethyl ether, tert-butyl methyl ether, and cyclopentyl methyl ether) in the presence of a Lewis acid (such as Ti(O- i Pr)4) (see Synlett [Synthesis Letters] 2007, (4), 652 - 654). This reaction is shown in Scheme 11.

[0617]

[0618] Alternatively, a compound of formula (XIII) in which R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 8 、R 9 、B 1 and B 2 are as defined for compounds of formula (I), and in which R 5 、R 6 are hydrogen) (i.e., a compound of formula (XIIIa)) can be prepared by one skilled in the art by reacting an unsaturated nitro compound of formula (XIIIb) in which R 1 、R 2 、R 3 、R 4 、R 8 、R 9 、B 1 and B 2 are as defined for compounds of formula (I)) with a compound of formula (VIII) in which R 1 、R 2 and R 3 are as defined for compounds of formula (I), and X 0 is a halogen, preferably iodine), and then reacting the compound of formula (XIIIb) in which R 1 、R 2 、R 3 、R 4 、R 8 、R 9 、B 1 and B 2Subsequent reduction to a compound of formula (XIIIa) (as defined for the compounds of formula (I)) is described in the Preparation section under Example P1 Step 8 (Option B - Steps A and B). This reaction is shown in Scheme 12.

[0619]

[0620] A compound of formula (XII) wherein R 1 , R 2 , R 3 , R 4 , R 8 , R 9 , B 1 and B 2 are as defined for the compounds of formula (I)) can be prepared by those skilled in the art according to known methods. More specifically, the compounds of formula (XII) and their intermediates can be prepared from compounds of formula (XVII) as shown in Scheme 13.

[0621]

[0622] For example, a compound of formula (XII) wherein R 1 , R 2 , R 3 , R 8 , R 9 , B 1 and B 2 are as defined for the compounds of formula (I), and R 4 is not hydrogen) can be prepared by those skilled in the art by deprotonating a compound of formula (XIIa) wherein R 4 -X (wherein R 4 is C1-C4 alkyl and X is a halogen) (such as methyl iodide) with a strong base (such as n-butyllithium or sodium hydride) in an inert solvent (such as THF) at cryogenic temperatures, followed by addition of a suitable alkylating agent R 1 , R 2 , R 3 , R 8 , R 9 , B 1 and B 2 are as defined for the compounds of formula (I)).

[0623] A compound of formula (XIIa) wherein R 1 , R 2 , R 3 , R 8 , R 9 , B 1 and B2 (as defined for compounds of formula (I)) can be prepared by treating an alcohol of formula (XVII) with trimethylsilyl cyanide (TMSCN) in the presence of a base (such as lithium carbonate) in a non-polar solvent (such as DCM) at a temperature between 0 °C and the boiling point of the reaction mixture. Such transformations are well known in the literature under various conditions, for example as described in Org. Lett. [Organic Letters] 2008, 10, 4570 and references therein. This reaction is shown in Scheme 15.

[0624] A compound of formula (III) wherein B 1 is CR 10 and B 2 is CR 11 and R 1a is C1-C4 alkyl, R 2a is hydrogen, halogen, or C1-C4 alkyl, R 3 is hydrogen, R 4a , R 5a , R 6a , R 7a is hydrogen or C1-C4 alkyl, and R 8 , R 9 , R 10 and R 11 is as defined for compounds of formula (I)) (i.e., a compound of formula (IIIc)) is described below.

[0625]

[0626] A compound of formula (IIIc) can also be prepared by treating a compound of formula (XVIII) with a strong acid (such as sulfuric acid, hydrochloric acid, hydrobromic acid, trifluoroacetic acid, trifluoromethanesulfonic acid (trifllic), or methanesulfonic acid, etc.) or a Lewis acid (such as aluminum trichloride, or bismuth(III) trifluoromethanesulfonate) in an inert solvent (such as chlorobenzene, nitrobenzene) at a temperature between 0 °C and 180 °C

[0627]

[0628] (wherein R 1 is C1-C4 alkyl, R 2 is hydrogen, halogen, or C1-C4 alkyl, R 3 is hydrogen, R 4 is hydrogen or C1-C4 alkyl, R 5 , R 6 , R 7 is hydrogen or C1-C4 alkyl, and R 8 , R 9 , R10 and R 11 is as previously defined) to produce a compound having formula (IIIc). As described previously, these compounds are converted to compounds having formula (I). Those skilled in the art will recognize that such cyclization can proceed through intermediates such as: compounds having formula (XIX),

[0629]

[0630] and (when R 4 is methyl), compounds having formula (XX)

[0631]

[0632] and wherein the substituents R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、and R 11 are as defined for compounds having formula (I). Depending on the reaction conditions, these intermediates can be isolated and / or further directly converted to compounds having formula (IIIc). Those skilled in the art will also recognize that when R 7 is C1-C4 alkyl, a mixture of diastereomeric racemates - (cis-IIIc) and racemic - (trans-IIIc) can be obtained, and the ratio thereof can be controlled to direct the preferential formation of one isomer over the other (Scheme 14).

[0633]

[0634] Intermediates (XVIII), (XIX) and (XX) are novel and thus form part of the present invention.

[0635] Compounds (XVIII), (XIX) and (XX) can be prepared as shown in Scheme 15 below and as described in the experimental section.

[0636]

[0637] As shown in Scheme 15, in the presence of a base (such as Et3N), in an inert solvent (such as DMF), a compound of formula (XXII) is alkylated with a benzylamine of formula (XXI). The thus obtained compound (XXIII) can be isolated or directly treated in situ with BOC-anhydride to give a compound of formula (XXIV). The compound of formula (XXIV) can be reduced with a hydride source (such as NaBH4 in MeOH / THF) to give the target molecule (XVIIIb), which can then be cyclized with, for example, camphorsulfonic acid in EtOAc to give a compound of formula (XIXb). Alternatively, the compound of formula (XXIV) can be reacted with a Grignard reagent R 4 MgBr in an inert ethereal solvent (such as THF) to give a compound of formula (XVIIIa), which can be cyclized with camphorsulfonic acid in, for example, EtOAc to give a compound of formula (XIXa). In compounds (XIX) and (XVIII), R 1a is a C1-C4 alkyl group, R 2a is hydrogen, halogen, or a C1-C4 alkyl group, R 4a is hydrogen or a C1-C4 alkyl group, R 5a 、R 6a 、and R 7a are hydrogen or a C1-C4 alkyl group, and R 8 、R 9 、R 10 、and R 11 are as defined for the compound of formula (I).

[0638] It should be noted that there are additional aspects to this Friedel-Crafts chemical reaction. If the chemical reaction starts with a chiral amine (XXIa) (i.e., R 7 is a C1-C4 alkyl group), the final compound of formula (I) will retain its stereochemistry. This is shown in Scheme 16 below, for when R 7 is methyl:

[0639]

[0640] The compound of formula (XVII) can be prepared by methods known to those skilled in the art. The compounds of formula (XXI) and (XXII) are readily prepared by those skilled in the art or can be purchased.

[0641] Alternative methods for preparing the compound of formula (I) involve late-stage functionalization of advanced intermediates. This is shown in Schemes 17 and 18.

[0642]

[0643] As shown in Scheme 17, the compound of formula (III) can be converted to a compound of formula (IIIe) by acylation with a compound of formula (XXVI) (wherein X 0 is a leaving group, such as a halogen) by methods known to those skilled in the art and described above. The compound of formula (IIIe) can then be reacted with an amine (Z 1 -NH2), an alcohol (Z 1 -OH), or a thiol (Z 1 -SH), optionally in the presence of a base, to give respectively compounds of formula (Id), (Ie), and (If), and wherein Z 1 and W are as described under formula (I). Such nucleophilic displacement reactions with nucleophiles at the Sp 3 carbon are well known to those skilled in the art. Examples and conditions are described in the Preparation Examples.

[0644] Another example of such late-stage functionalization is shown in Scheme 18:

[0645]

[0646] As shown in Scheme 18, acylation of the compound of formula (III) with a compound of formula (XXVII) (wherein X 0 is a leaving group, such as a halogen, preferably Cl) is carried out by methods known to those skilled in the art and already described in Scheme 1. The resulting compound of formula (IIIf) can then be processed with a heteroatom or carbon nucleophile, where R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、B 1 and B 2 are as defined for the compound of formula (I). For example, optionally in the presence of a base, with a compound of formula Z 1Treatment of a compound of -NH2 with a compound of formula (IIId) gives a compound of formula (Ig). Examples of such reactions have been described, for example, in J. Polym. Sci. Part A: Pol. Chem. 2012, 50(23), 4947 - 4957. Nucleophilic catalysis generally also favors such Michael addition reactions, as discussed for nitrogen nucleophiles used with acrylamide catalyzed by imidazolium chloride (see Molecules 2019, 24(23), 4224). A compound of formula (III) can be reacted with a compound of formula Z 1 -OH and Z 1 -SH to give compounds of formula (Ih) and (Ii), respectively. Such Michael addition reactions of alcohols and thiols are known in the literature, for example, see Polym, Chem. 2018, 9(38), 4716 - 4723 (alcohol Michael addition); Org. Biomol. Chem. 2020, 18, 6364 - 6377 (thiol Michael addition). There are a variety of methods known to those skilled in the art that can be used for Michael addition with carbon nucleophiles to α,β-unsaturated carbonyl derivatives (giving compounds of formula (Ij)). These have been reviewed in Tetrahedron Organic Chemistry Series, Conjugate Addition Reactions in Organic Synthesis, Elsevier, 1992, Volume 9, pages 1 - 61. Michael reaction addition of boronic acid derivatives using a catalyst system such as 2.5 mol% [RhCl(C2H4)2]2 / (±)-BINAP (5 mol%) in the presence of K3PO4 base in an inert solvent such as dioxane at a temperature between 50 °C and 100 °C to α,β-unsaturated carbonyl compounds is also known. Such reactions are also described in the literature, for example, in Adv. Synth. Catal. 2013, 355, 1874 - 1880.

[0647] Salts of the compounds of formula (I) can be prepared in a manner known per se. Thus, for example, acid addition salts of the compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchange reagent, and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchange reagent.

[0648] Salts of the compounds of formula (I) can be converted in a conventional manner into the free compounds (I), into acid addition salts (e.g. by treatment with a suitable basic compound or with a suitable ion-exchange reagent), and into salts with bases (e.g. by treatment with a suitable acid or with a suitable ion-exchange reagent).

[0649] Salts of the compounds of formula (I) can be converted in a manner known per se into other salts of the compounds of formula (I), into acid addition salts, e.g. into other acid addition salts, e.g. by treatment of a salt of an inorganic acid (such as a hydrochloride) with a suitable metal salt of an acid (such as a salt of sodium, barium or silver, e.g. silver acetate) in a suitable solvent in which the inorganic salt formed (e.g. silver chloride) is insoluble and thus precipitates from the reaction mixture.

[0650] Depending on the procedure or reaction conditions, the compounds of formula (I) having salt-forming properties can be obtained in free form or in the form of salts.

[0651] The compounds of formula (I) and, where appropriate, their tautomers (in each case in free form or in salt form) can be present in the form of one of the possible isomers or in the form of a mixture of these isomers, e.g. in the form of pure isomers (such as enantiomers and / or diastereoisomers) or in the form of an isomer mixture (such as a mixture of enantiomers, e.g. a racemate; or a mixture of diastereoisomers), depending on the number of asymmetric carbon atoms present in the molecule, the absolute and relative configuration and / or depending on the configuration of the non-aromatic double bonds present in the molecule; the invention relates to the pure isomers as well as to all possible mixtures of isomers, and in each case in the context, even in each case where no stereochemical details are specifically mentioned, this should be understood in this sense.

[0652] Mixtures of diastereoisomers or racemates of the compounds of formula (I) in free form or in salt form (the obtaining of which can depend on the starting materials and the procedure chosen) can be separated in a known manner into the pure diastereoisomers or racemates on the basis of the physicochemical differences of these constituents, e.g. by fractional crystallization, distillation and / or chromatography.

[0653] Racemic mixtures (such as racemates) that can be obtained in a similar manner can be resolved into the optical enantiomers by known methods, for example by recrystallization from an optically active solvent; by chromatography on a chiral adsorbent, for example high performance liquid chromatography (HPLC) on acetylcellulose; by cleavage with a specific immobilized enzyme with the aid of a suitable microorganism; via the formation of inclusion compounds, for example using a chiral crown ether in which only one enantiomer is complexed; or by conversion into 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), and separating the resulting diastereomeric mixture, for example by fractional crystallization based on their different solubilities, to give diastereomers, from which the desired enantiomer can be liberated by the action of a suitable reagent (such as a basic reagent).

[0654] The pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable mixtures of isomers, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention with starting materials having the appropriate stereochemistry.

[0655] If the individual components have different biological activities, it is advantageous in each case to separate or synthesize the biologically more effective isomers, such as enantiomers or diastereomers or mixtures of isomers, such as mixtures of enantiomers or mixtures of diastereomers.

[0656] As an example, a compound having more than one asymmetric carbon atom can exist in diastereomeric forms, which can optionally be separated by chromatography, such as supercritical fluid chromatography (SFC) with a chiral column. Such diastereomers can exhibit different fungicidal activity profiles, but all isomers and diastereomers form part of the invention.

[0657] The compounds of formula (I) have at least three chiral carbon atoms (three stereocenters, where the asterisk (*) indicates a chiral carbon atom), such that at least eight stereoisomers are available. These at least eight stereoisomers consist of four pairs of enantiomers.

[0658]

[0659] For the compounds of formula (I), where R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R8 , R 9 , B 1 , B 2 , W and Z 1 is as defined for compounds of formula (I), and wherein R 7 is not hydrogen, and the relationship between enantiomers and diastereoisomers is shown in Scheme 21.

[0660]

[0661] Those skilled in the art are well aware of these diastereoisomers and enantiomers of formula (I) (as shown in Scheme 21) (wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 , B 2 , W and Z 1 is as defined for formula (I), and wherein R 7 is not hydrogen) are within the scope of the present invention.

[0662] For compounds of formula (I), wherein R 1 is methyl, R 3 , R 4 , R 5 , R 6 is hydrogen and R 2 , R 7 , R 8 , R 9 , B 1 , B 2 , W and Z 1 is as defined for compounds of formula (I), and wherein R 7 is not hydrogen, and the relationship between enantiomers and diastereoisomers is shown in Scheme 22.

[0663]

[0664] In one embodiment, a compound of formula (I) (wherein R 1 is methyl, R 3 , R 4 , R 5 , R 6 is hydrogen and R 2 , R 7 , R 8 , R 9, B 1 , B 2 , W and Z 1 is as defined for the compounds of formula (I), and wherein R 7 is not hydrogen), the pyrazole - moiety and R 7 have a cis - relationship to each other.

[0665] The compound of formula (I) (R 1 is methyl, R 3 , R 4 , R 5 , R 6 are hydrogen and R 2 , R 7 , R 8 , R 9 , B 1 , B 2 , W and Z 1 is as defined for the compounds of formula (I), and wherein R 7 is not hydrogen) cis - isomer is shown in Scheme 23.

[0666]

[0667] Preferably, the compound of formula (I) (wherein R 1 is methyl, R 3 , R 4 , R 5 , R 6 are hydrogen and R 2 , R 7 , R 8 , R 9 , B 1 , B 2 , W and Z 1 is as defined for the compounds of formula (I), and wherein R 7 is not hydrogen), the pyrazole - moiety and R 7 have a cis - relationship to each other, as shown in Scheme 23.

[0668] The compound of formula (I) and, where appropriate, its tautomers (in each case in free form or in salt form) can, if appropriate, also be obtained in the form of hydrates and / or include other solvents, such as those which can be used to crystallize the compounds present in solid form.

[0669] As has been indicated, surprisingly, it has now been found that, for practical purposes, the compounds of formula (I) according to the invention have a very advantageous level of biological activity for protecting plants against diseases caused by fungi.

[0670] The compounds of formula (I) according to the invention can be used in the agricultural sector and related fields of use, for example, as active ingredients for controlling phytopathogens, or on inanimate materials for controlling spoilage microorganisms or organisms potentially harmful to humans. These novel compounds are characterized by excellent activity at low application rates, good plant tolerance, and environmental safety. They have very useful therapeutic, prophylactic, and systemic properties and can be used to protect many cultivated plants. The compounds of formula (I) can be used to inhibit or destroy pests that appear on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of different useful plant crops, while also protecting those later-growing plant parts from, for example, infestation by phytopathogenic microorganisms.

[0671] The invention further relates to a method for controlling or preventing the infestation of plants or plant propagation materials and / or harvested food crops susceptible to microbial attack by treating the plants or plant propagation materials and / or harvested food crops, wherein an effective amount of a compound of formula (I) according to the invention is applied to the plants, their parts, or their sites.

[0672] It is also possible to use the compounds of formula (I) according to the invention as fungicides. As used herein, the term "fungicide" means a compound that controls, modifies, or prevents the growth of fungi. The term "fungicidally effective amount" when used means the amount of such a compound or combination of such compounds that is capable of having an effect on fungal growth. The effects of control or modification include all deviations from natural development, such as killing, retardation, etc., and prevention includes forming a barrier or other defense within or on the plant to prevent fungal infestation.

[0673] It is also possible to use the compounds of formula (I) according to the invention as seed dressings for treating plant propagation materials (e.g., seeds, if fruits, tubers, or grains) or plant cuttings to protect them from fungal infections and from phytopathogenic fungi present in the soil. The propagation materials can be treated with a composition comprising a compound of formula (I) before planting: for example, the seeds can be dressed before sowing. The active compound of formula (I) can also be applied to the grains (coating) by impregnating the seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the planting site when planting the propagation materials, for example, applied to the furrows of the seeds during sowing. The invention also relates to such methods of treating plant propagation materials and to plant propagation materials so treated.

[0674] In addition, the compounds of formula (I) according to the invention can be used to control fungi in related fields, for example, in the protection of industrial materials (including wood and wood-related technical products), in food storage, and in hygiene management.

[0675] In addition, the present invention can also be used to protect non-living materials (such as wood, wall panels, and coatings) from fungal attack.

[0676] Compounds having formula (I) according to the present invention are effective, for example, against fungal and fungal vectors of diseases and phytopathogenic bacteria and viruses. Such fungal and fungal vectors of diseases and phytopathogenic bacteria and viruses are, for example: Apophysomyces elegans, Alternaria species, Aphanomyces species, Ascochyta species, Aspergillus species (including Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans, Aspergillus niger, Aspergillus terreus), Aureobasidium species (including Aureobasidium pullulans), Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria species (including Botryosphaeria dothidea, Botryosphaeria obtusa), Botrytis species (including Botrytis cinerea), Candida species (including Candida albicans, Candida glabrata, Candida krusei, Candida lusitaniae, Candida parapsilosis, Candida tropicalis), Cephaloascus fragrans, Ceratocystis species, Cercospora species (including Cercospora arachidicola), Cercosporidium personatum, Cladosporium species, Claviceps purpurea, Coccidioides immitis, Cochliobolus species, Colletotrichum species (including Colletotrichum musae), Cryptococcus neoformans, Diaporthe species, Didymella species, Drechslera species, Elsinoë species, Epidermophyton species, Erwinia amylovora, Erysiphe species (including Erysiphe cichoracearum), Eutypa lata, Fusarium species (including Fusarium culmorum, Fusarium graminearum, Fusarium langsethiae, Fusarium moniliforme, Fusarium oxysporum, Fusarium solani, Fusarium verticillioides), Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulata, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium species, Hemileia species, Histoplasma species (including Histoplasma capsulatumcapsulatum)), red thread fungus, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum species, Monilinia species, Mucor species, Mycosphaerella species (including Mycosphaerella graminicola, M. pomi), twig blight fungus, spruce pathogen, Paracoccidioides species, Penicillium species (including Penicillium digitatum, Penicillium italicum), Myrothecium species, Peronosclerospora species (including Peronosclerospora maydis, Peronosclerospora philippinensis, Peronosclerospora sorghi), Peronospora species, Septoria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Sepedonium species, Phoma species, Phomopsis viticola, Phytophthora species (including Phytophthora infestans), Plasmopara species (including Plasmopara halstedii, Plasmopara viticola), Pleospora species, Podosphaera species (including Podosphaera leucotricha), Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas species, Pseudoperonospora species (including Pseudoperonospora cubensis, Pseudoperonospora humuli), Pseudopeziza tracheiphila, Puccinia species (including Puccinia hordei, Puccinia recondita, Puccinia striiformis, Puccinia triticina), Sclerotinia species, Pyrenophora species, Pyricularia species (including Pyricularia oryzae), Pythium species (including Pythium ultimum), Ramularia species, Rhizoctonia species, Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium species, Stilbella species (including Scedosporium apiospermum, Scedosporium prolificans), Schizothyrium pomi, Sclerotinia species, Sclerotium species, Septoria species (including Septoria nodorum, Septoria triticiPuccinia tritici, Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea on cucurbits), Sporothorix species, Stagonosporanodorum, Stemphylium species, Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia species, Trichoderma species (including Trichoderma harzianum, Trichoderma pseudokoningii, Trichoderma viride), Trichophyton species, Typhula species, Uncinula necator, Urocystis species, Ustilago species, Venturia species (including Venturia inaequalis), Verticillium species, and Xanthomonas species.

[0677] The compounds of formula (I) according to the invention can be used, for example, for turf, ornamental plants such as flowers, shrubs, broad-leaved trees or evergreens such as conifers, and tree injections, pest management, etc.

[0678] Within the scope of the present invention, the target crops and / or useful plants to be protected typically include perennial and annual crops such as berry plants, e.g., blackberry, blueberry, cranberry, raspberry, and strawberry; cereals, e.g., barley, maize (corn), millet, oats, rice, rye, sorghum, triticale, and wheat; fiber plants, e.g., cotton, flax, hemp, jute, and sisal; field crops, e.g., sugar beet and fodder beet, coffee bean, hops, mustard, rapeseed (canola), poppy, sugar cane, sunflower, tea, and tobacco; fruit trees, e.g., apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear, and plum; grasses, e.g., Bermuda grass, bluegrass, bentgrass, centipede grass, foxtail, ryegrass, St. Augustine grass, and zoysia grass; herbs, such as basil, borage, chive, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage, and thyme; legumes, e.g., kidney bean, lentil, pea, and soybean; nuts, e.g., almond, cashew, groundnut, hazelnut, peanut, pecan, pistachio, and walnut; palm plants, e.g., oil palm; ornamental plants, e.g., flowers, shrubs, and trees; other trees, e.g., cocoa tree, coconut tree, olive tree, and rubber tree; vegetables, e.g., asparagus, eggplant, broccoli, cabbage, carrot, cucumber, garlic, lettuce, zucchini, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach, and tomato; and grapevines, e.g., grape.

[0679] The term "useful plant" shall also be understood to include useful plants that have been made tolerant to herbicides (such as bromoxynil) or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors such as flupyrsulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enolpyruvylshikimate-3-phosphate synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen oxidase) inhibitors) by conventional breeding methods or genetic engineering. Examples of crops that have been made tolerant to imidazolinones (such as imazamox) by conventional breeding methods (mutation) are summer rape (canola). Examples of crops that have been made tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate-resistant and glufosinate-resistant maize varieties that are commercially available under the Herculex and trade names.

[0680] The term "useful plant" shall also be understood to include useful plants that have been so transformed by the use of recombinant DNA technology that they are capable of synthesizing one or more selectively acting toxins, such as those known, for example, from toxin-producing bacteria, in particular those of the genus Bacillus.

[0681] Examples of such plants are (maize variety expressing the CryIA(b) toxin); YieldGard (maize variety expressing the CryIIIB(b1) toxin); YieldGard (maize variety expressing the CryIA(b) and CryIIIB(b1) toxins); (maize variety expressing the Cry9(c) toxin); Herculex (maize variety expressing the CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) conferring tolerance to the herbicide glufosinate); NuCOTN (cotton variety expressing the CryIA(c) toxin); Bollgard (cotton variety expressing the CryIA(c) toxin); Bollgard (cotton variety expressing the CryIA(c) and CryIIA(b) toxins); (cotton variety expressing the VIP toxin); (potato variety expressing the CryIIIA toxin); GT Advantage (GA21 glyphosate tolerance trait), CB Advantage (CB trait of Ostrinia nubilalis), RW (western corn rootworm trait), and

[0682] The term "crop" shall be understood to also include crop plants that have been so transformed by recombinant DNA techniques that they are capable of synthesizing one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, in particular those of the genus Bacillus.

[0683] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, for example, Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example, Vip1, Vip2, Vip3 or Vip3A; or insecticidal proteins that colonize nematodes, such as species of Photorhabdus or Xenorhabdus, such as Photorhabdus luminescens, Xenorhabdus nematophilus; 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, lectins, such as pea lectin, barley lectin or snowdrop lectin; agglutinins; protease inhibitors, such as trypsin inhibitors, serine protease inhibitors, potato protease inhibitor, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, saporin, soya bean ribosome-inactivating protein, or bryodin; steroid-metabolizing enzymes, such as 3-hydroxy-steroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers such as sodium or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptors, stilbene synthases, bibenzyl synthases, chitinases and glucanases.

[0684] Furthermore, in the context of the present invention, δ-endotoxins (such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C) or vegetative insecticidal proteins (Vips) (such as Vip1, Vip2, Vip3 or Vip3A) should be understood to clearly also include hybrid toxins, truncated toxins, and modified toxins. Hybrid toxins are recombinantly produced by new combinations of different domains of those proteins (see, for example, WO 02 / 15701). Truncated toxins, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid substitutions, preferably a non-naturally occurring protease recognition sequence is inserted into the toxin, for example, in the case of Cry3A055, a cathepsin-G-recognition sequence was inserted into the Cry3A toxin (see WO 2003 / 018810).

[0685] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-0374753, WO93 / 07278, WO 95 / 34656, EP 0427529, EP 0451878, and WO 03 / 052073.

[0686] Methods for preparing such transgenic plants are generally known to those skilled in the art and are described, for example, in the above-mentioned publications. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP 0367474, EP 0401979, and WO 90 / 13651.

[0687] The toxins contained in transgenic plants render the plants tolerant to harmful insects. Such insects can be present in any insect taxon but are particularly common among beetles (Coleoptera), dipterous insects (Diptera), and moths (Lepidoptera).

[0688] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known and some of them are commercially available. Examples of such plants are: (maize variety expressing the Cry1Ab toxin); YieldGard (maize variety expressing the Cry3Bb1 toxin); YieldGard (maize variety expressing the Cry1Ab and Cry3Bb1 toxins); (maize variety expressing the Cry9C toxin); Herculex (Maize variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) conferring tolerance to the herbicide glufosinate); NuCOTN (Cotton variety expressing the Cry1Ac toxin); Bollgard (Cotton variety expressing the Cry1Ac toxin); Bollgard (Cotton variety expressing the Cry1Ac and Cry2Ab toxins); (Cotton variety expressing the Vip3A and Cry1Ab toxins); (Potato variety expressing the Cry3A toxin); GT Advantage (GA21 glyphosate tolerance trait), CBAdvantage (Bt11 European corn borer (CB) trait) and

[0689] Further examples of such genetically modified crops are:

[0690] 1. Bt11 maize from Syngenta Seeds SAS, Chemindel’Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified maize that expresses a truncated Cry1Ab toxin by genetic engineering, making it resistant to the attack of the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides). Bt11 maize also expresses the PAT enzyme by genetic engineering to obtain tolerance to the herbicide glufosinate.

[0691] 2. Bt176 maize from Syngenta Seeds, Chemindel’Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified maize that expresses the Cry1Ab toxin by genetic engineering, making it resistant to the attack of the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides). Bt176 maize also expresses the enzyme PAT by genetic engineering to obtain tolerance to the herbicide glufosinate.

[0692] 3. MIR604 maize from Syngenta Seeds, Chemindel’Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Maize with insect resistance by expressing a modified Cry3A toxin by genetic engineering. This toxin is Cry3A055 modified by inserting a cathepsin-G protease recognition sequence. The preparation of such genetically modified maize plants is described in WO 2003 / 018810.

[0693] 4. MON 863 maize, from Monsanto Europe S.A., 270 - 272 Avenue de Tervuren, B - 1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses the Cry3Bb1 toxin and is resistant to certain Coleoptera insects.

[0694] 5. IPC 531 cotton, from Monsanto Europe, 270 - 272 Avenue de Tervuren, B - 1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0695] 6. 1507 maize, from Pioneer Overseas Corporation, Avenue Tedesco, 7B - 1160 Brussels, Belgium, registration number C / NL / 00 / 10. Genetically modified maize that expresses the protein Cry1F to obtain resistance to certain Lepidoptera insects and expresses the PAT protein to obtain tolerance to the herbicide glufosinate.

[0696] 7. NK603×MON 810 maize, from Monsanto Europe, 270 - 272 Avenue de Tervuren, B 1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. Constituted by a hybrid maize variety obtained by conventional breeding by crossing the genetically modified varieties NK603 and MON 810. NK603×MON 810 maize is genetically modified to express the protein CP4 EPSPS obtained from the Agrobacterium strain CP4, making it tolerant to the herbicide (containing glyphosate), and also the Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki, making it tolerant to certain Lepidoptera insects, including the European corn borer.

[0697] The compound having formula (I) according to the invention can be used for controlling or preventing phytopathogenic diseases, in particular phytopathogenic fungi such as Alternaria spp. on fruits, vegetables and potatoes; Botrytis cinerea on strawberries, tomatoes, sunflowers, leguminous crops, vegetables and grapes; Rhizoctonia solani on potatoes and vegetables; Uncinula necator on grapes; Cladosporium spp., Erysiphe cichoracearum, Sphaerotheca fuliginea and Glomerella lagenarium on cucurbits; Meloidogyne incognita on cucurbits and solanaceous crops; Fusarium spp. on cereals; Leptosphaeria spp. on cereals; and yeast species on cereals.

[0698] As used herein, the term "locality" means the place where the plant grows in or on, or the place where the seeds of the cultivated plant are sown, or the place where the seeds are to be placed in the soil. It includes the soil, the seeds and the seedlings, together with the established vegetation.

[0699] The term "plant" refers to all the tangible parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves and fruits.

[0700] The term "plant propagation material" shall be understood to mean the reproductive parts of plants, such as seeds, which can be used for the propagation of plants, and vegetative material, such as cuttings or tubers (e.g. potatoes). Seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants may be mentioned, for example. Germinated plants and young plants which are to be transplanted after germination or after emergence may also be mentioned. These young plants can be protected before transplantation by being treated completely or partially by drenching. Preferably, "plant propagation material" shall be understood to mean seeds.

[0701] The compounds of formula (I) according to the invention can be used in unmodified form or, preferably, together with auxiliaries which are conventionally employed in the field of formulations. For this purpose, they can be conveniently formulated in known manner as emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granules and also encapsulations, for example in polymeric substances. For the type of composition, the method of application, such as spraying, atomizing, dusting, broadcasting, spreading, or watering, is selected according to the intended purpose and the circumstances at the time. The compositions can also contain further auxiliaries, such as stabilizers, defoamers, viscosity regulators, binders or tackifiers, together with fertilizers, micronutrient donors or other formulations for obtaining special effects.

[0702] Suitable carriers and auxiliaries, for example for agricultural use, can be solid or liquid and are substances which are useful in formulation technology, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are described, for example, in WO 1997 / 33890.

[0703] A suspension concentrate is an aqueous formulation in which finely divided solid particles of the active compound are suspended. Such formulations contain anti-settling agents and dispersants and can further contain wetting agents to enhance the activity, as well as defoamers and crystal growth inhibitors. In use, these concentrates are diluted in water and are generally applied as sprays to the area to be treated. The amount of the active ingredient can range from 0.5% to 95% of the concentrate.

[0704] Wettable powders are in the form of finely divided particles that are readily dispersible in water or other liquid carriers. These particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller's earth, kaolin, silica, and other readily wettable organic or inorganic solids. Wettable powders usually contain from 5% to 95% of the active ingredient plus small amounts of wetting agents, dispersants, or emulsifiers.

[0705] Emulsifiable concentrates are homogeneous liquid compositions that are dispersible in water or other liquids and can consist entirely of the active compound with liquid or solid emulsifiers, or can also contain liquid carriers such as xylene, heavy aromatic naphtha, isophorone, and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquids and are usually applied as sprays to the area to be treated. The amount of active ingredient can range from 0.5% to 95% of the concentrate.

[0706] Granular formulations include both extrudates and coarser granules and are usually applied to the area to be treated without dilution. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite, montmorillonite, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, stucco, wood flour, ground corn cobs, ground peanut hulls, sugar, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesium oxide, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate, and other organic or inorganic materials that absorb the active compound or can be coated with the active compound. Granular formulations usually contain from 5% to 25% of the active ingredient, which can include surfactants such as heavy aromatic naphtha, kerosene, and other petroleum fractions, or vegetable oils; and / or adhesives such as dextrin, glue, or synthetic resins.

[0707] Dusts are free-flowing mixtures of the active ingredient with finely divided solids such as talc, clay, flour, and other organic and inorganic solids that act as dispersants and carriers.

[0708] Microcapsules are typically droplets or particles of an active ingredient encapsulated within an inert, porous shell that permits the encapsulated material to escape into the environment at a controlled rate. The diameter of the encapsulated droplets is typically from 1 to 50 microns. The encapsulated liquid typically comprises from 50% to 95% by weight of the capsule and may contain solvents in addition to the active compound. The encapsulated particles are generally porous particles in which a porous membrane seals the particle orifice, retaining the active species in liquid form within the particle pores. The diameter of the particles typically ranges from 1 mm to 1 cm and preferably from 1 mm to 2 mm. The particles are formed by extrusion, aggregation or spheronization, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and carbon grains. The shell or membrane materials include natural and synthetic rubbers, fibrous materials, styrene-butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

[0709] Other useful formulations for agrochemical applications include simple solutions of the active ingredient in solvents such as acetone, alkylated naphthalenes, xylenes and other organic solvents in which the active ingredient is completely soluble at the desired concentration. Pressurized sprays may also be used, in which the active ingredient is dispersed in finely divided form as a result of the evaporation of a low-boiling dispersant solvent carrier.

[0710] Suitable agricultural adjuvants and carriers useful for formulating the compositions of the present invention in the above formulation types are well known to those skilled in the art.

[0711] Liquid carriers that can be used include, for example, water, toluene, xylene, naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol rosin acid ester, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol (diproxitol), alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, α-pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexanediol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, cumene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isopentyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, dichloromethane, m-xylene, n-hexane, n-octylamine, stearic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin wax, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols (such as pentanol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc.), ethylene glycol, propylene glycol, glycerol, and N-methyl-2-pyrrolidone. Water is usually the preferred carrier for diluting the concentrate.

[0712] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite, bleaching earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell powder, and lignin.

[0713] A wide range of surfactants are advantageously employed in the liquid and solid compositions, especially those designed to be diluted with a carrier prior to application. These reagents usually make up 0.1% to 15% by weight of the formulation when in use. They can be anionic, cationic, nonionic, or polymeric in nature and can be used as emulsifiers, wetting agents, suspending agents, or for other purposes. Typical surfactants include alkyl sulfates, such as diethanolammonium lauryl sulfate; alkyl aryl sulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol-C 18 ethoxylate; alcohol-alkylene oxide addition products, such as tridecanol-C 16Ethoxylates; soaps such as sodium stearate; alkylnaphthalenesulfonates such as sodium dibutylnaphthalenesulfonate; salts of dialkyl esters of sulfosuccinic acid such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitan esters such as sorbitan oleate; quaternary amines such as lauryltrimethylammonium chloride; polyethylene glycol esters of fatty acids such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and dialkyl phosphates.

[0714] Other adjuvants commonly used in agricultural compositions include crystallization inhibitors, viscosity regulators, suspending agents, spray droplet regulators, pigments, antioxidants, foaming agents, defoaming agents, light blockers, compatibilizers, defoaming agents, masking agents, neutralizing agents and buffers, corrosion inhibitors, dyes, flavoring agents, spreading agents, penetration aids, micronutrients, emollients, lubricants, and fixing agents.

[0715] In addition, further, other biocidal active ingredients or compositions can be combined with the compositions of the present invention and used in the methods of the present invention and applied simultaneously or sequentially with the compositions of the present invention. When applied simultaneously, these additional active ingredients can be formulated or mixed together with the compositions of the present invention in, for example, a spray tank. These additional biocidal active ingredients can be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides, and / or plant growth regulators.

[0716] The pesticidal agents mentioned by their common names herein are known, for example, from “The Pesticide Manual”, 15th Edition, British Crop Protection Council 2009.

[0717] In addition, the compositions of the present invention can also be applied together with one or more systemic acquired resistance inducers (“SAR” inducers). SAR inducers are known and described, for example, in U.S. Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.

[0718] The compounds of formula (I) according to the present invention are generally used in the form of agrochemical compositions and can be applied simultaneously or sequentially with additional compounds to the crop area or plants to be treated. For example, these additional compounds can be fertilizers or micronutrient donors or other preparations that affect plant growth. They can also be selective or non-selective herbicides, together with insecticides, fungicides, bactericides, nematicides, molluscicides, or mixtures of several of these preparations, if desired together with additional carriers, surfactants, or adjuvants commonly employed in the formulation art to facilitate application.

[0719] The compounds of formula (I) according to the invention can be used in the form of (fungicidal) compositions for controlling or protecting against phytopathogenic microorganisms, which compositions comprise, as active ingredient, at least one compound of formula (I) or at least one preferred individual compound as defined herein (in free form or in agrochemically acceptable salt form) and at least one of the above adjuvants.

[0720] Accordingly, the invention provides compositions, preferably fungicidal compositions, comprising at least one compound of formula (I) according to the invention, an agriculturally acceptable carrier and optionally adjuvants. An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural carriers are well known in the art. Preferably, in addition to the compound of formula (I), the composition may further comprise at least one or more pesticidal active compounds, for example, additional fungicidal active ingredients.

[0721] The compound of formula (I) according to the invention can be the sole active ingredient of the composition or, as appropriate, it can be admixed with one or more additional active ingredients, such as pesticidal agents, fungicides, synergists, herbicides or plant growth regulators. In some cases, the additional active ingredients can produce an unexpected synergistic activity.

[0722] Examples of suitable additional active ingredients include the following: acycloamino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, aniline fungicides, antibiotic fungicides, aromatic fungicides, arsenic-containing fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzoyl aniline fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, bridged biphenyl fungicides, carbamate fungicides, phenylcarbamate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furanamide fungicides, furan aniline fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, morpholine fungicides, organophosphorus fungicides, organotin fungicides, oxathiin fungicides, oxazole fungicides, phenylthioamide fungicides, polysulfide fungicides, pyrazole fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungicides, quinone fungicides, quinoxaline fungicides, strobulurin fungicides, sulfonanilide fungicides, thiadiazole fungicides, thiazole fungicides, thiazolidine fungicides, thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolo pyrimidine fungicides, urea fungicides, valinamide fungicides, and zinc fungicides.

[0723] Examples of suitable additional active ingredients include the following: mineral oil, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenyl benzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylethanamide, 4-chlorophenyl phenyl sulfone, acetoprole, aldicarb, amidithion, amidothioate, amitron, amitron hydrogencarbonate, amitraz, bromopropylate, arsenic trioxide, azobenzene, azinphos, benomyl, benoxa-fos, benzyl benzoate, bixafen, brofluthrinate, bromocyclen, bromophos, bromopropylate, buprofezin, butocarboxim, butoxycarboxim, butylpyridaben, calcium polysulfide, camphechlor, carbaryl, carbophenothion, cycloimid, chinomethionat, chlorbenside, chlordimeform, chlordimeform hydrochloride, chlorobenzilate, chlorfenson, chlorfensulfide, chlorobenzilate, chloromebuform, chloromethiuron, chloropropylate, chlorthiophos, cinerin I, cinerin II, cinerins, closantel, coumaphos, crotamiton, crotoxyphos, cyhexatin, cyanthoate, DCPM, DDT, demephion, demephion-O, demephion-S, demeton, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulfon, dichlofluanid, dichlorvos, dicliphos, dicofol, dimefox, dinex, dinex-diclexine, dinocap-4, dinocap-6, dinoseb, dinopenton, dinosulfon, dinoterbon, dioxathion, diphenyl sulfone, disulfiram, DNOC, dofenapyn, doramectin, endothion, eprinomectin, ethion, etrimfos, fenazaflor, fenbutatin oxide, fenothiocarb,fenpyrad, fenpyroximate, fenpyrazamine, fenson, fentrifanil, flubenzimine, flucycloxuron, fluenetil, fluorbenside, FMC 1137, amitraz, amitraz hydrochloride, formparanate, γ-HCH, glyodin, halfenprox, hexadecyl cyclopropanecarboxylate, isocarbophos, jasmolin I, jasmolin II, jodfenphos, lindane, malonoben, mecarbam, mephosfolan, methathion, methacrifos, methyl bromide, metolcarb, mexacarbate, milbemycin oxime, mipafox, monocrotophos, morphothion, moxidectin, naled, 4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodopyridin-3-yl)methoxy]pyridazin-3-one, nifluridide, nikkomycin, nitrilacarb, nitrilacarb 1:1 zinc chloride complex, omethoate, oxydeprofos, oxydisulfoton, pp'-DDT, parathion, permethrin, phenkapton, phosalone, phosfolan, phosphamidon, polychloroterpenes, polynactins, propiconazole, promacyl, propoxur, prothidathion, prothoate, pyrethrin I, pyrethrin II, pyrethrum, pyridaphenthion, pyrimitate, quinalphos, quintiofos, R-1492, phosglycin, rotenone, schradan, sebufos, selamectin, sophamide, SSI-121, sulfenuron, sulfluramid, sulfotepSulfur, diflovidazin, tau-fluvalinate, TEPP, terbam, tetradifon, tetrasul, thiafenox, thiocarboxime, thiofanox, thiometon, chlorobenzilate, thuringiensin, triamiphos, triarathene, triazophos, triazuron, trifenofos, trinactin, formetanate, vaniliprole, bethoxazin, copper dioctoate, copper sulfate, cybutryne, dichlone, dichlorophen, galic acid, triphenyltin, slaked lime, sodium thiosulfate, quinoclamine, quinonamid, simazine, triphenyltin acetate, triphenyltin hydroxide, crotoxyphos, piperazine, thiophanate-methyl, chlorozolinate, fenthion, pyridin-4-amine, strychnine, 1-hydroxy-1H-pyridine-2-thione, 4-(quinoxalin-2-ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, copper hydroxide, cresol, bipyrithione, dodine, fenaminosulf, formaldehyde, mercuric chloride, kasugamycin, kasugamycin hydrochloride hydrate, nickel bis(dimethyldithiocarbamate), nitrapyrin, octhilinone, oxolinic acid, oxytetracycline, potassium 8-hydroxyquinoline sulfate, probenazole, streptomycin, streptomycin sesquisulfate, tetrachloroisophthalonitrile, thimerosal, Adoxophyes orana granulovirus, Agrobacterium radiobacter, Amblyseius spp., Autographa gamma nuclear polyhedrosis virus, Anagrus atomus, Aphelinus abdominalis, Aphidius colemani, Aphidoletes aphidimyza, Autographa californica nuclear polyhedrosis virus, Bacillus sphaericus Neide, Beauveria brongniartii, Chrysoperla carnea, Cryptolaemus montrouzieri, Cydia pomonella granulovirus, Dacnusa sibirica, Diglyphus isaea,Encarsia formosa, Eretmocerus eremicus, Heterorhabditis bacteriophora and H. megidis, Hippodamia convergens, Leptomastix dactylopii, Macrolophus caliginosus, Mamestra brassicae NPV, Metaphycus helvolus, Metarhizium anisopliae var. acridum, Metarhizium anisopliae var. anisopliae, Neodiprion sertifer NPV and N. lecontei NPV, Orius species, Paecilomyces fumosoroseus, Phytoseiulus persimilis, Steinernema bibionis, Steinernema carpocapsae, Steinernema feltiae, Steinernema glaseri, Steinernema riobrave, Steinernema riobravis, Steinernema scapterisci, Steinernema spp., Trichogramma spp., Typhlodromus occidentalis, Verticillium lecanii, apholate, bisazir, busulfan, dimatif, hemel, hempa, metepa, methiotepa, methyl apholate, morzid, penfluron, tepa, thiohempa, thiotepa, tretamine, uredepa, (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol, (E)-tridec-4-en-1-yl acetate,(E)-6-Methylhept-2-en-4-ol, (E,Z)-tetradeca-4,10-dien-1-yl acetate, (Z)-dodec-7-en-1-yl acetate, (Z)-hexadec-11-enal, (Z)-hexadec-11-en-1-yl acetate, (Z)-hexadec-13-en-11-yn-1-yl acetate, (Z)-heneicosa-13-en-10-one, (Z)-tetradec-7-en-1-al, (Z)-tetradec-9-en-1-ol, (Z)-tetradec-9-en-1-yl acetate, (7E,9Z)-dodec-7,9-dien-1-yl acetate, (9Z,11E)-tetradec-9,11-dien-1-yl acetate, (9Z,12E)-tetradec-9,12-dien-1-yl acetate, 14-methyloctadec-1-ene, 4-methylnon-5-ol and 4-methylnon-5-one, alpha-multistriatin, brevicomin, codlelure, codlemone, cuelure, disparlure, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodec-8,10-dien-1-yl acetate, dominicalure, ethyl 4-methylcaprylate, eugenol, frontalin, grandlure, grandlure I, grandlure II, grandlure III, grandlure IV, hexalure, ipsdienol, ipsenol, japonilure, lineatin, litlure, looplure, medlure, megatomoic acid, methyleugenol, muscalure, octadec-2,13-dien-1-yl acetate, octadec-3,13-dien-1-yl acetate, orfralure, oryctalure, ostramone, siglure, sordidin, sulcatol, tetradec-11-en-1-yl acetate, Mediterranean fruit fly attractant, Mediterranean fruit fly attractant A, Mediterranean fruit fly attractant B1, Mediterranean fruit fly attractant B2, Mediterranean fruit fly attractant C, trunc-call, 2-(octylthio)-ethanol,Butopyronoxyl, butoxy(polypropylene glycol), dibutyl adipate, dibutyl phthalate, dibutyl succinate, diethyltoluamide, dimethylcarbate, dimethyl phthalate, ethylhexylglycerin, hexanamide, methoquin-butyl, methyl neodecanoamide, oxamate, picaridin, 1,1-dichloro-1-nitroethane, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane, 1,2-dichloropropane and 1,3-dichloropropene, 1-bromo-2-chloroethane, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate, 2-(2-butoxyethoxy)ethyl thiocyanate, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate, 2-(4-chloro-3,5-dimethylphenoxy)ethanol, 2-chlorovinyl diethyl phosphate, 2-imidazolidinone, 2-isovalerylindan-1,3-dione, 2-methyl(propargyl)aminophenyl methylcarbamate, 2-thiocyanatoethyl laurate, 3-bromo-1-chloropropene, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate, 4-methyl(propargyl)amino-3,5-dimethylphenyl methylcarbamate, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate, Muscatox, acrylonitrile, aldrin, allomurin, asprocarb, α-ecdysone, aluminium phosphide, aminocarb, neonicotinoid, ethyl methidathion, pirimiphos-methyl, Bacillus thuringiensis delta-endotoxins, barium hexafluorosilicate, barium polysulfide, chrysanthemum cinerariifolium, Bayer 22 / 190, Bayer 22408, beta-cyfluthrate, beta-cypermethrin, bioethanomethrin, bioallethrin, bis(2-chloroethyl)ether, borax, bromfenvinfos, bromo-DDT, BPMC, butacarb, butathiofos, butonate, calcium arsenate, calcium cyanide, carbon disulfide, carbon tetrachloride, cartap hydrochloride, cefadroxil, celestamine, chlordane, kepone, chloroform, chloropicrin, chlorphoxim, chlorprazophos, cis-resmethrin, cismethrin, cyhalothrin, copper acetoarsenite, copper arsenate, copper oleate, chlorthiophos, cryolite, CS 708, cyanofenphos, cyanophos, cycloprothrin, chlorfensulphide, d-tetramethrin, DAEP, dazomet, decarbofuran, diamidafos, isocarbophos, dichlorvos, dicresyl, dioxadimethrine, dieldrin, diethyl 5-methylpyrazol-3-yl phosphate,Diprophylline (dilor), transfluthrin, dimetan, dimethrin, dimethylvinphos, dimetilan, binapacryl, dinoterb, ethofenprox, dioxabenzofos, dithicrofos, DSP, ecdysone, EI 1642, EMPC, EPBP, etaphos, ethiofencarb, ethyl formate, dibromoethane, dichloroethane, ethylene oxide, EXD, fenthion, fenethacarb, fenitrothion, fenoxacrim, fenpirithrin, fensulfothion, fenthion-ethyl, fipronil, butathiofos, fospirate, fosthietan, furathiocarb, furethrin, biguanide, biguanide acetate, sodium tetrathiocarbonate, halfenprox, HCH, HEOD, heptachlor, phocidil, HHDN, hydrocyanic acid, hyquincarb, IPSP, chlorpyrifos, carbonochlorid, isodrin, isofenphos, isolane, isoprothiolane, isoxathion, juvenile hormone I, juvenile hormone II, juvenile hormone III, chloropentacycle, kinoprene, lead arsenate, bromophos, lirimfos, fosthiazate, mipc, magnesium phosphide, azinphos, tetramethrin, menazon, mercurous chloride, mesulfenfos, metam, metam-potassium, metam-sodium, methanesulfonyl fluoride, methocrotophos, methoprene, methothrin, methoxychlor, methyl isothiocyanate, methyl chloroform, dichloromethane, metoxadiazone, mirex, naftalofos, naphthalene, NC-170, nicotine, nicotine sulfate, nithiazine, nornicotine, O-5-dichloro-4-iodophenyl O-ethyl ethylphosphonothioate, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate, O,O,O',O'-tetrapropyl dithiopyrophosphate,Oleic acid, p-dichlorobenzene, parathion-methyl, pentachlorophenol, pentachlorophenyl laurate, PH 60-38, phenthoate, para-chlorothion, phosphine, phoxim-methyl, pirimetaphos, polychlorodicyclopentadiene isomers, potassium arsenite, potassium thiocyanate, precocene I, precocene II, precocene III, primidophos, profluthrin, promecarb, profenofos, pyrazophos, pyresmethrin, quassia, quinalphos-methyl, quinothionate, rafoxanide, resmethrin, rotenone, kadethrin, ryania, ryanodine, sabadilla, schradan, sebufos, SI-0009, thiapronil, sodium arsenite, sodium cyanide, sodium fluoride, sodium hexafluorosilicate, sodium pentachlorophenate, sodium selenate, sodium thiocyanate, sulcofuron, sulcofuron-sodium, sulfuryl fluoride, sulprofos, tar, thiodicarb, TDE, butylpyrimiphos, temephos, empenthrin, tetrachloroethane, thicrofos, thiocyclam, thiocyclam hydrogen oxalate, thionazin, thiosultap, thiosultap-sodium, tralomethrin, transpermethrin, triazamate, trichlormetaphos-3, trichlorfon, trimethacarb, tolprocarb, triclopyricarb, triprene, veratridine, veratrine, XMC, zetamethrin, zinc phosphide, zolaprofos, meperfluthrin, tetramethrin, bis(tributyltin) oxide, bromoacetamide, iron phosphate, niclosamide ethanolamine, tributyltin oxide, pyrimorph, trifenmorph, 1,2-dibromo-3-chloropropane, 1,3-dichloropropene, 3,4-dichlorotetrahydrothiophene 1,1-dioxide, 3-(4-chlorophenyl)-5-methylrhodanine, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid, 6-isopentenylaminopurine, anisiflupurin, benclothiaz,Cytokinins, DCIP, furfural, isamidophos, kinetin, Myrothecium verrucaria composition, tetrachlorothiophene, xylenol, zeatin, potassium ethylxanthate, acibenzolar, acibenzolar-S-methyl, Reynoutria sachalinensis extract, alpha-chlorohydrin, antu, barium carbonate, bithiosemi, brodifacoum, bromadiolone, bromofacitin, chlorofacitin, cholecalciferol, chlorfenac, coumatetralyl, crimidine, difenacoum, difethialone, diphacinone, ergocalciferol, fluoride flocoumafen, fluoroacetamide, flupropadine, flupropadine hydrochloride, flucoumafen, flucoumafen, phosphorus, pindone, pyrinuron, scilla glycoside, sodium fluoroacetate, thallium sulfate, warfarin, 2-(2-butoxyethoxy)ethyl piperonate, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, farnesol with nerolidol, piperonyl butoxide, MGK 264, piperonyl butoxide, pipertal, propyl ester isomer), S421, sesamex, sesasmolin, sulfoxide, anthraquinone, copper cyclohexane, copper oxychloride, dicyclopentadiene, thiram, zinc cyclohexane, zinc zirconia, imanin, ribavirin, chloroindole hydrazide, mercuric oxide, thiophanate-methyl, azaconazole, bifenthrin, oxadiazole, cyproconazole, fenpropimorph, diniconazole, epoxiconazole, nitrobenzene, fluquinconazole, flusilazole, flutriafol, furopyram, hexaconazole, imazalil, imipenem, phyconazole, metconazole, nitrobenzene azole, paclobutrazol, pyrimethanol, penconazole, prothioconazole, pyrifenox, prochloraz, propiconazole, pyrisoxazole, simeconazole, tebuconazole, tetrafluthrin, triadimefon, triadimenol, triflumizole, trichlorfonazole, pyrimidine, chlorfenapyr, flufenapyr, bupirimate, dimethirimol, ethirimol, dodecacyclic morpholine, fenpropidin, fenbutrazol, spiroxaplanol, tridecamorph, cyprodinil, pyrimidine,pyrimethanil, fenpiclonil, fludioxonil, benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl, carbendazim, debacarb, dimethirimol, thiabendazole, chlozolinate, dichlozoline, myclozoline, procymidone, vinclozoline, boscalid, carboxin, mepronil, flutolanil, fenpropidin, oxycarboxin, penthiopyrad, thifluzamide, dodine, iminoctadine, azoxystrobin, enestroburin, enoxastrobin, enostamide, flufenoxystrobin, fluoxastrobin, metominostrobin, metrafenone, trifloxystrobin, triclopyricarb, picoxystrobin, pyraoxystrobin, pyraclostrobin, ferbam, mancozeb, maneb, metiram, propineb, zineb, captafol, captan, fluoroimide, chlorothalonil, tolylfluanid, bordeaux mixture, copper oxide, mancopper, oxine-copper, nitrothal-isopropyl, blasticidin-S, chloroneb, chlorothalonil, cyflufenamid, cymoxanil, cyprodinil, diclocymet, diclomezine, dicloran, diethofencarb, dimethomorph, flumorph, dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, ferimzone, fluazinam, flumetylsulforim, fluopicolide, fluoxytioconazole, flusulfamide,fluxapyroxad, fenhexamid, fosetyl-aluminium, hymexazol, propineb, cyazofamid, methasulfocarb, metrafenone, pencycuron, picoxystrobin, polyoxins, propamocarb, pyribencarb, proquinazid, pyroquilon, pyriofenone, quinoxyfen, quintozene, tiadinil, triazoxide, tricyclazole, tridemorph, validamycin, valifenalate, zoxamide, mandipropamid, flubeneteram, isopyrazam, sedaxane, benzovindiflupyr, pydiflumetofen, 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide, isoflucypram, isotianil, dipymetitrone, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithieno[1,2-c]isothiazole-3-carbonitrile, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethyl-indan-4-yl]pyrazole-4-carboxamide, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-2,5-dimethyl-pyrazol-3-amine, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, fluindapyr, coumethoxystrobin (jiaxiangjunzhi), lvbenmixianan, dichlobentiazox, mandestrobin, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol, fluopyram,tert-Butyl N-[6-[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxymethyl]-2-pyridinyl]carbamate, pyraziflumid, inpyrfluxam, trolprocarb, fluopyram, ipfentrifluconazole, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-inden-4-yl]pyridine-3-carboxamide, N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylformamidine, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethylphenyl]-N-ethyl-N-methylformamidine, methyl [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chlorophenyl]methanesulfonate, N-[6-[[(Z)-[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxymethyl]-2-pyridinyl]but-3-ynylcarbamate, methyl N-[[5-[4-(2,4-dimethylphenyl)-1,2,4-triazol-2-yl]-2-methylphenyl]methyl]carbamate, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine, pyridachlometyl, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylinden-4-yl]pyrazole-4-carboxamide, 1-[2-[[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxymethyl]-3-methylphenyl]-4-methyl-1H-tetrazol-5-one, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethyl-1H-pyrazol-1-yl)phenoxy]methyl]phenyl]-1H-tetrazol-5-one, aminopyrifen, ametoctradin, amisulbrom, penflufen, (Z,2E)-5-[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethylpent-3-enamide, florylpicoxamid, fenpicoxamid, metarylpicoxamid, tebufloquin, ipflufenoquin, quinofumelin, isofetamid,Ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate (which can be prepared by the method described in WO 2020 / 056090), ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoroprop-1-enoxy]phenyl]methyl]pyrazole-3-carboxylate (which can be prepared by the method described in WO 2020 / 056090), methyl N-[[4-[1-(4-cyclopropyl-2,6-difluorophenyl)pyrazol-4-yl]-2-methylphenyl]methyl]carbamate (which can be prepared by the method described in WO 2020 / 097012), methyl N-[[4-[1-(2,6-difluoro-4-isopropylphenyl)pyrazol-4-yl]-2-methylphenyl]methyl]carbamate (which can be prepared by the method described in WO 2020 / 097012), 6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoroethyl]-5-methylpyridazine-4-carboxamide (which can be prepared by the method described in WO 2020 / 109391), 6-chloro-N-[2-(2-chloro-4-methylphenyl)-2,2-difluoroethyl]-3-(3-cyclopropyl-2-fluorophenoxy)-5-methylpyridazine-4-carboxamide (which can be prepared by the method described in WO 2020 / 109391), 6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoroethyl]-5-methylpyridazine-4-carboxamide (which can be prepared by the method described in WO 2020 / 109391), N-[2-[2,4-dichlorophenoxy]phenyl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide, benzothiostrobin, phenamacril, zinc 5-amino-1,3,4-thiadiazole-2-thiolate (2:1), fluopyram, flufenoxadiazam, flutianil, fluopimomide, pyrapropoyne, picarbutrazox, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethylinden-4-yl)pyridine-3-carboxamide, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylinden-4-yl)pyridine-3-carboxamide,4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridinyl]oxy]benzonitrile, metyltetraprole, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidine methanol, fluoxapiprolin, enoxastrobin, methyl (Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)-1,2,4-triazol-2-yl]phenoxy]prop-2-enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-(4-propyl-1,2,4-triazol-2-yl)phenoxy]prop-2-enoate, methyl (Z)-2-[5-(3-isopropyl-1H-pyrazol-1-yl)-2-methylphenoxy]-3-methoxyprop-2-enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-(3-propyl-1H-pyrazol-1-yl)phenoxy]prop-2-enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)-1H-pyrazol-1-yl]phenoxy]prop-2-enoate (these compounds can be prepared by the methods described in WO 2020 / 079111), methyl (Z)-2-(5-cyclohexyl-2-methylphenoxy)-3-methoxyprop-2-enoate, methyl (Z)-2-(5-cyclopentyl-2-methylphenoxy)-3-methoxyprop-2-enoate (these compounds can be prepared by the methods described in WO 2020 / 193387), 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridinyl]oxy]benzonitrile, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridinyl]oxy]benzonitrile, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridinyl]oxy]benzonitrile, trinexapac, coumoxystrobin, zhongshengmycin, thiodiazole copper, thiazole zinc, amectotractin, iprodione, seboctylamine, N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxyethoxy]-3-pyridinyl]-N-ethyl-N-methylformamidine,N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-isopropyl-N-methyl-formamidine (these compounds can be prepared by the methods described in WO 2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared by the methods described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine (these compounds can be prepared by the methods described in WO 2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine (these compounds can be prepared by the methods described in WO 2019 / 110427); N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide,N-[(1S)-1-Benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide (these compounds can be prepared by the methods described in WO 2017 / 153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline (these compounds can be prepared by the methods described in WO2017 / 025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolinyl)-7,8-dihydro-6H-cyclopenta[d]benzimidazole (these compounds can be prepared by the methods described in WO 2016 / 156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide,4,4-Dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine (these compounds can be prepared by the methods described in WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 093348 and WO 2017 / 118689); 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared by the method described in WO 2017 / 029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared by the method described in WO 2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile (this compound can be prepared by the method described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile (this compound can be prepared by the method described in WO 2016 / 156290); (4-phenoxyphenyl)methyl 2-aminopyridine-3-carboxylate (this compound can be prepared by the method described in WO 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone (this compound can be prepared by the method described in WO 2011 / 138281),N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]thiobenzamide; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine (this compound can be prepared by the method described in WO2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methyl-formamidine; N'-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared by the method described in WO2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (this compound can be prepared by the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone (these compounds can be prepared by the method described in WO 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide (this compound can be prepared by the method described in WO 2018 / 065414); ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate (this compound can be prepared by the method described in WO 2018 / 158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[N-methoxy-methyl-carbimino]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (these compounds can be prepared by the method described in WO 2018 / 202428).

[0724] The compounds of the present invention can also be used in combination with anthelmintics. Such anthelmintics include compounds selected from macrolide compounds, such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin, and milbemycin derivatives, as described in EP 0357460, EP 0444964, and EP 0594291. Additional anthelmintics include semi-synthetic and biosynthetic avermectin / milbemycin derivatives, such as those described in US 5,015,630, WO 9415944, and WO 9522552. Additional anthelmintics include benzimidazoles, such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxibendazole, parbendazole, and other members of this class. Additional anthelmintics include imidazothiazoles and tetrahydropyrimidines, such as tetramisole, levamisole, pyrantel pamoate, oxantel, or morantel. Additional anthelmintics include trematocides (such as triclabendazole and clorsulon) and cestocides (such as praziquantel and epsiprantel).

[0725] The compounds of the present invention can be used in combination with derivatives and analogs of anthelmintics of the paraherquamide / marcfortine class, as well as anti-parasitic oxazolines (such as those disclosed in US 5478855, US 4639771, and DE-19520936).

[0726] The compounds of the present invention can be used in combination with derivatives and analogs of dioxolane anti-parasitic agents of the general class described in WO 9615121, as well as cyclic peptides having anthelmintic activity (such as those described in WO 9611945, WO 9319053, WO 9325543, EP 0626375, EP 0382173, WO 9419334, EP 0382173, and EP 0503538).

[0727] The compounds of the present invention can be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide, etc.; neonicotinoids such as imidacloprid, etc.

[0728] The compounds of the present invention can be used in combination with terpene alkaloids, such as those described in WO95 / 19363 or WO 04 / 72086, especially the compounds disclosed therein.

[0729] Other examples of such bioactive compounds that can be used in combination with the compounds of the present invention include, but are not limited to, the following:

[0730] Organophosphates: Acephate, Azamethiphos, Azinphos-ethyl, Azinphos-methyl, Bromophos, Bromophos-ethyl, Cadusafos, Chlorethoxyphos, Chlorpyrifos, Chlorfenphos, Chloromethiophos, Demeton, Demeton-S-methyl, Demeton-S-methyl sulfone, Chlorphoxim, Diazinon, Dichlorvos, Dicrotophos, Dimethoate, Disulfoton, Ethoprophos, Etrimfos, Famphur, Fenamiphos, Fenthion, Flupyrazofos, Fonofos, Formothion, Fosthiazate, Heptenophos, Isazofos, Isopropyl parathion, Isoxathion, Malathion, Methacrifos, Methamidophos, Methidathion, Methyl parathion, Omethoate, Phosphamidon, Phosalone, Phosfolan, Pirimiphos-methyl, Profenofos, Prothiofos, Proetamphos, Prothiofos, Pyraclofos, Pyridaphenthion, Quinalphos, Sulfotep, Tebupirimfos, Terbufos, Tetrachlorvinphos, Thimeton, Triazophos, Trichlorfon, Trimethacarb.

[0731] Carbamates: Aldicarb, Aldoxycarb, Benfuracarb, Butocarboxim, Carbaryl, Carbofuran, Carbosulfan, Cloethocarb, Crotoxyphos, Dimethacarb, Ethiofencarb, Fenoxycarb, Fenchlorphos, Formetanate, Furathiocarb, HCN-801, Isoprocarb, Indoxacarb, Methiocarb, Methomyl, (Methyl) 5-methyl-m-isopropylphenyl butynylcarbamate, Oxamyl, Pirimicarb, Propoxur, Thiodicarb, Trimethacarb, UC-51717.

[0732] Pyrethroids: Acrinathrin, Allethrin, Alphamethrin, 5-Benzyl-3-furylmethyl (E)-(1R)-cis-2,2-dimethyl-3-(2-oxothiolan-3-ylidene) cyclopropanecarboxylate, Bifenthrin, Beta-cyfluthrin, Cyfluthrin, Alpha-cypermethrin, Beta-cypermethrin, Bioallethrin, Bioallethrin ((S)-cyclopentyl isomer), Bioresmethrin, Bifenthrin, NCI-85193, Pyrethroid, Cyhalothrin, Cypermethrin, Cyanobenzilate, Deltamethrin, Empenthrin, Esfenvalerate, Etofenprox, Fenfluthrin, Fenpropathrin, Flucythrinate (D isomer), Imiprothrin, Lambda-cyhalothrin, Permethrin, Phenothrin, Pyrethrins (natural products), Resmethrin, Tetramethrin, Theta-cypermethrin, Silafluofen, Tefluthrin, Tefluthrin, Tefluthrin, Tebufenpyrad, Zeta-cypermethrin.

[0733] Arthropod growth regulators: a) Chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, flonicamid, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, ethofenprox, hexythiazox, etoxazole, clofentezine; b) Ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide; c) Juvenile hormone analogs: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) Lipid biosynthesis inhibitors: spirodiclofen.

[0734] Other antiparasitic drugs: acequinocyl, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidin, cyanaguanide, diacloden, dimite, DBI-3204, diomycin, dihydroxymethyl dihydroxypyrrolidine, dienochlor, dinocap, endosulfan, ethiprole, etofenprox, fenazaquin, flumite, MTI-800, fenpyroximate, fluacrypyrim, flufenerim, flumethrin, flutenzin, trifloxystrobin, fluproxyfen, halofenprox, hydramethylnon, IKI-220, hydrocerussite, NC-196, neem guard, nidinorterfuran, nitenpyram, SD-35651, WL-108477, pyridalyl, propargite, protrifenbute, pymetrozine, pyridaben, pyrimidifen, NC-1111, R-195, RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601, silafluofen, silomadine, spinosad, pyridaben, tetradifon, tetra-antibiotics, thiacloprid, thiosultap, thiamethoxam, tolfenpyrad, triazamate, triethylspinosad, triomycin, synergistic piperonyl ether, vertalec, YI-5301.

[0735] Biological agents: Bacillus thuringiensis ssp. aizawai, Bacillus thuringiensis ssp. kurstaki, Bacillus thuringiensis δ-endotoxin, baculovirus, entomopathogenic bacteria, viruses and fungi.

[0736] Bactericides: chlortetracycline, oxytetracycline, streptomycin.

[0737] Other biological agents: enrofloxacin, febantel, penethamate hydriodide, meloxicam, cephalexin, kanamycin, pimobendan, clenbuterol, omeprazole, thiomurin, benazepril, pyriprole, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, ceftiofur, carprofen, mefronil, praziquantel, triclabendazole.

[0738] The following mixtures of the compounds of formula (I) with active ingredients are preferred. The abbreviation "TX" means a compound selected from the compounds of formula (I), (I-A), (I-A1), (I-A2), (I-A3), (I-A4), (I-A5), or (I-A6), or a compound selected from the compounds listed in Tables B-1 to B-27 or the compounds listed in Table P (below), and compounds selected from the group consisting of: mineral oil + TX, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX, 2,4-dichlorophenyl benzenesulfonate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 4-chlorophenyl phenyl sulfone + TX, acetoprole + TX, aldicarb + TX, cythioate + TX, dimethirimol + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, bromopropylate + TX, arsenic trioxide + TX, azobenzene + TX, azinphos + TX, benomyl + TX, benoxathiaphos + TX, benzyl benzoate + TX, bixafen + TX, bromfenvinfos + TX, bromocyclen + TX, bromophos + TX, bromopropylate + TX, buprofezin + TX, butocarboxim + TX, butoxycarboxim + TX, butylpyridaben + TX, lime sulfur + TX, camphechlor + TX, carbaryl + TX, carbophenothion + TX, cycloimidazole + TX, chinomethionat + TX, chlorbenside + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorobenzilate + TX, chlorfenson + TX, chlorfenson + TX, dicofol-4 + TX, dicofol-6 + TX, dinitrophenol + TX, nitropenta + TX, nitroxynil + TX, nitrobutyl + TX, dioxathion + TX, diphenyl sulfone + TX, disulfiram + TX, DNOC + TX, fenazaquin + TX, doramectin + TX, dioxathion + TX, eprinomectin + TX, ethion + TX, etrimfos + TX, fenbutatin oxide + TX, benothiocarb + TX, fenpyroximate + TX, flufenerim + TX, fluacrypyrim + TX, fluacrypyrim + TX, flucycloxuron + TX, flubenzimine + TX, flufenzin + TX, flutenzin + TX, FMC 1137 + TX, formetanate + TX,Anti-mite hydrochloride + TX, carbendazim + TX, γ-HCH + TX, fruit green + TX, benzyl chlorpyrifos + TX, cyclopropanecarboxylic acid hexadecyl ester + TX, carbofuran + TX, jasmonate I + TX, jasmonate II + TX, iodine + TX, lindane + TX, propanil + TX, aphid + TX, dianphos + TX, methylthiophene + TX, insect acarb + TX, methyl bromide + TX, cypermethrin + TX, chlorpyrifos + TX, milbemid + TX, propylamine fluorophos + TX, monocrotophos + TX, chlorpyrifos + TX, moxidectin + TX, dibromophos + TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazine-3-one + TX, fluazifop + T X, nikkomycin + TX, pentocyanamide + TX, pentocyanamide 1:1 zinc chloride complex + TX, omethoate + TX, isothiophos + TX, sulfone + TX, pp'-DDT + TX, parathion + TX, permethrin + TX, fenthion + TX, phosalone + TX, thiocyanate + TX, chlorinated turpentine + TX, acarbamide + TX, chlorinated turpentine + TX, cypermethrin + TX, cypermethrin + TX, propoxur + TX, ethidium + TX, thiophanate + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrin + TX, pyrethrin + TX, pyrimethoate + TX, pyrithiophos + TX, quinalphos + TX, quinalphos + TX, R-1492 + TX, glyphosate + TX, rotenone + TX, octamidine + TX, Sulfasalazine + TX, selamectin + TX, thiophos + TX, SSI-121 + TX, sulfilam + TX, flubendiamide + TX, thiophos + TX, sulfur + TX, flumethrin + TX, τ-fluvalinate + TX, TEPP + TX, tert-butylcarb + TX, trichloroacetic acid sulfone + TX, thiocarb + TX, long-acting carb + TX, anthelmintic acid + TX, long-acting carb + TX, methyl thiocarb + TX, chlorpyrifos + TX, thiophanate + TX, thiophanate-methyl + TX, thiophanate-methyl + TX, triazophos + TX, thiophanate-methyl + TX, thiophanate-methyl + TX, triazophos + TX, chlorpyrifos + TX, triamcinol ... TX, dichlorophen + TX, fungicidal acid + TX, triphenyltin + TX, slaked lime + TX, sodium mancozeb + TX, algae quinone + TX, quinone + TX, simazine + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, clofosinate + TX, piperazine + TX, thiophanate + TX, chlorzoxazone + TX, fenthion + TX, pyridine-4-amine + TX, strychnine + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 4-(quinoxaline-2-ylamino)benzenesulfonamide + TX, 8-hydroxyquinoline sulfate + TX, bronopol + TX, copper hydroxide + TX, cresol + TX, dipyrithione + TX, dodesine + TX, sodium sulfone + TX, formaldehyde + TX, mercurophenic acid + TX, kasugamycin + TX,Kasugamycin hydrochloride hydrate + TX, nickel bis(dimethyldithiocarbamate) + TX, trichloromethylpyridine + TX, octhilinone + TX, oxolinic acid + TX, oxytetracycline + TX, potassium hydroxyquinoline sulfate + TX, thiabendazole + TX, streptomycin + TX, streptomycin sesquisulfate + TX, tetrachloroisophthalonitrile + TX, thimerosal + TX, Adoxophyes orana granulovirus + TX, Agrobacterium radiobacter + TX, Amblyseius species + TX, Autographa gamma nuclear polyhedrosis virus + TX, Anastatus sp. + TX, Aphytis proclia + TX, Aphelinus gossypii + TX, Aphidoletes aphidimyza + TX, Autographa californica nuclear polyhedrosis virus + TX, Bacillus sphaericus + TX, Beauveria brongniartii + TX, Chrysopa carnea + TX, Cryptolaemus montrouzieri + TX, Cydia pomonella granulovirus + TX, Dacnusa sibirica + TX, Diglyphus isaea + TX, Encarsia formosa + TX, Encarsia pergandiella + TX, Heterorhabditis bacteriophora and Heterorhabditis megidis + TX, Harmonia axyridis + TX, Metaphycus helvolus + TX, Miridae + TX, Mamestra brassicae nuclear polyhedrosis virus + TX, Microterys flavus + TX, Metarhizium anisopliae var. anisopliae + TX, Metarhizium anisopliae var. anisopliae f. sp. anisopliae + TX, Neodiprion sertifer nuclear polyhedrosis virus and Neodiprion lecontei nuclear polyhedrosis virus + TX, Orius species + TX, Paecilomyces fumosoroseus + TX, Phytoseiulus persimilis + TX, Romanomermis culicivorax + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobrave + TX, Steinernema scapterisci + TX, Steinernema species + TX, Trichogramma + TX, Typhlodromus occidentalis + TX, Verticillium lecanii + TX, Azamethiphos + TX, Bis(aziridinyl)methylaminophosphine sulfide + TX, Busulfan + TX, Dimethipin + TX, Altretamine + TX, Hexamethylphosphoramide + TX, Methiotepa + TX, Methylthioteepa + TX, Methylazamethiphos + TX, Iprodione + TX, Chlorfluazuron + TX, Tepa + TX, Thiohexamethylphosphoramide + TX, Thiotepa + TX, Tracaful + TX, Urethaneimine + TX, (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol + TX, (E)-tridec-4-en-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E,Z)-tetradec-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-heneicos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, (7E,9Z)-dodec-7,9-dien-1-yl acetate + TX,(9Z,11E)-tetradeca-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradeca-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, western pine beetle aggregation pheromone + TX, dodecadienol + TX, geraniol + TX, cue-lure + TX, epoxy nonadecane + TX, dodec-8-en-1-yl acetate + TX, dodec-9-en-1-yl acetate + TX, dodec-8,10-dien-1-yl acetate + TX, domicalure + TX, ethyl 4-methylcaprylate + TX, eugenol + TX, southern pine beetle aggregation pheromone + TX, grandlure mixture + TX, grandlure mixture I + TX, grandlure mixture II + TX, grandlure mixture III + TX, grandlure mixture IV + TX, hexalure + TX, ipsdienol + TX, pherocon AM + TX, sex pheromone of scarab beetles + TX, trimethyldioxatricyclononane + TX, litlure + TX, sex pheromone of tobacco budworm + TX, grandlure + TX, megametmic acid + TX, cucumerin + TX, cucurbitacin + TX, octadec-2,13-dien-1-yl acetate + TX, octadec-3,13-dien-1-yl acetate + TX, heptacon + TX, aggregation pheromone of coconut rhinoceros beetle + TX, nonylure + TX, cucumerol + TX, sodiun diethyldithiocarbamate + TX, myceliol + TX, tetradec-11-en-1-yl acetate + TX, medfly attractant + TX, medfly attractant A + TX, medfly attractant B1 + TX, medfly attractant B2 + TX, medfly attractant C + TX, tricoc + TX, 2-(octylthio)-ethanol + TX, dibutyl phthalate + TX, butyl octyl phthalate + TX, dioctyl phthalate + TX, diethyltoluamide + TX, dimethyl phthalate + TX, ethylhexylglycerin + TX, hexanamide + TX, mequitazine + TX, methyl neodecanoate + TX, oxamate + TX, picaridin + TX, 1,1-dichloro-1-nitroethane + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane + TX, 1,2-dichloropropane and 1,3-dichloropropene + TX, 1-bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2-(2-chloroethenyl)-2-ethylsulfinylethyl methyl phosphonate + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate + TX, 2-(4-chloro-3,5-dimethylphenoxy)ethanol + TX,2-chloroethenyl diethyl phosphate + TX, 2-imidazolidinone + TX, 2-isovalerylindane-1,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate + TX, 2-thiocyanatoethyl laurate + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate + TX, 4-methyl(prop-2-ynyl)amino-3,5-dimethylphenyl methylcarbamate + TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate + TX, malathion + TX, acrylonitrile + TX, aldrin + TX, allomurin + TX, xylylcarb + TX, α-ecdysone + TX, aluminium phosphide + TX, methomyl + TX, neonicotinoid + TX, ethyl thiophenephos + TX, pirimiphos-methyl + TX, Bacillus thuringiensis delta-endotoxins + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, resmethrin + TX, Bayer 22 / 190 + TX, Bayer 22408 + TX, beta-cyfluthrin + TX, beta-cypermethrin + TX, empenthrin + TX, bioallethrin + TX, bis(2-chloroethyl) ether + TX, borax + TX, bromfenvinfos + TX, bromo-DDT + TX, dimecarb + TX, butacarb + TX, demethylbutapyrimfos + TX, butonate + TX, calcium arsenate + TX, calcium cyanide + TX, carbon disulfide + TX, carbon tetrachloride + TX, cartap hydrochloride + TX, cevadine + TX, endosulfan + TX, chlordane + TX, kepone + TX, chloroform + TX, trichloronitromethane + TX, chlorphoxim + TX, chlorprazophos + TX, cis-resmethrin + TX, cis-resmethrin + TX, lambda-cyhalothrin + TX, cupric acetoarsenite + TX, cupric arsenate + TX, copper oleate + TX, cyanofenphos + TX, cryolite + TX, CS 708 + TX, cyanofenphos + TX, cyanophos + TX, cycloprothrin + TX, cyromazine + TX, d-tetramethrin + TX, DAEP + TX, dazomet + TX, carbofuran + TX, disulfoton + TX, isothioate + TX, dichlorvos + TX, Dicresyl + TX, diflubenzuron + TX, dieldrin + TX, diethyl 5-methylpyrazol-3-yl phosphate + TX, diprophylline + TX, transfluthrin + TX, dimefox + TX, pyrethrins + TX, methacrifos + TX, methiocarb + TX, methomyl + TX, binapacryl + TX, dinocap + TX, dinoseb + TX, ethofenprox + TX, sulfotep + TX, ecdysone + TX, EI 1642 + TX, EMPC + TX, EPBP + TX, oxydemeton-methyl + TX, ethiofencarb + TX, ethyl formate + TX, 1,2-dibromoethane + TX, 1,2-dichloroethane + TX, ethylene oxide + TX, EXD + TX, fenthion + TX, ethiofencarb + TX, fenitrothion + TX, flutolanil + TX, pyraclofos + TX,Fensulfothion + TX, Fenthion - ethyl + TX, Fipronil + TX, EPN + TX, Fosthiazate + TX, Cadusafos + TX, Furathiocarb + TX, Pyrethrins, synthetic + TX, Guazatine + TX, Guazatine acetate + TX, Sodium tetrathiocarbonate + TX, Bifenazate + TX, HCH + TX, HEOD + TX, Heptachlor + TX, Binapacryl + TX, HHDN + TX, Hydrocyanic acid + TX, Propoxur + TX, IPSP + TX, Isazofos + TX, Carbophenothion + TX, Isodrin + TX, Isofenphos + TX, Imazalil + TX, Isoprothiolane + TX, Oxydemeton - methyl + TX, Juvenile hormone I + TX, Juvenile hormone II + TX, Juvenile hormone III + TX, Chlorcyclizine + TX, Kinoprene + TX, Lead arsenate + TX, Bromophos + TX, Propyrisulf + TX, Thiazophos + TX, Isopropyl - m - tolylcarbamate + TX, Magnesium phosphide + TX, Azinphos - methyl + TX, Tetramethrin + TX, Pyridaphenthion + TX, Mercurous chloride + TX, Fenthion sulfoxide + TX, Metam - sodium + TX, Metam - potassium + TX, Metam - ammonium + TX, Methanesulfonyl fluoride + TX, Butamifos + TX, Methoprene + TX, Pyrethrins, natural + TX, Methoxychlor + TX, Methyl isothiocyanate + TX, Methyl chloroform + TX, Methylene chloride + TX, Oxythioquinox + TX, Mirex + TX, Naphthalophos + TX, Naphthalene + TX, NC - 170 + TX, Nicotine + TX, Nicotine sulfate + TX, Nitrothal - isopropyl + TX, Nornicotine + TX, O - 5 - Dichloro - 4 - iodophenyl O - ethyl ethylphosphonothioate + TX, O,O - Diethyl O - 4 - methyl - 2 - oxo - 2H - chromen - 7 - yl phosphorothioate + TX, O,O - Diethyl O - 6 - methyl - 2 - propylpyrimidin - 4 - yl phosphorothioate + TX, O,O,O',O' - Tetrapropyl pyrophosphorodithioate + TX, Oleic acid + TX, p - Dichlorobenzene + TX, Parathion - methyl + TX, Pentachlorophenol + TX, Pentachlorophenyl laurate + TX, PH 60 - 38 + TX, Phenthoate + TX, Parathion + TX, Phosphine + TX, Phoxim - methyl + TX, Methamidophos + TX, Chlordene isomers + TX, Potassium arsenite + TX, Potassium thiocyanate + TX, Precocene I + TX, Precocene II + TX, Precocene III + TX, Acephate + TX, Profluthrin + TX, Carbaryl + TX, Prothiofos + TX, Triforine + TX, Resmethrin + TX, Quassia extract + TX, Quinalphos - methyl + TX, Chlorthiophos + TX, Rafoxanide + TX, Resmethrin + TX, Rotenone + TX, Tienilic acid + TX, Nicotine + TX, Ryanodine + TX, Veratrum sabadilla + TX, Schradan + TX, Cartap + TX, SI - 0009 + TX, Etoxazole + TX, Sodium arsenite + TX, Sodium cyanide + TX, Sodium fluoride + TX, Sodium hexafluorosilicate + TX, Sodium pentachlorophenate + TX, Sodium selenate + TX, Sodium thiocyanate + TX, Sarkophore + TX,Sulcofuron-sodium + TX, Sulfuryl fluoride + TX, Prothiofos + TX, Tar + TX, Tebufenpyrad + TX, TDE + TX, Butylpyrimiphos + TX, Dibrom + TX, Allethrin + TX, 1,1,2,2-Tetrachloroethane + TX, EPN + TX, Thiosultap + TX, Thiosultap hydrogen oxalate + TX, Sulfotep + TX, Monosultap + TX, Bisultap + TX, Tetramethrin + TX, Transfluthrin + TX, Triazamate + TX, Trichloromelamine-3 + TX, Chlorbufam + TX, BPMC + TX, Methfuroxam + TX, Chlorothalonil + TX, Teflubenzuron + TX, Veratridine + TX, Veratrine + TX, XMC + TX, Zeta-cypermethrin + TX, Zinc phosphide + TX, Zolaprofos + TX, and Chloroflurane + TX, Tetramethrin + TX, Bis(tributyltin) oxide + TX, Bromoacetamide + TX, Iron phosphate + TX, Niclosamide-ethanolamine + TX, Tributyltin oxide + TX, Pyrimorph + TX, Metaldehyde + TX, 1,2-Dibromo-3-chloropropane + TX, 1,3-Dichloropropene + TX, 3,4-Dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-(4-Chlorophenyl)-5-methylrhodanine + TX, 5-Methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid + TX, 6-Isopentenylaminopurine + TX, 2-Fluoro-N-(3-methoxyphenyl)-9H-purin-6-amine + TX, Benzyl chloride + TX, Cytokinin + TX, DCIP + TX, Furfural + TX, Isamidofos + TX, Kinetin + TX, Myrothecium verrucaria composition + TX, Tetrachlorothiophene + TX, Xylenol + TX, Zeatin + TX, Potassium ethylxanthate + TX, Benzoic acid + TX, Benzoic acid-S-methyl + TX, Reynoutria japonica Houtt. extract + TX, α-Chloroalcohol + TX, Antu + TX, Barium carbonate + TX, Diphacinone + TX, Brodifacoum + TX, Bromadiolone + TX, Bromethalin + TX, Chlorophacinone + TX, Cholecalciferol + TX, Chlorophacinone + TX, Coumatetralyl + TX, Coumatetralyl + TX, Difenacoum + TX, Tazimoxan + TX, Warfarin + TX, Piperic acid 2-(2-butoxyethoxy)ethyl ester + TX, 5-(1,3-Benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, Farnesol with nerolidol + TX, Sesamex + TX, MGK 264 + TX, Piperonyl butoxide + TX, Octyl polyoxyethylene aldehyde + TX, Octyl polyoxyethylene phthalate + TX, S421 + TX, Synergistic powder + TX, Sesamin + TX, Sulfoxide + TX, Anthraquinone + TX, Copper naphthenate + TX, Copper oxychloride + TX, Dicyclopentadiene + TX, Thiram + TX, Zinc naphthenate + TX,ziram + TX, imazalil + TX, ribavirin + TX, mercuric oxide + TX, thiophanate-methyl + TX, azaconazole + TX, bitertanol + TX, bromuconazole + TX, cyproconazole + TX, difenoconazole + TX, diniconazole + TX, epoxiconazole + TX, fenbuconazole + TX, fluquinconazole + TX, flusilazole + TX, flutriafol + TX, furametpyr + TX, hexaconazole + TX, imazalil + TX, imibenconazole + TX, ipconazole + TX, metconazole + TX, myclobutanil + TX, paclobutrazol + TX, piroquilon + TX, penconazole + TX, prothioconazole + TX, pyrifenox + TX, prochloraz + TX, propiconazole + TX, pyrisoxazole + TX, silafluofen + TX, tebuconazole + TX, tetraconazole + TX, triadimefon + TX, triadimenol + TX, triflumizole + TX, triticonazole + TX, ancymidol + TX, fenarimol + TX, nuarimol + TX, ethirimol + TX, dimethirimol + TX, dodemorph + TX, fenpropidin + TX, fenpropimorph + TX, spiroxamine + TX, tridemorph + TX, cyprodinil + TX, fenoxanil + TX, pyrimethanil + TX, fenpiclonil + TX, fludioxonil + TX, benalaxyl + TX, ofurace + TX, metalaxyl + TX, R-metalaxyl + TX, furalaxyl + TX, oxadixyl + TX, carbendazim + TX, iminoctadine + TX, tecnazene + TX, thiabendazole + TX, chlozolinate + TX, procymidone + TX, methfuroxam + TX, iprodione + TX, vinclozolin + TX, boscalid + TX, carboxin + TX, methfuroxam + TX, fthalide + TX, oxycarboxin + TX, isopyrazam + TX, thifluzamide + TX, dodine + TX, guazatine + TX, azoxystrobin + TX, dimoxystrobin + TX, enestroburin + TX, enostamide + TX, fluacrypyrim + TX, fluoxastrobin + TX, metominostrobin + TX, metrafenone + TX, orysastrobin + TX, picoxystrobin + TX, pyraoxystrobin + TX, pyraclostrobin + TX, ferbam + TX, mancozeb + TX, maneb + TX, metiram + TX, zineb + TX, ziram + TX, captafol + TX, captan + TX, pyrazolate + TX, dichlofluanid + TX, tolylfluanid + TX, Bordeaux mixture + TX, copper oxide + TX, copper mancozeb + TX, copper quinolate + TX, phthalide + TX, blasticidin-S + TX, chloroneb + TX, chlorothalonil + TX, cyflufenamid + TX, cymoxanil + TX, cyflufenamid + TX, diclomezine + TX, dithianon + TX, thiazovivin + TX, terrazole + TX, famoxadone + TX, fenamidone + TXCarpropamid + TX, Ferimzone + TX, Fluazinam + TX, Fluopicolide + TX, Sulfluramid + TX, Fluxapyroxad + TX, Cyclanilide + TX, fosetyl-aluminum + TX, Hymexazol + TX, Propineb + TX, Cyazofamid + TX, Sulfosultap + TX, Metrafenone + TX, Teburon + TX, Blasticidin-S + TX, Polyoxin + TX, Propamocarb + TX, Pyribencarb + TX, Iodosulfuron-methyl + TX, Pyroquilon + TX, Picarbutrazox + TX, Quinoxyphen + TX, quintozene + TX, Thifluzamide + TX, Imazalil + TX, Tricyclazole + TX, Triforine + TX, Validamycin + TX, Dimethomorph + TX, Zoxamide + TX, Mandipropamid + TX, Fluopyram + TX, Isopyrazam + TX, Flutriafol + TX, Benzovindiflupyr + TX, Fluxametamide + TX, 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, Isofetamid + TX, Isotianil + TX, Dipyrithione + TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithieno[1,2-c]isothiazole-3-carbonitrile + TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethyl-indan-4-yl]pyrazole-4-carboxamide + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-2,5-dimethyl-pyrazol-3-amine + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine + TX, Fluindapyrad + TX, Jiaxiangjunzhi, Lebemina, Dichlobenam, Mendespin, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol + TX, Fluoxastrobin + TX, N-[6-[[[(1-methyltetrazol-5-yl)phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamic acid tert-butyl ester + TX, Bixafen + TX, Impetosulf + TX, Topcab, Chlorfluzuron + TX, Iprovalicarb + TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methyl-formamidine + TX,N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + TX, methylsulfonic acid [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl] ester + TX, N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamic acid but-3-ynyl ester + TX, N-[[5-[4-(2,4-dimethylphenyl)-1,2,3-triazol-2-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, Pydar + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylinden-4-yl]pyrazole-4-carboxamide + TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-1H-tetrazol-5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]-1H-tetrazol-5-one + TX, Amiphenazole + TX, Azoxystrobin + TX, Indaziflam + TX, Penthiopyrad + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX, Picoxystrobin + TX, Bixafen + TX, Isobutyl ethyloxquinoline + TX, Fluopicolide + TX, Chinomethionat + TX, Isotianil + TX, N-[2-[2,4-dichlorophenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, Benzothiazole + TX, Cyenopyrac + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, Fluopyram + TX, Fluopyram + TX, Flutianil + TX, Piraclostrobin + TX, Tricyclazole + TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-inden-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylinden-4-yl)pyridine-3-carboxamide + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridinyl]oxy]benzonitrile + TX, Metconazole + TX, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidine methanol + TX,Flufenoxypirin + TX, Enestroburin + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridinyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioalkyl-1,2,4-triazol-1-yl)propyl]-3-pyridinyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridinyl]oxy]benzonitrile + TX, Trinexapac-ethyl + TX, Cercosporamide + TX, Zhongshengmycin + TX, Thiodiazole copper + TX, Thiazole zinc + TX, Amitrole + TX, Iprodione + TX, N-octyl-N'-[2-(octylamino)methyl]ethane-1,2-diamine + TX; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds can be prepared by the methods described in WO 2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared by the methods described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenylethyl)phenyl]-N-methyl-formamidine + TX, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds can be prepared by the methods described in WO 2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[2-(trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX,N-ethyl-N'-[5-methoxy-2-methyl-4-[2-(trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine + TX (These compounds can be prepared by the methods described in WO 2019 / 110427); N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-en-1-yl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-en-1-yl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-en-1-yl)-8-fluoro-quinoline-3-carboxamide + TX, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-en-1-yl)-8-fluoro-quinoline-3-carboxamide + TX (These compounds can be prepared by the methods described in WO 2017 / 153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX (These compounds can be prepared by the methods described in WO 2017 / 025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX,1-(4,5-Dimethyl-1H-benzo[d]imidazol-1-yl)-4,4-difluoro-3,3-dimethylisoquinoline + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methyl-1H-benzo[d]imidazol-1-yl)isoquinoline + TX, 4,4-difluoro-1-(5-fluoro-4-methyl-1H-benzo[d]imidazol-1-yl)-3,3-dimethylisoquinoline + TX, 3-(4,4-difluoro-3,3-dimethylisoquinolin-1-yl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole + TX (these compounds can be prepared by the methods described in WO 2016 / 156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate + TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine + TX. The compounds in this paragraph can be prepared from WO 2017 / 055473, WO 2017 / 055469,Prepared by the methods described in WO 2017 / 093348 and WO 2017 / 118689; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound can be prepared by the method described in WO 2017 / 029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound can be prepared by the method described in WO2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate + TX (this compound can be prepared by the method described in WO2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithieno[2,3-c:5,6-c']bipyrrole-1,3,5,7(2H,6H)-tetrone + TX (this compound can be prepared by the method described in WO 2011 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]thiobenzamide + TX; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine + TX (this compound can be prepared by the method described in WO 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methyl-formamidine + TX; N'-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared by the method described in WO 2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX (this compound can be prepared by the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX,(3-Methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX (These compounds can be prepared by the methods described in WO 2017 / 220485); 2-Oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX (This compound can be prepared by the methods described in WO 2018 / 065414); Ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate + TX (This compound can be prepared by the methods described in WO 2018 / 158365); 2,2-Difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX, N-[(E)-Methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[(Z)-Methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[N-Methoxy-C-methyl-carbamimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX (These compounds can be prepared by the methods described in WO 2018 / 202428), Chloridazon + TX, Flusulfuron + TX, Fluopyram + TX, Fluazaindolizine + TX, Pyroxasulfone + TX.

[0739] References in parentheses after the active ingredients, such as [3878-19-1], refer to Chemical Abstracts Registry Numbers. The mixing combinations described above are known. Where the active ingredients are included in "The Pesticide Manual", they are described therein by the entry numbers given in parentheses above for the specific compounds; for example, the compound "abamectin" is described by the entry number (1). Where "[CCN]" is added above to a specific compound, the said compound is included in "Compendium of Pesticide Common Names", which can be found on the Internet [A. Wood; Compendium of Pesticide Common Names , obtained in [1995-2004]; for example, the compound "acetoprole" is described at the Internet address http: / / www.alanwood.net / pesticides / acetoprole.html.

[0740] Most of the above active ingredients are referred to above by means of the so-called "common name", using the corresponding "ISO common name" or another "common name" in a single case. If the name is not a "common name", the type of name used is replaced by the name given in parentheses for the particular compound; in this case, the IUPAC name, the IUPAC / Chemical Abstracts name, the "chemical name", the "trivial name", the "compound name" or the "development code" is used, or if neither one of those names nor the "common name" is used, the "alias" is adopted. "CAS Registry Number" means the Chemical Abstracts Registry Number.

[0741] A mixture of active ingredients of compounds selected from the compounds of formula (I), (I-A), (I-A1), (I-A2), (I-A3), (I-A4), (I-A5), or (I-A6), or from the compounds listed in Tables B-1 to B-27 or in Table P (below) is preferably in a mixing ratio of 100:1 to 1:100, in particular 50:1 to 1:50, more particularly 20:1 to 1:20, even more particularly 10:1 to 1:10 and still more particularly 5:1 to 1:5. Those mixing ratios are by weight.

[0742] A mixture as described above can be used in a method for controlling pests, which method comprises applying a composition comprising a mixture as described above to the pests or their environment, except for methods for treating the human or animal body by surgery or therapy and diagnostic methods carried out on the human or animal body.

[0743] Compounds comprising a compound selected from the compounds of formula (I), (I-A), (I-A1), (I-A2), (I-A3), (I-A4), (I-A5), or (I-A6), or a compound selected from the compounds listed in Tables B-1 to B-27 or the compounds listed in Table P (below), and a mixture of one or more active ingredients as described above can be applied, for example, in a single "ready-to-use" form, in a combined spray mixture consisting of separate formulations of the individual active ingredient components, such as a "tank mix", and when applied in a sequential manner, i.e., one after the other within a reasonably short period of time (such as a few hours or days), the individual active ingredients are used in combination. The order of application of a compound selected from the compounds of formula (I), (I-A), (I-A1), (I-A2), (I-A3), (I-A4), (I-A5), or (I-A6), or a compound selected from the compounds listed in Tables B-1 to B-27 or the compounds listed in Table P (below), and one or more active ingredients as described above is not critical for carrying out the invention.

[0744] The compositions according to the invention can also contain further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (such as epoxidized coconut oil, rapeseed oil or soybean oil), defoamers (such as silicone oils), preservatives, viscosity regulators, binders and / or tackifiers, fertilizers or other active ingredients for obtaining specific effects, such as bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0745] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries, for example by grinding, sieving and / or compressing the solid active ingredient; and in the presence of at least one auxiliary, for example by intimately mixing the active ingredient with one or more auxiliaries and / or by grinding the active ingredient together with one or more auxiliaries. These methods for preparing the compositions and the use of the compound (I) for preparing these compositions are also the subject of the invention.

[0746] Another aspect of the invention relates to the use of a composition according to the invention comprising at least one compound of formula (I) or at least one individual compound preferably defined herein, or a fungicidal or insecticidal mixture comprising at least one compound of formula (I) or at least one individual compound preferably defined herein (mixed with other fungicides or insecticides as described above), for controlling or preventing the infestation of plants (such as useful plants (e.g., crop plants)), their propagation material (e.g., seeds), harvested crops (e.g., harvested food crops), or non-living materials by insects or phytopathogenic microorganisms (preferably fungal organisms).

[0747] Another aspect of the present invention relates to a method for controlling or preventing plants (such as useful plants (e.g., crop plants)), their propagation materials (such as seeds), harvested crops (such as harvested food crops), or inanimate materials from being infested by phytopathogenic microorganisms or spoilage microorganisms or organisms potentially harmful to humans (especially fungal organisms), the method comprising applying a compound of formula (I) according to the present invention or preferably an individual compound as defined herein as an active ingredient to these plants, parts thereof or their sites, their propagation materials, or any part of these inanimate materials.

[0748] Controlling or preventing means reducing the infestation by insects or phytopathogenic microorganisms or spoilage microorganisms or organisms potentially harmful to humans (especially fungal organisms) to a level proven to be improved.

[0749] A preferred method for controlling or preventing crop plants from being infested by phytopathogenic microorganisms (especially fungal organisms) or insects is foliar application, which comprises applying a compound of formula (I) according to the present invention or an agrochemical composition containing at least one compound of formula (I). The frequency and rate of application will depend on the risk of infestation by the corresponding pathogen or insect. However, the compound of formula (I) according to the present invention can also penetrate plants via the roots (systemic action) through the soil by soaking the site of the plants with a liquid formulation or by applying the compound in solid form, for example in granular form, to the soil (soil application). In rice crops, such granules can be applied to flooded paddy fields. The compound of formula (I) can also be applied to seeds (coating) by impregnating the seeds or tubers with a liquid formulation of a fungicide or coating them with a solid formulation.

[0750] Formulations (such as compositions containing a compound of formula (I) according to the present invention and, if desired, solid or liquid auxiliaries or monomers for encapsulating the compound of formula (I)) can be prepared in a known manner, typically by intimately mixing and / or grinding the compound with extenders (such as solvents, solid carriers and optionally surface-active compounds (surfactants)).

[0751] Advantageous application rates are generally 5 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably 10 g to 1 kg a.i. / ha, most preferably 20 g to 600 g a.i. / ha. When used as a seed soaking reagent, a suitable dose is 10 mg to 1 g of active substance per kg of seeds.

[0752] As used herein, the term "g a.i. / ha" refers to an application rate given in grams [g] of active ingredient [a.i.] per unit surface [ha]. The unit hectare (symbol ha) is a metric unit of area equal to the area of a square with a side length of 100 m (1 hm 2 ) or 10,000 square meters. The hectare is a commonly used unit of area in the metric system.

[0753] When the combinations according to the invention are used for treating seeds, application rates of from 0.001 to 50 g of the compound of formula (I) per kg of seeds, preferably from 0.01 to 10 g / kg of seeds, are generally sufficient.

[0754] Compositions comprising a compound of formula (I) according to the invention are preferably applied preventively (i.e. before the development of the disease) or curatively (i.e. after the development of the disease).

[0755] The compositions according to the invention can be employed in any conventional form, for example in the form of a two-pack, a powder for dry seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspoemulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), a water-in-oil emulsion (EO), an oil-in-water emulsion (EW), a microemulsion (ME), a dispersible oil suspension (OD), an oil suspension (OF), an oil-soluble liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0756] Such compositions can be produced in a conventional manner, for example by mixing the active ingredient with suitable formulation inert ingredients (diluents, solvents, fillers and optionally other formulation ingredients such as surfactants, biocides, antifreeze agents, adhesives, thickeners and compounds providing auxiliary effects). Conventional slow release formulations intended for long-lasting efficacy can also be employed. In particular, formulations to be applied in spray form, such as water dispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO, etc.), wettable powders and granules, can contain surfactants such as wetting agents and dispersants and other compounds providing auxiliary effects, such as condensation products of formaldehyde with naphthalene sulfonates, alkylaryl sulfonates, lignin sulfonates, fatty alkyl sulfates and ethoxylated alkyl phenols and ethoxylated fatty alcohols.

[0757] The combination and diluent according to the invention are used in the form of a suitable seed dressing formulation, for example in the form of an aqueous suspension or a dry powder having good adhesiveness to seeds, and the seed dressing formulation is applied to the seeds in a manner known per se. Such seed dressing formulations are known in the art. The seed dressing formulation may contain a single active ingredient or a combination of active ingredients in encapsulated form, for example as a slow-release capsule or a microcapsule.

[0758] Generally, these formulations contain 0.01% to 90% by weight of an active agent, 0% to 20% of an agriculturally acceptable surfactant, and 10% to 99.99% of a solid or liquid formulation inert agent and one or more adjuvants. The active agent consists of at least a compound of formula (I) according to the invention, optionally together with other active agents (especially microbicides or preservatives, etc.). The concentrated form of the composition usually contains 2% to 80% by weight, preferably 5% to 70% by weight of the active agent. The application form of the formulation may contain 0.01% to 20% by weight, preferably 0.01% to 5% by weight of the active agent. However, commercial products will preferably be formulated as concentrates, and the end user will generally use diluted formulations.

[0759] However, it is preferred to formulate commercial products as concentrates, and the end user will generally use diluted formulations.

[0760] The application rate varies within a wide range and depends on the nature of the soil, the application method, the crop plant, the pest to be controlled, the main climatic conditions, and other factors governed by the application method, the application time, and the target crop. Generally speaking, the compound can be applied at a rate of 1 to 2000 l / ha, especially 10 to 1000 l / ha.

[0761] Preferred formulations may have the following composition (% by weight):

[0762] Emulsifiable concentrate :

[0763] Active ingredient: 1% to 95%, preferably 60% to 90%

[0764] Surfactant: 1% to 30%, preferably 5% to 20%

[0765] Liquid carrier: 1% to 80%, preferably 1% to 35%

[0766] Dust :

[0767] Active ingredient: 0.1% to 10%, preferably 0.1% to 5%

[0768] Solid carrier: 99.9% to 90%, preferably 99.9% to 99%

[0769] Suspension concentrate:

[0770] Active ingredient: 5% to 75%, preferably 10% to 50%

[0771] Water: 94% to 24%, preferably 88% to 30%

[0772] Surfactant: 1% to 40%, preferably 2% to 30%

[0773] Wettable powder :

[0774] Active ingredient: 0.5% to 90%, preferably 1% to 80%

[0775] Surfactant: 0.5% to 20%, preferably 1% to 15%

[0776] Solid carrier: 5% to 95%, preferably 15% to 90%

[0777] Granule:

[0778] Active ingredient: 0.1% to 30%, preferably 0.1% to 15%

[0779] Solid carrier: 99.5% to 70%, preferably 97% to 85%

[0780] The disclosure of the present application enables each combination of the embodiments disclosed herein to be obtained.

[0781] The compounds according to Tables B-1 to B-27 below can be prepared by the methods described above. These subsequent examples are intended to illustrate the invention and to show the preferred compounds of formula (I). The presence of one or more possible asymmetric carbon atoms in the compounds of formula (I) according to the invention in any of the following Tables B-1 to B-27 means that these compounds can exist in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms.

[0782] Table A : This table discloses 22 compounds of formula (A):

[0783]

[0784] wherein R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、B1 and B 2 is as defined above for the compounds of formula (I), and Q has the formula wherein the dashed line indicates a bond to the remainder of the molecule, as defined below:

[0785]

[0786] Table B-1: This table provides 22 compounds of formula (A), B-1.01 to B-1.22, wherein R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 is H, B 1 and B 2 is C-H, and Q is as defined in Table A.

[0787] For example, compound B-1.17 has the following structure:

[0788]

[0789] Table B-2: This table provides 22 compounds of formula (A), B-2.01 to B-2.22, wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 is H, R 2 is CH3, B 1 and B 2 is C-H, and Q is as defined in Table A.

[0790] Table B-3: This table provides 22 compounds of formula (A), B-3.01 to B-3.22, wherein R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 is H, R 2 is CH3, B 1 is C-H, and B 2 is C-Cl, and Q is as defined in Table A.

[0791] Table B-4:This table provides 22 compounds of formula (A), B-4.01 to B-4.22, where R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 is H, R 2 is CH3, B 1 is C-H, and B 2 is C-Br, and Q is as defined in Table A.

[0792] Table B-5: This table provides 22 compounds of formula (A), B-5.01 to B-5.22, where R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 is H, R 2 is CH3, B 1 is C-H, and B 2 is C-F, and Q is as defined in Table A.

[0793] Table B-6: This table provides 22 compounds of formula (A), B-6.01 to B-6.22, where R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 is H, R 2 is CH3, B 1 is C-H, and B 2 is C-CN, and Q is as defined in Table A.

[0794] Table B-7: This table provides 22 compounds of formula (A), B-7.01 to B-7.22, where R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 is H, R 2 is CH3, B 1 is C-H, and B 2 is C-CH3, and Q is as defined in Table A.

[0795] Table B-8: This table provides 22 compounds of formula (A), racemic-cis-B-8.01 to racemic-cis-B-8.22, where R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 is H, R 7 is CH3, B 1 and B 2 are C-H, and Q is as defined in Table A. In these compounds, the pyrazole substituent and the R 7 substituent have a cis-relationship to each other.

[0796] For example, the compound racemic-cis-B-8.22 has the following structure:

[0797]

[0798] Table B-9: This table provides 22 compounds of formula (A), racemic-cis-B-9.01 to racemic-cis-B-9.22, where R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 is H, R 7 is CH3, B 1 is C-H and B 2 is C-Cl, and Q is as defined in Table A. In these compounds, the pyrazole substituent and the R 7 substituent have a cis-relationship to each other.

[0799] Table B-10: This table provides 22 compounds of formula (A), racemic-cis-B-10.01 to racemic-cis-B-10.22, where R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 is H, R 7 is CH3, B 1 is C-H and B 2 is C-F, and Q is as defined in Table A. In these compounds, the pyrazole substituent and the R 7 substituent have a cis-relationship to each other.

[0800] Table B-11: This table provides 22 compounds of formula (A) racemic-cis-B-11.01 to racemic-cis-B-11.22, where R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 is H, R 7 is CH3, B 1 is C-H and B 2 is C-Br, and Q is as defined in Table A. Among these compounds, the pyrazole substituent and the R 7 substituent have a cis-relationship with each other.

[0801] Table B-12: This table provides 22 compounds of formula (A) racemic-cis-B-12.01 to racemic-cis-B-12.22, where R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 is H, R 7 is CH3, B 1 is C-H and B 2 is C-CN, and Q is as defined in Table A.

[0802] Table B-13: This table provides 22 compounds of formula (A) racemic-cis-B-13.01 to racemic-cis-B-13.22, where R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 is H, R 7 is CH3, B 1 is C-H and B 2 is C-CH3, and Q is as defined in Table A.

[0803] Table B-14: This table provides 22 compounds of formula (A) racemic-cis-B-14.01 to racemic-cis-B-14.22, where R 3 , R 4 , R 5 , R 6 , R 8 , R9 is H, R 2 and R 7 is CH3, B 1 and B 2 is C-H, and Q is as defined in Table A. Among these compounds, the pyrazole substituent and R 7 substituents have a cis-relationship with each other.

[0804] For example, the compound racemic-cis-B-14.16 has the following structure:

[0805]

[0806] Table B-15: This table provides 22 compounds of formula (A) racemic-cis-B-15.01 to racemic-cis-B-15.22, where R 3 , R 4 , R 5 , R 6 , R 8 , R 9 is H, R 2 and R 7 is CH3, B 1 is C-H, B 2 is C-Cl, and Q is as defined in Table A. Among these compounds, the pyrazole substituent and R 7 substituents have a cis-relationship with each other.

[0807] Table B-16: This table provides 22 compounds of formula (A) racemic-cis-B-16.01 to racemic-cis-B-16.22, where R 3 , R 4 , R 5 , R 6 , R 8 , R 9 is H, R 2 and R 7 is CH3, B 1 is C-H, B 2 is C-F, and Q is as defined in Table A. Among these compounds, the pyrazole substituent and R 7 substituents have a cis-relationship with each other.

[0808] Table B-17: This table provides 22 compounds of formula (A) racemic-cis-B-17.01 to racemic-cis-B-17.22, where R 3 , R 4 , R 5 , R 6 , R8 , R 9 is H, R 2 and R 7 is CH3, B 1 is C-H, B 2 is C-Br, and Q is as defined in Table A.

[0809] Table B-18: This table provides 22 compounds of formula (A) from racemic-cis-B-18.01 to racemic-cis-B-18.22, where R 3 , R 4 , R 5 , R 6 , R 8 , R 9 is H, R 2 and R 7 is CH3, B 1 is C-H and B 2 is C-CN, and Q is as defined in Table A.

[0810] Table B-19: This table provides 22 compounds of formula (A) from racemic-cis-B-19.01 to racemic-cis-B-19.22, where R 3 , R 4 , R 5 , R 6 , R 8 , R 9 is H, R 2 and R 7 is CH3, B 1 is C-H and B 2 is C-CH3, and Q is as defined in Table A.

[0811] Table B-20: This table provides 22 compounds of formula (A) from racemic-cis-B-20.01 to racemic-cis-B-20.22, where R 3 , R 4 , R 5 , R 6 , R 8 , R 9 is H, R 2 is Cl, R 7 is CH3, B 1 and B 2 is C-H, and Q is as defined in Table A.

[0812] Table B-21:This table provides 22 compounds with formula (A), racemic-cis-B-21.01 to racemic-cis-B-21.22, where R 3 , R 4 , R 5 , R 6 , R 8 , R 9 is H, R 2 is Cl, R 7 is CH3, B 1 is C-H, and B 2 is C-Br, and Q is as defined in Table A.

[0813] Table B-22: This table provides 22 compounds with formula (A), racemic-cis-B-22.01 to racemic-cis-B-22.22, where R 3 , R 4 , R 5 , R 6 , R 8 , R 9 is H, R 2 is Cl, R 7 is CH3, B 1 is C-H, and B 2 is C-Br, and Q is as defined in Table A.

[0814] Table B-23: This table provides 22 compounds with formula (A), racemic-cis-B-23.01 to racemic-cis-B-23.22, where R 3 , R 4 , R 5 , R 6 , R 8 , R 9 is H, R 2 is Cl, R 7 is CH3, B 1 is C-H, and B 2 is C-CN, and Q is as defined in Table A.

[0815] Table B-24: This table provides 22 compounds with formula (A), B-24.01 to B-24.22, where R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 is H, R 4 is CH3, B 1 and B2 is C-H, and Q is as defined in Table A.

[0816] Table B-25: This table provides 22 compounds of formula (A), B-25.01 to B-25.22, where R 3 , R 5 , R 6 , R 7 , R 8 , R 9 is H, R 2 and R 4 are CH3, B 1 and B 2 is C-H, and Q is as defined in Table A.

[0817] Table B-26: This table provides 22 compounds of formula (A), B-26.01 to B-26.22, where R 3 , R 5 , R 6 , R 7 , R 8 , R 9 is H, R 2 and R 4 are CH3, B 1 is C-H, B 2 is C-Cl, and Q is as defined in Table A.

[0818] Table B-27: This table provides 22 compounds of formula (A), B-27.01 to B-27.22, where R 3 , R 5 , R 6 , R 7 , R 8 , R 9 is H, R 2 and R 4 are CH3, B 1 is C-H, B 2 is C-CN, and Q is as defined in Table A.

[0819] Examples

[0820] The following examples are used to illustrate the invention and are not meant to limit the invention in any way.

[0821] The compounds of the invention may differ from known compounds in greater efficacy at low application rates, which can be confirmed by those skilled in the art using the experimental procedures outlined in the examples, using lower application rates (if necessary), for example, 60 ppm, 20 ppm or 2 ppm.

[0822] Compounds having the formula (I) can have any number of benefits, including in particular favorable levels of biological activity for protecting plants against diseases caused by fungi or superior properties for use as agrochemical active ingredients (e.g., higher biological activity, favorable activity spectrum, increased safety (including improved crop tolerance), improved physicochemical properties, or increased biodegradability).

[0823] Throughout this specification, temperatures are given in degrees Celsius and "m.p." means melting point. LC / MS means liquid chromatography mass spectrometry, and the description of the apparatus and method is as follows.

[0824] Recorded on a Bruker 400 MHz spectrometer 1 H NMR and 19 F NMR measurements, with chemical shifts relative to TMS ( 1 H) and CFCl3 ( 19 F) standards given in ppm. The spectra were measured in the deuterated solvents indicated. The compounds were characterized using any one of the following LCMS methods. The characteristic LCMS values obtained for each compound are the retention time ("Rt", recorded in minutes) and the measured molecular ion (M+H) + or (M-H) - .

[0825] LC-MS method A: Spectra were recorded on a mass spectrometer from Waters (SQD, SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ions, capillary: 3.00 kV, cone voltage 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 to 900 Da) and an Acquity UPLC from Waters: binary pump, heated column compartment, diode array detector and ELSD detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 x 2.1 mm, temperature: 60 °C, DAD wavelength range (nm): 210 to 500, solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; gradient: 10% - 100% B in 1.2 min; flow rate (ml / min): 0.85.

[0826] LC-MS method B:Spectra were recorded on an ACQUITY mass spectrometer (SQD or SQDII single quadrupole mass spectrometer) from Waters Corporation, equipped with an electrospray source (polarity: positive or negative ion, capillary: 3.0 kV, cone: 30 V, extractor: 3.00 V, source temperature: 150 °C, desolvation temperature: 400 °C, cone gas flow: 60 L / hr, desolvation gas flow: 700 L / hr, mass range: 140 to 800 Da) and an ACQUITY UPLC from Waters Corporation, which has a solvent degassing device, a binary pump, a heated column compartment, and a diode array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 x 2.1 mm, temperature: 60 °C, DAD wavelength range (nm): 210 to 400, solvent gradient: A = water / methanol 9:1 + 0.1% formic acid, B = acetonitrile + 0.1% formic acid, gradient: 0 - 100% B in 2.5 min; flow rate (ml / min) 0.75.

[0827] LC-MS method C: LCMS was recorded using the following specifications on an Agilent 1260 series LC / MSD system with DAD\ELSD and an Agilent LC\MSD (G6120B) mass spectrometer or on a UHPLC Agilent 1290 series LC / MSD system with DAD\ELSD and an Agilent LC\MSD (G6125B) mass spectrometer: Column: Agilent Poroshell 120SB-C18 4.6 x 30 mm 2.7 μm; column temperature: 60 °C; mobile phase: A - water (0.1% formic acid), B - acetonitrile (0.1% formic acid); flow rate: 3 ml / min; gradient: 0.01 min - 1% B, 1.5 min - 100% B, 1.73 min - 100% B; MS ionization mode: electrospray ionization (ESI); MS scan range: 83 - 600 m / z; UV detection: 215 nm, 254 nm, 280 nm

[0828] Formulation example

[0829]

[0830] The combination was thoroughly mixed with adjuvants and the mixture was thoroughly ground in a suitable grinder to obtain a wettable powder that can be diluted with water to give a suspension of the desired concentration.

[0831]

[0832] The combination was thoroughly mixed with adjuvants and the mixture was thoroughly ground in a suitable grinder to obtain a powder that can be directly used for seed treatment.

[0833] Emulsifiable concentrate

[0834]

[0835] An emulsion of any desired dilution that can be used in plant protection can be obtained by diluting this concentrate with water.

[0836]

[0837] A ready-to-use dust is obtained by mixing this combination with a carrier and grinding the mixture in a suitable grinder. Such dusts can also be used for dry seed dressing.

[0838] Extruded granule

[0839]

[0840] Mix this combination with adjuvants and grind, and moisten the mixture with water. Extrude the mixture and then dry it in an air stream.

[0841] Coated granule

[0842] Active ingredient 8%

[0843] Polyethylene glycol (molecular weight 200) 3%

[0844] Kaolin 89%

[0845] Apply the finely ground combination evenly to kaolin moistened with polyethylene glycol in a mixer. Dust-free coated granules are obtained in this way.

[0846] Suspension concentrate

[0847]

[0848] Mix the finely ground combination tightly with adjuvants to give a suspension concentrate, from which suspensions of any desired dilution can be obtained by diluting with water. Using such dilutions, living plants together with plant propagation materials can be treated and protected against microbial infestation by spraying, watering or dipping.

[0849] Flowable concentrate for seed treatment

[0850]

[0851] The finely ground combination is intimately mixed with adjuvants to give a flowable concentrate, resulting in a flowable concentrate that can be directly used for seed treatment. Further, the finely ground combination is intimately mixed with adjuvants to give a flowable concentrate from which flowable concentrates of any desired dilution can be obtained by dilution with water. Using such dilutions, seeds, living plants, and plant propagation materials can be treated and protected against microbial infestation by spraying, watering, or dipping.

[0852] Sustained-release capsule suspension

[0853] 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 part of an antifoaming agent, and 51.6 parts of water until the desired particle size is reached. A mixture of 2.8 parts of 1,6-hexanediamine in 5.3 parts of water is added to this emulsion. The mixture is stirred until the polymerization reaction is complete. The obtained capsule suspension is stabilized by adding 0.25 part of a thickening agent and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredient. The diameter of the medium capsules is 8 - 15 microns. The resulting formulation is applied as an aqueous suspension in a device suitable for this purpose to the seeds.

[0854] Formulation types include emulsion concentrate (EC), suspension concentrate (SC), suspoemulsion (SE), capsule suspension (CS), water dispersible granule (WG), emulsifiable granule (EG), emulsion, water-in-oil emulsion (EO), oil-in-water emulsion (EW), microemulsion (ME), oil dispersion (OD), oil suspension (OF), oil soluble concentrate (OL), soluble concentrate (SL), ultra-low volume suspension (SU), ultra-low volume liquid (UL), technical concentrate (TK), dispersible concentrate (DC), wettable powder (WP), soluble granule (SG), or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0855] Abbreviation

[0856] CDCl3 deuterated chloroform

[0857] DABCO 1,4-diazabicyclo[2.2.2]octane, also known as triethylenediamine or TEDA

[0858] DCC dicyclohexylcarbodiimide

[0859] DCM dichloromethane or methylene dichloride or methylene chloride

[0860] DMF N,N-Dimethylformamide

[0861] DMSO Dimethyl sulfoxide

[0862] DMSO-d6 Deuterated dimethyl sulfoxide

[0863] EDC 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide

[0864] Et3N Triethylamine or TEA

[0865] EtOAc Ethyl acetate

[0866] HATU 1-[Bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium-3-oxide hexafluorophosphate

[0867] HCl Hydrochloric acid

[0868] h / hrs Hour / hours

[0869] LC-MS Liquid chromatography - mass spectrometry (LC-MS or LCMS)

[0870] rh Relative humidity

[0871] rt Room temperature (rt or RT)

[0872] Rt Retention time

[0873] ssp. Subspecies

[0874] T3P Propane phosphonic anhydride, also known as 2,4,6-Tripropyl-1,3,5,2,4,6-trioxatriphosphinane 2,4,6-trioxide

[0875] THF Tetrahydrofuran

[0876] Preparation example

[0877] The compounds of formula (I) according to the invention can be prepared using the synthetic techniques described above and below.

[0878] “Mp” means melting point in °C. The radical represents a methyl group. Recorded on a Bruker 400 MHz spectrometer (or 600 MHz as indicated) 1 1H NMR and 19 19F NMR measurements, chemical shifts relative to TMS ( 1 1H) and CFCl3 ( 19F) Standards are given in ppm. Spectra were measured in the deuterated solvent as indicated. These compounds were characterized using any of the following LC-MS methods. The characteristic LCMS values obtained for each compound are the retention time (“Rt”, recorded in minutes) and the measured molecular ion (M+H) + or (M-H) - .

[0879] Example P1: Preparation of 1-[racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H- isoquinolin-2-yl]heptan-1-one (Compound P-11, Table P)

[0880]

[0881] Step 1: Preparation of (1,5-dimethylpyrazol-4-yl)-phenyl-methanol

[0882]

[0883] A sample of 1-methyl-1H-pyrazole-4-carbaldehyde (25 g, 201.39 mmol) dissolved in THF (400 mL) was treated with phenylmagnesium bromide 1 M in THF (228 mL, 227.57 mmol) (added dropwise at 0 °C - 5 °C over 15 minutes under an argon atmosphere). After the addition, the ice bath was removed and the white suspension was stirred at room temperature for 3 hours. The reaction mixture was poured into saturated ammonium chloride solution and extracted with EtOAc. The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo to give the crude product as a colorless oil. The crude material was purified by gradient elution on SiO2 with EtOAc:EtOH 3:1 / cyclohexane to give the desired product (1-methylpyrazol-4-yl)-phenyl-methanol as a colorless oil.

[0884] LCMS (Method A): m / z (M+H) 203, retention time 0.68 min

[0885] 1 H NMR (400 MHz, CDCl3) δ ppm: 2.23 (s, 3H) 2.28 (d, J = 4.00 Hz, 1H) 3.76 (s, 3H) 5.80 (d, J = 3.63 Hz, 1H) 7.22 (s, 1H) 7.27 - 7.32 (m, 1H) 7.33 - 7.44 (m, 4H)

[0886] Step 2: Preparation of 2-(1,5-dimethylpyrazol-4-yl)-2-phenyl-acetonitrile

[0887]

[0888] Charge a round-bottom flask equipped with a magnetic stir bar and a condenser with (1-methylpyrazol-4-yl)-phenyl-methanol (4.5 g, 22 mmol) and DCM (45 mL). Then, sequentially add lithium carbonate (0.33 g, 4.4 mmol), trimethylsilyl cyanide (10 g, 13 mL, 100 mmol), and iodine (10 g, 40 mmol) at room temperature. Stir the reaction mixture at 35 °C for 1 h, cool to room temperature, and pour into saturated sodium thiosulfate (250 mL) and extract with DCM (2 x 100 mL). Wash the combined organic layers with brine, dry over Na2SO4, and concentrate in vacuo to give the crude product, which is purified by combiflash (silica gel, gradient: EtOAc in cyclohexane) to give the desired title compound as a yellow oil.

[0889] LCMS (method A): m / z (M+H) 212, retention time 0.82 min

[0890] 1 H NMR (400 MHz, CDCl3-d) δ ppm: 7.46 - 7.28 (m, 6H), 5.05 (s, 1H), 3.78 (s, 3H), 2.18 (s, 3H)

[0891] Step 3: Preparation of 2-(1,5-dimethylpyrazol-4-yl)-2-phenyl-ethylamine (Option A)

[0892]

[0893] Charge a 750 mL - 3-neck flask equipped with a magnetic stir bar with 2-(1-methylpyrazol-4-yl)-2-phenyl-propanenitrile (11 g, 52.06 mmol) and THF (160 mL). At room temperature under an argon atmosphere, add borane dimethyl sulfide complex (12.62 g, 15.8 mL, 156.2 mmol) dropwise to the yellow solution, and stir the resulting colorless reaction mixture at 65 °C for 2 h. Cool the reaction mixture to 0 °C, then add HCl (23 g, 34.71 mL, 208.2 mmol) dropwise (vigorous gas evolution), and stir the mixture at 65 °C for 1 h and allow to stand overnight at room temperature. Dilute the mixture with water and treat with 6 M NaOH (to pH 12). Extract the mixture twice with EtOAc and wash the combined organic layers with brine, dry over Na2SO4, and concentrate in vacuo to give the title compound as a yellow oil, which is used in the next step without further purification.

[0894] LCMS (method A): m / z (M+H) 216, retention time 0.60 min

[0895] 11H NMR (400 MHz, CDCl3) δ ppm: 2.09 (s, 3H) 3.20 (dd, J = 7.45, 2.00 Hz, 2H) 3.75 (s, 3H) 3.79 (t, J = 7.27 Hz, 1H) 7.16 - 7.25 (m, 3H) 7.26 - 7.33 (m, 2H) 7.42 (s, 1H)

[0896] Preparation of 2-(1,5-dimethylpyrazol-4-yl)-2-phenyl-ethylamine (Option B)

[0897] Option B - Step A: Preparation of 1,5-dimethyl-4-(2-nitro-1-phenyl-ethyl)pyrazole

[0898]

[0899] A solution of 4-iodo-1,5-dimethyl-pyrazole (2.6 g, 12 mmol) in THF (40 mL) was degassed with argon and treated with isopropylmagnesium chloride-lithium chloride-complex (Turbo-Grignard, 1.3 mol / L in THF, 12 mL, 16 mmol) at 0 °C - 5 °C under argon. The resulting white suspension was stirred at 0 °C to 5 °C for 20 min and then treated at 0 °C - 5 °C with a solution of [(E)-2-nitrovinyl]benzene (1.5 g, 9.9 mmol) in THF (5 mL). The mixture was stirred at 0 °C to 5 °C for 40 min and then at room temperature for 1 h, at which point LCMS analysis showed completion of the reaction. The reaction mixture was quenched with ice water and acidified to pH 5 by addition of 2 M aqueous HCl. The aqueous phase was extracted 3× with EtOAc, then the combined organic phases were washed with brine, dried over Na2SO4 and concentrated in vacuo. The crude product was purified by silica gel chromatography eluting with a gradient of cyclohexane + 0 - 40 EA / EtOH 3:1 to afford the title compound.

[0900] LC-MS (method A): 246 [M+H], Rt: 0.84 min

[0901] 1 1H NMR (400 MHz, CDCl3) δ ppm: 7.40 - 7.44 (m, 1H) 7.30 - 7.36 (m, 2H) 7.23 - 7.29 (m, 3H) 4.88 (d, J = 1.1 Hz, 1H) 4.86 (s, 1H) 4.74 (d, J = 7.6 Hz, 1H) 3.77 (s, 3H) 2.15 (s, 3H)

[0902] The two enantiomers of the title compound were separated by chiral column using the following method:

[0903] Sepiatec Prep SFC M5, column: Daicel IB, 5 μm, 2.0 cm x 25 cm, mobile phase: A: CO2, B: IPA, isocratic: 4% B, backpressure: 150 bar, GLS: -, flow rate: 90 ml / min, detection: UV 220 nm, sample concentration: 1.6 g in 25 ml ACN / MeOH (1 / 1), injection: 500 μl

[0904] Option B - Step B: Preparation of 2-(1,5-dimethylpyrazol-4-yl)-2-phenyl-ethylamine

[0905]

[0906] A solution of 1,5-dimethyl-4-(2-nitro-1-phenylethyl)pyrazole (35 mg, 0.1427 mmol) in absolute ethanol (3 mL) was treated with platinum 1% vanadium 2% supported on activated carbon (Evonik P8078, 0.00014 mmol, 0.0070 g). The mixture was degassed and hydrogenated at 50 °C and 10 bar H2 for 18 h. The reaction mixture was filtered through a Celite pad and evaporated to afford the title compound. Spectral data as in Example 1 step 8, see above.

[0907] Step 4: Preparation of methyl N-[2-(1,5-dimethylpyrazol-4-yl)-2-phenyl-ethyl]carbamate

[0908]

[0909] A three-necked flask equipped with a mechanical stirrer was charged with 2-(1,5-dimethylpyrazol-4-yl)-2-phenylethylamine (3.5 g, 16 mmol, sample from Option A step 8), EtOAc (65 mL) and TEA (6.8 mL, 49 mmol). Then methyl chloroformate (1.5 mL, 20 mmol) was added dropwise over 30 min at 0 °C under an argon atmosphere, and the mixture was stirred at room temperature for 1 h. The reaction mixture was poured into water (800 mL) and extracted with EtOAc (2 x 150 mL). The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated in vacuo. The crude material was purified by flash chromatography (80 g SiO2, eluting with a gradient of EtOAc / cyclohexane) to afford methyl N-[2-(1,5-dimethylpyrazol-4-yl)-2-phenylethyl]carbamate.

[0910] LC-MS (method A): retention time 0.76 min, 274 (M+H)

[0911] 11H NMR (400 MHz, CDCl3) δ ppm: 2.03 - 2.13 (m, 3H) 3.62 - 3.74 (m, 5H) 3.77 (s, 3H) 3.94 - 4.05 (m, 1H) 4.72 (br s, 1H) 7.21 - 7.26 (m, 3H) 7.27 - 7.34 (m, 2H) 7.38 (s, 1H)

[0912] Step 5: Preparation of methyl racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-iso quinoline-2-carboxylate

[0913]

[0914] Charge a single-necked round-bottomed flask equipped with a magnetic stir bar with methyl N-[2-(1,5-dimethylpyrazol-4-yl)-2-phenylethyl]carbamate (2.0 g, 7.3 mmol), hydrochloric acid (concentrated, 37 mL, 450 mmol) and acetaldehyde (0.83 mL, 15 mmol). Stir the mixture at room temperature for 2 h. Slowly pour the reaction mixture into water (500 mL) and slowly neutralize it in portions with NaHCO3 (vigorous gas evolution) to pH 8. Extract the mixture with EtOAc (3 x 50 mL) and wash the combined organic layers with brine, dry over sodium sulfate and concentrate in vacuo. Purify the crude product by chromatography to obtain racemic -(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxylic acid methyl ester, determined by 1 1H NMR to be a single cis-diastereomer.

[0915] LC-MS (method A): retention time 0.87 min, 300 (M + H)

[0916] 1 1H NMR (400 MHz, CDCl3) δ ppm: 1.56 (d, J = 6.90 Hz, 3H); 2.18 (br s, 3H); 3.02 - 3.27 (m, 1H); 3.76 (br s, 3H); 3.83 (s, 3H); 3.97 - 4.09 (m, 1H); 4.09 - 4.37 (m, 1H); 5.18 - 5.45 (m, 1H); 6.86 - 7.02 (m, 1H); 7.04 - 7.24 (m, 4H).

[0917] Step 6: Preparation of racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-1,2,3,4-tetrahydroiso quinoline

[0918]

[0919] Charge a 100 mL single-necked round-bottom flask equipped with a magnetic stir bar with racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxylic acid methyl ester (1.3 g, 4.1 mmol), 1,2-dichloroethane (21 mL), and trimethylsilyl iodide (1.7 mL, 12 mmol). Stir the mixture at 60 °C for 1 h under an argon atmosphere. Cool the reaction to room temperature and then add 10% aqueous HCl (22 mL) to the reaction with ice cooling. Remove the organic solvent in vacuo and adjust the aqueous residue to pH 8 with 10% aqueous NaOH, and then extract with DCM. Dry the combined organic layers over MgSO4, filter, and concentrate in vacuo to give racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-1,2,3,4-tetrahydroisoquinoline, which is pure enough to be used without further purification.

[0920] LC-MS (method A): retention time 0.35 min, 242 (M+H)

[0921] 1 1H NMR (600 MHz, CDCl3) δ ppm: 1.86 (d, J = 6.9 Hz, 3H) 2.23 (s, 3H) 3.27 (dd, J = 12.5, 10.8 Hz, 1H) 3.59 (dd, J = 12.8, 5.6 Hz, 1H) 3.83 (s, 3H) 4.58 (dd, J = 10.6, 5.4 Hz, 1H) 4.80 (q, J = 6.8 Hz, 1H) 7.00 (d, J = 7.8 Hz, 1H) 7.11 (s, 1H) 7.16 (d, J = 7.6 Hz, 1H) 7.18 - 7.22 (m, 1H) 7.25 - 7.28 (m, 1H)

[0922] Step 7: Preparation of 1-[racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-iso quinolin-2-yl]heptan-1-one (Compound P-11, Table P)

[0923] Charge a 30 mL vial equipped with a magnetic stir bar with racemic -(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-1,2,3,4-tetrahydroisoquinoline (100 mg, 0.41 mmol), N-ethyl-N-isopropyl-propan-2-amine (0.284 mL, 1.7 mmol), heptanoic acid (62 mg, 0.46 mmol) and EtOAc (2.1 mL). Add T3P 50% in EtOAc (0.49 mL, 0.83 mmol) at room temperature and stir the resulting reaction mixture at 55 °C for 35 minutes. After cooling to room temperature, dilute the mixture with EtOAc, quench with NaHCO3 and extract with EtOAc. Wash the combined organic layers with water and brine, dry over sodium sulfate and concentrate in vacuo. Purify the crude product by chromatography to give the title compound, which is further purified by reverse phase chromatography to give pure 1-[(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]heptan-1-one.

[0924] LC-MS (method A): retention time 0.89 min, 354 (M+H)

[0925] 1 1H NMR (400 MHz, CDCl3) δ ppm: 0.83 - 0.98 (m, 3H), 1.21 - 1.45 (m, 7H), 1.55 (d, J = 6.9 Hz, 2H), 1.61 - 1.73 (m, 3H), 2.20 (d, J = 15.6 Hz, 3H), 2.34 - 2.53 (m, 2H), 3.45 (dd, J = 13.8, 12.0 Hz, 1H), 3.87 (d, J = 4.7 Hz, 3H), 3.98 - 4.08 (m, 1H), 5.80 (q, J = 6.9 Hz, 1H), 6.91 (d, J = 8.0 Hz, 1H), 7.08 - 7.22 (m, 2H), 7.27 - 7.31 (m, 1H), 8.13 (s, 1H).

[0926] Example P2: Preparation of 7,7,7-trifluoro-1-[racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3, 4-dihydro-1H-isoquinolin-2-yl]heptan-1-one (Compound P-29, Table P)

[0927]

[0928] Step 1: Preparation of methyl (E)-7,7,7-trifluorohept-2-enoate

[0929]

[0930] Under argon, a solution of DMSO (1.5 mL, 21 mmol) in DCM (28 mL) was cooled to -78 °C. Oxalyl chloride (1.3 mL, 14 mmol) was added dropwise, with exotherm and gas formation. The resulting solution was stirred at -78 °C for 15 minutes, then 5,5,5-trifluoropentan-1-ol (1.0 g, 7.0 mmol) was added dropwise. It was stirred at -78 °C for 30 minutes, and then triethylamine (4.0 mL, 28 mmol) was added dropwise. Stirring was continued for 10 minutes, then it was allowed to warm to room temperature and stirred for an additional 30 minutes under argon. The intermediate 5,5,5-trifluoropentanal was formed. Methyl (triphenylphosphoranylidene)acetate (2.5 g, 7.4 mmol) was added in portions to the solution, and the resulting reaction mixture was stirred at room temperature for 2 hours 30 minutes, then dissolved in water and pentane. The organic phase containing methyl (E)-7,7,7-trifluorohept-2-enoate was separated and used for the next step without evaporation.

[0931] Step 2: Preparation of (E)-7,7,7-trifluorohept-2-enoic acid

[0932]

[0933] To a solution of methyl (E)-7,7,7-trifluorohept-2-enoate (1.4 g, 7.0 mmol) in pentane was added THF (35 mL) and water (7.0 mL), followed by lithium hydroxide (511 mg, 21 mmol). The resulting reaction mixture was stirred at room temperature for 3 days, then EtOAc, water, and HCl 1N were added until pH 1 - 2, and the aqueous phase was extracted with EtOAc. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated in vacuo to obtain (E)-7,7,7-trifluorohept-2-enoic acid without further purification.

[0934] LC-MS (method A): retention time 1.05 min, 181 (M-H)

[0935] 1 1H NMR (400 MHz, CDCl3) δ ppm 1.73 - 1.88 (m, 2H) 2.04 - 2.22 (m, 2H) 2.36 (q, J = 7.39 Hz, 2H) 5.90 (dt, J = 15.62, 1.63 Hz, 1H) 7.05 (dt, J = 15.62, 6.90 Hz, 1H).

[0936] Step 3: Preparation of racemic-(E)-7,7,7-trifluoro-1-[racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4- yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]hept-2-en-1-one

[0937]

[0938] Under argon, to a solution of racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-1,2,3,4-tetrahydroisoquinoline (prepared as described above) (200 mg, 0.58 mmol) and (E)-7,7,7-trifluorohept-2-enoic acid (127 mg, 0.70 mmol) in EtOAc (2.9 mL) was added 1-propane phosphonic anhydride (0.69 mL, 1.2 mmol), followed by N,N-diisopropylethylamine (0.30 mL, 1.7 mmol). The resulting reaction mixture was stirred at room temperature for 1 hour. NaHCO3 and EtOAc were added, and then it was extracted with more EtOAc. The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by chromatography to afford racemic-(E)-7,7,7-trifluoro-1-[racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]hept-2-en-1-one.

[0939] LC-MS (Method A): retention time 1.01 min, 406 (M+H)

[0940] 1 1H NMR (400 MHz, CDCl3) δ ppm 1.58 - 1.65 (m, 2H), 1.68 (br d, J = 6.9 Hz, 2H), 1.72 - 1.84 (m, 3H), 2.02 - 2.16 (m, 2H), 2.16 - 2.24 (m, 3H), 2.30 - 2.39 (m, 2H), 3.86 (s, 3H), 4.01 - 4.09 (m, 1H), 5.73 - 5.93 (m, 1H), 6.32 - 6.45 (m, 1H), 6.85 - 7.04 (m, 2H), 7.09 - 7.18 (m, 1H), 7.18 - 7.26 (m, 2H), 7.44 - 7.60 (m, 1H)

[0941] Step 4: Preparation of 7,7,7-trifluoro-1-[racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3, 4-dihydro-1H-isoquinolin-2-yl]heptan-1-one (Compound P-29, Table P)

[0942] A solution of racemic-(E)-7,7,7-trifluoro-1-[racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]hept-2-en-1-one (70 mg, 0.17 mmol) in ethanol (3.5 mL) was hydrogenated twice in a H-Cube with a Pd / C cartridge in full H2 mode at 60 °C. The reaction mixture was evaporated and purified by chromatography to afford 7,7,7-trifluoro-1-[racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinolin-2-yl]hept-1-one.

[0943] LC-MS (Method A): retention time 1.04 min, 408 (M+H)

[0944] Example P3: Preparation of racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-iso quinoline-2-carboxylic acid pentyl ester (Compound P-28, Table P)

[0945]

[0946] Under argon at 0 °C, a mixture of racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-1,2,3,4-tetrahydroisoquinoline (prepared as described above) (50 mg, 0.21 mmol) and N,N-diisopropylethylamine (0.091 mL, 0.52 mmol) in 2-methyltetrahydrofuran (0.83 mL) was carefully treated with triphosgene (31 mg, 0.10 mmol). The resulting reaction mixture was stirred at 0 °C for 2 h. 1-Pentanol (0.057 mL, 0.52 mmol) was added and stirring was continued overnight at room temperature. The reaction mixture was transferred to a microwave vial and another portion of 1-pentanol (0.11 mL) was added. The vial was placed in a microwave and stirred at 150 °C for 1 h. Another portion of 1-pentanol (0.22 mL) was added and it was stirred again in the microwave at 150 °C for 1 h. The reaction mixture was then cooled, diluted with EtOAc and washed with water and brine. The organic layer was dried over sodium sulfate, filtered and concentrated in vacuo. The crude product was purified by reverse-phase chromatography to afford racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxylic acid pentyl ester.

[0947] LC-MS (Method A): retention time 1.13 min, 357 (M+H)

[0948] 11H NMR (400 MHz, CDCl3) δ ppm 0.88 - 0.99 (m, 3H), 1.38 (br d, J = 3.3 Hz, 4H), 1.57 (d, J = 6.9 Hz, 3H), 1.61 - 1.76 (m, 2H), 2.19 (br s, 3H), 3.84 (s, 3H), 3.97 - 4.08 (m, 1H), 4.08 - 4.22 (m, 3H), 4.24 - 4.42 (m, 1H), 5.20 - 5.51 (m, 1H), 6.89 - 7.03 (m, 1H), 7.06 - 7.14 (m, 1H), 7.15 - 7.24 (m, 3H).

[0949] Example P4: Preparation of racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-iso quinoline-2-carboxylic acid 2-cyclohexylethyl ester (Compound P-16, Table P)

[0950]

[0951] Step 1: Preparation of 2-cyclohexylethyl imidazole-1-carboxylate

[0952]

[0953] At room temperature, 2-cyclohexylethanol (1.1 mL, 7.6 mmol) was added dropwise to a solution of CDI (1.6 g, 9.6 mmol) in THF (20 mL). The reaction mixture was stirred at room temperature for 24 hours, then diluted with EtOAc and carefully quenched with water. The mixture was then extracted with EtOAc, and the combined organic layers were washed with water, brine, dried over sodium sulfate and concentrated in vacuo to give ethyl 2-cyclohexylimidazole-1-carboxylate.

[0954] LC-MS (method A): retention time 0.98 min, 223 (M + H)

[0955] 1 1H NMR (400 MHz, CDCl3) δ ppm 0.89 - 1.07 (m, 3H), 1.12 - 1.36 (m, 5H), 1.36 - 1.54 (m, 2H), 1.74 - 1.80 (m, 3H), 4.47 (t, J = 6.9 Hz, 2H), 7.44 (t, J = 1.5 Hz, 1H), 7.71 (s, 1H), 8.14 - 8.17 (m, 1H).

[0956] Step 2: Preparation of 3-methylimidazol-3-ium-1-carboxylic acid 2-cyclohexylethyl; iodide

[0957]

[0958] In a vial, a solution of ethyl 2-cyclohexylethyl imidazole-1-carboxylate (0.50 g, 2.3 mmol) in acetonitrile (5.0 mL) was prepared and methyl iodide (0.71 mL, 11.2 mmol) was added. The tube was sealed and the reaction mixture was stirred overnight at room temperature and for 6 hours at 40 °C. The solvent was evaporated and the crude ethyl 2-cyclohexylethyl 3-methylimidazole-3-ium-1-carboxylate; iodide was used in the next step without further purification.

[0959] LC-MS (method A): retention time 0.70 min, 237 (M+H)

[0960] Step 3: Preparation of racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-iso quinoline-2-carboxylic acid 2-cyclohexylethyl ester (Compound P-16, Table P)

[0961] In a vial, racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-1,2,3,4-tetrahydroisoquinoline (prepared as described above) (65 mg, 0.27 mmol) was dissolved in acetonitrile (0.65 mL). To this solution, ethyl 2-cyclohexylethyl 3-methylimidazole-3-ium-1-carboxylate; iodide (184 mg, 0.40 mmol) and triethylamine (0.094 mL, 0.67 mmol) were added and the mixture was stirred at room temperature for 2 hours. The reaction mixture was then diluted with EtOAc, quenched with water and extracted with EtOAc. The combined organic layers were washed with water and brine, dried over sodium sulfate and concentrated in vacuo. The crude product was purified by chromatography to afford racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-2-cyclohexylethyl 3,4-dihydro-1H-isoquinoline-2-carboxylate.

[0962] LC-MS (method A): retention time 1.22 min, 396 (M+H)

[0963] 1 1H NMR (400 MHz, CDCl3) δ ppm 0.88 - 1.04 (m, 2H), 1.13 - 1.31 (m, 3H), 1.33 - 1.47 (m, 1H), 1.51 - 1.61 (m, 5H), 1.62 - 1.80 (m, 5H), 2.17 (br s, 3H), 3.02 - 3.25 (m, 1H), 3.83 (s, 3H), 3.97 - 4.09 (m, 1H), 4.09 - 4.37 (m, 3H), 5.21 - 5.47 (m, 1H), 6.90 - 7.01 (m, 1H), 7.09 (br s, 1H), 7.12 - 7.25 (m, 3H).

[0964] Example P5: Preparation of 4-(1,5-dimethylpyrazol-4-yl)-N-pentyl-3,4-dihydro-1H-isoquinoline-2-carboxamide (compound P-31, Table P)

[0965]

[0966] Step 1: Preparation of 4-(1,5-dimethylpyrazol-4-yl)isoquinoline

[0967]

[0968] In a microwave vial, a suspension of 4-bromoisoquinoline (2.0 g, 9.4204 mmol), 1,5-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (2.3484 g, 10.362 mmol) and potassium carbonate (1.4322 g, 10.362 mmol) in a toluene / methanol mixture (30 mL, 5:1) was degassed with argon for a few minutes and then tetrakis(triphenylphosphine)palladium(0) (0.545 g, 0.471 mmol) was added. Under microwave irradiation, the reaction mixture was heated at 100 °C and stirred for 1 h. After cooling to room temperature, the reaction mixture was partitioned between water and EtOAc and the organic layer was separated, dried over Na2SO4, filtered, and concentrated in vacuo. The crude material was purified by flash column chromatography on silica gel (eluting with EtOAc / 30% methanol) to give the title product.

[0969] LCMS (method A): m / z 225 [M+H], retention time 0.51 min

[0970] Step 2: Preparation of 4-(1,5-dimethylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline

[0971]

[0972] At room temperature, to 4-(1,5-dimethylpyrazol-4-yl)isoquinoline (2.00 g, 8.96 mmol) in methanol (90 mL) was added sodium cyanoborohydride (3.55 g, 53.7 mmol). The reaction mixture was stirred at room temperature and then HCl (1.25 M in methanol) was added until the pH reached 2 - 3. After stirring for 30 min at room temperature, the reaction mixture was diluted with water and basified with 2N NaOH and the mixture was extracted with EtOAc (×3). The combined organic layers were dried over Na2SO4, filtered, and concentrated in vacuo. The resulting yellow oil was used without further purification.

[0973] LCMS (method A): m / z 228 [M+H]. Retention time 0.29 min

[0974] The hydrochloride salt of the title product (4-(1,5-dimethylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline; hydrochloride) can be obtained by treating the yellow oil with 2M HCl in diethyl ether and then concentrating in vacuo.

[0975] Step 3: Preparation of N-pentylimidazole-1-carboxamide

[0976]

[0977] At 0 °C, pentan-1-amine (0.66 mL, 5.5 mmol) was added dropwise to a solution of CDI (1.0 g, 6.0 mmol) in THF (10 mL). The reaction mixture was stirred overnight at room temperature, then diluted with EtOAc and carefully quenched with water. The mixture was then extracted with EtOAc, and the combined organic layers were washed with water, brine, dried over sodium sulfate and concentrated in vacuo to give N-pentylimidazole-1-carboxamide, which was used in the next step without further purification.

[0978] LC-MS (method A): retention time 0.57 min, 182 (M+H)

[0979] Step 4: Preparation of 4-(1,5-dimethylpyrazol-4-yl)-N-pentyl-3,4-dihydro-1H-isoquinoline-2-carboxamide (compound P-31, Table P)

[0980] In a vial, 4-(1,5-dimethylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline (prepared as described above) (0.25 g, 0.88 mmol) was dissolved in acetonitrile (6.3 mL) and cooled to 0 °C. It was then treated with N-pentylimidazole-1-carboxamide (0.18 g, 0.88 mmol), triethylamine (0.25 mL, 1.8 mmol) and DMAP (0.11 g, 0.88 mmol), and allowed to stir at room temperature for 48 h. The reaction mixture was diluted with EtOAc, quenched with water and extracted with EtOAc. The combined organic layers were washed with water and brine, dried over sodium sulfate, filtered and concentrated in vacuo. The crude product was purified by chromatography to give the title compound, which was further purified by reverse phase chromatography to give pure 4-(1,5-dimethylpyrazol-4-yl)-N-pentyl-3,4-dihydro-1H-isoquinoline-2-carboxamide.

[0981] LC-MS (method A): retention time 0.91 min, 341 (M+H)

[0982] 11H NMR (400 MHz, CDCl3) δ ppm 0.90 (t, J = 7.1 Hz, 3H), 1.24 - 1.40 (m, 4H), 1.49 (quin, J = 7.2 Hz, 2H), 2.17 (s, 3H), 3.20 - 3.28 (m, 2H), 3.42 (dd, J = 8.5, 12.5 Hz, 1H), 3.81 (s, 3H), 3.89 (dd, J = 4.5, 12.5 Hz, 1H), 4.07 (dd, J = 4.7, 8.4 Hz, 1H), 4.38 (br t, J = 5.1 Hz, 1H), 4.54 - 4.76 (m, 2H), 6.99 (d, J = 7.6 Hz, 1H), 7.13 (s, 1H), 7.14 - 7.25 (m, 3H).

[0983] Example P6: Preparation of racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-N-pentyl-3,4-dihydro- 1H-isoquinoline-2-carboxamide (Compound P-43, Table P)

[0984]

[0985] At 0 °C under argon, a suspension of racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-1,2,3,4-tetrahydroisoquinoline (prepared as described above) (50 mg, 0.21 mmol) and N,N-diisopropylethylamine (0.091 mL, 0.52 mmol) in 2-methyltetrahydrofuran (0.83 mL) was carefully treated with triphosgene (31 mg, 0.10 mmol). The reaction mixture was allowed to stir at 0 °C for 2 h, then pentylamine (0.062 mL, 0.52 mmol) was added and the resulting reaction mixture was stirred overnight at room temperature. After 2 h, another portion of pentylamine (0.062 mL, 0.52 mmol) was added. After completion of the reaction, the reaction mixture was diluted with EtOAc and washed with water and brine. The organic layer was dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by reverse-phase chromatography to afford pure racemic-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-N-pentyl-3,4-dihydro-1H-isoquinoline-2-carboxamide.

[0986] LC-MS (method A): retention time 0.96 min, 355 (M + H)

[0987] 11H NMR (400 MHz, CDCl3) δ ppm 0.92 (t, J = 6.9 Hz, 3H), 1.30 - 1.38 (m, 4H), 1.50 - 1.57 (m, 2H), 1.59 (d, J = 6.9 Hz, 3H), 2.18 (s, 3H), 3.06 - 3.22 (m, 1H), 3.29 (dt, J = 7.4, 5.6 Hz, 2H), 3.84 (s, 3H), 4.02 - 4.18 (m, 2H), 4.56 (br s, 1H), 5.12 (q, J = 6.9 Hz, 1H), 6.96 (d, J = 8.0 Hz, 1H), 7.07 - 7.23 (m, 4H).

[0988] Example P7: Preparation of 2-(2,4-difluorophenyl)sulfanyl-1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H- isoquinolin-2-yl]ethanone (Compound P-14, Table P)

[0989]

[0990] Step 1: Preparation of 2-chloro-1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]ethanone Step 2: Preparation of 2-(2,4-difluorophenyl)sulfanyl-1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-

[0991]

[0992] In a round-bottom flask, 4-(1,5-dimethylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline (prepared as described above) (1.1 g, 5.0 mmol) was dissolved in THF (15 mL) and cooled to 0 °C. Triethylamine (1.4 mL, 10 mmol) was added dropwise, followed by 2-chloroacetyl chloride (0.40 mL, 5.0 mmol). After stirring at 0 °C for 40 min, it was allowed to warm to room temperature and stirring was continued for 2.5 h. The reaction mixture was quenched with water and extracted with EtOAc. The combined organic layers were washed with water and brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by chromatography to afford 2-chloro-1-[4-(1,5-dimethylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]ethanone.

[0993] LC-MS (Method A): retention time 0.77 min, 304 (M + H)

[0994] 1 1H NMR (400 MHz, CDCl3) δ ppm 2.15 - 2.38 (m, 3H), 3.83 (s, 3H), 3.87 - 4.04 (m, 2H), 4.04 - 4.27 (m, 3H), 4.81 (s, 2H), 6.96 - 7.11 (m, 1H), 7.11 - 7.34 (m, 4H).

[0995] isoquinolin-2-yl]ethanone (Compound P-16, Table P) ​

[0996] In a vial, combine 2,4-difluorobenzenethiol (CAS: 1996-44-7) (50 mg, 0.34 mmol), ...

Claims

1. A compound of formula (I) or an agrochemically acceptable salt, stereoisomer, or N - oxide thereof, wherein, R 1 selected from hydrogen, C1-C 4- alkyl, C2-C 4- alkenyl, C2-C4-alkynyl, or C3-C6-cycloalkyl; R 2 selected from hydrogen, halogen, C1-C 4- alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, C1-C 4- alkylcarbonyl, N-C1-C4-alkoxy-C-C1-C4-alkyl-carbodiimide, N-hydroxy-C-C1-C4-alkyl-carbodiimide, or C1-C 4- alkoxycarbonyl; R 3 selected from hydrogen, a halogen, a C1-C4-haloalkyl, or a C1-C4-alkyl; R 4 selected from hydrogen, a halogen, C1-C4-haloalkyl, C3-C6-cycloalkyl, or C1-C4-alkyl; R 5 and R 6 are independently selected from hydrogen, or C1-C4-alkyl; R 7 selected from hydrogen, C1-C4-alkyl, C1-C4-alkylcarbonyl, N-C1-C4-alkoxy-C-C1-C4-alkyl-carbodiimide, N-hydroxy-C-C1-C 4- alkyl-carbodiimide, C1-C4-alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4-alkylaminocarbonyl, bis(C1-C4-alkylamino)carbonyl, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- to 6-membered heteroaryl contains 1, 2, 3 or 4 identical or different heteroatoms selected from N, O or S, provided that not more than one is O or S; wherein the phenyl and 5- to 6-membered heteroaryl are unsubstituted or substituted by 1, 2 or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4-haloalkyl, cyano, carboxyl, C1-C4-alkyl and C1-C4-alkoxy; and wherein the C3-C6-cycloalkyl is unsubstituted or substituted by 1, 2 or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4-haloalkyl, cyano, C1-C4-alkyl, or C1-C4-alkoxy; B 1 selected from CR 10 or N; B 2 selected from CR 11 or N; R 8 、R 9 、R 10 and R 11 are independently selected from hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C2-C4-alkenyloxy, C2-C4-alkynyloxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-alkoxy-C1-C4-alkyl, N-C 1- C4-alkylamino, N,N-bis(C 1- C4-alkyl)amino, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, N-C1-C4-alkoxy-C1-C4-alkyl-carbodiimide, N-hydroxy-C1-C4-alkyl-carbodiimide, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, amino, phenyl, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein the 5- to 6-membered heteroaryl contains 1, 2, 3 or 4 identical or different heteroatoms selected from N, O or S, provided that not more than one is O or S; and wherein any one of the phenyl, 5- to 6-membered heteroaryl and C3-C6-cycloalkyl is unsubstituted or substituted with 1, 2, 3 or up to the maximum possible number of identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, and C1-C4-alkoxy; W is selected from O, N, S, *-CH2O- # , *-CH2NH- # , *-CH2S- # , or a bond, where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 ; and Z 1 selected from C1-C6 alkyl, phenyl, or 6-membered heteroaryl; wherein the C1-C6-alkyl is unsubstituted or substituted with 1, 2, or 3 identical or different substituents selected from the following: halogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C2-C4-alkenyloxy, C2-C4-alkynyloxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxycarbonyl, C1-C4-alkylcarbonyl, N-C1-C4-alkoxy-C-C1-C4-alkyl-carbimino, N-hydroxy-C-C1-C4-alkyl-carbimino, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxyl, phenyl, 5- to 6-membered saturated or partially saturated heterocycle, 5- to 6-membered heteroaryl, or C3-C6-cycloalkyl; wherein any one of the 6-membered heteroaryl and the 5- to 6-membered heteroaryl contains 1, 2, or 3 identical or different heteroatoms selected from N, O, or S, provided that no more than one is O or S; wherein any one of the 5- to 6-membered saturated or partially saturated heterocycles contains 1, 2, or 3 identical or different heteroatoms selected from N, O, or S, provided that no more than one is O or S; wherein any one of the phenyls, any one of the 6-membered heteroaryls, any one of the 5- to 6-membered heteroaryls, and any one of the 5- to 6-membered saturated or partially saturated heterocycles is unsubstituted or substituted with 1, 2, 3, or up to the maximum possible number of identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, and C1-C4-alkoxy; and wherein any one of the C3-C6-cycloalkyls is unsubstituted or substituted with 1, 2, 3, or up to the maximum possible number of identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl, and C1-C4-alkoxy, provided that the compound of formula (I) is not PubChem CID 121198298 / CAS No.: 2309773-83-7 PubChem CID / CAS No.: 2034366-76-0 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N - oxide thereof.

2. The compound of formula (I) according to claim 1, wherein, R 1 is methyl, and R 3 , R 5 , R 6 is hydrogen.

3. A compound of formula (I) according to claim 1 or claim 2, wherein, R 2 is hydrogen, a halogen, or a C1-C4-alkyl group.

4. A compound having the formula (I) according to any one of claims 1 to 3, wherein, R 4 is hydrogen or a C1-C4-alkyl group.

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

6. The compound of formula (I) according to claim 5, wherein, R 7 is hydrogen or methyl.

7. A compound having the formula (I) according to any one of claims 1 to 6, wherein, B 1 is CR 10 ,B 2 is CR 11 ,and wherein R 10 and R 11 are independently selected from hydrogen, bromine, chlorine, or cyano.

8. A compound of formula (I) according to any one of claims 1 to 7, wherein, W is O, N, *-CH2O- # , *-CH2NH- # , *-CH2S- # , or *-CH2- # , where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 attached position.

9. The compound of formula (I) according to claim 8, wherein, W is O, N, or *-CH2-#, where the asterisk (*) represents the position attached to the carbonyl group, and # represents the position attached to Z 1 attachment position.

10. A compound of formula (I) according to any one of claims 1 to 9, wherein, Z 1 is a C1-C6-alkyl group, a phenyl group, or a 6-membered heteroaryl group; wherein the C1-C6-alkyl group is unsubstituted or substituted with 1, 2, or 3 identical or different substituents selected from the group consisting of: halogen, C1-C4-alkyl, C1-C4-haloalkyl, phenyl, 5- to 6-membered heteroaryl, and C3-C6-cycloalkyl; wherein any one of the 6-membered heteroaryl group and the 5- to 6-membered heteroaryl group contains 1 or 2 identical or different heteroatoms selected from N or O; and wherein any one of the phenyl groups, the 6-membered heteroaryl group, and the 5- to 6-membered heteroaryl group is unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: halogen, cyano, C1-C4-alkyl, and C3-C6-cycloalkyl.

11. A compound having the formula (I) according to any one of claims 1 to 9, wherein, Z 1 is a C1-C6-alkyl group, phenyl group, 2,4-difluorophenyl group, 3,5-difluoro-2-furanyl group, 3-fluoro-2-furanyl group, 5-fluoro-2-furanyl group, 3,5-difluoro-2-thienyl group, 3-fluoro-2-thienyl group, 5-fluoro-2-thienyl group, 2-fluorophenyl group, 4-fluorophenyl group, 3-fluoro-2-pyridyl group, 5-fluoro-2-pyridyl group, 3,4-difluoro-2-pyridyl group, 3,5-difluoro-2-pyridyl group, 4-fluoropyridazin-3-yl group, 4,5-difluoropyridazin-3-yl group, or 5-fluoropyridazin-4-yl group; wherein the C1-C6-alkyl group is unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: chlorine, fluorine, bromine, methyl, ethyl, trifluoromethyl, difluoromethyl, cyclopropyl, cyclohexyl, phenyl, and 6-membered heteroaryl; wherein the 6-membered heteroaryl contains 1 heteroatom selected from N; and wherein the phenyl group and the 6-membered heteroaryl are unsubstituted or substituted with 1 or 2 identical or different substituents selected from the group consisting of: chlorine, bromine, fluorine, cyano, methyl, ethyl, and cyclopropyl.

12. An agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 11.

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

14. A method for controlling or preventing useful plants from being infected by phytopathogenic microorganisms, wherein, Applying a fungicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 11, or a composition comprising the compound of formula (I), to the plant, its parts, or its locus.

15. Use of a compound of formula (I) as defined in any one of claims 1 to 11 as a fungicide.

Images