Microbicide Tetrahydroisoquinoline Derivatives

Abstract

Compounds of formula (I) which can be used as fungicides: [Formula 1] JPEG2024522009000175.jpg63157, wherein the substituents are as defined in claim 1, and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of these compounds are provided.

Description

[Technical field]

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

[0002] According to a first aspect of the present invention, there is provided a compound of formula (I): [ka] (In the formula, R 1 is selected from the group consisting of hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, and C3-C6 cycloalkyl; R 2 is selected from the group consisting of hydrogen, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimidoyl and C1-C4 alkoxycarbonyl; R 3 and R 4 is independently selected from the group consisting of hydrogen, halogen, and C1-C4 alkyl; R 5 and R 6 is independently selected from the group consisting of hydrogen and C1-C4 alkyl; R 7 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimidoyl, C1-C4 alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4 alkylaminocarbonyl, di(C1-C4 alkylamino)carbonyl, phenyl, 5- or 6-membered heteroaryl and C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein any of the phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl may be optionally substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl or C1-C4 alkoxy; B 1 is CR 10 or N; B 2 is CR 11 or N; R 8 , R 9 , R 10 and R 11is hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimidoyl, hydroxy, thiamine, ethyl ... independently selected from the group consisting of trifluoromethylsulfonyloxy, cyano, carboxy, phenyl, 5- or 6-membered heteroaryl, and C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S, and wherein any of said phenyl, 5- or 6-membered heteroaryl, and C3-C6-cycloalkyl may be optionally substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy; A 1 , A 2 and A 3 CR 12 , N, N.R. 13 , O and S, with the proviso that A 1 , A 2 and A 3 is selected from N, O and S, and A 1 , A 2 and A 3 is at most one of O or S; R 12 is selected from the group consisting of hydrogen, C1-C4 alkyl, C2-C4 alkenyl, and C2-C4 alkynyl; R 13 is selected from the group consisting of hydrogen, C1-C4 alkyl, C2-C4 alkenyl, and C2-C4 alkynyl; and Z 1is selected from the group consisting of C1-C4 alkyl, phenyl, 5- or 6-membered heteroaryl, and C3-C6-cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S, and wherein any of said phenyl, 5- or 6-membered heteroaryl, and C3-C6-cycloalkyl may be optionally substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, or C2-C4 alkynyl. or the use of an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof as a fungicide.

[0003] According to this particular aspect of the invention, the use may not include a method involving the treatment of the human or animal body by surgery or therapy.

[0004] It has now been surprisingly found that the compounds of formula (I) have in fact a highly advantageous level of biological activity for the protection of plants against diseases caused by fungi.

[0005] According to a second aspect of the present invention, there is provided a method for controlling or preventing infestation of a useful plant by phytopathogenic microorganisms, comprising applying a fungicidally effective amount of a compound of formula (I) according to the present invention or a composition containing a compound of formula (I) to the plant, its parts or its habitat. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] As used herein, the term "halogen" or "halo" refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine.

[0007] As used herein, cyano refers to the group --CN.

[0008] As used herein, the terms "hydroxyl" or "hydroxy" refer to an --OH group.

[0009] As used herein, oxo refers to a =O group, e.g., a sulfinyl (-S(O)-) or sulfonyl (-S(O)2-) oxygen.

[0010] As used herein, the term "C1-C4 alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having 1-4 carbon atoms, and attached to the remainder of the molecule by a single bond. The terms "C1-C3 alkyl", "C3-C4 alkyl" and "C1-C2 alkyl" should be interpreted similarly. Examples of C1-C4 alkyl include, but are not limited to, methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, and 1,1-dimethylethyl (t-butyl). A "C1-C4 alkylene" group refers to the corresponding definition of C1-C4 alkyl, except that such group is attached to the remainder of the molecule by two single bonds. Examples of C1-C4 alkylene are -CH2- and -CH2CH2-.

[0011] As used herein, the term "C2-C4 alkenyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one double bond which may be in the (E) or (Z) configuration, having 2 to 4 carbon atoms, and attached to the remainder of the molecule by a single bond. The term "C3-C4 alkenyl" should be interpreted similarly. Examples of C2-C4 alkenyl include, but are not limited to, ethenyl and prop-1-enyl.

[0012] As used herein, the term "C2-C4 alkynyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having 2-4 carbon atoms, and attached to the remainder of the molecule by a single bond. The term "C3-C4 alkynyl" should be interpreted similarly. Examples of C3-C4 alkynyl include, but are not limited to, ethynyl, prop-1-ynyl, propargyl (prop-2-ynyl), but-1-ynyl, and 3-methyl-but-1-ynyl.

[0013] As used herein, the term "C1-C4 haloalkyl" refers to a C1-C4 alkyl group, as generally defined above, substituted with one or more identical or different halogen atoms. Examples of C1-C4 haloalkyl include, but are not limited to, fluoromethyl, fluoroethyl, chloroethyl, difluoromethyl, dichloroethyl, trifluoromethyl, fluoropropyl, chloropropyl, difluoropropyl, dichloropropyl, trifluoropropyl, trichloropropyl, 2,2-difluoroethyl, 2,2-dichloroethyl, 2,2,2-trifluoroethyl, and 3,3,3-trifluoropropyl.

[0014] As used herein, the term "C1-C4 alkoxy" refers to R a is a C1-C4 alkyl group as generally defined above; a It refers to the group O-. The terms "C1-C3 alkoxy" and "C1-C2 alkoxy" should be interpreted similarly. Examples of C1-C4 alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, iso-propoxy, and t-butoxy.

[0015] As used herein, the term "C1-C4 alkoxy-C1-C4 alkyl" refers to R b is a C1-C4 alkyl group as generally defined above, and R ais a C1-C4 alkylene group as generally defined above, b -OR a - refers to the group.

[0016] As used herein, the term "C1-C4 alkylcarbonyl" refers to R a is a C1-C4 alkyl group as generally defined above; a Refers to the group.

[0017] As used herein, the term "C1-C4 alkoxycarbonyl" refers to R a is a C1-C4 alkyl group as generally defined above, a Refers to the group.

[0018] As used herein, the term "C1-C4 alkylaminocarbonyl" refers to R a is a C1-C4 alkyl group as generally defined above, a Refers to the group.

[0019] As used herein, the term "di(C1-C4 alkylamino)carbonyl" refers to each R a are C1-C4 alkyl groups, which may be identical or different, as generally defined above; a (R a ) group.

[0020] As used herein, the term "C2-C4 alkenyloxy" refers to R a is a C2-C4 alkenyl group as generally defined above; a Refers to the group.

[0021] As used herein, the term "C2-C4 alkynyloxy" refers to R a is a C2-C4 alkynyl group as generally defined above; a Refers to the group.

[0022] As used herein, the term "C3-C6 cycloalkyl" refers to a stable monocyclic ring group that is saturated or partially saturated and contains 3 to 6 carbon atoms. The terms "C3-C4 cycloalkyl" and "C3-C5 cycloalkyl" should be interpreted similarly. Examples of C3-C6 cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopenten-1-yl, cyclopenten-3-yl, and cyclohexen-3-yl.

[0023] As used herein, the term "C3-C6 cycloalkyl C1-C4 alkyl" refers to a C3-C6 cycloalkyl ring as defined above that is attached to the remainder of the molecule by a C1-C4 alkylene group as defined above. Examples of C3-C6 cycloalkyl C1-C4 alkyl include, but are not limited to, cyclopropyl-methyl, cyclobutyl-ethyl, and cyclopentyl-methyl.

[0024] As used herein, the term "N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl" refers to R a is a C1-C4 alkyl group as generally defined above, and R b is a C1-C4 alkyl group as generally defined above, a )=NO(R b ) group.

[0025] As used herein, the term "N-hydroxy-C-C1-C4 alkyl-carbonimidoyl" refers to R a is a C1-C4 alkyl group as generally defined above a )=NOH group.

[0026] Examples of 5- or 6-membered heteroaryl rings containing 1 to 4 heteroatoms independently selected from nitrogen, oxygen and sulfur include, but are not limited to, pyridyl, pyrimidyl, pyrrolyl, pyrazolyl, furyl, thienyl, imidazolyl, isoxazolyl, oxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, pyrazinyl, pyridazinyl and triazinyl.

[0027] The compounds of formula (I) or intermediate compounds of formula (III) or (IV) according to the invention having at least one basic centre can form, for example, acid addition salts with strong inorganic acids, such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, phosphoric acid or hydrohalic acids, with strong organic carboxylic acids, such as C1-C4 alkane carboxylic acids, which are unsubstituted or substituted, for example by halogen, for example acetic acid, with saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, with hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or with strong organic sulfonic acids, such as C1-C4 alkane- or arylsulfonic acids, which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid.

[0028] The compounds of formula (I) or intermediate compounds of formula (III) or (IV) according to the invention having at least one acidic group can form salts with bases, for example inorganic salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or can form salts with ammonia or organic amines, such as morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower-alkylamines, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or mono-, di- or trihydroxy-lower-alkylamines, for example mono-, di- or triethanolamine.

[0029] The possible presence of one or more asymmetric carbon atoms in the compounds of formula (I) according to the invention means that the compounds can occur in chiral isomeric forms, i.e. enantiomeric or diastereomeric forms. Atropisomers can also occur as a result of restricted rotation about a single bond. Formula (I) is intended to include all of these possible isomeric forms and mixtures thereof. The invention includes all of these possible isomeric forms and mixtures thereof of the compounds of formula (I) according to the invention. Similarly, the compounds of formula (I) are intended to include all possible tautomers, if any, including lactam-lactim tautomers and keto-enol tautomers. The invention includes all possible tautomeric forms of the compounds of formula (I) according to the invention.

[0030] In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form as N-oxides, in covalently hydrated form or in salt form, for example in agriculturally usable or agrochemically acceptable salt form. N-oxides are the oxidized forms of tertiary amines or nitrogen-containing aromatic heterocyclic compounds. These are described, for example, in the book "Heterocyclic N-oxides", A. Albini and S. Pietra, CRC Press, Boca Raton 1991. The compounds of formula (I) according to the invention also include hydrates that may be formed during salt formation.

[0031] The following list refers to the compounds of formula (I) of the present invention and is intended to illustrate the substituent R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , A 1 , A 2 , A 3 , B 1 , B 2 and Z1 For any one of these substituents, any of the definitions set forth below may be combined with any of the definitions of any other substituents set forth below or elsewhere in this document.

[0032] In an embodiment of the present invention, R 1 is selected from the group consisting of hydrogen, C1-C4 alkyl and C2-C4 alkynyl. 1 is selected from the group consisting of hydrogen, methyl, ethyl and isopropyl. More preferably, R 1 is selected from the group consisting of hydrogen, methyl and ethyl. Even more preferably, R 1 is methyl.

[0033] In an embodiment of the present invention, R 2 is selected from the group consisting of hydrogen, halogen, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl and N-hydroxy-C-C1-C4 alkyl-carbonimidoyl. 2 is selected from the group consisting of hydrogen, halogen, methyl, ethyl, cyclopropyl, C1-C2 alkylcarbonyl, N-C1-C2 alkoxy-C-C1-C2 alkyl-carbonimidoyl and N-hydroxy-C-C1-C2 alkyl-carbonimidoyl. More preferably, R 2 is selected from the group consisting of hydrogen, bromine, fluorine, chlorine, methyl, ethyl, cyclopropyl, acetyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3 and -C(CH3)=NOH. Even more preferably, R 2 is selected from the group consisting of hydrogen, bromine, fluorine, chlorine, methyl, acetyl and -C(CH3)=NOCH3. Even more preferably, R 2 is selected from the group consisting of hydrogen, fluorine, chlorine and methyl.

[0034] In an embodiment of the present invention, R 3is selected from the group consisting of hydrogen, halogen and C1-C4 alkyl. 3 is selected from the group consisting of hydrogen, fluorine, chlorine, methyl and ethyl. More preferably, R 3 is selected from the group consisting of hydrogen and methyl.

[0035] In an embodiment of the present invention, R 4 is selected from the group consisting of hydrogen, halogen and C1-C4 alkyl. 4 is selected from the group consisting of hydrogen, fluorine, chlorine, methyl, ethyl and isopropyl. More preferably, R 4 is selected from the group consisting of hydrogen, fluorine, chlorine, methyl and ethyl. Even more preferably, R 4 is selected from the group consisting of hydrogen and methyl.

[0036] In an embodiment of the present invention, R 5 and R 6 is independently selected from the group consisting of hydrogen, methyl and ethyl. 5 and R 6 is independently selected from the group consisting of hydrogen and methyl.

[0037] In an embodiment of the present invention, R 7is hydrogen, methyl, ethyl, n-propyl, isopropyl, acetyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methylaminocarbonyl, dimethylaminocarbonyl, methoxycarbonyl, ethoxycarbonyl, N-methoxy-N-methyl-carbonyl, methylaminocarbonyl, dimethylaminocarbonyl, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, [4-(triphenylphosphine)-2-yl]. Preferably, R is selected from the group consisting of, for example, [3-(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 and 1-cyanocyclopropyl. 7 is selected from the group consisting of 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 and 1-cyanocyclopropyl. More preferably, R 7 is selected from the group consisting of hydrogen, methyl, acetyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, phenyl, 4-cyanophenyl, pyrazol-1-yl, cyclopropyl and 1-cyanocyclopropyl. Even more preferably, R 7is selected from the group consisting of hydrogen, methyl, cyclopropyl and 1-cyanocyclopropyl. Even more preferably, R 7 is selected from the group consisting of hydrogen, methyl and cyclopropyl.

[0038] In another embodiment of the present invention, R 7 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimidoyl, C1-C4 alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, phenyl, 4-cyanophenyl, cyclopropyl and 1-cyanocyclopropyl. 7 is selected from the group consisting of hydrogen, methyl, acetyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methoxycarbonyl, ethoxycarbonyl, N-methoxy-N-methyl-carbonyl, phenyl and cyclopropyl. More preferably, R 7 is selected from the group consisting of hydrogen and methyl.

[0039] In another embodiment of the present invention, R 7 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl and phenyl. 7 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, acetyl, methoxycarbonyl, -C(CH3)=NOCH3 and phenyl. More preferably, R 7 is selected from the group consisting of hydrogen, methyl and acetyl.

[0040] 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 2is CR 11 or B 1 is CR 10 and B 2 is N. Preferably, B 1 is CR 10 and B 2 is CR 11 It is.

[0041] In an embodiment of the present invention, R 8 and R 11 are independently selected from the group consisting of hydrogen, halogen and C1-C4 alkyl. 8 and R 11 are independently selected from the group consisting of hydrogen, chlorine, fluorine and methyl. More preferably, R 8 and R 11 is hydrogen.

[0042] In another embodiment of the present invention, R 8 and R 11 are independently selected from the group consisting of hydrogen, halogen and C1-C4 alkyl. 8 and R 11 are independently selected from the group consisting of hydrogen and halogen. More preferably, R 8 and R 11 are independently selected from the group consisting of hydrogen, chlorine, bromine and fluorine.

[0043] In an embodiment of the present invention, R 9 and R 10is hydrogen, halogen, C1-C3 alkyl, C1-C2 haloalkyl, C1-C3 haloalkoxy, C1-C4 alkoxy, C2-C3 alkenyloxy, C2-C3 alkynyloxy, C1-C2 alkylsulfanyl, C1-C2 alkylsulfinyl, C1-C2 alkylsulfonyl, C1-C2 alkoxy-C1-C2 alkyl, C1-C3 alkoxycarbonyl, C1-C2 alkylcarbonyl, N-C1-C2 alkoxy-C-C1-C2 alkyl-carbonimidoyl, N-hydroxy-C-C1-C2 alkyl-carbonimidoylhydroxy, C1-C2 alkylaminocarbonyl, di(C1-C2 alkylamino)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 and 1-cyanocyclopropyl. 9 and R 10is hydrogen, chloro, fluoro, bromo, methyl, ethyl, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, methoxy, ethoxy, propoxy, allyloxy, prop-2-ynoxy, methylsulfanyl, methylsulfinyl, methylsulfonyl, methoxymethyl, ethoxymethyl, 2-methoxyethoxymethyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, acetyl, propanoyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methylaminocarbonyl, di(methylamino)carbonyl, trifluoromethylsulfonyloxy, cyano, carboxy, phenyl, 2-cyanophenyl, 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 and 1-cyanocyclopropyl. More preferably, R 9 and R 10is hydrogen, chloro, fluoro, methyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, methoxy, propoxy, allyloxy, prop-2-ynoxy, methylsulfanyl, methylsulfinyl, methylsulfonyl, methoxymethyl, 2-methoxyethoxymethyl, methoxycarbonyl, acetyl, propanoyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methylaminocarbonyl, di(methylamino)carbonyl, trifluoromethylsulfonyloxy, cyano, carboxy, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, [4-(

[0036] Independently selected from the group consisting of (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 and 1-cyanocyclopropyl.

[0044] In another embodiment of the present invention, R and R 10 is independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C3 alkyl, C1-C2 haloalkyl, C1-C3 haloalkoxy, C1-C4 alkoxy, C1-C3 alkoxycarbonyl, cyano, and phenyl. 9 and R 10 are independently selected from the group consisting of hydrogen, bromine, chlorine, fluorine, hydroxy, methyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, methoxy, cyano, and phenyl. More preferably, R 9 and R10 is independently selected from the group consisting of hydrogen, bromine, chlorine, fluorine, hydroxy, methyl, trifluoromethyl, difluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, methoxy, cyano, and phenyl. 1 and A 2 CR 12 , N and O; and A 3 CR 12 , N, O or S, preferably A 1 and A 2 is independently selected from the group consisting of N and O, and A 3 is CR 12 , O or S, where A 1 , A 2 and A 3 At least one of is N or O, and A 1 , A 2 and A 3 At most one of them is O.

[0045] In an embodiment of the present invention, R 12 is hydrogen or C1-C4 alkyl, preferably hydrogen or methyl.

[0046] In an embodiment of the present invention, R 13 is hydrogen or C1-C4 alkyl, preferably hydrogen or methyl.

[0047] In an embodiment of the present invention, Z 1is selected from the group consisting of 1-methylpyrazol-4-yl, 2,3,4-trifluorophenyl, 2,3-difluorophenyl, 3,4-difluorophenyl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2-fluoro-4-methoxy-phenyl, 2-fluoro-4-methylsulfonyl-phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-furyl, 2-thienyl, 3-thienyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3-methoxyphenyl, 4-ethynyl-2-fluoro-phenyl, 4-fluoro-2-methoxy-phenyl, cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, n-propyl and phenyl.

[0048] In another embodiment of the present invention, Z 1 is selected from the group consisting of C3-C4 alkyl, phenyl, 5- or 6-membered heteroaryl, and C3-C6-cycloalkyl, wherein the 5- or 6-membered heteroaryl contains at least one heteroatom selected from N, O, and S, and any of the phenyl, 5- or 6-membered heteroaryl, and C3-C6-cycloalkyl may be optionally substituted with 1, 2, or 3 substituents independently selected from halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfonyl, and C2-C4 alkynyl. Preferably, Z 1is n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorphyenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 3,4-difluorophenyl, 2-fluoro-4-chloro-phenyl, 2,3,4-trifluorophenyl, 2,4,6-trifluorophenyl, 2-fluoro-4-methoxy-phenyl, Selected from the group consisting of 2-fluoro-4-methylsulfonyl-phenyl, 4-fluoro-2-methoxy-phenyl, 4-ethynyl-2-fluoro-phenyl, 4-trifluoromethyl-phenyl, 2-furyl, 2-thienyl, 3-thienyl, m-tolyl, o-tolyl, p-tolyl, 4-ethylphenyl, 3-methoxyphenyl, 4-pyridyl, cyclobutyl, cyclohexyl, cyclopentyl, cyclopropyl, 1-methylcyclopropyl, 1,5-dimethylpyrazol-4-yl and 1-methylpyrrol-2-yl.

[0049] In one embodiment, in the compound of formula (I) according to the present invention, R 1 is hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or C3-C6 cycloalkyl; R 2 is hydrogen, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimidoyl or C1-C4 alkoxycarbonyl; R 3 and R 4 are each independently hydrogen, halogen, or C1-C4 alkyl; R 5 and R 6 are each independently hydrogen or C1-C4 alkyl; R 7is hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimidoyl, C1-C4 alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4 alkylaminocarbonyl, di(C1-C4 alkylamino)carbonyl, phenyl, 5- or 6-membered heteroaryl or C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein any of the phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl may be optionally substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkoxy; B 1 is CR 10 or N; B 2 is CR 11 or N; R 8 , R 9 , R 10 and R 11are each independently hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimido yl, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, phenyl, 5- or 6-membered heteroaryl or C3-C6 cycloalkyl, where the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and where any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl may be optionally substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkoxy; A 1 , A 2 and A 3 are mutually independent, CR 12 , N, N.R. 13 , O and S, where A 1 , A 2 and A 3 is selected from N, O and S, and A 1 , A 2 and A 3 is at most one of O or S; R 12 is hydrogen, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl; R 13 is hydrogen, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl; and Z 1is C3-C4 alkyl, phenyl, 5- or 6-membered heteroaryl or C3-C6-cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl may be optionally substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl and C2-C4 alkynyl.

[0050] In an embodiment of the invention, the compound of formula (I) is a compound of formula (IA): [ka] (In the formula, A is: [ka] wherein: [ka] indicates a bond to a C(=O) group and the arrow indicates Z 1 indicates a bond to a group, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , B 1 , B 2 and Z 1 is as defined for the compounds of formula (I) according to the invention, and R 12a , R 13a , R 14a , R 12b , R13b and R 14b are independently selected from the group consisting of hydrogen, C1-C4 alkyl, C2-C4 alkenyl, and C2-C4 alkynyl. It could be.

[0051] In an embodiment of the invention, in a compound of formula (IA), A is: [ka] (In the formula, [ka] indicates a bond to a C(=O) group and the arrow indicates Z 1 indicates a bond to the group, and R 12a , R 13a and R 14a are each independently hydrogen or C1-C4 alkyl. is selected from the group consisting of:

[0052] In another embodiment of the invention, in the compound of formula (IA), A is: [ka] (In the formula, [ka] indicates a bond to a C(=O) group and the arrow indicates Z 1 indicates a bond to the group, and R 12a , R 13a and R 14a are independently selected from the group consisting of hydrogen, C1-C4 alkyl, C2-C4 alkenyl, and C2-C4 alkynyl. is selected from the group consisting of:

[0053] In another embodiment of the invention, in the compound of formula (IA), A is: [ka] (In the formula, [ka] indicates a bond to a C(=O) group and the arrow indicates Z 1 (indicating the bond to the group) is selected from the group consisting of:

[0054] In another embodiment of the invention, in the compound of formula (IA), A is [ka] (In the formula, [ka] indicates a bond to a C(=O) group and the arrow indicates Z 1 (indicating the bond to the group) is selected from the group consisting of:

[0055] In another embodiment of the invention, in the compound of formula (IA), A is [ka] (In the formula, [ka] indicates a bond to a C(=O) group and the arrow indicates Z 1 (indicating the bond to the group) is selected from the group consisting of:

[0056] In an embodiment of the present invention, R 12a , R 13a , R 14a , R 12b , R 13b and R 14b is independently selected from the group consisting of hydrogen and methyl.

[0057] In another embodiment of the present invention, R 12a , R 13a , R14a , R 12b , R 13b and R 14b is hydrogen.

[0058] In another embodiment of the present invention, R 12a , R 13a , R 14a , R 12b , R 13b and R 14b is methyl.

[0059] In an embodiment of the invention, the compound of formula (IA) is 1 and B. 2 is CH; and A is as defined for compound (IA), [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the present invention. It could be.

[0060] In a variant of this embodiment of the invention, the compound of formula (IA) is B 1 and B. 2 is CH and R 4 , R 5 , R 6 and R 7 Compounds of formula (I-A2) in which is hydrogen and A is as defined for compound (IA): [ka] (In the formula, R 1 , R 2 , R 3 , R 8 , R 9 and Z1 is as defined for the compounds of formula (I) according to the present invention. It could be.

[0061] Preferably, in the compound of formula (I-A2) of the present invention, R 1 is hydrogen, C1-C4 alkyl or C2-C4 alkynyl, preferably hydrogen, methyl or ethyl; R 2 and R 3 are each independently hydrogen, a halogen, such as bromine or chlorine, methyl, -C(O)OCH2CH3, N-methoxy-C-methyl-carbonimidoyl or -COCH3, R 8 and R 9 are each independently hydrogen, halogen in fluorine or chlorine, cyano, methyl, trifluoromethyl, methoxy, -C(O)OCH3 or -SO2CH3, A is as defined for compounds of formula (IA), and Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0062] In another variation of this embodiment of the invention, the compound of formula (IA) is 1 and B. 2 is CH and R 4 , R 5 and R 6 Compounds of formula (I-A3), in which is hydrogen and A is as defined for compound (IA): [ka] (In the formula, R 1 , R 2 , R 3 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the invention, and R 7 is C1-C4 alkyl) It could be.

[0063] Preferably, in the compound of formula (I-A3) of the present invention, R 1 is methyl, R 2 and R 3 is hydrogen or methyl; R 7 is methyl, ethyl or n-propyl or iso-propyl or phenyl or -C(O)OCH3, R 8 and R 9 is hydrogen or methoxy; A is as defined for compound (iA), and Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0064] In another variation of this embodiment of the invention, the compound of formula (IA) is 1 and B. 2 is CH and R 4 , R 5 and R 7 is hydrogen and R 6 Compounds of formula (I-A4) in which is methyl and A is as defined for compound (IA): [ka] (In the formula, R 1 , R 2 , R 3 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the present invention. It could be.

[0065] Preferably, in the compound of formula (I-A4) of the present invention, R 1 is methyl, R 2 and R 3 is hydrogen or methyl; R 8 and R 9 is hydrogen, A is as defined for compound (IA), and Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0066] In another variation of this embodiment of the invention, the compound of formula (IA) is 1 and B. 2 is CH and R 4 and R 7 is hydrogen, and R 5 and R 6 Compounds of formula (I-A5) in which is methyl: [ka] (In the formula, R 1 , R 2 , R 3 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the invention, and A is as defined for compound (IA) according to the present invention. It could be.

[0067] Preferably, in the compound of formula (I-A5) of the present invention, R 1 is methyl, R 2 and R 3 is hydrogen or methyl; R 8 and R 9 is hydrogen, A is as defined for compound (IA), and Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0068] In another variation of this embodiment of the invention, the compound of formula (IA) is 1and B. 2 is CH, and R 5 , R 6 and R 7 Compounds of formula (I-A6) where is hydrogen: [ka] (In the formula, R 1 , R 2 , R 3 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the invention, A is as defined for compound (IA), and R 4 is C1-C4 alkyl) It could be.

[0069] Preferably, in the compound of formula (I-A6) of the present invention, R 1 is methyl, R 2 and R 3 is hydrogen or methyl; R 4 is methyl, R 8 and R 9 is hydrogen, A is as defined for compound (IA), and Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0070] In another variation of this embodiment of the invention, the compound of formula (IA) is 1 and B. 2 is CH, and R 5 and R 6 is hydrogen, [ka] (In the formula, R 1, R 2 , R 3 , R 8 , R 9 and Z 1 is as defined for the compounds of formula (I) according to the invention, A is as defined for compound (IA), and R 4 and R 7 is C1-C4 alkyl) It could be.

[0071] Preferably, in the compound of formula (I-A7) of the present invention, R 1 is methyl, R 2 and R 3 is hydrogen, a halogen such as fluorine, or methyl, R 4 and R 7 is methyl, R 8 and R 9 is hydrogen, hydroxy, methoxy, difluoromethoxy, 2,2-difluoroethoxy or 2,2,2-trifluoroethoxy, A is as defined for compound (IA), and Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0072] In another variation of this embodiment of the invention, the compound of formula (IA) is 2 is CH, and R 4 , R 5 , R 6 , R 7 , R 8 and R 9 Compounds of formula (I-A8) where is hydrogen: [ka] (In the formula, B 1 is CR 10 and R 1, R 2 , R 3 , R 10 and Z 1 is as defined for the compounds of formula (I) according to the invention, and A is as defined for compound (IA). It could be.

[0073] Preferably, in the compound of formula (I-A8) of the present invention, R 1 is methyl, R 2 and R 3 are each independently hydrogen, a halogen such as fluorine, or methyl; R 10 is halogen, such as fluorine, methyl, trifluoromethyl, methoxy or phenyl; A is as defined for compound (IA), and Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0074] In another variation of this embodiment of the invention, the compound of formula (IA) is 1 is CH, and R 4 , R 5 , R 6 , R 7 , R 8 and R 9 Compounds of formula (I-A9) where is hydrogen: [ka] (In the formula, B 2 is CR 11 and R 1 , R 2 , R 3 , R 11 and Z 1 is as defined for the compounds of formula (I) according to the invention, and A is as defined for compound (IA). It could be.

[0075] Preferably, in the compound of formula (I-A9) of the present invention, R 1 is methyl, R 2 and R 3 are each independently hydrogen, a halogen such as fluorine, or methyl; R 11 is halogen, such as fluorine, methyl, trifluoromethyl, methoxy or phenyl; A is as defined for compound (IA), and Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0076] In another variation of this embodiment of the invention, the compound of formula (IA) is 1 is CH and B 2 is N, and R 4 , R 5 , R 6 , R 7 , R 8 and R 9 is hydrogen, [ka] (In the formula, R 1 , R 2 , R 3 and Z 1 is as defined for the compounds of formula (I) according to the invention, and A is as defined for compound (IA). It could be.

[0077] Preferably, in the compound of formula (I-A10) of the present invention, R 1 is methyl, R 2 and R 3 are each independently hydrogen, a halogen such as fluorine, or methyl; A is as defined for compound (IA), and Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0078] The possible presence of one or more asymmetric carbon atoms in any of the compounds of formulae (I), (IA) and (I-A1) to (I-A10) according to the present invention means that the compounds can occur in chiral isomeric forms, i.e. enantiomeric or diastereomeric forms.

[0079] More preferably, the compounds of formula (I) according to the present invention are selected from the compounds listed in any one of Tables A-1 to A-32 or Table T1.

[0080] According to a third aspect of the present invention there is provided a compound of formula (I) as defined in any one of the embodiments of the present invention or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, with the proviso that the compound of formula (I) [ka] [ka] [ka] [ka] [ka] [ka] isn't it.

[0081] The PubChem compound IDs assigned to the compounds excluded from the above claims refer to the identification numbers of each compound on the PubChem website (https: / / pubchem.ncbi.nlm.nih.gov / ).

[0082] In one embodiment, in the compound of formula (I) according to the present invention, R 1 is hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or C3-C6 cycloalkyl; R 2 is hydrogen, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimidoyl or C1-C4 alkoxycarbonyl; R 3 and R 4 are each independently hydrogen, halogen, or C1-C4 alkyl; R 5 and R 6 are each independently hydrogen or C1-C4 alkyl; R 7 is hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimidoyl, C1-C4 alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4 alkylaminocarbonyl, di(C1-C4 alkylamino)carbonyl, phenyl, 5- or 6-membered heteroaryl or C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein any of the phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl may be optionally substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkoxy; B 1 is CR 10 or N; B 2 is CR 11 or N; R 8 , R 9 , R 10 and R 11 are each independently hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimido yl, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, phenyl, 5- or 6-membered heteroaryl or C3-C6 cycloalkyl, where the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and where any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl may be optionally substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkoxy; A 1 , A 2 and A 3 are mutually independent, CR 12 , N, N.R. 13 , O and S, where A 1 , A 2 and A 3 is selected from N, O and S, and A 1 , A 2 and A 3 is at most one of O or S; R 12 is hydrogen, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl; R 13 is hydrogen, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl; and Z 1is C3-C4 alkyl, phenyl, 5- or 6-membered heteroaryl or C3-C6-cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are optionally substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl and C2-C4 alkynyl; However, the compound of formula (I) has the following identification numbers: PubChem compound ID 119105753, PubChem compound ID 119105755, PubChem compound ID 119105758, PubChem compound ID 119105768, PubChem compound ID 121022987, PubChem compound ID 121023008, PubChem compound ID 121198339, PubChem compound ID 121198395, PubChem compound ID 121198398, PubChem compound ID 121198478, PubChem compound ID 121198479, PubChem compound ID 121198480, PubChem compound ID 121198481, PubChem compound ID 121198482, PubChem Compound ID 121198502, PubChem Compound ID 121198515, PubChem Compound ID 129530178, PubChem Compound ID 129530183, PubChem Compound ID 129530240, PubChem Compound ID 129530241, PubChem Compound ID 129530774, PubChem Compound ID 129530780, PubChem Compound ID 129530918, PubChem Compound ID 129530919, PubChem Compound ID 129530931, PubChem Compound ID 129530933, PubChem Compound ID 129531203, PubChem Compound ID 129531204 and are not any of the compounds excluded from the above claims.

[0083] In one embodiment, in the compound of formula (I) according to the present invention, R 1 is hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, or C3-C6 cycloalkyl; R 2is hydrogen, halogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimidoyl or C1-C4 alkoxycarbonyl; R 3 and R 4 are each independently hydrogen, halogen, or C1-C4 alkyl; R 5 and R 6 are each independently hydrogen or C1-C4 alkyl; R 7 is hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimidoyl, C1-C4 alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4 alkylaminocarbonyl, di(C1-C4 alkylamino)carbonyl, phenyl, 5- or 6-membered heteroaryl or C3-C6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein any of the phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl may be optionally substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkoxy; B 1 is CR 10 or N; B 2 is CR 11 or N; R 8 , R 9 , R 10 and R 11are each independently hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, C1-C4 alkoxycarbonyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C-C1-C4 alkyl-carbonimido yl, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, phenyl, 5- or 6-membered heteroaryl or C3-C6 cycloalkyl, where the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and where any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl may be optionally substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkoxy; A 1 , A 2 and A 3 are mutually independent, CR 12 , N, N.R. 13 , O and S, where A 1 , A 2 and A 3 is selected from N, O and S, and A 1 , A 2 and A 3 is at most one of O or S; R 12 is hydrogen, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl; R 13 is hydrogen, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl; and Z 1is n-propyl, phenyl, 5- or 6-membered heteroaryl or C3-C6-cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl are optionally substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl and C2-C4 alkynyl; However, the compound of formula (I) has the following identification numbers: PubChem compound ID 119105753, PubChem compound ID 119105755, PubChem compound ID 119105758, PubChem compound ID 119105768, PubChem compound ID 121022987, PubChem compound ID 121023008, PubChem compound ID 121198339, PubChem compound ID 121198395, PubChem compound ID 121198398, PubChem compound ID 121198478, PubChem compound ID 121198479, PubChem compound ID 121198480, PubChem compound ID 121198481, PubChem compound ID 121198482, PubChem Compound ID 121198502, PubChem Compound ID 121198515, PubChem Compound ID 129530178, PubChem Compound ID 129530183, PubChem Compound ID 129530240, PubChem Compound ID 129530241, PubChem Compound ID 129530774, PubChem Compound ID 129530780, PubChem Compound ID 129530918, PubChem Compound ID 129530919, PubChem Compound ID 129530931, PubChem Compound ID 129530933, PubChem Compound ID 129531203, PubChem Compound ID 129531204 and are not any of the compounds excluded from the above claims.

[0084] In another embodiment, the compound of formula (I) according to the present invention comprises R 1 is C1-C4 alkyl, R 2 is hydrogen, halogen, C1-C4 alkyl, C1-C4 alkylcarbonyl or N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl; R 3 and R 4 are each independently hydrogen or C1-C4 alkyl; R5 and R 6 is hydrogen or C1-C4 alkyl, R 7 is hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl or phenyl; B 1 is CR 10 or N; B 2 is CR 11 or N; R 8 and R 11 are each independently hydrogen, halogen or C1-C4 alkyl; R 9 and R 10 are each independently hydrogen, halogen, hydroxy, C1-C3 alkyl, C1-C2 haloalkyl, C1-C3 haloalkoxy, C1-C4 alkoxy, C1-C3 alkoxycarbonyl, cyano, or phenyl; A 1 and A 2 are mutually independent, CR 12 , N and O, and A 3 is CR 12 , N, O or S, except that A 1 , A 2 and A 3 At least one of is N or O, and A 1 , A 2 and A 3 at most one of is O; R 12 is hydrogen or C1-C4 alkyl, and Z 1is C3-C4 alkyl, phenyl, 5- or 6-membered heteroaryl or C3-C6-cycloalkyl, wherein the 5- or 6-membered heteroaryl contains at least one heteroatom selected from N, O and S, or wherein any of said phenyl, 5- or 6-membered heteroaryl or C3-C6-cycloalkyl may be optionally substituted with 1, 2 or 3 substituents independently selected from halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfonyl or C2-C4 alkynyl.

[0085] In one embodiment, in the compound of formula (I) according to the present invention, R 1 is hydrogen or C1-C4 alkyl, R 2 is hydrogen, halogen, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl or N-hydroxy-C1-C4 alkyl-carbonimidoyl; R 3 and R 4 are each independently hydrogen, halogen or C1-C4 alkyl; R 5 and R 6 are each independently hydrogen, methyl or ethyl, R 7 is hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkyl-carbonimidoyl, N-hydroxy-C1-C4 alkyl-carbonimidoyl, C1-C4 alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, phenyl, 4-cyanophenyl, cyclopropyl and 1-cyanocyclopropyl; B 1 is CR 10 and B 2 is CR 11 and R 8 and R 11are each independently hydrogen, halogen or C1-C4 alkyl; R 9 and R 10 are each independently hydrogen, chloro, fluoro, methyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, methoxy, propoxy, allyloxy, prop-2-ynoxy, methylsulfanyl, methylsulfinyl, methylsulfonyl, methoxymethyl, 2-methoxyethoxymethyl, methoxycarbonyl, acetyl, propanoyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methylaminocarbonyl, di(methylamino)carbonyl, trifluoromethylsulfonyloxy, cyano, carboxy, phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, nophenyl, [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; A 1 and A 2 are mutually independent, CR 12 , N or O, and A 3 is CR 12 , N, O or S, except that A 1 , A 2 and A 3 At least one of is N or O, and A 1 , A 2 and A 3 At most one of is O, R 12 is hydrogen or methyl; Z 1is 1-methylpyrazol-4-yl, 2,3,4-trifluorophenyl, 2,3-difluorophenyl, 3,4-difluorophenyl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2-fluoro-4-methoxy-phenyl, 2-fluoro-4-methylsulfonyl-phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-furyl, 2-thienyl, 3-thienyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3-methoxyphenyl, 4-ethynyl-2-fluoro-phenyl, 4-fluoro-2-methoxy-phenyl, cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, n-propyl or phenyl.

[0086] In another embodiment, the compound of formula (I) according to the present invention comprises R 1 is C1-C4 alkyl, R 2 is hydrogen, halogen, C1-C4 alkyl, C1-C4 alkylcarbonyl or N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl; R 3 and R 4 are each independently hydrogen or C1-C4 alkyl; R 5 and R 6 is hydrogen or C1-C4 alkyl, R 7 is hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl or phenyl; B 1 is CR 10 or N; B 2 is CR 11 or N; R 8 and R 11are each independently hydrogen, halogen or C1-C4 alkyl; R 9 and R 10 are each independently hydrogen, halogen, hydroxy, C1-C3 alkyl, C1-C2 haloalkyl, C1-C3 haloalkoxy, C1-C4 alkoxy, C1-C3 alkoxycarbonyl, cyano, or phenyl; A 1 and A 2 are mutually independent, CR 12 , N and O, and A 3 is CR 12 , N, O or S, except that A 1 , A 2 and A 3 At least one of is N or O, and A 1 , A 2 and A 3 at most one of is O; R 12 is hydrogen or C1-C4 alkyl, and Z 1 is C3-C4 alkyl, phenyl, 5- or 6-membered heteroaryl or C3-C6-cycloalkyl, wherein the 5- or 6-membered heteroaryl contains at least one heteroatom selected from N, O and S, or wherein any of said phenyl, 5- or 6-membered heteroaryl or C3-C6-cycloalkyl may be optionally substituted with 1, 2 or 3 substituents independently selected from halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfonyl or C2-C4 alkynyl.

[0087] In one embodiment, the compound of formula (I) may be compound (IB): In the formula, B 1 is CR 10 and B 2 is CR 11 and In the formula, R 1 , R 2 , R 3 , R 4 , R5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 corresponds to the same definition as for the compounds of formula (I) according to the present invention.

[0088] Preferably, in compound (IB), R 1 is C1-C4 alkyl, R 2 is hydrogen, halogen, C1-C4 alkyl, C1-C4 alkylcarbonyl or N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl; R 3 and R 4 are each independently hydrogen or C1-C4 alkyl; R 5 and R 6 is hydrogen or C1-C4 alkyl, R 7 is hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkyl-carbonimidoyl or phenyl; R 8 and R 11 are each independently hydrogen, halogen or C1-C4 alkyl; R 9 and R 10 are each independently hydrogen, halogen, hydroxy, C1-C3 alkyl, C1-C2 haloalkyl, C1-C3 haloalkoxy, C1-C4 alkoxy, C1-C3 alkoxycarbonyl, cyano, or phenyl; A 1 and A 2 are mutually independent, CR 12 , N and O, and A 3 is CR 12 , N, O or S, except that A 1 , A 2 and A 3 At least one of is N or O, and A1 , A 2 and A 3 at most one of is O; R 12 is hydrogen or C1-C4 alkyl, and Z 1 is C3-C4 alkyl, phenyl, 5- or 6-membered heteroaryl or C3-C6-cycloalkyl, wherein the 5- or 6-membered heteroaryl contains at least one heteroatom selected from N, O and S, or wherein any of said phenyl, 5- or 6-membered heteroaryl or C3-C6-cycloalkyl may be optionally substituted with 1, 2 or 3 substituents independently selected from halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfonyl or C2-C4 alkynyl.

[0089] In one embodiment, the compound of formula (I) may be compound (IB): In the formula, B 1 is CR 10 and B 2 is CR 11 and wherein R 5 and R 6 is hydrogen; and In the formula, R 1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 , R 10 and R 11 corresponds to the same definition as for the compounds of formula (I) according to the present invention.

[0090] Preferably, in compound (IB), R 1 is C1-C4 alkyl, R 2 is hydrogen, halogen or C1-C4 alkyl; R 3 and R 4 are each independently hydrogen or C1-C4 alkyl; R 7 is hydrogen or C1-C4 alkyl, and R 8 , R 9 , R 10 , R 11 , A 1 , A 2 , A 3 , R 12 , R 13 and Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0091] In other embodiments, the compound of formula (I) may be compound (IB): In the formula, B 1 is CR 10 and B 2 is CR 11 and wherein R 4 , R 5 , R 6 and R 7 is hydrogen; and In the formula, R 1 , R 2 , R 3 , R 8 , R 9 , R 10 and R 11 corresponds to the same definition as for the compounds of formula (I) according to the present invention.

[0092] Preferably, in compound (IB), R 1 is C1-C4 alkyl, R 2 is hydrogen, halogen or C1-C4 alkyl; R 3 is hydrogen or C1-C4 alkyl, and R 8 , R 9 , R 10 , R 11 , A 1 , A 2 , A 3 , R 12 , R 13 and Z 1is as defined for the compounds of formula (I) according to the present invention.

[0093] In yet other embodiments, the compound of formula (I) may be compound (IB): In the formula, B 1 is CR 10 and B 2 is CR 11 and wherein R 7 is methyl; and In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 and R 11 corresponds to the same definition as for the compounds of formula (I) according to the present invention.

[0094] Preferably, in compound (IB), R 1 is C1-C4 alkyl, R 2 is hydrogen, halogen or C1-C4 alkyl; R 3 and R 4 are each independently hydrogen or C1-C4 alkyl; R 5 and R 6 is hydrogen, and R 8 , R 9 , R 10 , R 11 , A 1 , A 2 , A 3 , R 12 , R 13 and Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0095] According to a fourth aspect of the present invention there is provided an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) according to the present invention, such agricultural composition may further comprise at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

[0096] According to a fifth aspect of the present invention, there is provided an intermediate compound of formula (III): [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B. 2 corresponds to the same definition as for the compounds of formula (I) according to the present invention) or a salt thereof is provided.

[0097] The intermediate compound of formula (III) is R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B. 2 have the same definitions and corresponding preferences as in the compounds of formula (I) according to the present invention.

[0098] In one embodiment, the intermediate compound of formula (III) may be compound (III-c): In the formula, B 1 is CR 10 and B 2 is CR 11 and In the formula, R 1 , R 2 , R 3 , R 4 , R5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 corresponds to the same definition as for the compounds of formula (I) according to the present invention.

[0099] The possible presence of one or more asymmetric carbon atoms in the compounds of formula (III) according to the invention means that the compounds can occur in chiral isomeric forms, i.e. enantiomeric or diastereomeric forms.

[0100] According to a sixth aspect of the present invention, there is provided an intermediate compound of formula (IV): [ka] (In the formula, R 1 , R 2 , R 3 , R 5 , R 7 , R 8 , R 9 , B 1 and B. 2 corresponds to the same definition as for the compounds of formula (I) according to the present invention) is provided.

[0101] The intermediate compound of formula (IV) is R 1 , R 2 , R 3 , R 5 , R 7 , R 8 , R 9 , B 1 and B. 2 have the same definitions and corresponding preferences as in the compounds of formula (I) according to the present invention.

[0102] In one embodiment, the intermediate compound of formula (IV) may be compound (IV-a): In the formula, B 1 is CR 10 and B 2 is CR 11 and In the formula, R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 corresponds to the same definition as for the compounds of formula (I) according to the present invention.

[0103] The possible presence of one or more asymmetric carbon atoms in the compounds of formula (IV) according to the invention means that the compounds can occur in chiral isomeric forms, i.e. enantiomeric or diastereoisomeric forms.

[0104] According to a seventh aspect of the present invention, there is provided an intermediate compound of formula (XVIII): [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B. 2 corresponds to the same definition as for the compounds of formula (I) according to the present invention) is provided.

[0105] The intermediate compound of formula (XVIII) is 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B. 2 have the same definitions and corresponding preferences as in the compounds of formula (I) according to the present invention.

[0106] In one embodiment, the intermediate compound of formula (XVIII) may be compound (XVIII-a): In the formula, B 1 is CR 10 and B 2 is CR 11 and In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 corresponds to the same definition as for the compounds of formula (I) according to the present invention.

[0107] The possible presence of one or more asymmetric carbon atoms in the compounds of formula (XVIII) according to the invention means that the compounds can occur in chiral isomeric forms, i.e. enantiomeric or diastereomeric forms.

[0108] According to an eighth aspect of the present invention, there is provided an intermediate compound of formula (XIX): [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B. 2 corresponds to the same definition as for the compounds of formula (I) according to the present invention) is provided.

[0109] The intermediate compound of formula (XIX) is R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R8 , R 9 , B 1 and B. 2 have the same definitions and corresponding preferences as in the compounds of formula (I) according to the present invention.

[0110] In one embodiment, the intermediate compound of formula (XIX) may be compound (XIX-a): In the formula, B 1 is CR 10 and B 2 is CR 11 and In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 corresponds to the same definition as for the compounds of formula (I) according to the present invention.

[0111] In one embodiment, the intermediate compound of formula (XIX) may be compound (XIX-b): In the formula, R 4 is hydrogen, B 1 is CR 10 and B 2 is CR 11 and In the formula, R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 corresponds to the same definition as for the compounds of formula (I) according to the present invention.

[0112] The possible presence of one or more asymmetric carbon atoms in the compounds of formula (XIX) according to the invention means that the compounds can occur in chiral isomeric forms, i.e. enantiomeric or diastereomeric forms.

[0113] According to a ninth aspect of the present invention, there is provided an intermediate compound of formula (XX): [ka] (In the formula, R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B. 2 corresponds to the same definition as for the compounds of formula (I) according to the present invention) is provided.

[0114] The intermediate compound of formula (XX) is R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B. 2 have the same definitions and corresponding preferences as in the compounds of formula (I) according to the present invention.

[0115] In one embodiment, the intermediate compound of formula (XX) may be compound (XX-a): In the formula, B 1 is CR 10 and B 2 is CR 11 and In the formula, R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 corresponds to the same definition as for the compounds of formula (I) according to the present invention.

[0116] The possible presence of one or more asymmetric carbon atoms in the compounds of formula (XX) according to the invention means that the compounds can occur in chiral isomeric forms, i.e. enantiomeric or diastereoisomeric forms.

[0117] Certain intermediates set out in the above schemes are novel and therefore form further aspects of the invention.

[0118] Compounds of formula (I) according to the present invention can be formed as shown in Schemes 1-12 below, where, unless otherwise specified, the definition of each variable is as defined above for compounds of formula (I).

[0119] In particular, R 4 and R 6 is hydrogen, and R 5 Compounds of formula (I), where is hydrogen or methyl, can be formed as shown in Schemes 1-7 below, where, unless otherwise specified, the definition of each variable is as defined above for compounds of formula (I).

[0120] In any of the following schemes 1 to 12, the possible presence of one or more asymmetric carbon atoms in the compound of formula (I) according to the invention means that this compound can occur in chiral isomeric forms, i.e. in enantiomeric or diastereomeric forms.

[0121] The compound of formula (I) can be prepared by a person skilled in the art according to known methods. More specifically, the compound of formula (I) can be prepared by a compound of formula (III) or a salt thereof, 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B. 2 is as defined above for compounds of formula (I)) to a compound of formula (II)1 , A 2 , A 3 and Z 1 can be prepared by reaction of a cycloalkyl group with a cycloalkyl group, which is as defined above for compounds of formula (I). This reaction is shown in Scheme 1. [ka] Scheme 1

[0122] In Scheme 1, a compound of formula (II) 1 , A 2 , A 3 and Z 1 X is as defined above for compounds of formula (I) can be activated to compounds of formula (IIa) by methods known to those skilled in the art and described, for example, in Tetrahedron, 61(46), 10827-10852, 2005. For example, compounds of formula (IIa) (wherein X is 0 is halogen) is formed by treatment of compounds of formula (II) with, for example, oxalyl chloride or thionyl chloride in the presence of a catalytic amount of N,N-dimethylformamide (DMF) in an inert solvent such as dichloromethane or tetrahydrofuran (THF) at temperatures between 20° C. and 100° C., preferably 25° C. Optionally, compounds of formula (III) (wherein R is a halogen) can be ... base such as, for example, triethylamine or pyridine. 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B. 2 Treatment of a compound of formula (IIa) with an activated compound of formula (IIa) (wherein X is as defined above for compounds of formula (I)) provides a compound of formula (I). Alternatively, a compound of formula (I) can be prepared by activating a compound of formula (IIa) (wherein X is as defined above for compounds of formula (I)) in an inert solvent such as pyridine, DMF, acetonitrile, CHCl or THF, optionally in the presence of a base such as triethylamine, at a temperature between 30° C. and 180° C.0 As described below, X 01 , X 02 Or X 03 Compounds of formula (II) may be prepared by treatment 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 compounds of formula (IIa), where X 0 As described below, X 04 Further reaction of the compound of formula (III) with an amine (or a salt thereof) can provide the compound of formula (I). [ka]

[0123] A compound of formula (IIIa) 4 and R 6 is hydrogen, and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B. 2 is as defined above for compounds of formula (I), may be prepared by those skilled in the art according to known methods.

[0124] For example, a compound of formula (IIIa) 4 and R 6 is hydrogen, and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , R8 , R 9 , B 1 and B. 2 is as defined above for compounds of formula (I), 4 and R 6 is hydrogen, and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B. 2 can be prepared from compounds of formula (I) (as defined above for compounds of formula (I)) by treatment with a reducing agent such as NaBH3CN and an acid such as hydrochloric acid or acetic acid in a protic solvent such as methanol or ethanol. Such reactions are well known in the literature and similar reactions are described, for example, in Deng, Zeping et al, China Patent No. CN103772278 and Synthesis (1979), 4, 281-3. Alternatively, compounds of formula (IIIa) can be prepared from compounds of formula (IV) by reduction with hydrogen in the presence of a suitable metal catalyst such as Pd, Ir, Rh, with a suitable ligand, for example a diphosphine [1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp) or 1,4-bis(diphenylphosphino)butane (dppb)]. A similar reaction has been reported, for example, in Reaction Kinetics and Catalysis Letters (2007), 92, 99-104. This reaction is shown in Scheme 2. [ka] Scheme 2

[0125] Alternatively, compounds of formula (IIIa) may be prepared as shown in Scheme 4.

[0126] As shown in Scheme 3, a compound of formula (IIIb), 4 , R 6 and R 7 is hydrogen, and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 8 , R 9 , B 1 and B. 2 is as defined above for compounds of formula (I), can be converted to compounds of formula (VI), where X is a substituted or unsubstituted aryl group, by methods known to those skilled in the art and as described in Scheme 1. 0 is a leaving group such as a halogen, and R 0 is C1-C4 alkyl) to give a compound of formula (V), 4 , R 6 and R 7 is hydrogen, and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 8 , R 9 , B 1 and B. 2 is as defined above for compounds of formula (I). Alternatively, compounds of formula (V) can be converted to compounds of formula (R 0 CO)2O(wherein, R 0 Compounds of formula (V) can be prepared by treatment with an anhydride of (wherein N is C1-C4 alkyl). Compounds of formula (V) are then metallated with a base, for example an alkyl metal base such as tert-butyllithium, and an additive such as N,N,N',N'-tetramethylethylenediamine (TMEDA), in an inert polar solvent such as THF or 2-methyl-THF at low temperatures, for example from -78°C to room temperature. X -X 0 (wherein X 0is as previously defined, and R X is C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C1-C4 alkylaminocarbonyl, di(C1-C4 alkylamino)carbonyl or C3-C6 cycloalkyl, where C3-C6-cycloalkyl may be optionally substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkoxy, to give a compound of formula (Va), where R 4 and R 6 is hydrogen, and R 5 is hydrogen or methyl, R 0 is C1-C4 alkyl, and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B. 2 is as defined above for compounds of formula (I), giving a product which is shown in Scheme 3. [ka] Scheme 3

[0127] Compounds of formula (Va) can be prepared by methods known to those skilled in the art from compounds of formula (IIIa), 4 and R 6 is hydrogen, and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B. 2 is as defined above for compounds of formula (I). For example, a compound of formula (Va), 0(Ilia) can be treated with an organic or inorganic acid, such as trifluoroacetic acid or HCl, to give compounds of formula (IIIa). This reaction is shown in Scheme 4. [ka] Scheme 4

[0128] A compound of formula (IVa) 4 and R 6 is hydrogen, and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B. 2 is as defined above for compounds of formula (I), can be converted to compounds of formula (VIII), typically by a C—C bond forming reaction under palladium-catalyzed (or alternatively nickel-catalyzed) cross coupling conditions, 1 , R 2 and R 3 is as defined above for compounds of formula (I), and X 0 is a halogen, preferably chlorine, bromine or iodine, with a compound of formula (VII), 5 is hydrogen or methyl, and R 7 , R 8 , R 9 , B 1 and B. 2 can be prepared by reacting (as defined above for compounds of formula (I)) with (which is shown in Scheme 5). [ka] Scheme 5

[0129] The Suzuki-Miyaura cross-coupling reaction of compounds of formula (VIII) with compounds of formula (VII) is well known to those skilled in the art and is usually carried out in the presence of a palladium catalyst such as tetrakis(triphenylphosphine)-palladium(0) or [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane complex and a base such as sodium carbonate or potassium carbonate, in a solvent such as N,N-dimethylformamide, dioxane or a dioxane-water mixture, at a temperature between room temperature and 160°C, optionally under microwave heating conditions and preferably under an inert atmosphere. Such reactions are reviewed, for example, in J. Organomet. Chem. 576, 1999, 147-168. The skilled artisan will also appreciate that the reaction is reversible, i.e., the reaction of the compound of formula (X) (wherein R 1 , R 2 and R 3 is as defined above for compounds of formula (I)) and a compound of formula (IX) 5 is hydrogen or methyl, R 7 , R 8 , R 9 , B 1 and B. 2 is as defined above for compounds of formula (I), and X 0 is a halogen, preferably chlorine, bromine or iodine, to give a compound of formula (IVa), 4 and R 6 is hydrogen, and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B. 2 It will be appreciated that the reaction can result in a 2-amino-2-propanediol (as defined above for compounds of formula (I)). This reaction is shown in Scheme 6. [ka] Scheme 6

[0130] Further cross-coupling chemistry, i.e., C-H activation, can also be used to give compounds of formula (IVa), 4 and R 6 is hydrogen, and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B. 2 may also be used to prepare compounds of formula (I) (as defined above for compounds of formula (I)). This reaction is shown in Scheme 7. [ka] Scheme 7

[0131] As shown in Scheme 7, a compound of formula (IX), 5 is hydrogen or methyl, R 7 , R 8 , R 9 , B 1 and B. 2 is as defined above for compounds of formula (I), and X 0 is a halogen, preferably chlorine, bromine or iodine, in the presence of a palladium catalyst, typically palladium acetate Pd(OAc)2, a suitable ligand, for example 1,10-phenanthroline, in the presence of a base, such as cesium carbonate or potassium carbonate, in an inert solvent, such as chlorobenzene, toluene or xylene, at a temperature between room temperature and 180°C, optionally under microwave heating conditions, preferably under an inert atmosphere, to give a compound of formula (XI), where R 1 , R 2 and R 3 is reacted with (as defined above for compounds of formula (I)). Similar reactions have been reported in the literature, for example in Chemical Science (2013), 4, 2374-2379.

[0132] Compounds of formula (III) can also be prepared from compounds of formula (XVI), the reaction of which is shown in Scheme 8. [ka] Scheme 8

[0133] As shown in Scheme 8, a compound of formula (III) can be prepared by reacting a compound of formula (XVI), 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B. 2 is as defined above for compounds of formula (I), and R 01 can be prepared by one skilled in the art by carbamate deprotection reaction of common carbamate protecting group substituents, such as methyl, tert-butyl, allyl, 2,2,2-trichloroethyl, or benzyl. For example, R 01 When is methyl, for example, a suitable solvent such as dichloromethane and a suitable reagent such as iodotrimethylsilane may be employed 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 in Journal of the American Chemical Society 1992, 114, 5959. The compound of formula (III) thus obtained is converted to the compound of formula (I) as shown in Scheme 1.

[0134] A compound of formula (XVI) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B. 2is as defined above for compounds of formula (I), and 01 where R is as above), can be reacted with an aldehyde of formula (XV) (including formaldehyde in its various forms) (where R is as above), in combination with an acid, in a suitable solvent, as described, for example, in Tetrahedron 1987, 43, 439. 7 is as defined above for compounds of formula (I)) and a compound of formula (XIV) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , B 1 and B. 2 is as defined above for compounds of formula (I), and 01 can be formed by the Pictet-Spengler reaction with 2-(2-(2-phenylpropanediol)-2-propanediol), as shown in Scheme 9. [ka] Scheme 9

[0135] A compound of formula (XIV) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , B 1 and B. 2 is as defined above for compounds of formula (I), and 01 where R is as above) can be reacted with an amine of formula (XIII) (where R is as above) in a suitable solvent such as dichloromethane, optionally in the presence of a base such as triethylamine or pyridine, at a temperature between −20° C. and the boiling point of the mixture, as described, for example, in Organic & Biomolecular Chemistry 2016 14, 6853. 1 , R 2 , R 3 , R4 , R 5 , R 6 , R 8 , R 9 , B 1 and B. 2 can be prepared by reaction of a 2-aminopropyl ether (which is as defined above for compounds of formula (I)) with a suitable protecting reagent, such as methyl chloroformate. This reaction is shown in Scheme 10. [ka] Scheme 10

[0136] 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 above for compounds of formula (I), can be reacted with a nitrile of formula (XII), where R 1 , R 2 , R 3 , R 4 , R 8 , R 9 , B 1 and B. 2 can be prepared by one skilled in the art by reaction of the Grignard reagent R (as defined above for compounds of formula (I)) with a suitable nucleophile such as (dimethylsulfide)dihydroboron (BMS). 5 MgBr or R 6 MgBr (wherein, R 5 and R 6As defined above for compounds of formula (I), Ti(O-) can be added sequentially or simultaneously as a nucleophile to compounds of formula (XII) to allow the preparation of more highly substituted amines of formula (XIII). Such Grignard additions to nitriles can be carried out in inert solvents such as diethyl ether, tert-butyl methyl ether and cyclopentyl methyl ether using Ti(O-) as a nucleophile. i The reaction is carried out in the presence of a Lewis acid such as Pr) (see Synlett (2007), (4), 652-654). This reaction is shown in Scheme 11. [ka] Scheme 11

[0137] A compound of formula (XII) 1 , R 2 , R 3 , R 4 , R 8 , R 9 , B 1 and B. 2 (wherein X is as defined above for compounds of formula (I)) can be prepared by one skilled in the art according to known methods. More specifically, compounds of formula (XII) and intermediates thereto can be prepared from compounds of formula (XVII) as shown in Scheme 12. [ka] Scheme 12

[0138] For example, a compound of formula (XII) 1 , R 2 , R 3 , R 8 , R 9 , B 1 and B. 2 is as defined above for compounds of formula (I), and R 4 is different from hydrogen) can be prepared by the reaction of a compound of formula (XIIa), where R 4is hydrogen, and R 1 , R 2 , R 3 , R 8 , R 9 , B 1 and B. 2 is defined as above for compounds of formula (I), followed by the addition of a suitable alkylating agent R 4 -X, where X is a halogen.

[0139] A compound of formula (XIIa) 4 is hydrogen, and R 1 , R 2 , R 3 , R 8 , R 9 , B 1 and B. 2 (wherein is as defined above for compounds of formula (I)) may be prepared from alcohols of formula (XVII) by treatment with cyanotrimethylsilane (TMSCN) in the presence of a base such as lithium carbonate, in a non-polar solvent such as dichloromethane, at temperatures between 0° C. and the boiling point of the reaction mixture. Such transformations are well known in the literature under a variety of conditions, for example as described in Organic Letters 2008 10,4570 and references therein. This reaction is shown in Scheme 12.

[0140] Alternatively, a compound of formula (III) 1 , R 2 , R 3 , R 4 , R 8 , R 9 , B 1 and B. 2 where R is as defined above for compounds of formula (I), may be prepared from compounds of formula (XVIII), compounds of formula (XIX) or compounds of formula (XX), as shown in Scheme 13. [ka] Scheme 13

[0141] The intermediate compounds (XVIII), (XIX) and (XX) are novel and therefore form further aspects of the invention.

[0142] The compound of formula (III) can be prepared by reacting a compound of formula (XVIII) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B. 2 can be prepared by treating a compound of formula (III) (corresponding to the same definition as for the compound of formula (I) according to the present invention) with a strong acid. 1 is CR 10 And B 2 is CR 11 and R 1 is C1-C4 alkyl, R 2 is hydrogen, halogen or C1-C4 alkyl; R 3 is hydrogen, and R 4 , R 5 , R 6 R 7 is hydrogen or C1-C4 alkyl, and R 8 , R 9 , R 10 and R 11 is as defined above in formula (I), i.e., the compound of formula (III-c) is a compound of formula (XVIII-a) [ka] (In the formula, R 1 is C1-C4 alkyl, R 2 is hydrogen, halogen or C1-C4 alkyl; R 3 is hydrogen, and R 4 is hydrogen or C1-C4 alkyl, R 5 , R 6 , R 7is hydrogen or C1-C4 alkyl, and R 8 , R 9 , R 10 and R 11 (wherein is as defined previously in formula (I)) in an inert solvent such as chlorobenzene, nitrobenzene, etc., at a temperature between 0° C. and 180° C., with a strong acid such as sulfuric acid, hydrochloric acid, hydrobromic acid, trifluoroacetic acid, triflic acid, or methanesulfonic acid, or a Lewis acid such as aluminum oxychloride or bismuth(III) triflate, to give compounds of formula (IIIc), which are converted to compounds of formula (I) as previously described.

[0143] Those skilled in the art will appreciate that such cyclizations can proceed via intermediates such as compounds of formula (XIX). For example, compounds of formula (III-c) (wherein B 1 is CR 10 And B 2 is CR 11 and R 1 is C1-C4 alkyl, R 2 is hydrogen, halogen or C1-C4 alkyl; R 3 is hydrogen, and R 4 , R 5 , R 6 R 7a is hydrogen or C1-C4 alkyl, and R 8 , R 9 , R 10 and R 11 is as already defined in formula (I), a compound of formula (XIX-a) [ka] (In the formula, R 1 is C1-C4 alkyl, R 2 is hydrogen, halogen or C1-C4 alkyl; R 3 is hydrogen, and R 4 is hydrogen or C1-C4 alkyl, R 5 , R 6 , R 7 is hydrogen or C1-C4 alkyl, and R8 , R 9 , R 10 and R 11 can be prepared via cyclization via an intermediate such as (as previously defined for formula (I)).

[0144] Alternatively, a compound of formula (III) 4 is methyl, and R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B. 2 corresponds to the same definition as for the compound of formula (I), the compound of formula (XVIII), 4 is methyl, and R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B. 2 can be prepared by treating a compound of formula (XX) (wherein R corresponds to the same definition as for the compound of formula (I) according to the present invention) with a strong acid, and such cyclization leads to a compound of formula (XX) (wherein R 4 is methyl, and R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B. 2 can proceed via intermediates such as compounds of formula (III-c) (wherein B 1 is CR 10 And B 2 is CR 11 and R 1 is C1-C4 alkyl, R 2is hydrogen, halogen or C1-C4 alkyl; R 3 is hydrogen, and R 4 is methyl, R 5 , R 6 R 7a is hydrogen or C1-C4 alkyl, and R 8 , R 9 , R 10 and R 11 is as already defined in formula (I), the compound of formula (XX-a) [ka] (In the formula, R 1 is C1-C4 alkyl, R 2 is hydrogen, halogen or C1-C4 alkyl; R 3 is hydrogen, and R 4 is C1-methyl, R 5 , R 6 , R 7 is hydrogen or C1-C4 alkyl, and R 8 , R 9 , R 10 and R 11 can be prepared via intermediates such as those previously defined for formula (I).

[0145] In addition, the substituent R in these compounds 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 is as mentioned above.

[0146] Depending on the reaction conditions, these intermediates can be isolated and / or further converted directly to compounds of formula (III). 7It will be appreciated that when is a C1-C4 alkyl, mixtures of diastereomeric racemates (syn-IIIc) and racemates (anti-IIIc) can be obtained in ratios that are controllable such that one isomer is formed preferentially over the other (Scheme 13).

[0147] Compounds (XVIII), (XIX) and (XX) (wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B. 2 corresponds to the same definition as for the compound of formula (I) according to the present invention) can be easily prepared by a person skilled in the art or can be prepared from a commercially available compound of formula (XXI).

[0148] For example, compounds of formula (XVIII-a) and (XIX-a) 1 is C1-C4 alkyl, R 2 is hydrogen, halogen or C1-C4 alkyl; R 3 is hydrogen, and 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 , R 10 and R 11 As described in the experimental section, compounds of formula (XVIII-b) and (XIX-b), where R is as previously defined for formula (I), can be prepared via Friedel-Crafts acylation, followed by Grignard-reaction and cyclization, as shown in Scheme 14 below. Alternatively, compounds of formula (XVIII-b) and (XIX-b), where R 1 is C1-C4 alkyl, R 2 is hydrogen, halogen or C1-C4 alkyl; R 3 is hydrogen, and R 4 is hydrogen, and R5 , R 6 , R 7 is hydrogen or C1-C4 alkyl, and R 8 , R 9 , R 10 and R 11 where R is as previously defined for formula (I)), can be prepared via Friedel-Crafts acylation as described in the experimental section, followed by reduction with a hydride source, such as sodium borohydride, and cyclization as shown in Scheme 14 below. [ka] Scheme 14

[0149] As shown in Scheme 14, a benzylamine of formula (XXI), 7 , R 8 , R 9 , R 10 and R11 correspond to the same definition as for the compound of formula (I) according to the invention) are used to alkylate the compound of formula (XXII) in the presence of a base such as triethylamine (Et3N) in an inert solvent such as DMF or DMA. The compound (XXIII) thus obtained can be isolated or directly treated in situ with BOC-anhydride (Boc2-O) to give the compound of formula (XXIV). The compound of formula XXIV can be reduced with a hydride source such as sodium tetrahydridoborate (NaBH4) in MeOH / THF to give the target molecule (XVIII-b), which can then be cyclized, for example, with an acid such as camphorsulfonic acid (CSA) in a solvent such as ethyl acetate (EtOAc) to give the compound of formula (XIX-b). Alternatively, the compound of formula (XXIV) can be reacted with the Grignard reagent R 4 MgBr (wherein, R 4is C1-C4 alkyl) to give compounds of formula (XVIII-a), which can be cyclized with an acid, for example camphorsulfonic acid, in a solvent, such as EtOAc, to give compounds of formula (XIX-a). In compounds (XIX-a) and (XVIII-a), R 1 is C1-C4 alkyl, R 2 is hydrogen, halogen or C1-C4 alkyl; R 4 is hydrogen or C1-C4 alkyl, R 5 , R 6 and R 7 is hydrogen or C1-C4 alkyl, and R 8 , R 9 , R 10 and R 11 is as previously defined for formula (I).

[0150] Further aspects of this Friedel-Crafts chemistry should also be noted. Chiral amines (XXI-a), where R 7 is C1-C4 alkyl, and R 8 , R 9 , R 10 and R 11 corresponds to the same definition as for the compounds of formula (I) according to the invention), the stereochemistry is 7 is C1-C4 alkyl, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 and R 11 corresponds to the same definition as for the compound of formula (I)) and is retained in the final compound of formula (I). 7 When is methyl, this is shown below in Scheme 15. [ka] Scheme 15

[0151] Compounds of formula (II) are commercially available or easily prepared by compounds known in the art. Compounds of formula (XVII) can be prepared by methods known to those skilled in the art. Compounds of formulas XXI and XXII can be easily prepared by those skilled in the art or are commercially available.

[0152] Salts of compounds of formula (I) can be prepared in a manner known per se: thus, for example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or with a suitable ion exchange reagent, and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchange reagent.

[0153] The salts of the compounds of formula (I) can be converted in customary manner, for example into the free compounds I (acid addition salts) by treatment with a suitable basic compound or a suitable ion exchange reagent, and can also be converted into salts with bases, for example by treatment with a suitable acid or a suitable ion exchange reagent.

[0154] Salts of compounds of formula (I) can be converted into other salts (acid addition salts, e.g. other acid addition salts) of compounds of formula (I) in a manner known per se, for example by treating the salt of an inorganic acid, such as hydrochloric acid, with a suitable metal salt of the acid, such as sodium, barium or silver salt (e.g. silver acetate), in a suitable solvent (in which inorganic salts forming, e.g. silver chloride, are insoluble and therefore precipitate from the reaction mixture).

[0155] Depending on the procedure or reaction conditions, compounds of formula (I) having salt-forming properties may be available in the free form or in salt form.

[0156] The compounds of formula (I) and, where appropriate, their tautomers, in each free or salt form, can exist in the form of pure isomers, such as, for example, enantiomers and / or diastereomers, or as isomeric mixtures, such as enantiomeric mixtures, for example racemates, diastereomeric mixtures or racemic mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms occurring in the molecule and / or depending on the configuration of non-aromatic double bonds occurring in the molecule; the invention relates to the pure isomers and also to all possible isomeric mixtures, and is to be understood in this sense above and below, respectively, even if details of the stereochemistry are not specifically stated in each case.

[0157] Diastereomeric or racemic mixtures of compounds of formula I, in free or salt form, obtained depending on which starting materials and procedures are selected, may be separated in known manner into the pure diastereomers or racemates on the basis of the physical chemical differences of the components, for example by fractional crystallization, distillation and / or chromatography.

[0158] Enantiomeric mixtures, such as racemates, which can be obtained in a similar manner can be resolved into their optical antipodes by known methods, for example by recrystallization from optically active solvents; by chromatography in chiral adsorbents, for example by high performance liquid chromatography (HPLC) on cellulose acetate using suitable microorganisms; by cleavage by specific immobilized enzymes, via the formation of inclusion compounds, for example with chiral crown ethers, in which only one enantiomer is complexed; or by conversion into diastereomeric salts, for example by reacting the basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphoric acid, tartaric acid or malic acid, or a sulfonic acid, for example camphorsulfonic acid, and separating the diastereomeric mixtures which can be obtained thereby, for example by fractional crystallization according to their different solubilities, from which the desired enantiomer can be liberated by the action of a suitable agent, for example a basic agent.

[0159] Pure diastereomers or enantiomers can be obtained according to the invention not only by separating the appropriate isomeric mixture but also by diastereoselective or enantioselective synthesis, which is generally known in the art, e.g. by carrying out the process according to the invention using starting materials with the appropriate stereochemistry.

[0160] If the individual components have different biological activity, it may be advantageous to isolate or synthesize, in each case, the more biologically effective isomer, e.g., enantiomer or diastereomer, or a mixture of isomers, e.g., a mixture of enantiomers or diastereomers.

[0161] As an example, compounds with two or more asymmetric carbon atoms may exist in diastereoisomeric forms that can be optionally separated using, for example, supercritical fluid chromatography (SFC) chromatography with a chiral column. Such diastereomers may exhibit different fungicidal activity profiles, but all isomers and diastereomers form part of the present invention. The relationship between enantiomers and diastereomers is shown in the following scheme (Scheme 16). [ka] Scheme 16

[0162] The compounds of formula (I) and, where appropriate, their tautomers may also be available in free or salt form, where appropriate, also in the form of hydrates and / or include other solvents, such as those that may have been used for the crystallization of compounds present in solid form.

[0163] As stated above, it has now surprisingly been found that the compounds of formula (I) according to the invention have a highly advantageous level of biological activity for practical purposes in protecting plants against diseases caused by fungi.

[0164] 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 plant pests or non-living materials, for controlling spoilage microorganisms or organisms potentially harmful to humans. The novel compounds are distinguished by their excellent activity at low application rates, their excellent tolerance by plants, and their safety for the environment. They have highly useful curative, preventive and systemic properties and can be used to protect numerous cultivated plants. The compounds of formula (I) can be used to inhibit or eliminate pests occurring on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time also protecting these parts of later-growing plants from, for example, phytopathogenic microorganisms.

[0165] The present invention further relates to a method for controlling or preventing infestation of susceptible plants or plant propagation material and / or harvested food crops by microorganisms by treating the plants or plant propagation material and / or harvested food crops, wherein an effective amount of a compound of formula (I) according to the invention is applied to the plant, its part or its habitat.

[0166] The compounds of formula (I) according to the present invention may also be used as fungicides. The term "fungicide" as used herein means a compound that controls, modifies or prevents fungal growth. The term "fungicidally effective amount" as used herein means the amount of such a compound or combination of such compounds that is capable of producing an effect on fungal growth. A controlling or modifier effect includes any deviation from natural development such as killing, retardation, etc., and prevention includes the formation of a barrier or other defense in the plant to prevent infection by fungi.

[0167] It may also be possible to use the compounds of formula (I) according to the invention as dressings for treating plant propagation material, for example seeds such as fruits, tubers or grains or plant cuttings, for protection against fungal infections occurring in the soil as well as against phytopathogenic fungi. The propagation material can be treated with a composition comprising a compound of formula (I) before planting: for example, seeds can be dressed before being sown. The active compounds of formula (I) can also be applied to grains (coating) by impregnating the seeds in a liquid formulation or coating the seeds with a solid formulation. The composition can also be applied to the planting site when the propagation material is planted, for example in the sowing furrow during sowing. The invention also relates to a method for treating such plant propagation material and to the plant propagation material thus treated.

[0168] Furthermore, the compounds of formula (I) according to the present invention can be used for controlling fungi in related fields such as the protection of industrial materials, including wood and wood-based industrial products, food storage and hygiene control.

[0169] In addition, the present invention can be used to protect non-living materials such as timber, wallboard and paint from fungal attack.

[0170] The compounds of formula (I) according to the invention are effective against, for example, fungi and fungal vectors involved in diseases, as well as phytopathogenic bacteria and viruses, such as, for example: Alternaria spp. including Absidia corymbifera, Alternaria solani, Aphanomyces spp., Ascochyta spp., Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, lactucae, Aureobasidium spp., including B. dothidea, B. obtusa, Botryosphaeria spp., including Botryotinia fuckeliana, Botrytis spp., including Botrytis cinerea, C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Candida spp., including Cephaloascus fragrans spp., Cercospora spp. including Ceratocystis spp., Cercospora arachidicola, Cercospora kikuchii, Cercospora sojina, and Cercospora personatum.Cladosporium spp., including Cladosporium cucumerinum, Claviceps purpurea, and Coccidioides immitis; Cochliobolus spp., Colletotrichum spp., including Colletotrichum musae, Colletotrichum asianum, Corynespora cassiicola, and Cryptococcus neoformans; Diaporthe spp., Didymella spp., including Didymella bryoniae; spp., Drechslera spp., Elsinoe spp., Epidermophyton spp., Erwinia amylovora, Erysiphe spp. including Erysiphe cichoracearum, Eutypa lata, Fusarium culmorum, Fusarium graminearum, Fusarium langsethiae, Fusarium moniliforme, Fusarium oxysporum, Fusarium praliferatum Fusarium spp., including Fusarium proliferatum, Fusarium subglutinans, and Fusarium solani), Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate, Glomerella lagenarium, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium spp, Hemileia spp, Histoplasma spp including H. capsulatum spp., Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp., Monilinia spp., Mucor spp., Mycosphaerella spp. including Mycosphaerella graminicola, Mycosphaerella spp. including Mycosphaerella pomi, Oncobasidium theobromaeon theobromaeon, Ophiostoma piceae, Paracoccidioides spp., Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp., P. maydis, P.maydis, Peronosclerospora spp. including P. philippinensis and P. sorghi, Peronospora spp., Phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp., Phoma spp.,. Phytophthora spp. including Phomopsis viticola, P. infestans, Plasmopara spp. including Plasmopara halstedii, Plasmopara viticola, Pleospora spp., Podosphaera spp. including P. leucotricha, Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp. Pseudoperonospora spp. including P. cubensis and P. humuli, Puccinia spp. including Pseudopeziza tracheiphila, Puccinia hordei, Puccinia recondita, Puccinia striiformis and Puccinia triticina, Pyrenopeziza spp. including Pyrenophora teres, Pyricularia oryzae, Pythium spp. including P. ultimum,), Ramularia spp., Rhizoctonia spp. including Rhizoctonia solani, Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium spp., Scedosporium spp. including S. apiospermum and S. prolificans, Schizothyrium pomi, Sclerotinia spp. including Sclerotinia sclerotiorum, Sclerotium spp. spp., Septoria spp. including Septoria nodorum, Septoria tritici, Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix spp., Stagonospora nodorum, Stemphylium spp., Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia spp. Trichoderma spp., including T. harzianum, T. pseudokoningii, and T. viride.), Trichophyton spp., Typhula spp., Uncinula necator, Urocystis spp., Ustilago spp., Venturia spp. including Venturia inaequalis, Verticillium spp., and Xanthomonas spp..

[0171] The compounds of formula (I) according to the invention may be used, for example, on turf, ornamental plants such as flowers, shrubs, broadleaf or evergreen trees such as conifers, as well as for trunk injections, pest management and the like.

[0172] Within the scope of the present invention, the target crops and / or useful plants to be protected are typically berry plants, such as blackberries, blueberries, cranberries, raspberries and strawberries; cereals, such as barley, maize (corn), millet, oats, rice, rye, sorghum, triticale and wheat; fibre plants, such as cotton, flax, hemp, jute and sisal; agricultural crops, such as sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugarcane, sunflower, tea and tobacco; fruit trees, such as apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; and arable plants, such as bermuda grass, strawberry bush, bentgrass, centipede grass, fescue, ryegrass, lawn grass and wild grass. herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes such as beans, lentils, peas and soybeans; nuts such as almonds, cashews, peanuts, hazelnuts, peanuts, pecans, pistachios and walnuts; palms such as oil palm; ornamental plants such as flowers, shrubs and trees; other trees such as cocoa, coconut, olive and rubber; vegetables such as asparagus, eggplant, broccoli, cabbage, carrots, cucumber, garlic, lettuce, squash, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and perennial and annual crops such as vines, for example grapes.

[0173] The term "useful plants" should also be understood to include useful plants in which resistance to herbicides such as bromoxynil or to a class of herbicides (e.g. HPPD inhibitors, ALS inhibitors such as primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyroyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors, etc.) has been provided by conventional breeding or genetic engineering methods. An example of a crop in which resistance to imidazolinones, such as imazamox, has been provided by conventional breeding methods (mutagenesis) is Clearfield® summer rapeseed (canola). Examples of crops in which resistance to herbicides or to a class of herbicides has been provided by genetic engineering methods include crops under the trade names RoundupReady®, Herculex I, and others. * and glyphosate- and glufosinate-tolerant corn varieties commercially available under the trademark LibertyLink®.

[0174] The term "useful plants" should also be understood to include useful plants which have been transformed by recombinant DNA techniques so as to be capable of synthesizing one or more selectively acting toxins, such as the known ones derived from toxin-producing bacteria, especially those belonging to the genus Bacillus.

[0175] An example of such a plant is YieldGard * (CryIA(b) toxin expressing corn cultivars); YieldGard Rootworm * (Maize cultivar expressing CryIIIB(b1) toxin); YieldGard Plus * (Maize varieties expressing CryIA(b) and CryIIIB(b1) toxins); Starlink * (A corn variety expressing the Cry9(c) toxin); Herculex I *(A maize cultivar expressing CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B * (Cotton cultivar expressing CryIA(c) toxin); Bollgard I * (a cotton variety expressing CryIA(c) toxin); Bollgard II® (a cotton variety expressing CryIA(c) and CryIIA(b) toxins); VIPCOT * (Cotton varieties expressing VIP toxin); NewLeaf * (Potato cultivars expressing CryIIIA toxin); Nature-Gard * Agrisure® GT Advantage (GA21 glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), Agrisure® RW (corn root-eating nematode trait) and Protecta * It is.

[0176] The term "crop plant" should also be understood to include crop plants which have been transformed using recombinant DNA techniques so as to be capable of synthesizing one or more selectively acting toxins, such as those known from toxin-producing bacteria, particularly those belonging to the genus Bacillus.

[0177] Toxins which can be expressed by such transformed plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as d-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 from Photorhabdus spp. or Xenorhabdus spp., for example Photorhabdus luminescens, Xenorhabdus nematophilus. spp.); toxins produced by animals such as scorpion toxins, spider toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi such as Streptomycete toxins, plant lectins such as pea lectin, barley lectin or snowdrop lectin; agglutinins; proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ricin, Ribosome-inactivating proteins (RIPs) such as maize-RIP, abrin, rufin, saporin or bryodin; steroid metabolic enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers such as sodium or calcium blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

[0178] Furthermore, in the context of the present invention, delta-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or trophic insecticidal proteins (Vip), such as Vip1, Vip2, Vip3 or Vip3A, are also to be understood as being especially hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by new combinations of different domains of these proteins (see, for example, WO 02 / 15701). Truncated toxins, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the natural toxin are replaced. In such amino acid substitutions, preferably a non-naturally occurring protease recognition sequence is inserted into the toxin, for example, in the case of Cry3A055, a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see WO 03 / 018810).

[0179] Examples of such toxins or transformed plants capable of synthesizing such toxins are disclosed, for example, in EP 0 374 753, WO 93 / 07278, WO 95 / 34656, EP 0 427 529, EP 451 878 and WO 03 / 052073.

[0180] The processes for the preparation of such transformed 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 0 367 474, EP 0 401 979 and WO 90 / 13651.

[0181] The toxins contained in the transformed plants confer resistance to harmful insects on the plants, which can be from any taxonomic group of insects, but are particularly commonly found among beetles (Coleoptera), two-winged insects (Diptera), and butterflies (Lepidoptera).

[0182] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known, and some are commercially available. Examples of such plants include: YieldGard * (Cry1Ab toxin expressing corn cultivars); YieldGard Rootworm * (a corn variety expressing Cry3Bb1 toxin); YieldGard Plus * (Maize varieties expressing Cry1Ab and Cry3Bb1 toxins); Starlink * (a corn variety expressing Cry9C toxin); Herculex I * (A maize variety that has been made tolerant to the herbicide glufosinate ammonium by expressing Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT)); NuCOTN 33B * (cotton cultivar expressing Cry1Ac toxin); Bollgard I * (a cotton variety expressing Cry1Ac toxin); Bollgard II® (a cotton variety expressing Cry1Ac and Cry2Ab toxins); VipCot * (Cotton cultivar expressing Vip3A and Cry1Ab toxins); NewLeaf * (Potato cultivars expressing Cry3A toxin); NatureGard * , Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta * It is.

[0183] Further examples of such transformed crops are: 1. Bt11 maize, registration number C / FR / 96 / 05 / 10, manufactured by Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St.Sauveur, France. Genetically engineered maize (Zea mays) that is resistant to the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also achieves tolerance to the herbicide glufosinate ammonium by transgenic expression of the enzyme PAT.

[0184] 2. Bt176 maize, registration number C / FR / 96 / 05 / 10, manufactured by Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St.Sauveur, France. A genetically engineered maize (Zea mays) that is resistant to the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of the Cry1Ab toxin. Bt176 maize also achieves tolerance to the herbicide glufosinate ammonium by transgenic expression of the enzyme PAT.

[0185] 3. MIR604 maize, registration number C / FR / 96 / 05 / 10, from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France. Maize conferred insect resistance by transgenic expression of a modified Cry3A toxin. The toxin is Cry3A055 modified by the insertion of a cathepsin-G-protease recognition sequence. The preparation of such transformed maize plants is described in WO 03 / 018810.

[0186] 4. MON863 maize, registration number C / DE / 02 / 9, from Monsanto Europe SA 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium. MON863 expresses the Cry3Bb1 toxin and confers resistance to certain coleopteran insects.

[0187] 5. IPC531 Cotton made by Monsanto Europe SA 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0188] 6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Maize genetically engineered for expression of the protein Cry1F to achieve resistance to certain lepidopteran insects, and for expression of the PAT protein to achieve resistance to the herbicide glufosinate ammonium.

[0189] 7. NK603 x MON810 maize, registration number C / GB / 02 / M3 / 03, from Monsanto Europe SA 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium. It consists of a conventional hybrid maize variety by crossing the genetically engineered varieties NK603 and MON810. NK603 x MON810 maize transgenic expresses the protein CP4 EPSPS from the strain CP4 of Agrobacterium sp., which confers resistance to the herbicide Roundup® (containing glyphosate), and also transgenic expresses the Cry1Ab toxin from Bacillus thuringiensis subsp. kurstaki, which confers resistance to certain Lepidoptera, including the European corn borer.

[0190] The compounds of formula (I) according to the invention are useful in the control of phytopathogenic diseases, in particular Alternaria solani, Blumeria graminis, Botryotinia fuckeliana, Botrytis cinerea, Cercospora arachidicola, Cercospora kikuchii, Cercospora sojina, Cladosporium cucumerinum, Colletotrichum lagenarium, Corynespora cassiicola, Didymella bryoniae, Fusarium spp. spp, Glomerella lagenarium, Leptosphaeria spp, Leveillula taurica, Microdochium nivale, Plasmopara viticola, Puccinia recondita, Pyrenophora teres, Pyricularia oryzae, Rhizoctonia solani, Sclerotinia sclerotiorum, Septoria nodorum, Septoria tritici, Sphaerotheca fuliginea In some embodiments, the fungi may be used in the control or prevention of phytopathogenic fungi such as Pseudomonas fuliginea, Uncinula necator and Venturia inaequalis.In an embodiment of the invention, the compounds of formula (I) according to the invention are useful for the prevention and control of phytopathogenic diseases, in particular Septoria tritici, Pyrenophora teres, Puccinia recondita and Blumeria graminis in cereals; Cercospora arachidicola and Sclerotinia sclerotiorum in crops; Alternaria solani in fruits and vegetables, such as tomatoes and potatoes; Botrytis cinerea in fruits, vegetables and crops, such as strawberries, tomatoes, sunflowers, legumes and grapes; Glomerella lagenarium in vegetables, such as cucumbers; Uncinula necatr in vegetables, such as grapes. necator); Venturia inaequalis in fruits, e.g. apple; Rhizoctonia solani in vegetables, e.g. potato; Cladosporium cucumerinum, Didymella bryoniae and Sphaerotheca fuliginea in vegetables, e.g. cucumber; Leveillula taurica in cucumber and solanaceous vegetables; Fusarium spp. in cereals and vegetables; Leptosphaeria spp. in cereals.

[0191] As used herein, the term "habitat" refers to the field in which the plant is growing or in which the seeds of the cultivated plant have been sown or in which the seeds will be sown in the soil, including the soil, the seeds and seedlings, as well as the established vegetation.

[0192] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, seedlings, roots, tubers, stems, stalks, foliage and fruits.

[0193] The term "plant propagation material" is understood to refer to reproductive parts of plants, such as seeds, which can be used for their propagation, and vegetative bodies, such as cuttings or tubers, for example potatoes. For example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and plant parts may be mentioned. Also mentioned are sprouted plants and shoots that are to be transplanted after germination or emergence from the soil. These shoots may be protected by a complete or partial treatment by immersion before transplantation. Preferably, "plant propagation material" is understood to refer to seeds.

[0194] The compounds of formula (I) according to the invention can be used in their pure form or, preferably, together with auxiliaries that are conveniently employed in the field of formulation.For this purpose, they can be conveniently formulated in a known manner into emulsifiable concentrates, coating pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and capsules, for example, in polymeric materials.As well as the type of composition, the application method, such as spraying, misting, dusting, scattering, coating, or pouring, is selected according to the intended purpose and the current situation.The composition may also contain further auxiliaries, such as stabilizers, defoamers, viscosity regulators, binders or adhesives, as well as fertilizers, sources of trace elements, or other compounds for obtaining special effects.

[0195] Suitable carriers and adjuvants, for example for use in agriculture, can be solid or liquid and are substances useful in formulation technology, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers. Such carriers are described, for example, in WO 97 / 33890.

[0196] Suspension concentrates are aqueous formulations in which fine solid particles of the active compound are suspended. Such formulations contain anti-settling and dispersing agents and may further contain wetting agents to enhance activity, as well as anti-foaming agents and crystal growth inhibitors. In use, these concentrates are diluted in water and usually applied by spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

[0197] Wettable powders are in the form of fine particles that disperse easily in water or other liquid carriers. These particles contain the active ingredient held in a solid matrix. Typical solid matrices include Fuller's earth, kaolin clay, silica and other easily wet organic or inorganic solids. Wettable powders usually contain 5% to 95% of the active ingredient and small amounts of wetting agents, dispersing agents or emulsifying agents.

[0198] Emulsifiable concentrates are homogeneous liquid compositions that are dispersible in water or other liquids and may consist solely of the active compound and a liquid or solid emulsifier, or may contain a liquid carrier such as xylene, high boiling aromatic naphtha, isophorone, and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and usually applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

[0199] Granular formulations include both extrudates and relatively coarse particles, and are usually applied undiluted to the area where treatment is required. Typical carriers for granular formulations include sand, Fuller's earth, attapulgite clay, bentonite clay, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, gypsum, wood flour, ground corn cobs, ground peanut shells, sugar, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate, and other organic or inorganic materials that can absorb or be coated with the active compound. Granular formulations usually contain 5% to 25% active ingredient, which may include surfactants such as high-boiling aromatic naphtha, kerosene and other petroleum fractions, or vegetable oils; and / or spreading agents such as dextrin, glue or synthetic resins.

[0200] Dusts are free-flowing admixtures of the active ingredient and finely divided solids such as talc, clays, powders and other organic and inorganic solids which act as dispersants and carriers.

[0201] Microcapsules are typically droplets or granules of active ingredient enclosed in an inert porous shell that allows the encapsulated material to be released into the environment at a controlled rate. The encapsulated droplets are typically 1-50 microns in diameter. The encapsulated liquid typically constitutes 50-95% of the capsule's weight and may contain a solvent in addition to the active compound. Encapsulated granules are generally porous granules with a porous membrane that seals the pore openings of the granule and retains the active species in liquid form within the pores of the granule. The granules are typically in the range of 1 millimeter to 1 centimeter in diameter, preferably 1-2 millimeters. Granules are formed by extrusion, agglomeration or prilling, or are natural. Examples of such materials are vermiculite, calcined clay, kaolin, attapulgite clay, sawdust, and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xandates.

[0202] Other useful formulations for agricultural chemical applications include simple solutions of the active ingredient in solvents such as acetone, alkylated naphthalenes, xylenes and other organic solvents in which complete dissolution at the desired concentration is achieved. Pressurized sprayers may also be used in which the active ingredient is dispersed in finely divided form as the low boiling dispersant solvent carrier evaporates.

[0203] Suitable agricultural adjuvants and carriers useful in formulating the compositions of the present invention in the formulation types described above are well known to those skilled in the art.

[0204] Liquid carriers that may be utilized include, for example, water, toluene, xylene, petroleum naphtha oil, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-Trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, kutadeca Examples of suitable solvents include ethyl acetate, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerin, and N-methyl-2-pyrrolidinone. For dilution of concentrates, water is the typical carrier of choice.

[0205] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, Kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, Fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut hulls, and lignin.

[0206] A wide range of surfactants may be advantageously utilized in both the liquid and solid compositions, particularly those designed to be diluted with a carrier prior to application. These surfactants, when used, typically comprise from 0.1% to 15% by weight of the formulation. They may be anionic, cationic, nonionic or polymeric in nature and may be utilized as emulsifying agents, wetting agents, suspending agents, or for other purposes. Typical surfactants include alkyl sulfates such as diethanolammonium lauryl sulfate; alkylaryl sulfonate salts such as calcium dodecylbenzene sulfonate; alkylphenol-alkylene oxide adducts such as nonylphenol-C.sub.18 ethoxylate; alcohol-alkylene oxide adducts such as tridecyl alcohol-C.sub.16 ethoxylate; soaps such as sodium stearate; alkylnaphthalene sulfonates such as sodium dibutylnaphthalene sulfonate; dialkyl esters of sulfosuccinates such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters such as sorbitol oleate; quaternary amines such as lauryl trimethyl ammonium 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 phosphate esters.

[0207] Other adjuvants commonly utilized in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray size regulators, pigments, antioxidants, foaming agents, defoamers, light blocking agents, compatibilizers, antifoaming agents, sequestering agents, neutralizing and buffering agents, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, trace elements, emollients, lubricants and adhesives.

[0208] In addition, other biocidal active ingredients or compositions may be combined with the compositions of the present invention, 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 may be formulated together with the compositions of the present invention or may be mixed together, for example, in a spray tank. These additional biocidal active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and / or plant growth regulators.

[0209] Pesticides are referred to herein using their common names as known, for example from “The Pesticide Manual”, 15th Ed., British Crop Protection Council 2009.

[0210] In addition, the compositions of the present invention may also be applied together with one or more systemic acquired resistance inducers ("SAR" inducers). SAR inducers are known and are described, for example, in U.S. Patent No. 6,919,298, and include, for example, salicylates and the commercially available SAR inducer acibenzolar-S-methyl.

[0211] The compounds of formula (I) according to the present invention are usually used in the form of agrochemical compositions and can be applied to the crop areas or plants to be treated simultaneously or sequentially with further compounds. These further compounds can be, for example, fertilizers or trace element donors or other preparations that affect plant growth. They can also be selective or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired with further carriers, surfactants or application-promoting adjuvants customarily used in the field of formulations.

[0212] The compounds of formula (I) according to the present specification may be used in the form of a (fungicidal) composition for the control or protection against phytopathogenic microorganisms, comprising at least one compound of formula (I) as active ingredient, or in the form of at least one preferred individual compound as defined herein, in free form or in the form of an agrochemically usable salt, and at least one of the abovementioned auxiliaries.

[0213] The present invention therefore provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I) according to the present invention, an agriculturally acceptable carrier, and optionally an adjuvant. An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural carriers are well known in the art. Preferably, the composition may comprise, in addition to the compound of formula (I), at least one or more pesticidal active compounds, for example an additional fungicidal or fungicidal active ingredient.

[0214] The compounds of formula (I) according to the present invention may be the sole active ingredient in the composition or, where appropriate, may be mixed with one or more additional active ingredients, such as pesticides, fungicides, synergists, herbicides or plant growth regulators, which may in some cases result in unexpected synergistic activity.

[0215] Examples of suitable additional active ingredients are the following: acyl amino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenic fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, Morpholine fungicides and fungicides, organophosphate fungicides and fungicides, organotin fungicides and fungicides, oxathiin fungicides and fungicides, oxazole fungicides and fungicides, phenylsulfamide fungicides and fungicides, polysulfide fungicides and fungicides, pyrazole fungicides and fungicides, pyridine fungicides and fungicides, pyrimidine fungicides and fungicides, pyrrole fungicides and fungicides, quaternary ammonium fungicides and fungicides, quinoline fungicides and fungicides, quinone fungicides and fungicides, quinoxaline fungicides These include fungicides, strobilurin fungicides, sulfonanilide fungicides, thiadiazole fungicides, thiazole fungicides, thiazolidine fungicides, thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, valinamide fungicides and zinc fungicides.

[0216] Examples of suitable additional active ingredients that may be selected include: petroleum, 1,1-bis(4-chloro-phenyl)-2-ethoxyethanol, 2,4-dichlorophenylbenzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylacetamide, 4-chlorophenylphenylsulfone, acetoprole, aldoxicarb, amidithione, amidothioate, amiton, amiton hydrogen oxalate, amitraz, aramite, arsenic oxide, azobenzene, azotoate, benomyl, benoxa-phos, benzyl benzoate, benzoic acid ... nil, bixafen, brofenvalerate, bromo-cyclen, bromophos, bromopropylate, buprofezin, butocarboxim, butoxycarboxim, butylpyridaben, calcium polysulfide, camphorchlor, carbanolate, carbophenothione, cymiazole, quino-methionate, chlorbenside, chlordimeform, chlordimeform hydrochloride, chlorphenetole, chlorfenson, chlorphenesulfide, chlorobenzilate, chloromebuform, chloromethiron, Chloropropylate, Chlorthiophos, Cinerin I, Cinerin II, Cinerin, Closantel, Coumaphos, Crotamiton, Crotoxifos, Cufraneb, Cyanthoate, DCPM, DDT, Demefion, Demefion-O, Demefion-S, Demeton-methyl, Demeton-O, Demeton-O-Methyl, Demeton-S, Demeton-S-Methyl, Demeton-S-Methyl Sulfone, Dichlofluanid, Dichlorvos, Diglifos, Dienochlor, Dimefox, Zinex, Zinex-Diclexin, Zinocyanide zip-4, dinoc-cap-6, dinoctone, dinopentone, dinosulfone, dinotervone, dioxathion, diphenylsulfone, disulfiram, DNOC, dofenapine, doramectin, endothion, eprinomectin, ethoeate methyl, etrimphos, fenazaflor, fenbutatin oxide, fenothiocarb, fenpyrad, fen-pyroximate, fenpyrazamine, fenson, fentrifanil, flubenzimine, flucycloxuron, fluentil, fluorobenside, FMC 1137, formetanate, formetanate hydrochloride, forparanate, gamma-HCH, gliodin, halfenprox, hexadecylcyclopropanecarboxylate,Isocarbophos, Jasmolin I, Jasmolin II, Iodofenphos, Lindane, Malonoben, Mecarbam, Mesfolan, Mesulfen, Methacrifos, Methyl Bromide, Metolcarb, Mexacarbate, Milbemycin Oxime, Mipafox, Monocrotophos, Morphothion, Moxidectin, Naled, 4-Chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one, Nifluridide, Nikkomycin, Nitrilacarb, Nitrilacarb 1:1 Zinc Chloride Complex, Omethoate , oxydeprophos, oxydisulfoton, pp'-DDT, parathion, permethrin, fencapton, phosalone, phospholane, phosphamidon, polychloroterpenes, polynactin, proclonol, promacyl, propoxur, prothidathion, protoate, pyrethrin I, pyrethrin II, pyrethrins, pyridaphenthion, pyrimitate, quinalphos, quinthiophos, R-1492, phosglycine, rotenone, shladan, cebufos, selamectin, sofamide, SSI-121, sulfiram, sulfuramide, sulfotep, sulfur, di Flovidazin, tau-fluvalinate, TEPP, terbam, tetradifon, tetrasul, thiafenox, thiocarboxim, thiofanox, thiometon, thioquinox, thuringensin, triamiphos, triaraten, triazophos, triazuron, tripenophos, trinactin, vamidothion, vaniliprole, bethoxazin, copper dioctanoate, copper sulfate, sibutrin, dichloron, dichlorophen, endothal, fentin, hydrated lime, nabam, quinoclamine, quinonamide, simazine, triphenyltin acetate, triphenylsulphate , crufomate, piperazine, thiophanate, chloralose, fenthion, pyridin-4-amine, strychnine, 1-hydroxy-1H-pyridine-2-thione, 4-(quinoxalin-2-ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, copper hydroxide, cresol, dipyrithione, dodysin, phenaminosulf, formaldehyde, hydralgafen, kasugamycin, kasugamycin hydrochloride hydrate, nickel bis(dimethyldithiocarbamate), nitropyrine, octhilinone, oxolinic acid,Oxytetracycline, Potassium Hydroxyquinoline Sulfate, Probenazole, Streptomycin, Streptomycin Sesquisulfate, Tecloftalam, Thiomersal, Adoxophyes Orana GV, Agrobacterium radiobacter, Amblyseius species, Anagrapha falcifera NPV, Anagrus atomus, Aphelinus abdominalis, Aphidius colemani, Aphidoletes aphidimyza, Autographa californica NPV, Bacillus sphaericus Neide, Beauveria brongniartii, Chrysoperla carnea, Cryptolaemus montrouzieri, Cydia pomonella GV, Dacnusa sibirica, Diglyphus isaea, Encarsia formosa, Eretmocerus eremicus, Heterorhabditis bacteriophora and H. megidis, Hippodamia convergens, Leptomastix dactylopii dactylopii, Macrolophus caliginosus, Mamestra brassicae NPV, Metaphycus helvolus,Metarhizium anisopliae var. acridum, Metarhizium anisopliae var. anisopliae, Neodiprion sertifer NPV and N. lecontei NPV, Orius spp., Paecilomyces fumosoroseus, Phytoseiulus persimilis, Steinernema bibionis, Steinernema carpocapsae, Steinernema feltiae, Steinernema glaseri, Steinernema riobrave, Steinernema riobravis, Steinernema scapterisci, Steinernema spp., Trichogramma spp., Typhlodromus occidentalis, Verticillium lecanii lecanii), afolate, bisazir, busulfan, dimatif, hemel, hempa, metepa, methiotepa, methyl afolate, molzide, penfluron, tepa, thiohempa, thiotepa, toretamine, uredepa, (E)-tridec-4-en-1-yl acetate with (E)-dec-5-en-1-ol, (E)-dec-5-en-1-yl acetate, (E)-6-methylhept-2-en-4-ol, (E,Z)-tetradec-4,10-dien-1-yl acetate, (Z)-dodec-7-en-1-yl acetate, (Z)-Hexadecate-11-enal, (Z)-hexadecate-11-en-1-yl acetate, (Z)-hexadecate-13-en-11-yn-1-yl acetate, (Z)-icos-13-en-10-one, (Z)-tetradec-7-en-1-al, (Z)-tetradec-9-en-1-ol, (Z)-tetradec-9-en-1-yl acetate, (7E,9Z)-dodeca-7,9-dien-1-yl acetate, (9Z,11E)-tetradec-9,11-dien-1-yl acetate, (9Z,12E)-tetradec-9,12-dien-1-yl acetate, 14-methyloctadec-1-ene, 4-methylnonan-5-ol α-multistriatin with 4-methylnonan-5-one, brevicomin, chordalure, chordramone, curar, disparlure, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodec-8,10-dien-1-yl acetate, dominicalure, ethyl 4-methyloctanoate, eugenol, Frontalin, Grand Lure, Grand Lure I, Grand Lure II, Grand Lure III, Grand Lure IV, Hexal Lure, Ipsdienol, Ipsenol, Japoniluer, Lineatin, Little Lure, Loop Lure, Medi Lure, Megaatomic Acid, Methyl Eugenol, Muscaluer, Octadeca-2,13-dien-1-yl Acetate, Octadeca-3,13-dien-1-yl Acetate, Olfla Lure, Orictaluer, Ostra Lure Mon, Sigluer, Soldidin Sulcatol, Tetradec-11-en-1-yl Acetate, Trimedulla, Trimedulla A, Trimedulla B1, Trimedulla B2, Trimedulla C, trunc-call, 2-(octylthio)-ethanol, butyronoxyl, butoxy(polypropylene glycol), dibutyl adipate, dibutyl phthalate, dibutyl succinate, diethyl toluamide, dimethyl carbate, dimethyl phthalate, ethyl Hexanediol, hexamide, methoquin-butyl, methyl neodecaneamide, oxamate, picaridin, 1-dichloro-1-nitroethane, 1,1-dichloro-2,2-bis(4-ethylphenyl)-ethane, 1,2-dichloropropane with 1,3-dichloropropene, 1-bromo-2-chloroethane, 2,2,2-trichloro-1-(3,4-dichloro-phenyl)ethyl acetate, 2,2-dichlorovinyl 2-ethylsulfinylethyl Methyl phosphate, 2-(1,3-dithiolan-2-yl)phenyl dimethyl carbamate, 2-(2-butoxyethoxy)ethyl thiocyanate, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methyl carbamate, 2-(4-chloro-3,5-xylyloxy)ethanol, 2-chlorovinyl diethyl phosphate, 2-imidazolidone, 2-isovalerindane-1,3-dione, 2-methyl(prop-2-ynyl)aminophenyl methyl carbamate, 2-thiocyanate ethyl laurate, 3-bromo-1-chloroprop-1-ene, 3-methyl-1-phenylpyrazol-5-yl dimethyl carbamate, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methyl carbamate, 5,5-Dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate, acetione, acrylonitrile, aldrin, allosamidin, alixalbu, alpha-ecdysone, aluminum phosphide, aminocarb, anabasine, atidathione, azamethiphos, Bacillus thuringiensis deltaendotoxins, barium hexafluorosilicate, barium polysulfide, bartholin, Bayer 22 / 190, Bayer 22408, beta-cyfluthrin, beta-cypermethrin, bioethanomethrin, bioethanomethrin, bis(2-chloroethyl)ether, borax, bromfenbufos, bromo-DDT, bufencarb, butacarb, butathiophos, butonate, calcium arsenate, calcium cyanide, carbon disulfide, tetrasodium salt Carbon hydride, cartap hydrochloride, sebazine, chlorbicyclen, chlordane, chlordecone, chloroform, chloropicrin, chlorphoxim, chlorprazophos, cis-resmethrin, simetryn, clocitrin, copper acetoarsenite, copper arsenate, copper oleate, kumitoate, acrolite, CS708, cyanofenphos, cyanophos, ciclethrin, cithioate, d-tetramethrin, DAEP, dazomet, decarbofuran, diamidaphos, dicaprylate Ton, diclofenthion, dicresyl, dicyclanil, dieldrin, diethyl 5-methylpyrazol-3-yl phosphate, dirol, dimefluthrin, dimethane, dimethyrin, dimethylvinphos, dimethyllan, dinoprop, dinosam, dinoseb, diofenolan, dioxabenzophos, dicyclophos, DSP, ecdysterone, EI1642, EMPC, EPBP, ethaphos, ethiofencarb, ethyl formate, ethylene dibromide, ethyl Dichloride, ethylene oxide, EXD, fenchlorphos, fenetacarb, fenitrothion, fenoxacrim, fenpyritrin, fenthion ethyl, flucofuron, fosmetiran, fospirate, fostietan, furathiocarb, fretrin, guazatine, guazatine acetate, sodium tetrathiocarbonate, half-fenprox, HCH, HEOD, heptachlor, heterophos, HHDN, Hydrogen cyanide, hikincarb, IPSP, isofunofos, isobenzane, isodrin, isofenphos, isoprothiolane, isoxathion, juvenile hormone I, juvenile hormone II, juvenile hormone III, kereban, kinoprene, lead arsenate, leptophos, lilimphos, ritidathion, m-cumenylmethylcarbamate, magnesium phosphide, magidox, mecarfone, menazone, mercurous chloride, mesulfenphos, metam, meta-potassium, meta-sodium, methanesulfonyl fluoride, methoclotophos, methoprene, methotrin, methoxychlor, iso Methyl thiocyanate, methyl chloroform, methylene chloride, methoxadiazone, Mirex, naphthalophos, naphthalene, NC-170, nicotine, nicotine sulfate, nithiazine, nornicotine, O-5-dichloro-4-iodophenyl O-ethyl phosphonothioate, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate, O,O,O',O'-tetrapropyl dithiopyrophosphate, oleic acid, paradichlorobenzaldehyde Zene, Parathion-methyl, Pentachlorophenol, Pentachlorophenyllaurate, PH60-38, Fenkapton, Phosniclor, Phosphine, Phoxim-methyl, Pyrimetaphos, Polychlorodicyclopentadiene Isomers, Potassium Arsenite, Potassium Thiocyanate, Precocene I, Precocene II, Precocene III, Primidophos, Profluthrin, Promecarb, Prothiophos, Pyrazophos, Pyresmethrin, Cassia, Quinophos-methyl, Quinothione, Lafoxanide, Resmethrin, Rotenone, Cadethrin, Lyania, Ryanodine, Saba Zira), Shradan, Cebufos, SI-0009, Thiapronil, Sodium arsenite, Sodium cyanide, Sodium fluoride, Sodium hexafluorosilicate, Sodium pentachlorophenoxide, Sodium selenate, Sodium thiocyanate, Sulcofuron, Sulcofuron sodium, Sulfuryl fluoride, Sulprofos, Tall oil, Tadinecarb, TDE, Tebupirimfos, Temephos, Terallethrin, Tetrachloroethane, Cyclofos, Thiocyclam, Thiocyclam hydrogen oxalate, Thionazine, Thiosultap, Thiosultap-sodium,Tralomethrin, transpermethrin, triazamate, trichloromethaphos-3, trichloronate, trimethacarb, tolprocarb, triclopyricarb, triplen, veratridine, veratrine, XMC, zetamethrin, zinc phosphate, zolaprophos, and meperfluthrin, tetramethylfluthrin, bis(tributyltin) oxide, bromoacetamide, ferric phosphate, niclosamide-olamine, tributyltin oxide, pyrimorph, triphenmorph, 1,2-dibromo-3-chloropropane, 1,3-dichloropropene, 3,4-dichlorotetrahydrothiophene 1,1-Dioxide, 3-(4-chlorophenyl)-5-methylrhodanine, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid, 6-isopentenylaminopurine, 2-fluoro-N-(3-methoxyphenyl)-9H-purin-6-amine, Benclothiaz, Cytokinins, DCIP, Furfural, Isamidophos, Kinetin, Myrothecium verrucaria composition, Tetrachlorothiophene, Xylenols, Zeatin, Potassium ethylxanthinate, Acibenzolar, Acibenzolar-S-methyl, Reynoutria sakarinensis (Reynoutria sachalinensis) extract, alpha-chlorohydrin, antu, barium carbonate, bisthiosemi, brodifacoum, bromadiolone, bromethalin, chlorophacinone, cholecalciferol, coumachlor, coumafuryl, coumatetralyl, crimidine, difenacoum, difethialone, diphacinone, ergocalciferol, flocoumafen, fluoroacetamide, flupropazine, flupropazine hydrochloride, norbormide, phosacetin, phosphorus, pindone, pyrinuron, sciriloside, fluoroacetamide Sodium phosphate, thallium sulfate, warfarin, 2-(2-butoxyethoxy)-ethyl piperonylate, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, farnesol with nerolidol, berubutin, MGK264, piperonyl butoxide, piperotal, propyl isomer, S421, sesamex, sesamolin, sulfoxide, anthraquinone, copper naphthenate, copper oxychloride, dicyclopentadiene, thiram, zinc naphthenate, ziram, imanin, ribavirin, mercuric oxide,Thiophanate methyl, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, furamepyr, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, paclobutrazol, pefurazoate, penconazole, prothioconazole, pyrifenox, prochloraz, propiconazole, pyrisoxazole, simeconazole, tebuconazole , tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole, ancymidol, fenarimol, nuarimol, bupirimate, dimethirimol, ethirimol, dodemorph, fenpropidin, fenpropimorph, spiroxamine, tridemorph, cyprodinil, mepanipyrim, pyrimethanil, fenpiclonil, fludioxonil, benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurase, oxadixyl, carbendazim, debacarb, fuberidazole, thiabendazole, chlozolinate, Diclozolin, mycrozolin, procymidone, vinclozolin, boscalid, carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, penthiopyrad, thifluzamide, dodine, iminoctadine, azoxystrobin, dimoxystrobin, enestrobulin, phenaminestrobin, flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, ferbam , mancozeb, maneb, metiram, propineb, zineb, captafol, captan, fluoroimide, folpet, tolylfluanid, boldeax mixture, copper oxide, mancopper, oxine copper, nitrothalisopropyl, edifenphos, iprobenfos, phosdifen, tolclofos methyl, anilazine, benthiavalicarb, blasticidin-S, chloroneb, chlorothalonil, cyflufenamid, cymoxanil, cyclobutrifluram, diclocymet, diclomedine, dicloran, diethofencarb, dimethomorph, flumorph,Dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, ferimzone, fluazinam, fluopicolide, flusulfamide, fluxapyroxad, fenhexamid, fosetylaluminum, hymexazole, iprovalicarb, cyanofamide, methasulfocarb, metrafenone, pencycuron, phthalide, polyoxin, propamocarb, pyribencarb, proquinazid, pyroquilon, pyriophenone, quinoxyfen, quintozene, thiadinil, triazoxide, tricyclazole, triforine, Validamycin, Valifenalate, Zoxamide, Mandipropamide, Fluveneram, Isopyrazam, Sedaxane, Benzovindiflupyr, Pydiflumetofen, 3-Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide, Isoflucipram, Isotianil, Dipimethitrone, 6-Ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile, 2-(Difluoromethyl)-N-[3-ethyl-1 ,1-Dimethyl-indan-4-yl]pyridine-3-carboxamide, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylidan-4-yl]pyrazole-4-carboxamide, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)- phenyl)-1,3-dimethyl-1H-pyrazol-5-amine, fluindapyr, methoxystrobin (jiaxiangjunzhi) lvbenmixianan, diclobenthiazox, mandestrubin, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol, oxathiapiproline, tert-butyl N-[6-[[[(1-methyltetrahydrofuran) trazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate, pyraziflumide, impirflusam, trolprocarb, mefentrifluconazole, ipfentrifluconazole, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-Dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl]methanesulfonate, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate, methyl N-[[5-[4-(2,4- dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine, pyridaclomethyl, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one, 1-methyl-4-[3- Methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one, aminopyrifen, amethoctrazine, amisulbrom, penflufen, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide, florylpicoxamide, fenpicoxamide, tebufloquine, ipflufenoquine, quinofumelin, isofetamide, N-[2-[2,4-dichloro- phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide, benzothiostrobin, phenamacryl, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1), fluopyram, flutianil, fluopimomide, pyrapropoin, picarbutorazox, 2-(difluoromethyl)-N-(3-ethyl-1,1-Dimethyl-indan-4-yl)pyridine-3-carboxamide, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, Tiltetraprole, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidinethanol, fluoxapiproline, enoxastrobin, 4-[[6-[2-(2,4-difluorophenyl)- 1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, trinexapac, comoxystrobin, zhongshengmycin, copper thiodiazole, zinc thiazole, amethotractin, iprodione, N-octyl-N'-[2-(octylamino)ethyl]ethane-1,2-Diamine, N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (these compounds can be prepared from the method described in WO 2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (these compounds can be prepared from the method described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine, 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 according to 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 according to 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 according to the method described in WO 2017 / 153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro- 3,3-Dimethyl-isoquinoline, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 1-(6-chloro-7-methyl-pyrazolo 1-(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-di ...1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl) Fluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole (these compounds can be prepared according to the method 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) 1,3-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]urea, N,N-dimethyl-1-[[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]isoxazolidin-3-one, -yl]phenyl]methyl]-1,2,4-triazol-3-amine (these compounds can be prepared from the methods described in WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 093348 and WO 2017 / 118689); 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared from the methods described in WO 2017 / 029179);2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared from the method described in WO 2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile (this compound can be prepared from the method described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate (this compound can be prepared from the method described in WO 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone (this compound can be prepared from the method described in WO 201 N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide (which can be prepared from the method described in WO 2018 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (this compound can be prepared from the method described in WO 2018 / 153707); N'- (2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine; N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared from the method described in WO 2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (this compound can be prepared from the method described in WO 2014 / 095675);(5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone (these compounds can be prepared from the method described in WO 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide (this compound can be prepared from the method described in WO 2018 / 065414); ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate (this compound can be prepared from the method described in A compound selected from the group of substances consisting of 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-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (these compounds can be prepared from the methods described in WO 2018 / 202428).

[0217] The compositions according to the invention may also comprise further solid or liquid auxiliaries, such as stabilizers, e.g. unepoxidized or epoxidized vegetable oils (e.g. epoxidized coconut oil, rapeseed oil or soybean oil), antifoaming agents, e.g. silicone oils, preservatives, viscosity regulators, binders and / or adhesives, fertilizers or other active ingredients to achieve a particular effect, e.g. fungicides, bactericides / fungicides, nematicides, plant activators, molluscicides or herbicides.

[0218] The compositions according to the invention are prepared in a manner known per se in the absence of auxiliaries, for example by pulverizing, screening and / or compressing the solid active ingredient, and in the presence of at least one auxiliary, for example by intimately mixing and / or pulverizing the active ingredient with one or more auxiliary agents. These preparation processes of the compositions and the use of compound (I) for preparing these compositions are also the subject of the present invention.

[0219] Another aspect of the present invention relates to the use of a compound of formula (I) according to the present invention or a preferred individual compound as defined herein, a composition comprising at least one compound of formula (I) or at least one preferred individual compound as defined herein, or a fungicidal or insecticidal mixture comprising at least one compound of formula (I) or at least one preferred individual compound as defined herein, in admixture with other fungicides or insecticides as defined herein above, for controlling or preventing infestation on plants, e.g. useful plants, such as crop plants, their propagation products, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living material by phytopathogenic microorganisms, e.g. insects or preferably fungal organisms.

[0220] A further aspect of the present invention relates to a method for controlling or preventing infestation on plants, e.g. useful plants, such as crop plants, their propagation materials, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living material by phytopathogenic or spoilage microorganisms or organisms that are potentially harmful to humans, in particular fungal organisms, which method comprises the step of applying a compound of formula (I) according to the present invention or a preferred individual compound as defined herein as active ingredient to the plant, a part of the plant or its habitat, its propagation materials, or any part of the non-living material.

[0221] By control or prevention is meant reducing infestation by insects or spoilage microorganisms or organisms that are plant pathogenic or potentially harmful to humans, particularly fungal organisms, to a level that demonstrates improvement.

[0222] A preferred method for controlling or preventing infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, or insects, which involves the application of a compound of formula (I) according to the invention or an agrochemical composition containing at least one compound of formula (I), is foliar treatment. The frequency and amount of application will depend on the risk of infestation by the corresponding pathogen or insect. However, the compounds of formula (I) according to the invention can also be introduced into the plant by the roots via the soil (systemic action) by irrigating the plant habitat with a liquid formulation or by applying the compounds to the soil in solid form, for example in granular form (soil application). In the case of rice crops, such granules can be applied to flooded rice fields. The compounds of formula (I) can also be applied to seeds (coating) by impregnating the seeds or tubers with a liquid formulation of the fungicide or by coating them with a solid formulation.

[0223] Formulations, e.g. compositions containing the compounds of formula (I) according to the invention and, if desired, solid or liquid auxiliaries or monomers encapsulating the compounds of formula (I), can be prepared in a known manner, typically by homogeneously mixing and / or grinding the compounds together with extenders, e.g. solvents, solid carriers and optional surface-active compounds (surfactants).

[0224] Advantageous applications are usually from 5 g to 2 kg of active ingredient (ai) per hectare (ha), preferably from 10 g to 1 kg ai / ha, most preferably from 20 g to 600 g ai / ha.When used as a seed drench, a convenient dosage is from 10 mg to 1 g of active substance per kg of seeds.

[0225] When the combinations of the invention are used for seed treatment, an amount of 0.001 to 50 g of a compound of formula (I) per kg of seed, preferably 0.01 to 10 g per kg of seed, will generally be sufficient.

[0226] Preferably, the compositions comprising the compounds of formula (I) according to the present invention are applied prophylactically, meaning before the onset of a disease, or therapeutically, meaning after the onset of a disease.

[0227] The compositions of the present invention may be in any conventional form, such as, for example, two-part systems, dry seed treatment powders (DS), seed treatment emulsions (ES), seed treatment flowable concentrates (FS), seed treatment solutions (LS), seed treatment water dispersible powders (WS), seed treatment capsule suspensions (CF), seed treatment gels (GF), emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water dispersible granules (WG), emulsifiable granules (WG), sorbent granules (RM ... The present invention may be employed in the form of an emulsion, such as an EG, an emulsion, a water-in-oil (EO), an emulsion, an oil-in-water (EW), a microemulsion (ME), an oil dispersion (OD), an oil-miscible fluid (OF), an oil-miscible liquid (OL), a soluble concentrate (SL), a very low volume suspension (SU), a very low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), or any technically desirable formulation in combination with an agriculturally acceptable adjuvant.

[0228] Such compositions can be produced in a conventional manner, for example by mixing the active ingredient with suitable inert compounding agents (diluents, solvents, fillers, and any other compounding agents such as surfactants, biocides, antifreeze agents, spreading agents, thickeners, and compounds that provide adjuvant activity effects). Conventional slow-release formulations can also be employed when long-lasting efficacy is intended. In particular, formulations applied in spray form, such as water-dispersible concentrates (e.g., EC, SC, DC, OD, SE, EW, EO, etc.), wettable powders, and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvant effects, such as, for example, condensates of formaldehyde with naphthalene sulfonates, alkylaryl sulfonates, lignin sulfonates, fatty alkyl sulfates, and ethoxylated alkylphenols and ethoxylated fatty alcohols.

[0229] The seed dressing formulation is applied to the seed in a manner known per se, utilizing the combination and diluent of the present invention in a suitable seed dressing formulation form, such as an aqueous suspension or a dry powder form with good adhesion to the seed. Such seed dressing formulations are known in the art. The seed dressing formulation may contain a single active ingredient or a combination of active ingredients in encapsulated form, for example as a slow release capsule or microcapsule.

[0230] In general, the formulations contain 0.01-90% by weight of active agent, 0-20% of agriculturally acceptable surfactants and 10-99.99% of solid or liquid inert compounding agents and adjuvants, the active agent being at least a compound of formula (I) according to the invention, optionally together with other active agents, in particular microbicides, preservatives, etc. Concentrated forms of the composition generally contain about 2-80%, preferably about 5-70% by weight of active agent. Application forms of the formulations may contain, for example, 0.01-20% by weight, preferably 0.01-5% by weight of active agent. Commercial products will preferably be formulated as concentrates, but end users will usually utilize diluted formulations.

[0231] Although it is preferred to formulate commercial products as concentrates, end users will typically dilute the formulations when used.

[0232] The disclosure in this application makes available each and every combination of the embodiments disclosed herein.

[0233] The compounds according to the following Tables A-1 to A-32 can be prepared according to the above-mentioned methods. The following examples are intended to illustrate the present invention and to show preferred compounds of formula (I). In any of the following Tables A-1 to A-32, the possible presence of one or more asymmetric carbon atoms in the compound of formula (I) according to the present invention means that the compound can occur in chiral isomeric form, i.e., in enantiomeric or diastereomeric form.

[0234] Table A: This table shows 12 compounds of formula (Ia) according to the invention: [ka] wherein G is as defined below. [ka] It is of the following.

[0235] [Table 1]

[0236] The following compounds represent certain compounds or formula (Ia) described in Tables A-1 to A-32, where G is as defined in Table A. For example, compound A-1.G1 represents R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and B. 2is as defined in Table A-1, and G is G1 as defined in Table A.

[0237] Table A-1: ​​This table provides 12 compounds A-1.G1 to A-1.G12 of formula (Ia), where R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 is H and B 2 is CH and G is as defined in Table A. For example, compound A-1.G9 has the structure: [ka] Compound A-1.G9

[0238] Table A-2: This table provides 12 compounds A-2.G1 to A-2.G12 of formula (Ia), where R 2 is CH3 and R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 is H and B 2 is CH and G is as defined in Table A. For example, compound A-2.G1 has the structure: [ka] Compound A-2.G1

[0239] Table A-3: This table provides 12 compounds A-3.G1 to A-3.G12 of formula (Ia), where R 2 is F and R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 is H and B 2is CH and G is as defined in Table A.

[0240] Table A-4: This table provides 12 compounds A-4.G1 to A-4.G12 of formula (Ia), where R 2 is Cl, R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 is H and B 2 is CH and G is as defined in Table A.

[0241] Table A-5: This table provides 12 compounds A-5.G1 to A-5.G12 of formula (Ia), where R 2 is cyclopropyl, R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 is H and B 2 is CH and G is as defined in Table A.

[0242] Table A-6: This table provides 12 compounds A-6.G1 to A-6.G12 of formula (Ia), where R 2 is COCH3, R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 is H and B 2 is CH and G is as defined in Table A.

[0243] Table A-7: This table provides 12 compounds A-7.G1 to A-7.G12 of formula (Ia), where R 2 is C=N(OCH3)CH3, and R 4 , R 5 , R 6 , R 7 , R8 , R 9 , R 10 is H and B 2 is CH and G is as defined in Table A.

[0244] Table A-8: This table provides 12 compounds A-8.G1 to A-8.G12 of formula (Ia), where R 2 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 is H and R 4 is CH3, B 2 is CH and G is as defined in Table A. For example, compound A-8.G1 has the structure: [ka] Compound A-8.G1

[0245] Table A-9: This table provides twelve compounds A-9.G1 to A-9.G12 of formula (Ia), where R 5 , R 6 , R 7 , R 8 , R 9 , R 10 is H and R 2 and R 4 is CH3, B 2 is CH and G is as defined in Table A.

[0246] Table A-10: This table provides 12 compounds of formula (Ia) A-10.G1 to A-10.G12, where R 5 , R 6 , R 7 , R 8 , R 9 , R 10 is H and R 2 and R 4 is CH3, B 2 is N, and G is as defined in Table A.

[0247] Table A-11: This table provides six compounds of formula (Ia): A-11.G1, A-11.G2, A-11.G5, A-11.G6, A-11.G9 and A-11.G10, in which R 2 , R 4 and R 7 is CH3 and R 5 , R 6 , R 8 , R 9 , R 10 is H and B 2 is CH and G is as defined in Table A. For example, compound A-11.G5 has the structure: [ka] Compound A-11.G5

[0248] Table A-12: This table provides six compounds of formula (Ia): A-12.G1, A-12.G2, A-12.G5, A-12.G6, A-12.G9 and A-12.G10, where R 2 is F and R 4 and R 7 is CH3 and R 5 , R 6 , R 8 , R 9 , R 10 is H and B 2 is CH and G is as defined in Table A.

[0249] Table A-13: This table provides six compounds of formula (Ia): A-13.G1, A-13.G2, A-13.G5, A-13.G6, A-13.G9 and A-13.G10, where R 2 is Cl, R 4 and R 7 is CH3 and R 5 , R 6 , R 8 , R 9 , R 10 is H and B 2 is CH and G is as defined in Table A.

[0250] Table A-14: This table provides six compounds of formula (Ia): A-14.G1, A-14.G2, A-14.G5, ​​A-14.G6, A-14.G9 and A-14.G10, where R 2 is cyclopropyl, R 4 and R 7 is CH3 and R 5 , R 6 , R 8 , R 9 , R 10 is H and B 2 is CH and G is as defined in Table A.

[0251] Table A-15: This table provides six compounds of formula (Ia): A-15.G1, A-15.G2, A-15.G5, A-15.G6, A-15.G9 and A-15.G10, where R 2 , R 4 and R 7 is CH3 and R 5 , R 6 , R 8 , R 9 , R 10 is H and B 2 is N, and G is as defined in Table A.

[0252] Table A-16: This table provides six compounds of formula (Ia): A-16.G1, A-16.G2, A-16.G5, A-16.G6, A-16.G9 and A-16.G10, where R 2 , R 4 and R 7 is CH3 and R 5 , R 6 , R 9 , R 10 is H and R 8 is OCH3, B 2 is CH and G is as defined in Table A.

[0253] Table A-17: This table provides six compounds of formula (Ia): A-17.G1, A-17.G2, A-17.G5, A-17.G6, A-17.G9 and A-17.G10, where R 2 , R 4 and R 7 is CH3 and R 5 , R 6 , R 8 , R 10 is H and R 9 is OCH3, B 2 is CH and G is as defined in Table A.

[0254] Table A-18: This table provides six compounds of formula (Ia): A-18.G1, A-18.G2, A-18.G5, A-18.G6, A-18.G9 and A-18.G10, where R 2 , R 4 and R 7 is CH3 and R 5 , R 6 , R 8 , R 10 is H and R 9 is OH, B 2 is CH and G is as defined in Table A.

[0255] Table A-19: This table provides six compounds of formula (Ia): A-19.G1, A-19.G2, A-19.G5, A-19.G6, A-19.G9 and A-19.G10, where R 2 , R 4 and R 7 is CH3 and R 5 , R 6 , R 8 , R 10 is H and R 9 is CF3, B 2 is CH and G is as defined in Table A.

[0256] Table A-20: This table provides six compounds of formula (Ia): A-20.G1, A-20.G2, A-20.G5, A-20.G6, A-20.G9 and A-20.G10, where R2 , R 4 and R 7 is CH3 and R 5 , R 6 , R 8 , R 10 is H and R 9 is CN and B 2 is CH and G is as defined in Table A.

[0257] Table A-21: This table provides six compounds of formula (Ia): A-21.G1, A-21.G2, A-21.G5, A-21.G6, A-21.G9 and A-21.G10, in which R 2 , R 4 and R 7 is CH3 and R 5 , R 6 , R 8 , R 9 is H and R 10 is OCH3, B 2 is CH and G is as defined in Table A.

[0258] Table A-22: This table provides six compounds of formula (Ia): A-22.G1, A-22.G2, A-22.G5, A-22.G6, A-22.G9 and A-22.G10, wherein R 2 , R 4 and R 7 is CH3 and R 5 , R 6 , R 8 , R 9 is H and R 10 is OH, B 2 is CH and G is as defined in Table A.

[0259] Table A-23: This table provides six compounds of formula (Ia): A-23.G1, A-23.G2, A-23.G5, A-23.G6, A-23.G9 and A-23.G10, where R 2 , R 4 and R 7 is CH3 and R 5 , R 6 , R8 , R 9 is H and R 10 is CF3, B 2 is CH and G is as defined in Table A.

[0260] Table A-24: This table provides six compounds of formula (Ia): A-24.G1, A-24.G2, A-24.G5, ​​A-24.G6, A-24.G9 and A-24.G10, where R 2 , R 4 and R 7 is CH3 and R 5 , R 6 , R 8 , R 9 is H and R 10 is CN and B 2 is CH and G is as defined in Table A.

[0261] Table A-25: This table provides six compounds of formula (Ia): A-25.G1, A-25.G2, A-25.G5, A-25.G6, A-25.G9 and A-25.G10, wherein R 2 , R 4 and R 7 is CH3 and R 5 , R 6 , R 8 is H and R 9 is OCH3, R 10 is CF3, B 2 is CH and G is as defined in Table A.

[0262] Table A-26: This table provides six compounds of formula (Ia): A-26.G1, A-26.G2, A-26.G5, A-26.G6, A-26.G9 and A-26.G10, wherein R 2 , R 4 and R 7 is CH3 and R 5 , R 6 , R 8 is H and R 9 is OCH3, R 10 is CN and B 2is CH and G is as defined in Table A.

[0263] Table A-27: This table provides six compounds of formula (Ia): A-27.G1, A-27.G2, A-27.G5, A-27.G6, A-27.G9 and A-27.G10, wherein R 2 , R 4 and R 7 is CH3 and R 5 , R 6 , R 8 is H and R 9 is CF3, R 10 is OCH3, B 2 is CH and G is as defined in Table A.

[0264] Table A-28: This table provides six compounds of formula (Ia): A-28.G1, A-28.G2, A-28.G5, A-28.G6, A-28.G9 and A-28.G10, where R 2 , R 4 and R 7 is CH3 and R 5 , R 6 , R 8 is H and R 9 is CN and R 10 is OCH3, B 2 is CH and G is as defined in Table A.

[0265] Table A-29: This table provides six compounds of formula (Ia): A-29.G1, A-29.G2, A-29.G5, A-29.G6, A-29.G9 and A-29.G10, wherein R 2 , R 5 , R 6 and R 7 is CH3 and R 4 , R 8 , R 9 , R 10 is H and B 2 is CH and G is as defined in Table A.

[0266] Table A-30: This table provides six compounds of formula (Ia): A-30.G1, A-30.G2, A-30.G5, A-30.G6, A-30.G9 and A-30.G10, where R 2 , R 4 , R 5 , R 6 and R 7 is CH3 and R 8 , R 9 , R 10 is H and B 2 is CH and G is as defined in Table A.

[0267] Table A-31: This table provides six compounds of formula (Ia): A-31.G1, A-31.G2, A-31.G5, A-31.G6, A-31.G9 and A-31.G10, in which R 2 , R 4 and R 7 is CH3 and R 5 , R 6 , R 9 , R 10 is H and R 8 is F and B 2 is CH and G is as defined in Table A.

[0268] Table A-32: This table provides six compounds of formula (Ia): A-32.G1, A-32.G2, A-32.G5, A-32.G6, A-32.G9 and A-32.G10, where R 2 , R 4 and R 7 is CH3 and R 5 , R 6 , R 8 , R 9 , R 10 is H and B 2 is CF and G is as defined in Table A. EXAMPLES

[0269] The examples which follow are intended to illustrate the invention and are not intended to limit it in any way.

[0270] The compounds of the present invention are distinguishable from known compounds by their high efficacy at low application rates, which can be verified by one skilled in the art using the experimental procedures outlined in the examples, and where necessary, low application rates, for example 60 ppm, 20 ppm or 2 ppm.

[0271] The compounds of formula (I) may have any number of benefits including, inter alia, an advantageous level of biological activity for protecting plants against diseases caused by fungi, or superior properties for use as an agrochemical active ingredient (e.g., high biological activity, an advantageous spectrum of activity, an enhanced safety profile (including improved crop tolerance), improved physico-chemical properties, or enhanced biodegradability).

[0272] Throughout this specification temperatures are given in degrees Celsius and "mp" means melting point. LC-MS means liquid chromatography mass spectrometry, with a description of the equipment and methods as follows.

[0273] 1 H NMR measurements were recorded on a Brucker 400 MHz spectrometer and chemical shifts are given in ppm relative to TMS standard. Spectra were run in deuterated solvents as specified. Compounds were characterized using one of the following LC-MS techniques. Characteristic LC-MS values ​​obtained for each compound are retention time ("Rt", reported in minutes) and molecular ion (M+H) + or (MH) - were the measured values.

[0274] Method A: Spectra were recorded on a Waters Corporation mass spectrometer (SQD, SQDII or QDA single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ion), capillary: 0.8-3.00 kV, cone: 5-30 V, source temperature: 120-150° C., desolvation temperature: 350-600° C., cone gas flow: 50-150 l / h, desolvation gas flow: 650-1000 l / h, mass range: 100-900 Da and a Waters Corporation Acquity UPLC: binary pump, heated column compartment, diode-array detector and ELSD. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm, Temperature: 60 °C, DAD wavelength range (nm): 210-400, Run time: 1.5 min; Solvents: A = water + 5% MeOH + 0.05% HC(O)OH, B = acetonitrile + 0.05% HC(O)OH; Flow rate (ml / min) 0.85, Gradient: 10% B isocratic for 0.2 min, then 10 to 100% B in 1.0 min, isocratic at 100% B for 0.2 min, 100 to 10% B in 0.05 min, isocratic at 10% B for 0.05 min.

[0275] Method B: Spectra were recorded on a Waters ACQUITY mass spectrometer (SQD or SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative, capillary: 3.0 kV, cone: 30 V, extractor: 3.00 V, source temperature: 150° C., desolvation temperature: 400° C., cone gas flow: 60 L / hr, desolvation gas flow: 700 L / hr, mass range: 140-800 Da) and a Waters Corporations ACQUITY UPLC with solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm; Temperature: 60 °C; DAD wavelength range (nm): 210–400; Solvent gradient: A = water / methanol 9:1 + 0.1% formic acid, B = acetonitrile + 0.1% formic acid; Gradient: 0 to 100% B in 2.5 min; Flow rate (ml / min) 0.75.

[0276] Method C: instrumentation: Mass spectrometer: Acquity QDA mass spectrometer manufactured by Waters HPLC: UPLC 'H' class

[0277] Optimal mass parameters: Ionization method: Electrospray (ESI) Polarity: Anode and cathode switch Scan Type: Full Scan Capillary (kV): 0.8 Cone voltage (V): 25.00 Source temperature (℃): 120 Desolvation gas flow rate (L / Hr): 1000 Desolvation temperature (℃): 600 Gas flow @ cone (L / Hr): 50 Mass range: 110-850 Da PDA wavelength range: 230~400nm

[0278] Optimal chromatographic parameters: Gradient conditions: Solvent A: Water + 0.1% formic acid:acetonitrile: 95:5 v / v Solvent B: Acetonitrile + 0.05% formic acid

[0279] [Table 2]

[0280] Column: Acquity UPLC HSS T3 C18 Column length: 30mm Column inner diameter: 2.1 mm Particle size: 1.8μ Column oven temperature: 40℃

[0281] Method D: instrumentation: Mass spectrometer: Waters Acquity SQD mass spectrometer HPLC: UPLC 'H' class

[0282] Optimal mass parameters: Ionization method: Electrospray (ESI) Polarity: Anode and cathode switch Scan Type: Full Scan Capillary (kV): 3.00 Cone voltage (V): 41.00 Source temperature (℃): 150 Desolvation gas flow rate (L / Hr): 1000 Desolvation temperature (℃): 500 Gas flow @ cone (L / Hr): 50 Mass range: 110-800 Da PDA wavelength range: 210~400nm

[0283] Optimal chromatographic parameters: Gradient conditions: Solvent A: Water + 0.1% formic acid:acetonitrile: 95:5 v / v Solvent B: Acetonitrile + 0.05% formic acid

[0284] [Table 3]

[0285] Column: Acquity UPLC HSS T3 C18 Column length: 30mm Column inner diameter: 2.1 mm Particle size: 1.8μ Column oven temperature: 40℃

[0286] Method E: instrumentation: Mass spectrometer: Agilent Technologies 6410 triple quadrupole mass spectrometer HPLC: Agilent 1200 Series HPLC

[0287] Optimal mass parameters: Ionization method: Electrospray (ESI) Polarity: Anode and cathode switch Scan Type: MS2 Scan Capillary (kV): 4.00 Fragmenter (V): 100.00 Gas temperature (℃): 350 Gas flow (L / min): 11 Nebulizer gas (psi): 40 Mass range: 110-1000Da Detection (VWD): 254 nm

[0288] Optimal chromatographic parameters: Gradient conditions: Solvent A: Water + 0.1% formic acid:acetonitrile: 95:5 v / v Solvent B: Acetonitrile + 0.1% formic acid

[0289] [Table 4]

[0290] Column: KINETEX EVO C18 Column length: 50mm Column inner diameter: 4.6 mm Particle size: 2.6μ Column oven temperature: 40℃

[0291] Preparation Example The compounds of formula (I) according to the invention may be prepared using the synthetic techniques described both above and below.

[0292] Example P1: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (compound P-180, Table T1) [ka] (Compound P-180, Table T1) Step 1: Preparation of 4-(1-methylpyrazol-4-yl)isoquinoline [ka] A suspension of 4-bromoisoquinoline (200 mg, 0.942 mmol), 1-methylpyrazole-4-boronic acid hydrochloride (234 mg, 1.41 mmol, 1.50 equiv) and cesium carbonate (1.23 g, 3.77 mmol, 4.00 equiv) in 1,4-dioxane (2.8 mL) and water (0.47 mL) in a microwave vial was degassed with argon for several minutes, then 1,1'-bis(diphenylphosphino)ferrocene-palladium(II) dichloride dichloromethane complex (40 mg, 0.047 mmol, 0.050 equiv) was added. The vial was sealed and the reaction mixture was heated at 120° C. and stirred under microwave irradiation for 1 h. After cooling to room temperature, the reaction mixture was partitioned between saturated ammonium chloride solution and dichloromethane, the organic layer was separated, and the aqueous layer was extracted twice with dichloromethane. The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. Purification of the crude material by flash chromatography on silica gel (eluted with ethyl acetate as cyclohexane) afforded the title compound as a brown oil (115 mg, 0.550 mmol). LC-MS (Method A): Retention time 0.41 min, m / z 210 [M+H+]. 1 H NMR (400 MHz, chloroform-d) δ ppm: 4.06 (s, 3H) 7.62-7.66 (m, 1H) 7.66-7.68 (m, 1H) 7.70-7.76 (m, 1H) 7.78-7.81 (m, 1H) 8.03 (d, J = 8.07 Hz, 1H) 8.10-8.18 (m, 1H) 8.51 (s, 1H) 9.20 (s, 1H).

[0293] Step 2: Preparation of 4-(1-methylpyrazol-4-yl)-1,2,3,4 tetrahydroisoquinoline hydrochloride [ka] To a solution of 4-(1-methylpyrazol-4-yl)isoquinoline (prepared as above in step 1, 115 mg, 0.550 mmol) in methanol (5.5 mL) at room temperature was added sodium cyanoborohydride (218 mg, 3.30 mmol, 6.00 equiv). The reaction mixture was stirred at room temperature and then hydrochloric acid (1.25 M in methanol) was added until the pH reached 2-3. After stirring at room temperature for 30 minutes, the reaction mixture was diluted with water and basified with 2N sodium hydroxide. Methanol was evaporated under reduced pressure and the aqueous layer was extracted three times with dichloromethane. The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. The resulting brown oil was treated with 2M HCl in diethyl ether and concentrated under reduced pressure to give the title compound (160 mg, 0.642 mmol), which was used in the next step without further purification.

[0294] Step 3: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (compound P-180, Table T1) [ka] (Compound P-180, Table T1) To a solution of 4-(1-methylpyrazol-4-yl)-1,2,3,4 tetrahydroisoquinoline hydrochloride (prepared as above in step 2, 200 mg, 0.664 mmol) in DMF (6.6 mL) at room temperature was added 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU) (312 mg, 0.797 mmol, 1.20 equiv.), followed by 5-(2,4-difluorophenyl)isoxazole-3-carboxylic acid (149 mg, 0.664 mmol, 1.00 equiv.) and N,N-diisopropylethylamine (0.464 mL, 2.66 mmol, 4.00 equiv.). The reaction mixture was stirred at room temperature until the reaction was complete (by LC-MS). The reaction mixture was partitioned between saturated ammonium chloride solution and dichloromethane, the organic layer was separated, and the aqueous layer was extracted twice with dichloromethane. The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo. The crude material was dissolved in dimethylsulfoxide (DMSO) (3 mL), acidified with a few drops of formic acid, and then purified by reverse phase chromatography (acetonitrile 30% to 100%), which afforded the desired product as a white solid (222 mg, 0.528 mmol). LC-MS (Method A): Retention time 1.04 min, m / z 421[M+H+].

[0295] Example P2: Preparation of 5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone (compound P-53, Table T1) [ka] (Compound P-53, Table T1) Step 1: Preparation of (1-methylpyrazol-4-yl)-phenyl-methanol [ka] A one-necked round bottom flask equipped with a magnetic stir bar was charged with 1-methyl-1H-pyrazole-4-carbaldehyde (2.20 g, 19.2 mmol) and THF (40 mL). To the colorless solution, 1 M phenylmagnesium bromide in THF (21 mL, 21.1 mmol) was added dropwise over 15 min at 0-5 °C under argon atmosphere. After addition, the ice bath was removed and the white suspension was stirred at room temperature for 2.5 h. The reaction mixture was poured into a saturated solution of NH4Cl (40 mL) and extracted with ethyl acetate (2 x 40 mL). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo to give the crude product as a colorless oil. The crude product was purified by combiflash (silica gel, gradient: ethyl acetate in cyclohexane) to give the desired product (1-methylpyrazol-4-yl)-phenyl-methanol as a colorless oil. LC-MS (Method A): 189[M+H]+; Retention time: 0.62 min. 1 H NMR(400MHz,CDCl3)δ ppm 2.89(br s,1H)3.81(s,3H)5.80(s,1H)7.18(s,1H)7.26-7.43(m,6H).

[0296] Step 2: Preparation of 2-(1-methylpyrazol-4-yl)-2-phenyl-acetonitrile [ka] A round-bottom flask equipped with a magnetic stir bar and a condenser was charged with (1-methylpyrazol-4-yl)-phenyl-methanol (prepared as above in step 1, 3.45 g, 15.6 mmol) and dichloromethane (156 mL). Lithium carbonate (0.23 g, 3.1 mmol), trimethylsilyl cyanide (9.0 mL) and iodine (7.23 g, 28.0 mmol) were then added sequentially at room temperature. The mixture was stirred at 35° C. for 1 h. The reaction mixture was then cooled to room temperature, poured into saturated sodium thiosulfate solution (250 mL) and extracted with dichloromethane (2×150 mL). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo to give the crude product, which was purified by combiflash (silica gel, gradient: ethyl acetate in cyclohexane) to give the desired title compound as a yellow oil. LC-MS (Method A): 198[M+H]+; Retention time: 0.78 min. 1 H NMR(400MHz,CDCl3)δ ppm 3.87(s,3H)5.09(s,1H)7.32(s,1H)7.33-7.43(m,6H).

[0297] Step 3: Preparation of 2-(1-methylpyrazol-4-yl)-2-phenyl-propanenitrile [ka] A 250 mL three-necked flask equipped with a magnetic stir bar and condenser was charged with 2-(1-methylpyrazol-4-yl)-2-phenyl-acetonitrile (prepared as above in step 2, 3.22 g, 16.3 mmol) and THF (65 mL). A solution of n-butyllithium in hexane (7.8 mL, 19.6 mmol) was added dropwise at -70°C under nitrogen atmosphere. The orange solution was stirred at this temperature for 30 min, after which iodomethane (1.54 mL, 24.5 mmol) was added dropwise at -70°C. The resulting yellow solution was stirred at -78°C for 5 min, then warmed to ambient temperature and stirred for 30 min. The reaction mixture was then poured into water (90 mL) and extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate, and concentrated in vacuo to give the crude product as an orange oil. This was purified by combiflash (silica gel, gradient: ethyl acetate in cyclohexane) to give the title compound as a yellow oil. LC-MS (Method A): 211[M+H]+; Retention time: 0.84 min. 1 H NMR(400MHz,CDCl3)δ ppm 2.04(s,3H)3.88(s,3H)7.28-7.49(m,7H).

[0298] Step 4: Preparation of 2-(1-methylpyrazol-4-yl)-2-phenyl-propan-1-amine [ka] A 250 mL three-necked flask equipped with a magnetic stir bar was charged with 2-(1-methylpyrazol-4-yl)-2-phenyl-propanenitrile (prepared as above in step 3, 2.82 g, 13.3 mmol) and THF (40 mL). To the yellow solution, borane dimethylsulfide complex (4.0 mL, 40.0 mmol) was added dropwise at room temperature under an argon atmosphere, and the resulting colorless mixture was stirred at 65° C. for 2 h. The reaction mixture was cooled to 0° C., after which hydrochloric acid (8.9 mL, 53.7 mmol) was added dropwise (strong gas evolution), and the mixture was stirred at 65° C. for 1 h and allowed to stand at room temperature overnight. The mixture was diluted with water (80 mL), basified with 13 mL 6 M NaOH (pH 12), and then extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated in vacuo to give the title compound as a yellow oil, which was used in the next step without further purification. LC-MS (Method A): 216[M+H]+; Retention time: 0.39 min.

[0299] Step 5: Preparation of methyl N-[2-(1-methylpyrazol-4-yl)-2-phenyl-propyl]carbamate [ka] A sealed tube equipped with a magnetic stir bar was charged with 2-(1-methylpyrazol-4-yl)-2-phenyl-propan-1-amine (prepared as above in step 4, 3.01 g, 11.2 mmol) and dichloromethane (45 mL). Methyl chloroformate (1.1 mL, 13.4 mmol) was added dropwise at 0-10° C., followed by triethylamine (4.7 mL, 33.6 mmol) under an argon atmosphere. The ice bath was removed and the mixture was stirred at room temperature for 1 h. The reaction mixture was poured into water and the organic phase was separated. The aqueous phase was extracted twice with ethyl acetate. The combined organic layers were dried over sodium sulfate and concentrated in vacuo. The crude material was purified by combiflash (silica gel, gradient: ethyl acetate in cyclohexane) to give the title compound as a colorless gum. LC-MS (Method A): 274[M+H]+; Retention time: 0.80 min.

[0300] Step 6: Preparation of methyl 4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinoline-2-carboxylate [ka] A one-necked round-bottom flask equipped with a magnetic stir bar was charged with methyl N-[2-(1-methylpyrazol-4-yl)-2-phenyl-propyl]carbamate (prepared as above in step 5, 422 mg, 1.544 mmol), hydrochloric acid (5.00 mL / mmol, 9.26 g, 7.720 mL, 94.0 mmol) and paraformaldehyde (93 mg, 0.978 mmol). The mixture was stirred at room temperature for 40 min, whereupon LC-MS analysis indicated completion of the reaction. The reaction mixture was slowly poured into water (30 mL), neutralized with NaHCO3 and extracted with ethyl acetate (3 x 20 mL). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo to give the crude title compound as a colorless gum, which was used as is without further purification. LC-MS (Method A): 286[M+H]+; Retention time: 0.87 min.

[0301] Step 7: Preparation of 4-methyl-4-(1-methylpyrazol-4-yl)-2,3-dihydro-1H-isoquinoline [ka] A one-necked round bottom flask equipped with a magnetic stir bar was charged with methyl 4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinoline-2-carboxylate (prepared as above in step 6, 3.86 g, 13.5 mmol), 1,2-dichloroethane (5.00 ml / mmol, 68 ml) and iodotrimethylsilane (8.37 g, 5.69 ml, 40.6 mmol). The mixture was stirred at 60° C. under argon atmosphere for 45 min, whereupon LC-MS analysis indicated completion of the reaction. After cooling to room temperature, the reaction mixture was slowly poured into water (30 mL), neutralized with NaHCO3 and extracted with ethyl acetate (2×50 mL). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo to give the title compound as a dark orange gum. LC-MS (Method A): 228[M+H]+; Retention time: 0.61 min.

[0302] Step 8: Preparation of 5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone (compound P-53, Table T1) [ka] (Compound P-53, Table T1) To a solution of 4-methyl-4-(1-methylpyrazol-4-yl)-2,3-dihydro-1H-isoquinoline (prepared as above in step 7, 1.50 g, 6.60 mmol) in ethyl acetate (27 mL) was added N,N-diisopropylethylamine (2.57 g, 3.40 mL, 19.8 mmol) and 5-(2,4-difluorophenyl)isoxazole-3-carboxylic acid (1.68 g, 7.26 mmol) at room temperature. To this solution was added T3P (7.56 g, 7.07 mL, 11.9 mmol) and the mixture was stirred at room temperature for 60 minutes. After this time, the reaction mixture was diluted with water (20 mL) and then extracted with ethyl acetate (2×20 mL). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo. The crude product was purified by combiflash (12 g SiO2 cartridge, eluting with an EtOAc / cyclohexane gradient) to give the title compound as a colourless gum. LC-MS (Method A): 435[M+H]+; Retention time: 1.06 minutes.

[0303] Examples P3 and P4: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[(4S)-4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone (compound P-48, Table T1) and [5-(2,4-difluorophenyl)isoxazol-3-yl]-[(4R)-4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone (compound P-49, Table T1) [ka] A racemic sample of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone (80 mg) was separated into its enantiomers by supercritical fluid chromatography (SFC) chiral HPLC.

[0304] Analytical SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IA, 3 μm, 0.3 cm x 10 cm, 40° C. Mobile phase: A:CO2 B:EtOH Isocratic: 20% B in 4.8 min ABPR: 1800psi Flow rate: 2.0ml / min Detection: 257nm Sample concentration: 1mg / mL in acetonitrile Injection: 1 μL

[0305] Preparative SFC method: Column: Daicel CHIRALPAK® AY, 5 μm, 2.0 cm x 25 cm Mobile phase: A:CO2B:MeOH isocratic composition: 30% B Back pressure: 150bar Flow rate: 60ml / min GLS Pump:- Detection: UV257nm Sample concentration: 80mg in 2ml acetonitrile Injection: 500μL

[0306] Two peaks were isolated: Peak 1: 21 mg, white crystals; retention time (min) 3.55; chemical purity (area % at 257 nm) >99%; enantiomeric excess (%) >99%. Peak 2: 21 mg, white solid; retention time (min) approx. 2.72; chemical purity (area % at 245 nm) >99%; enantiomeric excess (%) >99%.

[0307] Peak 1 was shown by X-ray analysis to have the (R) absolute configuration, while peak 2 was shown by X-ray analysis to have the (S) absolute configuration.

[0308] The (S) enantiomer (compound P48, Table T1) was found to be more fungicidally active than the (R) isomer (compound P49, Table T1).

[0309] Example P5: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (compound P-141, Table T1) [ka] (Compound P-141, Table T1) Step 1: Preparation of tert-butyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxylate [ka] To a suspension of 4-(1-methylpyrazol-4-yl)-1,2,3,4 tetrahydroisoquinoline hydrochloride (prepared as above in Example P1, step 2, 200 mg, 0.698 mmol) in dichloromethane (3.5 mL) at room temperature was added triethylamine (0.196 mL, 1.40 mmol), 4-dimethylaminopyridine (8.6 mg, 0.070 mmol) and di-tert-butyl dicarbonate (0.180 mL, 0.769 mmol). The reaction mixture was stirred overnight at room temperature. The reaction mixture was diluted with saturated ammonium chloride solution and extracted with dichloromethane (3 times). The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. Purification of the crude material by flash chromatography on silica gel (eluted with ethyl acetate such as cyclohexane) afforded the title product as a colorless oil. LC-MS (Method A): 314[M+H]+; Retention time: 1.01 min.

[0310] Step 2: Preparation of tert-butyl-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxylate [ka] To a solution of tert-butyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxylate (prepared as above in step 1, 50 mg, 0.16 mmol) and N,N,N',N'-tetramethylethylenediamine (0.073 mL, 0.48 mmol) in tetrahydrofuran (1.6 mL) was added dropwise at -78°C. The reaction mixture was stirred for 30 minutes at the same temperature. After this, a solution of iodomethane (0.020 mL, 0.32 mmol, 2.0 equiv.) in tetrahydrofuran (0.5 mL) was added dropwise at -78°C. The resulting reaction mixture was stirred for 40 minutes at the same temperature. The reaction mixture was brought to room temperature, diluted with saturated ammonium chloride solution and extracted with dichloromethane (3 times). The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo to give the desired product which was used without further purification. LC-MS (Method A): 328[M+H]+; Retention time: 1.05 min.

[0311] Step 3: Preparation of 1-methyl-4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinolin-2-ium trifluoroacetate [ka] To a solution of tert-butyl-1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxylate (prepared as above in step 2, 150 mg, 0.229 mmol) in dichloromethane (1.1 mL) at room temperature was added 2,2,2-trifluoroacetic acid (0.23 mL). The reaction mixture was stirred for 1 hour at room temperature. The reaction mixture was then concentrated under reduced pressure to give the product, which was used without further purification. LC-MS (Method A): 228[M+H]+; Retention time: 0.43 min.

[0312] Step 4: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinolin-2-yl]methanone (compound P-141, Table T1) [ka] (Compound P-141, Table T1) A solution of 1-methyl-4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinolin-2-ium trifluoroacetate (prepared as above in step 3, 280 mg, 0.6148 mmol) and HATU (313 mg., 0.7993 mmol) in DMF (2 ml) was treated with 5-(2,4-difluorophenyl)isoxazole-3-carboxylic acid (143 mg, 0.6148 mmol) and N,N-diisopropylethylamine (DIPEA) (405 mg, 0.54 ml, 3.074 mmol) and the reaction mixture was stirred at room temperature overnight. The reaction mixture was quenched with saturated NH4Cl solution and then extracted with dichloromethane (3 times). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuum. The crude product was purified by combiflash (24 g SiO2 cartridge, elution with cyclohexane ethyl acetate) to give the title compound as a diastereomeric mixture, a 3:1 mixture of anti and syn-isomers. LC-MS (Method A): 435[M+H]+; Retention time: 1.72 minutes. 1H NMR(600MHz,DMSO-d6)δ ppm 1.24(s,2H);1.40(s,5H);1.55(s,2H);1.57(d,J=6.7Hz,10H);1.63(d,J= 6.9Hz,2H);1.69(d,J=6.7Hz,1H);1.91(s,1H);2.52-2.55(m,5H);3.58(br d,J=9.3Hz,1H);3.66(s,8H);3.71-3.74(m,3H);3.80(s,2H);3.85(s,1H);3.90(dd,J=13.7,3.5Hz,3H);3.96-4.04(m,3H);4.14(br s,4H);4.20-4.28(m,2H);4.58-4.65(m,1H);5.33(d,J=6.7Hz,1H);5.76-5.80(m,3H);6.12(d,J=3.1Hz,3H);6.85(s,3H);6.92(br d,J=7.7Hz,1H);7.02-7.05(m,5H);7.06(s,2H);7.13-7.17(m,4H);7.17-7.22(m,6H);7.22-7.26(m,2H);7.26-7.30(m,4H);7.30(d,J =1.1Hz,1H);7.32-7.37(m,7H);7.41(d,J=7.8Hz,3H);7.44(s,1H);7.56-7.61(m,5H);8.02(td,J=8.7,6.4Hz,3H);8.06-8.12(m,2H).

[0313] Example P6: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[1,4-dimethyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone [ka] Step 1: Preparation of methyl 1,4-dimethyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinoline-2-carboxylate [ka] A 50 mL three-neck round bottom flask equipped with a magnetic stir bar was charged with methyl N-[2-(1-methylpyrazol-4-yl)-2-phenyl-propyl]carbamate (prepared as described in Example P2, step 5, 1.00 g, 3.7 mmol), hydrochloric acid (18.3 mL, 223 mmol) and acetaldehyde (0.4 mL, 7.3 mmol). The mixture was stirred at ambient temperature overnight. The reaction mixture was then slowly poured into water (65 mL), neutralized with NaHCO3 and extracted with ethyl acetate (3 times). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo to give the title compound as a brown gum, which was used in the next step without further purification. LC-MS standard: 300[M+H]+; retention time: 0.91 min.

[0314] Step 2: Preparation of 1,4-dimethyl-4-(1-methylpyrazol-4-yl)-2,3-dihydro-1H-isoquinoline [ka] A one-necked round-bottom flask equipped with a magnetic stir bar was charged with methyl 1,4-dimethyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinoline-2-carboxylate (prepared as above in step 1, 1.1 g, 3.3 mmol), 1,2-dichloroethane (16 mL) and iodotrimethylsilane (1.4 mL, 9.7 mmol). The mixture was stirred at 60° C. under an argon atmosphere for 1 h. The reaction mixture was then cooled to room temperature and poured slowly into saturated NaHCO3 (30 mL) (gas evolution). The mixture was extracted twice with ethyl acetate and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo to give the title compound as a brown gum, which was used directly in the next step. LC-MS standard: 242[M+H]+; retention time: 0.54 min.

[0315] Step 3: Preparation of 5-(2,4-difluorophenyl)isoxazole-3-carbonyl chloride [ka] A suspension of 5-(2,4-difluorophenyl)isoxazole-3-carboxylic acid (1.00 g, 4.3 mmol) in tetrahydrofuran (22 mL) was treated with one drop of DMF followed by oxalyl chloride (0.38 mL, 4.3 mmol) at room temperature. The bright yellow solution was stirred at ambient temperature under a nitrogen atmosphere for 14 hours and then the solvent was removed in vacuo to give the title compound as a yellow solid. LC-MS of the ester (quenched with MeOH): 240 [M+H]+, retention time: 0.97.

[0316] Step 4: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[1,4-dimethyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone [ka] A solution of 1,4-dimethyl-4-(1-methylpyrazol-4-yl)-2,3-dihydro-1H-isoquinoline (prepared as above in step 2, 0.24 g, 1.0 mmol) in tetrahydrofuran (2.4 mL) was transferred to a supelco vial under argon atmosphere. To this solution was added 5-(2,4-difluorophenyl)isoxazole-3-carbonyl chloride (0.40 g, 1.0 mmol) followed by triethylamine (0.42 mL, 3.0 mmol). The reaction mixture was stirred at room temperature for 17 hours, then poured into an aqueous solution of NaHCO3 and diluted with ethyl acetate. After separation of the layers, the aqueous phase was back-extracted with ethyl acetate and the combined organic phase was washed with water, brine. The organic layer was dried over sodium sulfate, filtered and concentrated in vacuum. The crude product was purified by combiflash (silica gel, gradient: ethyl acetate in cyclohexane) to give the title compound as a brown gum. LC-MS standard: 449(M+H)+; retention time: 1.07 min. NMR analysis showed the compound to be approximately a 1:1 mixture of syn and anti isomers.

[0317] A 260 mg sample of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[1,4-dimethyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone (80 mg) was separated into its enantiomers by supercritical fluid chromatography (SFC) chiral HPLC.

[0318] Analytical SFC method: SFC:Waters Acquity UPC 2 / QDa PDA detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® IH, 3 μm, 0.46 cm x 10 cm, 40° C. Mobile phase: A:CO2 B:MeOH Isocratic: 15% B in 10 min ABPR: 1800psi Flow rate: 2.0ml / min Detection: 255nm Sample concentration: 1mg / mL in dichloromethane / acetonitrile Injection: 1 μL

[0319] Preparative SFC method: Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK® IG, 5 μm, 2.0 cm x 25 cm Mobile phase: A: CO2B: IPA isocratic composition: 12% B Back pressure: 150bar Flow rate: 90ml / min GLS Pump:- Detection: UV255nm Sample concentration: 260 mg in 2 ml dichloroethane / acetonitrile Injection: 350μL

[0320] Four peaks were isolated: Peak 1: 46 mg, brown gum; retention time (min) 1.88 min; chemical purity (area % at 255 nm) >93%; enantiomeric excess (%) approx. 98%. Peak 2: 38 mg, brown gum; retention time (min) 2.09 min; chemical purity (area % at 255 nm) >96%; enantiomeric excess (%) approx. 98%. Peak 3: 43 mg, brown gum; retention time (min) 2.56 min; chemical purity (area % at 255 nm) >98%; enantiomeric excess (%) approx. 98%. Peak 4: 46 mg, brown gum; retention time (min) 2.09 min; chemical purity (area % at 255 nm) >99%; enantiomeric excess (%) approx. 99%.

[0321] 1 1 H NMR analysis showed that peaks 1 and 2 have identical NMR spectra and an anti relationship of the methyl to the pyrazole as determined by ROSY 2D NMR below. [ka] (anti isomer)

[0322] Peaks 3 and 4 also had comparable NMR spectra, but different from those of peaks 1 and 2. NMR analysis, especially ROSY 2D NMR, showed nOe confirming that the methyl and pyrazole groups have the following syn relationship: [ka] (syn isomer) Peak 1 corresponds to [5-(2,4-difluorophenyl)isoxazol-3-yl]-[(1R,4S)-1,4-dimethyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone (compound P9, Table T1).

[0323] Peak 2 corresponds to [5-(2,4-difluorophenyl)isoxazol-3-yl]-[(1S,4R)-1,4-dimethyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone (compound P8, Table T1).

[0324] Peak 3 corresponds to [5-(2,4-difluorophenyl)isoxazol-3-yl]-[(1R,4R)-1,4-dimethyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone (compound P7, Table T1).

[0325] Peak 4 corresponds to [5-(2,4-difluorophenyl)isoxazol-3-yl]-[(1S,S)-1,4-dimethyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinolin-2-yl]methanone (compound P6, Table T1).

[0326] The compound in peak 1 (compound P9, Table T1) has been shown to be more fungicidal and fungicidally active than the compound in peak 2 (compound P8, Table T1). Also, the compound in peak 4 (compound P6, Table T1) has been shown to be more fungicidal and fungicidally active than the compound in peak 3 (compound P7, Table T1).

[0327] Example P7: Preparation of rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-1,2,3,4-tetrahydroisoquinoline [ka] Step 1: Preparation of methyl N-[2-(1,5-dimethylpyrazol-4-yl)-2-phenyl-ethyl]carbamate [ka] A three-neck flask equipped with a mechanical stirrer was charged with 2-(1,5-dimethylpyrazol-4-yl)-2-phenyl-ethanamine (3.5 g, 16 mmol), ethyl acetate (65 mL) and triethylamine (6.8 mL, 49 mmol). Methyl chloroformate (1.5 mL, 20 mmol) was then added dropwise at 0° C. under argon atmosphere during 30 min and the mixture was stirred at RT for 1 h. The reaction mixture was poured into water (800 mL) and extracted with EtOAc (2×150 mL). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuum. The crude material was purified by FCC (80 g SiO2, EtOAc / cyclohexane gradient) to give methyl N-[2-(1,5-dimethylpyrazol-4-yl)-2-phenyl-ethyl]carbamate. LC-MS (Method A): Retention time 0.76 min, 274(M+H) 1H NMR(400MHz,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)

[0328] Step 2: Preparation of rac-methyl (1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxylate [ka] A one-necked round-bottom flask equipped with a magnetic stir bar was charged with methyl N-[2-(1,5-dimethylpyrazol-4-yl)-2-phenyl-ethyl]carbamate (2.0 g, 7.3 mmol), hydrochloric acid (concentrated, 37 mL, 450 mmol) and acetaldehyde (0.83 mL, 15 mmol). The mixture was stirred at RT for 2 h. The reaction mixture was slowly poured into water (500 mL) and slowly neutralized to pH 8 with NaHCO3 in several portions (strong gas evolution). The mixture was extracted with EtOAc (3 x 50 mL) and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo. The crude product was purified by chromatography to give rac-methyl (1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxylate as a single syn-diastereoisomer. 1 1 H NMR. LC-MS (Method A): Retention time 0.87 min, 300 (M+H) 1H NMR(400MHz,CDCl3)δ ppm:1.56(d,J=6.90Hz,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).

[0329] Step 3: Preparation of rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-1,2,3,4-tetrahydroisoquinoline [ka] A 100 mL one-neck round bottom flask equipped with a magnetic stir bar was charged with rac-methyl (1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxylate (1.3 g, 4.1 mmol), 1,2-dichloroethane (21 mL) and iodotrimethylsilane (1.7 mL, 12 mmol). The mixture was stirred at 60° C. for 1 h under an argon atmosphere. The reaction was cooled to RT and then 22 ml of 10% aqueous HCl was added to the reaction under ice cooling. The organic solvent was removed in vacuo and the aqueous residue was adjusted to pH 8 with 10% aqueous NaOH and then extracted with tert-dichloromethane. The combined organic layers were dried over magnesium sulfate, filtered, and concentrated in vacuo to give rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-1,2,3,4-tetrahydroisoquinoline, which was sufficiently pure to be used without further purification. LC-MS (Method A): Retention time 0.35 min, 242(M+H) 1 H NMR(600MHz,chloroform-d) δ ppm 1.86(d,J=6.9Hz,3H)2.23(s,3H)3.27(dd,J=12.5,10.8Hz,1H)3.59(dd,J=12.8,5.6Hz,1H)3.83(s,3H)4.58(dd,J=10.6, 5.4Hz,1H)4.80(q,J=6.8Hz,1H)7.00(d,J=7.8Hz,1H)7.11(s,1H)7.16(d,J=7.6Hz,1H)7.18-7.22(m,1H)7.25-7.28(m,1H)

[0330] Example P8: Preparation of 1,4-dimethyl-4-(1-methylpyrazol-4-yl)-2,3-dihydro-1H-isoquinoline [ka] Step 1: Preparation of tert-butyl N-[2-hydroxy-2-(1-methylpyrazol-4-yl)propyl]-N-(1-phenylethyl)carbamate [ka] Method 1: Step 1: Preparation of tert-butyl N-[2-(1-methylpyrazol-4-yl)-2-oxo-ethyl]-N-(1-phenylethyl)carbamate [ka] A three-necked flask equipped with a magnetic stirrer was charged with 2-bromo-1-(1-methyl-1H-pyrazol-4-yl)ethanone (1 g, 4.72 mmol) and N,N-dimethylacetamide (23.6 mL). The resulting mixture was cooled to 0° C. under an argon atmosphere, and then DL-α-methylbenzylamine (0.64 mL, 4.72 mmol) was added slowly (over 4 min). The mixture was stirred for 10 min, and triethylamine (0.993 mL, 7.09 mmol) was added at 0° C. under an Ar atmosphere. After 1.5 h at 0° C., di-tert-butylpyrocarbonate (1.14 g, 5.2 mmol) dissolved in N,N-dimethylacetamide (23.6 mL) was added dropwise at 0° C. under an argon atmosphere. The reaction mixture was warmed to RT and left under stirring overnight. HCl was added to the reaction mixture (adjusted to pH 3), and then the aqueous layer was extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over Na2SO4, filtered, and concentrated in vacuo to give the crude product, which was purified by chromatography on silica gel with a gradient of cyclohexane / ethyl acetate to give the title compound as a white solid. LC-MS (Method A): Retention time 0.99 min, 344(M+H) 1 H NMR(400MHz,CDCl3)δ ppm 1H NMR(400MHz,solvent)δ ppm 7.74-7.99(m,2H)7.35(br d,J=5.1Hz,4H)7.25-7.31(m,1H)5.29-5.80(m,1H)4.20-4.57(m,1H)3.92(s,3H)3.66-3.90(m,1H)1.31-1.54(m,12H)

[0331] Method 1: Step 2: Preparation of tert-butyl N-[2-hydroxy-2-(1-methylpyrazol-4-yl)propyl]-N-(1-phenylethyl)carbamate [ka] A round-bottom flask equipped with a magnetic stir bar was charged with tert-butyl N-[2-(1-methylpyrazol-4-yl)-2-oxo-ethyl]-N-(1-phenylethyl)carbamate (100 mg, 0.291 mmol) and tetrahydrofuran (1.5 mL) and the resulting mixture was cooled to 0° C. under an argon atmosphere. Then, methylmagnesium bromide solution 3M (0.24 ml, 0.728 mmol) was added dropwise at 0° C. under an argon atmosphere. After 1.5 h, the reaction mixture was allowed to warm to RT. An additional portion of methylmagnesium bromide solution 3M (0.24 mL., 0.728 mmol) was added at RT and the mixture was stirred at RT for 2.5 h and then at 60° C. for 21 h. The reaction mixture was cooled and added to a saturated aqueous solution of NH4Cl. The aqueous layer was then extracted with ethyl acetate, and the combined organic layers were washed with brine, dried over Na2SO4, filtered, and concentrated in vacuo to give a crude mixture containing tert-butyl N-[2-hydroxy-2-(1-methylpyrazol-4-yl)propyl]-N-(1-phenylethyl)carbamate (about 70%) and tert-butyl N-[2-(1-methylpyrazol-4-yl)-2-oxo-ethyl]-N-(1-phenylethyl)carbamate (about 30%). The desired product was not isolated using further purification methods. LC-MS (Method A): Retention time 1.02 minutes, 360 (M+H)

[0332] Method 2: Step 1: Preparation of tert-butyl N-acetonyl-N-(1-phenylethyl)carbamate [ka] A three-necked flask equipped with a magnetic stirrer was charged with 1-chloropropan-2-one (0.86 mL, 10.27 mmol), N,N-dimethylacetamide (51 mL) and potassium iodide (1.705 g, 10.27 mmol). The resulting mixture was cooled to 0° C. under an argon atmosphere, and then DL-α-methylbenzylamine (1.4 mL, 10.27 mmol) was added slowly. The mixture was stirred for 20 min and triethylamine (2.16 mL, 15.40 mmol) was added at 0° C. under an Ar atmosphere. After 3 h, 1-chloropropan-2-one (0.86 mL, 10.27 mmol) was added again since starting material was still present. The resulting mixture was stirred for 3 h at 0° C.-10° C., then di-tert-butyl pyrocarbonate (2.49 g, 11.22 mmol) dissolved in N,N-dimethylacetamide (51 mL) was added dropwise at 0° C. under argon atmosphere. The reaction mixture was warmed to RT and left under stirring overnight. HCl was then added to the mixture (to pH 3) and then the aqueous layer was extracted three times with ethyl acetate. The combined organic layers were washed with brine, dried over Na2SO4, filtered and concentrated in vacuo. The crude product was purified by chromatography on silica gel with a gradient of cyclohexane / ethyl acetate to give tert-butyl N-acetonyl-N-(1-phenylethyl)carbamate as an orange / brown liquid. LC-MS (Method A): Retention time 1.04 min, 300(M+Na) 1H NMR(400MHz,CDCl3)δ ppm 7.28-7.45(m,5H)5.27-5.85(m,1H)3.47(br s,2H)1.89-2.06(m,3H)1.41-1.53(m,12H)

[0333] Method 2: Step 2: Preparation of tert-butyl N-[2-hydroxy-2-(1-methylpyrazol-4-yl)propyl]-N-(1-phenylethyl)carbamate [ka] A 100 ml three-neck flask was charged with 4-iodo-1-methyl-1H-pyrazole (3.1 g, 14 mmol) and tetrahydrofuran (12 mL) and the mixture was cooled to 0° C. under argon atmosphere. A solution of isopropylmagnesium chloride lithium chloride complex (1.3 mol / L) in THF (12 mL, 16 mmol) was added slowly (over 15 min). The mixture was left under stirring at 0° C. After 45 min, tert-butyl N-acetonyl-N-(1-phenylethyl)carbamate (1.6 g, 5.8 mmol) dissolved in tetrahydrofuran (12 mL) was then added dropwise at 0° C. under argon atmosphere. The reaction mixture was allowed to reach room temperature (no precipitate remaining and a yellow solution was obtained) and stirred overnight at room temperature. The reaction mixture was neutralized with a saturated aqueous solution of HCl. The aqueous layer was then extracted three times with ethyl acetate, and the combined organic layers were washed, dried over Na2SO4, filtered, and concentrated in vacuo to give the crude product as a yellow sticky oil. The crude mixture was purified by chromatography on silica gel with a gradient of cyclohexane / ethyl acetate to give tert-butyl N-[2-hydroxy-2-(1-methylpyrazol-4-yl)propyl]-N-(1-phenylethyl)carbamate. LC-MS (Method A): Retention time 1.01 min, 361(M+2H) 1 H NMR(400MHz,CDCl3)δ ppm 7.15-7.42(m,7H)4.79-5.20(m,1H)3.86(m,Hz,3H)3.27-3.49(m,3H)1.30-1.51(m,12H)

[0334] Step 2: Preparation of 1,4-dimethyl-4-(1-methylpyrazol-4-yl)-2,3-dihydro-1H-isoquinoline [ka] Method 1: A 5 mL vial was charged with tert-butyl N-[2-hydroxy-2-(1-methylpyrazol-4-yl)propyl]-N-(1-phenylethyl)carbamate (50 mg, 0.139 mmol) at 0° C. Then a mixture of water (0.27 mL) and sulfuric acid (0.27 mL) was added at 0° C. The reaction mixture was stirred at 40° C. for 30 min and then at 60° C. for 24 h. The reaction mixture was cooled to RT. Sulfuric acid (0.2782 mL) was added again and the reaction mixture was heated at 40° C. for 2 h, at room temperature for 3 days and finally at 60° C. for 2 h. The reaction mixture was carefully poured into a saturated solution of sodium bicarbonate and the mixture was extracted with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo to give the crude title compound as a mixture of diastereoisomers (syn and anti ca. 1:3). LC-MS (Method A): Retention time 0.51 min, 242(M+H) 1H NMR(400MHz,CDCl3)δ ppm)7.28-7.41(m,1H)7.10-7.26(m,6H)6.87(s,1H)6.96(s,1H)4.15(dq,J=17.85,7.01Hz,2H)3.73-3.93(m,5H)2.98-3.13(m,3H)2.11 -2.27(m,2H)1.98-2.11(m,2H)1.59- 1.66(m,4H)1.44-1.55(m,4H)1.37(d,J=6.54Hz,1H)1.26(t,J=7.08Hz,2H)

[0335] Method 2: A 5 mL vial was charged with tert-butyl N-[2-hydroxy-2-(1-methylpyrazol-4-yl)propyl]-N-(1-phenylethyl)carbamate (50 mg, 0.139 mmol), chlorobenzene (0.4172 mL) and aluminum chloride (0.028 g, 0.208 mmol) at room temperature under an argon atmosphere. The resulting mixture was stirred at room temperature for 1 h, at 50° C. for 1 h, at room temperature overnight and finally at 60° C. for 3 h. Additional aluminum chloride (0.02782 g, 0.208 mmol) was added to the reaction mixture at RT and the reaction mixture was heated to 60° C. The reaction mixture was cooled to room temperature and poured into a saturated solution of sodium bicarbonate, then extracted with ethyl acetate, dried over sodium sulfate, filtered and concentrated in vacuo to give the title crude product. Analysis of the crude material was consistent with the product structure (approximately 1:1 mixture of diastereoisomers anti and syn). LC-MS (Method A): Retention time 0.51 min, 242(M+H) 1 H NMR(400MHz,CDCl3)δ ppm 7.28-7.41(m,1H)7.10-7.26(m,6H)6.87(s,1H)6.96(s,1H)4.15(dq,J=17.85,7.01Hz,2H)3.73-3.93(m,5H)2.98-3.13(m,3H)2.11 -2.27(m,2H)1.98-2.11(m,2H)1.59- 1.66(m,4H)1.44-1.55(m,4H)1.37(d,J=6.54Hz,1H)1.26(t,J=7.08Hz,2H)

[0336] Example P10: Preparation of 1-methyl-4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline [ka] Step 1: Preparation of tert-butyl N-[2-hydroxy-2-(1-methylpyrazol-4-yl)ethyl]-N-(1-phenylethyl)carbamate [ka] A 25 mL flask was charged with tert-butyl N-[2-(1-methylpyrazol-4-yl)-2-oxo-ethyl]-N-(1-phenylethyl)carbamate (0.52 g, 1.51 mmol), methanol (6 mL), tetrahydrofuran (1.5 mL) and sodium borohydride (0.1146 g, 3.02 mmol) at 0° C. The reaction mixture was then warmed to room temperature and stirred for 1.5 hours. The reaction mixture was diluted with a saturated solution of ammonium chloride and ethyl acetate. After separation of the layers, the aqueous layer was extracted once with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo to give tert-butyl N-[2-hydroxy-2-(1-methylpyrazol-4-yl)ethyl]-N-(1-phenylethyl)carbamate. LC-MS (Method A): Retention time 0.98 min, 346(M+H) 1 H NMR(400MHz,CDCl3)δ ppm 7.10(s,6H)6.95(br d,J=0.73Hz,7H)5.20-5.45(m,2H)4.85(br d,J=8.72Hz,1H)4.16-4.31(m,1H)3.85(d,J=13.08Hz,6H)3.31-3.65(m,2H)2. 91-3.15(m,2H)1.59(d,J=7.27Hz,3H)1.44-1.51(m,12H)1.59(d,J=7.27Hz,3H)

[0337] Step 2: Preparation of 1-methyl-4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline [ka] Method 1: A 5 mL vial was charged with N-[2-hydroxy-2-(1-methylpyrazol-4-yl)ethyl]-N-(1-phenylethyl)carbamate (50 mg, 0.14 mmol) at 0° C. Then, a mixture of water (0.1448 mL) and sulfuric acid (0.4343 mL) was added at 0° C. The reaction mixture was stirred at RT for 3 h and then at 40° C. for 3.5 h. The reaction mixture was carefully quenched with a saturated solution of sodium bicarbonate and diluted with ethyl acetate. After separation of the organic layer, the aqueous layer (pH=8-9) was back-extracted twice with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo to give 1-methyl-4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline as a mixture of anti:syn astereoisomers in a 3:1 ratio. LC-MS (Method A): Retention time 0.15-0.33 min, 228(M+H) 1H NMR(400MHz,CDCl3)δ ppm 7.30(s,1H)7.04-7.25(m,6H)6.99(s,1H)4.08-4.31(m,3H)3.99-4.04(m,1H)3.77-3.90(m,4H)3.45(dd,J=12.90, 4.90Hz,1H)3.11-3.37(m,1H)3.03(dd,J=12.90,7.81Hz,1H)2.79-2.98(m,2H)1.47-1.58(m,4H)2.79-2.98(m,2H)

[0338] Method 2: Step 1: Preparation of 5-(1-methylpyrazol-4-yl)-3-(1-phenylethyl)oxazolidin-2-one [ka] A 20 mL vial was charged with N-[2-hydroxy-2-(1-methylpyrazol-4-yl)ethyl]-N-(1-phenylethyl)carbamate (550 mg, 1.43 mmol), ethyl acetate (7 mL) and (1S)-(+)-camphor-10-sulfonic acid (0.509 g, 2.150 mmol) at RT. The resulting mixture was then heated at 50° C. for 1 h 30 min. The reaction mixture was cooled to RT and carefully poured into a saturated solution of sodium bicarbonate. It was then diluted with ethyl acetate. After separation of the organic layer, the aqueous layer (pH=8) was back-extracted twice with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuum. The crude material was purified by chromatography to give 5-(1-methylpyrazol-4-yl)-3-(1-phenylethyl)oxazolidin-2-one as a mixture of diastereoisomers (compound 1: 104 mg, 0.383 mmol and compound 2: 86 mg, 0.388 mmol).

[0339] compound 1 LC-MS (Method A): Retention time 0.77 min, 272(M+H) 1H NMR(400MHz,CDCl3)δ ppm 7.37(d,J=2.18Hz,5H)7.31(s,1H)7.22(s,1H)5.45(dd,J=8.36,6.90Hz,1H)5.30(q,J=7.15Hz,1H) 3.87(s,3H)3.76-3.81(m,1H)3.09(dd,J=8.90,6.72Hz,1H)2.63-2.90(m,1H)1.63(d,J=7.27Hz,3H) compound 2 LC-MS (Method A): Retention time 0.79 min, 272(M+H) 1H NMR(400MHz,CDCl3)δ ppm 7.52(s,1H)7.47(s,1H)7.30-7.42(m,5H)5.40(t,J=7.81Hz,2H)5.21-5.34( m,2H)3.95(s,3H)3.35-3.52(m,3H)2.91-3.13(m,1H)1.60(d,J=6.90Hz,3H)

[0340] Method 2: Step 2: Preparation of 1-methyl-4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline [ka] A 5 mL vial was charged with 5-(1-methylpyrazol-4-yl)-3-(1-phenylethyl)oxazolidin-2-one (50 mg, 0.184 mmol), chlorobenzene (0.55 mL) and nitroethane (0.033 mL, 0.460 mmol) at RT under an argon atmosphere. Aluminum chloride (0.06144 g, 0.460 mmol) was then added at RT. The reaction mixture was heated to 50° C. for 1 h and then at 60° C. overnight. The reaction mixture was carefully poured into a saturated solution of sodium bicarbonate and the mixture was diluted with ethyl acetate. After separation of the organic layer, the aqueous layer (pH=9) was back-extracted twice with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo to give 1-methyl-4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline as a mixture of diastereoisomers anti / syn 3:2. LC-MS (Method A): Retention time 0.34 min, 228(M+H)

[0341] Further examples of compounds of formula (I) that have been synthesised are shown in Table T1.

[0342] [Table 5-1] [Table 5-2] [Table 5-3] [Table 5-4] [Table 5-5] [Table 5-6]

Table 5-7

Table 5-8

Table 5-9

Table 5-10

Table 5-11

Table 5-12

Table 5-13

Table 5-14

Table 5-15

Table 5-16

Table 5-17

Table 5-18

Table 5-19

Table 5-20

Table 5-21

Table 5-22

Table 5-23

Table 5-24

Table 5-25

Table 5-26

Table 5-27

Table 5-28

Table 5-29

Table 5-30

Table 5-31

Table 5-32

Table 5-33

Table 5-34

Table 5-35

Table 5-36

Table 5-37

Table 5-38

Table 5-39

Table 5-40

Table 5-41

Table 5-42

Table 5-43

Table 5-44

Table 5-45

Table 5-46

Table 5-47

Table 5-48

Table 5-49

Table 5-50

Table 5-51

Table 5-52

Table 5-53

Table 5-54

Table 5-55

Table 5-56

[0343] Biological Examples Example B1: Alternaria solani / tomato / leaf disc (summer blight) Tomato leaf discs (cv. Baby) are placed on agar in multi-well plates (24-well type) and sprayed with the formulated test compounds diluted in water. The leaves are inoculated with a fungal spore suspension 2 days after application. The inoculated leaves are incubated in a climate cabinet under a 12 / 12 h (light / dark) light regime, 23°C / 21°C (day / night) and 80% relative humidity, and the efficacy of the compounds is evaluated as the percentage disease control compared to untreated leaf discs when an appropriate level of disease damage has developed on untreated leaf discs (5-7 days after application).

[0344] The following compounds provided at least 80% control of Alternaria solani at 200 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-2, P-6, P-10, P-11, P-13, P-18, P-38, P-42, P-45, P-46, P-48, P-51, P-52, P-53, P-55, P-56, P-63, P-64, P-65, P-92, P-100, P-104, P-105, P-108, P-109, P-110, P-115, P-118, P-119, P-120 , P-124, P-126, P-127, P-131, P-133, P-134, P-136, P-140, P-141, P-142, P-143, P-146, P-148 , P-151, P-158, P-163, P-165, P-168, P-180, P-181, P-182, P-191, P-207, P-208, P-225 and P-228

[0345] Example B2: Botryotinia fuckeliana (Botrytis cinerea) / liquid culture (grey mold) Fungal conidia stored at low temperature are mixed directly into nutrient liquid medium (Vogels liquid medium). A (DMSO) solution of the test compound is placed in a microtiter plate (96-well format) and then the nutrient liquid medium containing the fungal spores is added. The test plate is incubated at 24°C and the inhibition of growth is measured photometrically 3-4 days after application.

[0346] The following compounds provided at least 80% control of Botryotinia fuckeliana at 20 ppm when compared to untreated controls, which showed widespread disease development under identical conditions: P-1, P-6, P-11, P-16, P-38, P-42, P-45, P-47, P-48, P-49, P-52, P-53, P-63, P-6 4, P-65, P-100, P-105, P-108, P-109, P-110, P-119, P-120, P-135, P-140, P-141 , P-142, P-143, P-146, P-151, P-152, P-154, P-158, P-159, P-162, P-163, P-180 , P-192, P-207, P-208, P-209, P-212, P-215, P-216, P-218, P-223, P-224 and P-227

[0347] Example B3: Cercospora kikuchii (soybean leaf spot) Fungal conidia stored at low temperature were mixed directly into nutrient liquid medium (potato glucose liquid medium). A DMSO solution of the test compound was placed in a microtiter plate (96-well format) and the nutrient liquid medium containing the fungal spores was added to it. The test plates were incubated at 24°C and growth inhibition was measured photometrically at 620 nm after 3-4 days.

[0348] The following compounds provided at least 80% control of Cercospora kikuchii at 20 ppm when compared to untreated controls, which showed widespread disease development under identical conditions: P-38, P-53, P-65, P-140 and P-180.

[0349] Example B4: Cercospora sojina (soybean spot disease) Fungal conidia stored at low temperature were mixed directly into nutrient liquid medium (potato glucose liquid medium). A DMSO solution of the test compound was placed in a microtiter plate (96-well format) and the nutrient liquid medium containing the fungal spores was added to it. The test plates were incubated at 24°C and growth inhibition was measured photometrically at 620 nm after 3-4 days.

[0350] The following compounds provided at least 80% control of Cercospora sojina at 20 ppm when compared to untreated controls which showed widespread disease development under identical conditions: P-38, P-53, P-65, P-140 and P-180.

[0351] Example B5: Glomerella lagenarium (Colletotrichum lagenarium) / Liquid Culture (Anthracnose) Fungal conidia stored at low temperature are mixed directly into nutrient liquid medium (potato glucose liquid medium). A DMSO solution of the test compound is placed in a microtiter plate (96-well format) and then the nutrient liquid medium containing the fungal spores is added. The test plate is incubated at 24°C and the inhibition of growth is measured photometrically 3-4 days after application.

[0352] The following compounds provided at least 80% control of Glomerella lagenarium at 20 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-1, P-6, P-10, P-11, P-14, P-16, P-18, P-38, P-45, P-47, P-48, P-49, P-50, P-51, P-52, P-53, P-56, P-58, P-62, P-63, P-64, P-65, P-76, P -92, P-97, P-100, P-104, P-105, P-108, P-109, P-110, P-111, P-117, P-119, P-120, P-121, P-124, P-126, P-138, P-139, P-140, P-141, P-14 2, P-143, P-149, P-151, P-152, P-154, P-155, P-158, P-162, P-163, P-165, P-166, P-169, P-180, P-181, P-187, P-188, P-190, P-191, P-192 , P-194, P-205, P-206, P-207, P-208, P-209, P-212, P-215, P-216, P-223, P-224, P-225, P-226, P-227, P-228, P-229, P-231, P-232 and P-234

[0353] Example B6: Corynespora cassiicola (brown spot disease of tomato) Fungal conidia stored at low temperature were mixed directly into the nutrient broth (potato dextrose broth). A DMSO solution of the test compound was placed in a microtiter plate (96-well format) and the nutrient broth containing the fungal spores was added to it. The test plates were incubated at 24°C and growth inhibition was measured photometrically at 620 nm after 3-4 days. The following compounds provided at least 80% control of Corynespora cassiicola at 20 ppm when compared to untreated controls, which showed widespread disease development under identical conditions: P-38, P-53, P-65, P-140 and P-180.

[0354] Example B7: Blumeria graminis f.sp. tritici (Erysiphe graminis f.sp. tritici) / wheat / leaf disc preventative (powdery mildew in wheat) Wheat leaf segments (cv. Kanzler) are placed on agar in multi-well plates (24-well format) and sprayed with the formulated test compounds diluted in water. One day after application, the leaf segments are inoculated with powdery mildew infected plants by shaking them over the test plates. The inoculated leaf discs are incubated in a climate chamber under a light regime of 24 h darkness followed by 12 h light / 12 h darkness at 20° C. and 60% relative humidity, and compound efficacy is assessed as the percentage disease control compared to untreated when an appropriate level of disease damage appears on the untreated test leaf discs (6-8 days after application).

[0355] The following compounds provided at least 80% control of Blumeria graminis f.sp. tritici at 200 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-11, P-63, P-65, P-104, P-108, P-109, P-140, P-141, P-151, P-207 and P-208.

[0356] Example B8: Fusarium culmorum / liquid culture (blight disease) Fungal conidia stored at low temperature are mixed directly into nutrient liquid medium (potato glucose liquid medium). A DMSO solution of the test compound is placed in a microtiter plate (96-well format) and then the nutrient liquid medium containing the fungal spores is added. The test plate is incubated at 24°C and the inhibition of growth is measured photometrically 3-4 days after application.

[0357] The following compounds provided at least 80% control of Fusarium culmorum at 20 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-38, P-52, P-64, P-65, P-108, P-119, P-140, P-212 and P-223.

[0358] Example B9: Phaeosphaeria nodorum (Septoria nodorum) / Wheat / Leaf disc preventive (Septoria nodorum) Wheat leaf segments (cv. Kanzler) are placed on agar in multi-well plates (24-well format) and sprayed with the formulated test compounds diluted in water. The leaves are inoculated with a fungal spore suspension 2 days after application. The inoculated test leaf segments are incubated in a climate cabinet under a 12-h light / 12-h dark light regime at 20°C and 75% relative humidity, and the efficacy of the compounds is evaluated as the percentage disease control compared to untreated when an appropriate level of disease damage appears on the untreated test leaf segments (5-7 days after application).

[0359] The following compounds provided at least 80% control of Phaeosphaeria nodorum at 200 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-2, P-6, P-10, P-11, P-13, P-38, P-40, P-42, P-45, P-46, P-48, P-49, P-51, P-52, P-53, P-56, P-62, P-63, P-64, P-65, P-100, P-104, P- 105, P-108, P-109, P-110, P-117, P-119, P-120, P-136, P-140, P-141, P-142, P-143, P-146, P-151, P-180, P-204, P-208, P-221 and P-248

[0360] Example B10: Monographella nivalis (Microdochium nivale) / liquid culture (cereal root rot) Fungal conidia stored at low temperature are mixed directly into nutrient liquid medium (potato glucose liquid medium). A DMSO solution of the test compound is placed in a microtiter plate (96-well format) and then the nutrient liquid medium containing the fungal spores is added. The test plate is incubated at 24°C and the inhibition of growth is measured photometrically 4-5 days after application.

[0361] The following compounds provided at least 80% control of Monographella nivalis at 20 ppm when compared to untreated controls, which showed widespread disease development under identical conditions: P-1, P-2, P-6, P-9, P-11, P-13, P-14, P-16, P-17, P-18, P-30, P-33, P-34, P-36, P-38, P-39, P-40, P-42, P-45, P-46, P-47, P-48, P-49, P-51, P-52, P-53, P-56, P-58, P-62, P- 63, P-64, P-65, P-74, P-92, P-100, P-104, P-105, P-108, P-109, P-110, P-111, P-117, P -119, P-120, P-121, P-124, P-125, P-126, P-127, P-133, P-134, P-135, P-136, P-138, P -140, P-141, P-142, P-143, P-146, P-149, P-151, P-152, P-154, P-155, P-156, P-158, P-159, P-160, P-162, P-163, P-164, P-165, P-166, P-169, P-177, P-179, P-180, P-190, P-191, P-194, P-197, P-205, P-206, P-207, P-208, P-209, P-212, P-215, P-216, P-218, P-219, P-221, P-222, P-223, P-224, P-225, P-227, P-228, P-234, P-236, P-246 and P-248

[0362] Example B11: Mycosphaerella arachidis (Cercospora arachidicola) / liquid culture (early spot disease) Fungal conidia stored at low temperature are mixed directly into nutrient liquid medium (potato glucose liquid medium). A DMSO solution of the test compound is placed in a microtiter plate (96-well format) and then the nutrient liquid medium containing the fungal spores is added. The test plate is incubated at 24°C and the inhibition of growth is measured photometrically 4-5 days after application.

[0363] The following compounds provided at least 80% control of Mycosphaerella arachidis at 20 ppm when compared to untreated controls which showed extensive disease development under identical conditions: P-1, P-2, P-6, P-11, P-14, P-16, P-18, P-26, P-30, P-33, P-34, P-35, P-38, P-39, P- 40, P-42, P-45, P-46, P-47, P-48, P-50, P-51, P-52, P-53, P-63, P-64, P-65, P-92, P- 100, P-104, P-105, P-108, P-109, P-110, P-114, P-117, P-118, P-119, P-120, P-121 , P-123, P-124, P-125, P-126, P-133, P-134, P-135, P-137, P-138, P-139, P-140, P-1 41, P-142, P-143, P-146, P-148, P-151, P-152, P-154, P-155, P-158, P-159, P-162, P-163, P-165, P-166, P-172, P-176, P-179, P-180, P-181, P-182, P-188, P-191, P-19 4, P-205, P-207, P-208, P-209, P-212, P-215, P-218, P-220, P-221, P-222, P-223, P- 224, P-227, P-228, P-229, P-231, P-232, P-234, P-236, P-239, P-241, P-247 and P-248

[0364] Example B12: Plasmopara viticola / grape / leaf disc preventative (late blight) Grapevine leaf discs are placed on water agar in multi-well plates (24-well format) and sprayed with the formulated test compounds diluted in water. The leaves are inoculated with a fungal spore suspension one day after application. The inoculated leaves are incubated in a climate cabinet under a 12-h light / 12-h dark light regime at 19°C and 80% relative humidity, and the efficacy of the compound is assessed as the percentage disease control compared to untreated when an appropriate level of disease damage appears on the untreated test leaves (6-8 days after application).

[0365] The following compounds provided at least 80% control of Plasmopara viticola at 200 ppm when compared to untreated controls, which showed widespread disease development under identical conditions: P-146 and P-147.

[0366] Example B13: Puccinia recondita f.sp. tritici / wheat / leaf disc hardener (leaf rust) Wheat leaf segments (cv. Kanzler) are placed on agar in multi-well plates (24-well format). The leaf segments are inoculated with a fungal spore suspension. The plates are kept in the dark at 19°C and 75% relative humidity. The formulated test compounds diluted in water are applied 1 day after inoculation. The leaf segments are incubated in a climate cabinet under a 12-h light / 12-h dark light regime at 19°C and 75% relative humidity and the efficacy of the compounds is evaluated as the percentage disease control compared to the untreated when an appropriate level of disease damage appears on the untreated test leaf segments (6-8 days after application).

[0367] The following compounds provided at least 80% control of Puccinia recondita f.sp. tritici at 200 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-47, P-104, P-140 and P-234

[0368] Example B14: Puccinia recondita f.sp. tritici / wheat / leaf disc preventative (leaf rust) Wheat leaf segments (cv. Kanzler) are placed on agar in multi-well plates (24-well format) and sprayed with the formulated test compounds diluted in water. One day after application, the leaf segments are inoculated with a fungal spore suspension. The inoculated leaf segments are incubated in a climate cabinet under a 12-h light / 12-h dark light regime at 19°C and 75% relative humidity, and the efficacy of the compound is evaluated as the percentage disease control compared to the untreated when an appropriate level of disease damage appears on the untreated test leaf segments (7-9 days after application).

[0369] The following compounds provided at least 80% control of Puccinia recondita f.sp. tritici at 200 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-31, P-34, P-104, P-109, P-133, P-171, P-194 and P-206.

[0370] Example B15: Magnaporthe grisea (Pyricularia oryzae) / Rice / Leaf-piece preventative (Rice blast) Rice leaf segments (cv. Ballila) are placed on agar in multi-well plates (24-well format) and sprayed with the formulated test compounds diluted in water. The leaf segments are inoculated with a fungal spore suspension 2 days after application. The inoculated leaf segments are incubated in a climate cabinet under a light regime of 24 h darkness followed by 12 h light / 12 h darkness at 22°C and 80% relative humidity, and the efficacy of the compounds is evaluated as the percentage disease control compared to the untreated when an appropriate level of disease damage appears on the untreated test leaf segments (5-7 days after application).

[0371] The following compounds provided at least 80% control of Magnaporthe grisea at 200 ppm when compared to untreated controls, which showed extensive disease development under identical conditions: P-81, P-108, P-110, P-117, P-154 and P-194.

[0372] Example B16: Pyrenophora teres / barley / leaf disc preventative (net blotch) Barley leaf segments (cv. Hasso) are placed on agar in multi-well plates (24-well format) and sprayed with the formulated test compounds diluted in water. The leaf segments are inoculated with a fungal spore suspension 2 days after application. The inoculated leaf segments are incubated in a climate cabinet under a 12-h light / 12-h dark light regime at 20°C and 65% relative humidity, and the efficacy of the compound is assessed as disease control compared to untreated when an appropriate level of disease damage appears on the untreated test leaf segments (5-7 days after application).

[0373] The following compounds provided at least 80% control of Pyrenophora teres at 200 ppm when compared to untreated controls, which showed widespread disease development under identical conditions: P-2, P-6, P-14, P-18, P-38, P-45, P-48, P-51, P-52, P-53, P-54, P-56, P-63, P-64, P-65, P-100, P-104, P-105, P-108, P- 109, P-110, P-117, P-119, P-120, P-124, P-126, P-136, P-140, P-141, P-143, P-151, P-180, P-208, P-216, P-225 and P-228

[0374] Example B17: Thanatephorus cucumeris (Rhizoctonia solani) / Liquid culture (root rot, damping-off) Mycelium fragments from freshly cultured liquid fungi are mixed directly into nutrient broth (potato glucose broth). DMSO solutions of the test compounds are placed in microtiter plates (96-well format) and then the nutrient broth containing the fungal material is added. The test plates are incubated at 24°C and the inhibition of growth is measured photometrically 3-4 days after application.

[0375] The following compounds provided at least 80% control of Thanatephorus cucumeris at 20 ppm when compared to untreated controls which showed widespread disease development under identical conditions: P-109 and P-140.

[0376] Example B18: Sclerotinia sclerotiorum / liquid culture (sclerotinia rot) Mycelium fragments from freshly grown liquid cultures of the fungus are mixed directly into the nutrient broth (potato glucose broth). A DMSO solution of the test compound is placed in a microtiter plate (96-well format) and then the nutrient broth containing the fungal material is added. The test plates are incubated at 24°C and the inhibition of growth is measured photometrically 3-4 days after application.

[0377] The following compounds provided at least 80% control of Sclerotinia sclerotiorum at 20 ppm when compared to untreated controls, which showed widespread disease development under identical conditions: P-48, P-65, P-100, P-109, P-140, P-143, P-180, P-207, P-208, P-212 and P-223

[0378] Example B19: Wheat leaf spot fungus (Mycosphaerella graminicola) (Septoria tritici) / liquid culture (leaf spot) Fungal conidia stored at low temperature are mixed directly into nutrient liquid medium (potato glucose liquid medium). A DMSO solution of the test compound is placed in a microtiter plate (96-well format) and then the nutrient liquid medium containing the fungal spores is added. The test plate is incubated at 24°C and the inhibition of growth is measured photometrically 4-5 days after application.

[0379] The following compounds provided at least 80% control of Mycosphaerella graminicola at 20 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-1、P-2、P-6、P-7、P-9、P-10、P-11、P-13、P-14、P-16、P-17、P-18、P-20、 P-21、P-26、P-27、P-28、P-29、P-30、P-33、P-34、P-35、P-36、P-37、P-38、P -39、P-40、P-41、P-42、P-43、P-45、P-46、P-47、P-48、P-49、P-50、P-51、P -52、P-53、P-54、P-55、P-56、P-58、P-59、P-61、P-62、P-63、P-64、P-65、P- 66、P-68、P-69、P-83、P-84、P-88、P-90、P-92、P-100、P-103、P-104、P-10 5、P-108、P-109、P-110、P-111、P-112、P-113、P-114、P-115、P-116、P-117 、P-118、P-119、P-120、P-121、P-123、P-124、P-125、P-126、P-127、P-128、 P-129、P-131、P-133、P-134、P-135、P-136、P-137、P-138、P-139、P-140、P -141、P-142、P-143、P-144、P-146、P-147、P-148、P-149、P-150、P-151、P -152、P-154、P-155、P-156、P-158、P-159、P-160、P-161、P-162、P-163、P- 164、P-165、P-166、P-167、P-168、P-169、P-172、P-176、P-177、P-179、P- 180、P-181、P-182、P-184、P-187、P-188、P-190、P-191、P-192、P-194、P-1 95、P-197、P-201、P-202、P-204、P-205、P-206、P-207、P-208、P-209、P-2 12、P-215、P-216、P-217、P-218、P-219、P-220、P-221、P-222、P-223、P-22 4、P-225、P-226、P-227、P-228、P-229、P-231、P-232、P-233、P-234、P-235、P-236、P-237、P-239、P-241、P-242、P-244、P-245、P-246、P-247、P-248

Claims

1. Formula (I): 【Chemistry 1】 (In the formula, R 1 is hydrogen, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl, C 2 ~C 4 Alkynyl, and C 3 ~C 6 cycloalkyl; R 2 is hydrogen, halogen, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl, C 2 ~C 4 Alkynyl, C 1 ~C 4 Haloalkyl, C 3 ~C 6 Cycloalkyl, C 1 ~C 4 Alkylcarbonyl, N-C 1 ~C 4 Alkoxy-C-C 1 ~C 4 Alkyl-carbonimidoyl, N-hydroxy-C-C 1 ~C 4 Alkyl-carbonimidoyl, and C 1 ~C 4 alkoxycarbonyl; R 3 and R 4 is hydrogen, halogen, and C 1 ~C 4 independently selected from the group consisting of alkyl; R 5 and R 6 is hydrogen and C 1 ~C 4 independently selected from the group consisting of alkyl; R 7 is hydrogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Alkylcarbonyl, N-C 1 ~C 4 Alkoxy-C-C 1 ~C 4 Alkyl-carbonimidoyl, N-hydroxy-C-C 1 ~C 4 Alkyl-carbonimidoyl, C 1 ~C 4 Alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C 1 ~C 4 Alkylaminocarbonyl, di(C 1 ~C 4 alkylamino)carbonyl, phenyl, 5- or 6-membered heteroaryl, and C 3 ~C 6 cycloalkyl, wherein said 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S; said phenyl, 5- or 6-membered heteroaryl, and C 3 ~C 6 -Cycloalkyl is any of halogen, cyano, 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, or C 1 ~C 4 optionally substituted with 1, 2, or 3 substituents independently selected from alkoxy; B 1 is CR 10 or N; B 2 is CR 11 or N; R 8 , R 9 , R 10 , and R 11 is hydrogen, halogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 1 ~C 4 Alkoxy, C 1 ~C 4 Haloalkoxy, C 2 ~C 4 Alkenyloxy, C 2 ~C 4 Alkynyloxy, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 4 Alkoxy-C 1 ~C 4 Alkyl, C 1 ~C 4 Alkoxycarbonyl, C 1 ~C 4 Alkylcarbonyl, N-C 1 ~C 4 Alkoxy-C-C 1 ~C 4 Alkyl-carbonimidoyl, N-hydroxy-C-C 1 ~C 4 alkyl-carbonimidoyl, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, phenyl, 5- or 6-membered heteroaryl, and C 3 ~C 6 cycloalkyl, wherein said 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S; and said phenyl, 5- or 6-membered heteroaryl, and C 3 ~C 6 -Cycloalkyl is any of halogen, cyano, 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, or C 1 ~C 4 optionally substituted with 1, 2, or 3 substituents independently selected from alkoxy; A 1 , A 2 , and A 3 is CR 12 , N.R. 13 , O, and S, with the proviso that A 1 , A 2 , and A 3 At least one of is selected from N, O, and S; A 1 , A 2 , and A 3 is O or S; R 12 is hydrogen, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl, and C 2 ~C 4 alkynyl; R 13 is hydrogen, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl, and C 2 ~C 4 alkynyl; Z 1 is C 1 ~C 4 Alkyl, phenyl, 5- or 6-membered heteroaryl, and C 3 ~C 6 -cycloalkyl, wherein said 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms independently selected from N, O, and S; and said phenyl, 5- or 6-membered heteroaryl, and C 3 ~C 6 -Cycloalkyl is any of halogen, cyano, 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 1 ~C 4 Alkoxy, C 1 ~C 4 Haloalkoxy, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, or C 2 ~C 4 and optionally substituted with 1, 2, or 3 substituents independently selected from alkynyl. or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof as a bactericide or fungicide.

2. In the compound of formula (I), R 1 is hydrogen or C 1 ~C 4 The use according to claim 1, wherein the aryl group is an alkyl group.

3. In the compound of formula (I), R 2 is hydrogen, halogen, C 1 ~C 4 Alkyl, C 3 ~C 6 Cycloalkyl, C 1 ~C 4 Alkylcarbonyl, N-C 1 ~C 4 Alkoxy-C-C 1 ~C 4 Alkyl-carbonimidoyl and N-hydroxy-C-C 1 ~C 4 The use according to claim 1 or claim 2, wherein the alkyl group is selected from the group consisting of alkyl-carbonimidoyl.

4. In the compound of formula (I), R 3 and R 4 is hydrogen, halogen, and C 1 ~C 4 2. The method of claim 1, wherein said alkyl group is independently selected from the group consisting of alkyl.

5. In the compound of formula (I), R 5 and R 6 The use according to claim 1 , wherein is independently selected from the group consisting of hydrogen, methyl, and ethyl.

6. In the compound of formula (I), R 7 is hydrogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Alkylcarbonyl, N-C 1 ~C 4 Alkoxy-C-C 1 ~C 4 Alkyl-carbonimidoyl, N-hydroxy-C-C 1 ~C 4 Alkyl-carbonimidoyl, C 1 ~C 4 The use according to claim 1, wherein the aryl group is selected from the group consisting of alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, phenyl, 4-cyanophenyl, cyclopropyl, and 1-cyanocyclopropyl.

7. In the compound of formula (I), 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 The use according to claim 1 , wherein is N.

8. In the compound of formula (I), R 8 and R 11 is hydrogen, halogen, and C 1 ~C 4 2. The method of claim 1, wherein said alkyl group is independently selected from the group consisting of alkyl.

9. In the compound of formula (I), R 9 and R 10 is hydrogen, chloro, fluoro, methyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, methoxy, propoxy, allyloxy, prop-2-ynoxy, methylsulfanyl, methylsulfinyl, methylsulfonyl, methoxymethyl, 2-methoxyethoxymethyl, methoxycarbonyl, acetyl, propanoyl, -C(CH 3 ) = NOCH 3 , -C(CH 3 ) = NOCH 2 CH 3 , -C(CH 3 ) = NOH, methylaminocarbonyl, di(methylamino)carbonyl, trifluoromethylsulfonyloxy, cyano, carboxy, 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-chloropyrazole-1 2. The use of claim 1, wherein the pyrazol-1-yl is independently selected from the group consisting of (3-chloropyrazol-1-yl), (5-fluoropyrazol-1-yl), (4-fluoropyrazol-1-yl), (3-fluoropyrazol-1-yl), (3,5-dimethylpyrazol-1-yl), (5-methylpyrazol-1-yl), (4-methylpyrazol-1-yl), (3-methylpyrazol-1-yl), pyrazol-1-yl, cyclopropyl, and 1-cyanocyclopropyl.

10. In the compound of formula (I), A 1 and A 2 is CR 12 , N, and O; A 3 is CR 12 , N, O, or S, with the proviso that A 1 , A 2 , and A 3 At least one of is N or O, 1 , A 2 , and A 3 The use according to claim 1 , wherein one or less of the following is O.

11. In the compound of formula (I), R 12 is hydrogen or C 1 ~C 4 2. The use according to claim 1, wherein the alkyl is hydrogen or methyl.

12. In the compound of formula (I), Z 1 is selected from the group consisting of 1-methylpyrazol-4-yl, 2,3,4-trifluorophenyl, 2,3-difluorophenyl, 3,4-difluorophenyl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2-fluoro-4-methoxy-phenyl, 2-fluoro-4-methylsulfonyl-phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-furyl, 2-thienyl, 3-thienyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3-methoxyphenyl, 4-ethynyl-2-fluoro-phenyl, 4-fluoro-2-methoxy-phenyl, cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, n-propyl, and phenyl.

13. Formula (I): 【Chemistry 2】 (In the formula, R 1 is hydrogen, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl, C 2 ~C 4 Alkynyl, and C 3 ~C 6 cycloalkyl; R 2 is hydrogen, halogen, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl, C 2 ~C 4 Alkynyl, C 1 ~C 4 Haloalkyl, C 3 ~C 6 Cycloalkyl, C 1 ~C 4 Alkylcarbonyl, N-C 1 ~C 4 Alkoxy-C-C 1 ~C 4 Alkyl-carbonimidoyl, N-hydroxy-C-C 1 ~C 4 Alkyl-carbonimidoyl, and C 1 ~C 4 alkoxycarbonyl; R 3 and R 4 is hydrogen, halogen, and C 1 ~C 4 independently selected from the group consisting of alkyl; R 5 and R 6 is hydrogen and C 1 ~C 4 independently selected from the group consisting of alkyl; R 7 is hydrogen and C 1 ~C 4 Alkyl, C 1 ~C 4 Alkylcarbonyl, N-C 1 ~C 4 Alkoxy-C-C 1 ~C 4 Alkyl-carbonimidoyl, N-hydroxy-C-C 1 ~C 4 Alkyl-carbonimidoyl, C 1 ~C 4 Alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C 1 ~C 4 Alkylaminocarbonyl, di(C 1 ~C 4 alkylamino)carbonyl, phenyl, 5- or 6-membered heteroaryl, and C 3 ~C 6 cycloalkyl, wherein said 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S; said phenyl, 5- or 6-membered heteroaryl, and C 3 ~C 6 -Cycloalkyl is any of halogen, cyano, 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, or C 1 ~C 4 optionally substituted with 1, 2, or 3 substituents independently selected from alkoxy; B 1 is CR 10 or N; B 2 is CR 11 or N; R 8 , R 9 , R 10 , and R 11 is hydrogen, halogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 1 ~C 4 Alkoxy, C 1 ~C 4 Haloalkoxy, C 2 ~C 4 Alkenyloxy, C 2 ~C 4 Alkynyloxy, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 4 Alkoxy-C 1 ~C 4 Alkyl, C 1 ~C 4 Alkoxycarbonyl, C 1 ~C 4 Alkylcarbonyl, N-C 1 ~C 4 Alkoxy-C-C 1 ~C 4 Alkyl-carbonimidoyl, N-hydroxy-C-C 1 ~C 4 alkyl-carbonimidoyl, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, phenyl, 5- or 6-membered heteroaryl, and C 3 ~C 6 cycloalkyl, wherein said 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S; and said phenyl, 5- or 6-membered heteroaryl, and C 3 ~C 6 -Cycloalkyl is any of halogen, cyano, 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, or C 1 ~C 4 optionally substituted with 1, 2, or 3 substituents independently selected from alkoxy; A 1 , A 2 , and A 3 is CR 12 , N.R. 13 , O, and S, with the proviso that A 1 , A 2 , and A 3 At least one of is selected from N, O, and S; A 1 , A 2 , and A 3 is O or S; R 12 is hydrogen, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl, and C 2 ~C 4 alkynyl; R 13 is hydrogen, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl, and C 2 ~C 4 alkynyl; and Z 1 is C 3 ~C 4 Alkyl, phenyl, 5- or 6-membered heteroaryl, and C 3 ~C 6 -cycloalkyl, wherein said 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms independently selected from N, O, and S; and said phenyl, 5- or 6-membered heteroaryl, and C 3 ~C 6 -Cycloalkyl is any of halogen, cyano, 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 1 ~C 4 Alkoxy, C 1 ~C 4 Haloalkoxy, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, or C 2 ~C 4 and optionally substituted with 1, 2, or 3 substituents independently selected from alkynyl. or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof, provided that said compound of formula (I) is 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】 or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer, or N-oxide thereof.

14. Formula (III) 【Chemistry 9】 (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 , and B 2 corresponds to the same definition as in the compound of formula (I) according to claim 1. An intermediate compound or a salt thereof.

15. Formula (VXIII) 【Chemistry 10】 (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 , and B 2 corresponds to the same definition as in the compound of formula (I) according to claim 1. An intermediate compound.

16. A method for controlling or preventing infestation of useful plants by phytopathogenic microorganisms, comprising applying a fungicidally effective amount of a compound of formula (I) according to claim 1 or a composition containing said compound of formula (I) to said plant, its parts or its habitat.

17. 13. An agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) as defined in claim 1.

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