Microbiocidal derivatives of tetrahydroisoquinoline

Abstract

FIELD: organic chemistry.SUBSTANCE: tetrahydroisoquinoline derivatives of formula (I-A), with the exception of individual compounds specified in the invention formula, a fungicidal composition and a method for controlling or preventing infection of useful plants with phytopathogenic fungi. In formula (I-A), R1 is selected from C1-C4 alkyl; R2 is selected from hydrogen, halogen and C1-C4 alkyl; R3 and R4 are independently selected from the group of hydrogen, halogen and C1-C4 alkyl; R5 and R6 are independently selected from the group of hydrogen and C1-C4 alkyl; R7 is selected from hydrogen, C1-C4 alkyl and C3-C6 cycloalkyl; B1 is CR10 ; B2 is CR11 ; R8, R9, R10 and R11 are independently selected from hydrogen, halogen, C1-C 4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, C1-C4 alkoxycarbonyl, hydroxy or cyano; A is selected from the groups Al, A4, A6, A7, A9, A10, A13, A15 presented in the claims; Z1 is selected from phenyl and a 5- or 6-membered heteroaryl, wherein the 5- or 6-membered heteroaryl contains one heteroatom individually selected from N, O and S, and wherein any of said phenyl and 5- or 6-membered heteroaryl is unsubstituted or 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.EFFECT: tetrahydroisoquinoline derivatives of formula (I-A) possessing fungicidal activity.11 cl, 33 tbl, 29 ex

Description

[0001] The present invention relates to microbicidal tetrahydroisoquinoline derivatives, such as active ingredients, which have microbicidal activity, in particular fungicidal activity. The present invention also relates to the production of such tetrahydroisoquinoline derivatives, to intermediates useful in the production of such tetrahydroisoquinoline derivatives, to the production of such intermediates, to agrochemical compositions that contain at least one of the dihydroisoquinoline derivatives, to the production of such compositions and to the use of tetrahydroisoquinoline derivatives or compositions in agriculture or horticulture for the control or prevention of infection of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi.

[0002] In accordance with a first aspect of the present invention, there is provided the use of a compound of formula (I) as a fungicide:

[0003]

[0004] where

[0005] R 1 selected from the group consisting of hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl and C3-C6 cycloalkyl;

[0006] R 2 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 alkylcarbonimidoyl, N-hydroxy-C-C1-C4 alkylcarbonimidoyl and C1-C4 alkoxycarbonyl;

[0007] R 3 and R 4 independently selected from the group consisting of hydrogen, halogen, and C1-C4 alkyl;

[0008] R 5 and R 6 independently selected from the group consisting of hydrogen and C1-C4 alkyl;

[0009] R 7selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkylcarbonimidoyl, N-hydroxy-C-C1-C4 alkylcarbonimidoyl, C1-C4 alkoxycarbonyl, N-methoxy-N-methylcarbonyl, 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 said phenyl, 5- or 6-membered heteroaryl, and C3-C6 cycloalkyl is optionally substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl or C1-C4 alkoxy;

[0010] B 1 represents CR 10 or N;

[0011] B 2 represents CR 11 or N;

[0012] R 8 , R 9 , R 10 and R 11are independently selected from the group consisting of hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C1-C4 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 alkylcarbonimidoyl, N-hydroxy-C-C1-C4 alkylcarbonimidoyl, hydroxy, trifluoromethylsulfonyloxy, cyano, carboxy, phenyl, 5- or 6-membered heteroaryl and 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 wherein any of said phenyl, 5- or 6-membered heteroaryl and C3-C6-cycloalkyl is optionally substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl or C1-C4 alkoxy;

[0013] A 1 , A 2 and A 3 independently selected from the group consisting of CR 12 , N, NR 13, O and S, provided that at least one of A 1 , A 2 and A 3 selected from N, O and S and that no more than one of A 1 , A 2 and A 3 represents O or S;

[0014] R 12 selected from the group consisting of hydrogen, C1-C4 alkyl, C2-C4 alkenyl and C2-C4 alkynyl;

[0015] R 13 selected from the group consisting of hydrogen, C^C^alkyl, C2-C4alkenyl and C2-C4alkynyl; and

[0016] Z 1selected 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 is 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;

[0017] or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.

[0018] According to this particular aspect of the present invention, the use may exclude methods of treating the human or animal body by means of surgery or therapy.

[0019] It has been unexpectedly found that compounds of formula (I) have, from a practical point of view, a very effective level of biological activity for protecting plants from diseases caused by fungi. According to a second aspect of the present invention, there is provided a method for controlling or preventing the infection of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I) according to the present invention or a composition containing a compound of formula (I) is applied to the plants, their parts or their growing place. The term "halogen" or "halo" as used herein refers to fluorine (fluorine), chlorine (chlorine), bromine (bromine) or iodine (iodine), preferably fluorine, chlorine or bromine.

[0020] The term "cyano" used in this document means the -CN group.

[0021] The term "hydroxyl" or "hydroxy" used herein means an -OH group.

[0022] The term "oxo" used in this document means an =O group, such as sulfinyl (-S(O)-) or sulfonyl (-S(O)2-) oxygen.

[0023] As used herein, the term "C1-C4 alkyl" refers to a straight or branched chain hydrocarbon radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to four carbon atoms, and which is attached to the rest of the molecule by a single bond. The terms "C1-C3 alkyl," "C3-C4 alkyl," and "C1-C2 alkyl" shall be construed accordingly. Examples of C1-C4 alkyl include, but are not limited to, methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, and 1,1-dimethylethyl (tert-butyl). A "C1-C4 alkylene" group refers to the corresponding definition of C1-C4 alkyl, except that such a radical is attached to the rest of the molecule by two single bonds. Examples of C1-C4 alkylene are -CH2- and -CH2CH2-.

[0024] The term "C2-C4 alkenyl" as used herein refers to a group that is a straight or branched chain hydrocarbon radical consisting solely of carbon and hydrogen atoms, containing at least one double bond, which may be in either the (E) or (Z) configuration, containing from two to four carbon atoms, which is attached to the remainder of the molecule by a single bond. The term "C3-C4 alkenyl" should be construed accordingly. Examples of C2-C4 alkenyl include, but are not limited to, ethenyl and prop-1-enyl.

[0025] The term "C2-C4 alkynyl" as used herein refers to a group that is a straight or branched chain hydrocarbon radical consisting solely of carbon and hydrogen atoms, containing at least one triple bond containing from two to four carbon atoms, and which is attached to the remainder of the molecule by a single bond. The term "C3-C4 alkynyl" should be construed accordingly. 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.

[0026] The term "C1-C4 haloalkyl" as used herein refers to a C1-C4 alkyl radical, 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.

[0027] The term "C1-C4 alkoxy" as used herein refers to a radical of formula R a O-, where Ra is a C1-C4 alkyl radical, as generally defined above. The terms "C1-C3 alkoxy" and "C1-C2 alkoxy" should be construed accordingly. Examples of C1-C4 alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, and tert-butoxy.

[0028] The term "C1-C4 alkoxy-C1-C4 alkyl" as used herein refers to a radical of the formula R b -ORa -, where R b represents a C1-C4 alkyl radical as generally defined above, and R a represents a C1-C4 alkylene radical, which is generally defined above.

[0029] As used herein, the term "C1-C4 alkylcarbonyl" refers to a radical of the formula -C(O)R a , where R a represents a C1-C4 alkyl radical as generally defined above.

[0030] As used herein, the term "C1-C4 alkoxycarbonyl" refers to a radical of the formula -C(O)OR a , where R a represents a C1-C4 alkyl radical as generally defined above.

[0031] As used herein, the term “C1-C4alkylaminocarbonyl” refers to the radical of the formula -C(O)NHR a , where R a represents a C1-C4 alkyl radical as generally defined above.

[0032] As used herein, the term “di(C1-C4alkylamino)carbonyl” refers to the radical of the formula -C(O)NRa (R a ), where each R a represents a C1-C4 alkyl radical, which may be the same or different, as generally defined above.

[0033] The term "C2-C4 alkenyloxy" as used herein refers to a radical of the formula -OR a , where R a represents a C2-C4 alkenyl radical, which is generally defined above.

[0034] As used herein, the term "C2-C4 alkynyloxy" refers to a radical of the formula -OR a , where R a represents a C2-C4 alkynyl radical, which is generally defined above.

[0035] The term "C3-C6cycloalkyl" as used herein refers to a stable monocyclic ring radical that is saturated or partially unsaturated and contains from 3 to 6 carbon atoms. The terms "C3-C4cycloalkyl" and "C3-C5cycloalkyl" should be construed accordingly. Examples of C3-C6cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopenten-1-yl, cyclopenten-3-yl, and cyclohexen-3-yl.

[0036] As used herein, the term "C3-C6cycloalkylC1-C4alkyl" refers to a C3-C6cycloalkyl ring, as defined above, attached to the parent molecular moiety via a C1-C4alkylene radical, as defined above. Examples of C3-C6cycloalkylC1-C4alkyl include, but are not limited to, cyclopropylmethyl, cyclobutylethyl, and cyclopentylmethyl.

[0037] As used herein, the term "N-C1-C4alkoxy-C-C1-C4alkylcarbonimidoyl" refers to a radical of the formula -C(R a )=NO(R b ), where R arepresents a C1-C4 alkyl radical as generally defined above, and R b represents a C1-C4 alkyl radical as generally defined above. As used herein, the term "N-hydroxy-C1-C4 alkylcarbonimidoyl" refers to a radical of the formula -C(R a )=NOH, where R a is a C1-C4 alkyl radical as generally defined above. Examples of a 5- or 6-membered heteroaryl ring that contains 1-4 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.

[0038] The compounds of formula (I) or intermediates of formula (III) or (IV) according to the present invention, which contain at least one basic centre, can form, for example, acid addition salts, for example with strong inorganic acids, such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, phosphoric acid or hydrohalic acid, with strong organic carboxylic acids, such as C1-C4 alkanecarboxylic acids, which are unsubstituted or substituted, for example by a halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids,such as C1-C4 alkane or aryl sulfonic acids, which are unsubstituted or substituted, for example, by halogen, for example, methane or p-toluene sulfonic acid.

[0039] The compounds of formula (I) or intermediates of formula (III) or (IV) according to the present invention, which contain at least one acidic group, can form, for example, salts with bases, for example, mineral salts, such as alkali metal or alkaline earth metal salts, for example, sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a lower mono-, di- or trialkylamine, for example, ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a lower mono-, di- or trihydroxyalkylamine, for example, mono-, di- or triethanolamine.

[0040] The presence of one or more possible asymmetric carbon atoms in a compound of formula (I) according to the present invention means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. Atropisomers may also occur as a result of limited rotation about a single bond. Formula (I) is intended to include all such possible isomeric forms and mixtures thereof. The present invention includes all such possible isomeric forms and mixtures thereof for the compound of formula (I) according to the present invention. Similarly, the compound of formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism), if present. The present invention contemplates all possible tautomeric forms of the compound of formula (I) according to the present invention.

[0041] In each case, the compounds of formula (I) according to the present invention are in free form, in oxidized form as an N-oxide, in covalently hydrated form, or in salt form, for example in the form of an agronomically applicable or agrochemically acceptable salt. N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen-containing heteroaromatic compounds. They are described, for example, in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton 1991. The compounds of formula (I) according to the present invention also include hydrates, which can be formed during salt formation.

[0042] The following list provides definitions that include preferred definitions for R substituents 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 , IN 1 , IN 2 and Z 1 with reference to the compounds of formula (I) of the present invention. For any of these substituents, any of the definitions below may be combined with any definition of any other substituent given below or elsewhere in this document. In one embodiment of the present invention, R 1 selected from the group consisting of hydrogen, C1-C4 alkyl and C2-C4 alkynyl. Preferably R 1 selected from the group consisting of hydrogen, methyl, ethyl and isopropyl. More preferably R 1 selected from the group consisting of hydrogen, methyl, and ethyl. Even more preferably, R 1 is methyl.

[0043] In one embodiment of the present invention, R 2selected from the group consisting of hydrogen, halogen, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkylcarbonimidoyl and N-hydroxy-C-C1-C4 alkylcarbonimidoyl. Preferably R 2 selected from the group consisting of hydrogen, halogen, methyl, ethyl, cyclopropyl, C1-C2 alkylcarbonyl, N-C1-C2 alkoxy-C-C 1- C2alkylcarbonimidoyl and N-hydroxy-C-C1-C2alkylcarbonimidoyl.

[0044] More preferable R 2 selected from the group consisting of hydrogen, bromine, fluorine, chlorine, methyl, ethyl, cyclopropyl, acetyl, -C(CH3)=NOCH3, -C(CH3)=MOCH2CH3 and -C(CH3)=NOH. Even more preferably R 2 selected from the group consisting of hydrogen, bromine, fluorine, chlorine, methyl, acetyl and -C(CH3)=NOCH3, even more preferably R 2 selected from the group consisting of hydrogen, fluorine, chlorine and methyl.

[0045] In one embodiment of the present invention, R 3selected from the group consisting of hydrogen, halogen and C1-C4 alkyl. Preferably R 3 selected from the group consisting of hydrogen, fluorine, chlorine, methyl and ethyl. More preferably R 3 selected from the group consisting of hydrogen and methyl.

[0046] In one embodiment of the present invention, R 4 selected from the group consisting of hydrogen, halogen and C1-C4 alkyl. Preferably R 4 selected from the group consisting of hydrogen, fluorine, chlorine, methyl, ethyl and isopropyl. More preferably R 4 selected from the group consisting of hydrogen, fluorine, chlorine, methyl and ethyl. Even more preferably R 4 selected from the group consisting of hydrogen and methyl.

[0047] In one embodiment of the present invention, R 5 and R 6 independently selected from the group consisting of hydrogen, methyl, and ethyl. Preferably R 5 and R 6are independently selected from the group consisting of hydrogen and methyl. In one embodiment of the present invention, R 7 selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, acetyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methylaminocarbonyl, dimethylaminocarbonyl, methoxycarbonyl, ethoxycarbonyl, N-methoxy-N-methylcarbonyl, 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. Preferably R 7selected from the group consisting of hydrogen, methyl, acetyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methoxycarbonyl, ethoxycarbonyl, N-methoxy-N-methylcarbonyl, 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 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 7 selected from the group consisting of hydrogen, methyl, cyclopropyl and 1-cyanocyclopropyl. Even more preferably R 7 selected from the group consisting of hydrogen, methyl and cyclopropyl.

[0048] In another embodiment of the present invention, R 7 selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkylcarbonimidoyl, N-hydroxy-C-C1-C4 alkylcarbonimidoyl, C1-C4 alkoxycarbonyl, N-methoxy-N-methylcarbonyl, phenyl, 4-cyanophenyl, cyclopropyl and 1-cyanocyclopropyl. Preferably R 7 selected from the group consisting of hydrogen, methyl, acetyl, -C(CH3)=NOCH3, -C(CH3)=NOCH2CH3, -C(CH3)=NOH, methoxycarbonyl, ethoxycarbonyl, N-methoxy-N-methylcarbonyl, phenyl and cyclopropyl. More preferably R 7 selected from the group consisting of hydrogen and methyl.

[0049] In another embodiment of the present invention, R 7 selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkylcarbonimidoyl and phenyl, preferably R 7selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, acetyl, methoxycarbonyl, -C(CH3)=NOCH3 and phenyl. More preferably R 7 selected from the group consisting of hydrogen, methyl and acetyl.

[0050] In one embodiment of the present invention, B 1 represents CR 10 , and B 2 represents CR 11 , or B 1 represents N, and B 2 represents CR 11 , or B 1 represents CR 10 , and B 2 represents N. Preferably B 1 represents CR 10 , and B 2 represents CR 11 .

[0051] In one embodiment of the present invention, R 8 and R 11 independently selected from the group consisting of hydrogen, halogen, and C1-C4 alkyl. Preferably R 8 and R 11independently selected from the group consisting of hydrogen, chlorine, fluorine, and methyl. More preferably, R 8 and R 11 represent hydrogen.

[0052] In another embodiment of the present invention R 8 and R 11 independently selected from the group consisting of hydrogen, halogen, and C1-C4 alkyl. Preferably R 8 and R 11 independently selected from the group consisting of hydrogen and halogen. More preferably R 8 and R 11 independently selected from the group consisting of hydrogen, chlorine, bromine, and fluorine.

[0053] In one embodiment of the present invention, R 9 and R 10are independently selected from the group consisting of 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 alkylcarbonimidoyl, N-hydroxy-C-C1-C2 alkylcarbonimidoylhydroxy, 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-cyanocyatopropyl. Preferably R9 and R 10are independently selected from the group consisting of hydrogen, chlorine, fluorine, bromine, 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 10are independently selected from the group consisting of hydrogen, chlorine, fluorine, 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-(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.

[0054] In another embodiment of the present invention, R 9and R 10 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. Preferably R 9 and R 10 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.

[0055] More preferable R 9 and R 10 are 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. In one embodiment of the present invention, A 1 and A 2 independently selected from the group consisting of CR 12 , N and O, and A 3 represents CR 12 , N, O or S, preferably A 1 and A 2independently selected from the group consisting of N and O, and A 3 represents CR 12 , O or S, provided that at least one of A 1 , A 2 and A 3 represents N or O and that no more than one of A 1 , A 2 and A 3 represents O.

[0056] In one embodiment of the present invention, R 12 represents hydrogen or C1-C4 alkyl, preferably hydrogen or methyl.

[0057] In one embodiment of the present invention R 13 represents hydrogen or C1-C4 alkyl, preferably hydrogen or methyl.

[0058] In one embodiment of the present invention, Z 1selected 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-methoxyphenyl, 2-fluoro-4-methylsulfonylphenyl, 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-fluorophenyl, 4-fluoro-2-methoxyphenyl, cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, n-propyl and phenyl.

[0059] In another embodiment of the present invention, Z 1selected 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 wherein any of said phenyl, 5- or 6-membered heteroaryl, and C3-C6 cycloalkyl is 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 1selected from the group consisting of n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 3,4-difluorophenyl, 2-fluoro-4-chlorophenyl, 2,3,4-trifluorophenyl, 2,4,6-trifluorophenyl, 2-fluoro-4-methoxyphenyl, 2-fluoro-4-methylsulfonylphenyl, 4-fluoro-2-methoxyphenyl, 4-ethynyl-2-fluorophenyl, 4-trifluoromethylphenyl, 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.

[0060] In one embodiment, in the compound of formula (I) according to the present invention

[0061] R 1 represents hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl or C3-C6 cycloalkyl;

[0062] R 2represents 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 alkylcarbonimidoyl, N-hydroxy-C-C1-C4 alkylcarbonimidoyl or C1-C4 alkoxycarbonyl;

[0063] R 3 and R 4 independently of each other represent hydrogen, halogen or C1-C4 alkyl;

[0064] R 5 and R 6 independently of each other represent hydrogen or C1-C4 alkyl;

[0065] R 7represents hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkylcarbonimidoyl, N-hydroxy-C-C1-C4 alkylcarbonimidoyl, C1-C4 alkoxycarbonyl, N-methoxy-N-methylcarbonyl, 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 said phenyl, 5- or 6-membered heteroaryl, and C3-C6 cycloalkyl is optionally substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4alkyl, C1-C4haloalkyl and C1-C4alkoxy;

[0066] B 1 represents CR 10 or N;

[0067] B 2 represents CR 11 or N;

[0068] R 8 , R 9 , R 10 and R 11independently of one another are 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 alkylcarbonimidoyl, N-hydroxy-C-C1-C4 alkylcarbonimidoyl, 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 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 and C1-C4 alkoxy;

[0069] A 1 , A 2 and A 3 independently of each other represent CR 12 , N, NR 13, O and S, provided that at least one of A 1 , A 2 and A 3 selected from N, O and S and that no more than one of A 1 , A 2 and A 3 represents O or S;

[0070] R 12 represents hydrogen, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl;

[0071] R 13 represents hydrogen, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl; and

[0072] Z 1 is 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 is 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.

[0073] In one embodiment of the present invention, the compound of formula (I) may be a compound of formula (IA):

[0074]

[0075] where

[0076] A is selected from the group consisting of:

[0077]

[0078] where denotes the bond with the C(=O) group and the arrow denotes the bond with the Z group 1 ,

[0079] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , IN 1 , IN 2 and Z 1 defined for the compounds of formula (I) according to the present invention, and

[0080] R 12a , R 13a , R 14a , R 12b , R 13b hR 14b independently selected from the group consisting of hydrogen, C1-C4 alkyl, C2-C4 alkenyl and C2-C4 alkynyl.

[0081] In one embodiment of the present invention, in the compound of formula (IA), A is selected from the group consisting of:

[0082]

[0083] where denotes the bond with the C(=O) group and the arrow denotes the bond with the Z group 1 , and R 12a , R 13a and R 14a independently of each other represent hydrogen or C1-C4 alkyl.

[0084] In another embodiment of the present invention, in the compound of formula (I-A), A is selected from the group consisting of:

[0085]

[0086] where denotes the bond with the C(=O) group and the arrow denotes the bond with the Z group 1 , and R 12a , R 13a and R 14a independently selected from the group consisting of hydrogen, C1-C4 alkyl, C2-C4 alkenyl, and C2-C4 alkynyl.

[0087] In another embodiment of the present invention, in the compound of formula (I-A), A is selected from the group consisting of:

[0088]

[0089] where denotes the bond with the C(=O) group and the arrow denotes the bond with the Z group 1 In another embodiment of the present invention, in the compound of formula (I-A), A is selected from the group consisting of

[0090]

[0091] where denotes the bond with the C(=O) group and the arrow denotes the bond with the Z group 1 .

[0092] In another embodiment of the present invention, in the compound of formula (I-A), A is selected from the group consisting of

[0093]

[0094] where denotes the bond with the C(=O) group and the arrow indicates the bond with the Z group 1 .

[0095] In one embodiment of the present invention, R 12a , R13a , R 14a , R 12b , R 13b and R 14b are independently selected from the group consisting of hydrogen and methyl. In another embodiment of the present invention, R 12a , R 13a , R 14a , R 12b , R 13b and R 14b represent hydrogen.

[0096] In another embodiment of the present invention, R 12a , R 13a , R 14a , R 12b , R 13b and R 14b are methyl.

[0097] In one embodiment of the present invention, the compound of formula (IA) may be a compound of formula (I-A1), wherein B 1 and B 2 represent CH and A is defined for compound (IA):

[0098]

[0099] where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and Z 1defined for the compounds of formula (I) according to the present invention.

[0100] In one embodiment of this embodiment of the present invention, the compound of formula (I-A) may be a compound of formula (I-A2), wherein B 1 and B 2 represent CH, R 4 , R 5 , R 6 and R 7 represent hydrogen and A is defined for compound (I-A):

[0101]

[0102] where R 1 , R 2 , R 3 , R 8 , R 9 and Z 1 defined for the compounds of formula (I) according to the present invention.

[0103] Preferably, in the compound of formula (I-A2) of the present invention, R 1 represents hydrogen, C1-C4 alkyl or C2-C4 alkynyl, preferably hydrogen, methyl or ethyl,

[0104] R 2 and R 3independently of one another are hydrogen, a halogen such as bromine or chlorine, methyl, -C(O)OCH2CH3, N-methoxy-C-methylcarbonimidoyl or -COCH3, R 8 and R 9 independently of one another, represent hydrogen, a halogen such as fluorine or chlorine, cyano, methyl, trifluoromethyl, methoxy, -C(O)OCH3 or -SO2CH3,

[0105] A is defined for compounds of formula (IA) and

[0106] Z 1 defined for compounds of formula (G) according to the present invention.

[0107] In another embodiment of this embodiment of the present invention, the compound of formula (I-A) may be a compound of formula (I-A3), wherein

[0108] B 1 and B 2 represent CH, R 4 , R 5 and R 6 represent hydrogen and A is defined for compound (I-A):

[0109]

[0110] where

[0111] R 1 , R 2 , R 3 , R 8, R 9 and Z 1 defined for the compounds of formula (I) according to the present invention, and

[0112] R 7 is C1-C4 alkyl.

[0113] Preferably, in the compound of formula (I-A3) of the present invention

[0114] R 1 is methyl,

[0115] R 2 and R 3 represent hydrogen or methyl,

[0116] R 7 is methyl, ethyl, or n-propyl, or isopropyl, or phenyl, or -C(O)OCH3,

[0117] R 8 and R 9 represent hydrogen or methoxy,

[0118] A is defined for connection (iA) and

[0119] Z 1 defined for the compounds of formula (I) according to the present invention.

[0120] In another embodiment of this embodiment of the present invention, the compound of formula (I-A) may be a compound of formula (I-A4), wherein

[0121] B 1 and B 2represent CH, R 4 , R 5 and R 7 represent hydrogen, R 6 is methyl and A is defined for compound (I-A):

[0122]

[0123] where R 1 , R 2 , R 3 , R 8 , R 9 and Z 1 defined for the compounds of formula (I) according to the present invention.

[0124] Preferably, in the compound of formula (I-A4) of the present invention

[0125] R 1 is methyl,

[0126] R 2 and R 3 represent hydrogen or methyl,

[0127] R 8 and R 9 represent hydrogen,

[0128] A is defined for compound (I-A) and

[0129] Z 1 defined for the compounds of formula (I) according to the present invention.

[0130] In another embodiment of this embodiment of the present invention, the compound of formula (I-A) may be a compound of formula (I-A5), wherein

[0131] B 1 and B 2 represent CH, R 4 and R 7 represent hydrogen and R 5 and R 6 represent methyl:

[0132]

[0133] where R 1 , R 2 , R 3 , R 8 , R 9 and Z 1 defined for the compounds of formula (I) according to the present invention and

[0134] wherein A is defined for the compound (I-A) according to the present invention.

[0135] Preferably, in the compound of formula (I-A5) of the present invention

[0136] R 1 is methyl,

[0137] R 2 and R 3 represent hydrogen or methyl,

[0138] R 8 and R 9 represent hydrogen,

[0139] A is defined for compound (I-A) and

[0140] Z 1 defined for the compounds of formula (I) according to the present invention.

[0141] In another embodiment of this embodiment of the present invention, the compound of formula (I-A) may be a compound of formula (I-A6), wherein B 1 and B 2 represent CH and R 5 , R 6 and R 7 represent hydrogen:

[0142]

[0143] where

[0144] R 1 , R 2 , R 3 , R 8 , R 9 and Z 1 defined for the compounds of formula (I) according to the present invention,

[0145] A is defined for compound (I-A) and

[0146] R 4 is C1-C4 alkyl.

[0147] Preferably, in the compound of formula (I-A6) of the present invention

[0148] R 1 is methyl,

[0149] R 2and R 3 represent hydrogen or methyl,

[0150] R 4 is methyl,

[0151] R 8 and R 9 represent hydrogen,

[0152] A is defined for compound (I-A) and

[0153] Z 1 defined for compounds of formula (I) according to the present invention. In another embodiment of this embodiment of the present invention, the compound of formula (I-A) may be a compound of formula (I-A7), wherein B 1 and B 2 represent CH and R 5 and R 6 represent hydrogen:

[0154]

[0155] where

[0156] R 1 , R 2 , R 3 , R 8 , R 9 and Z 1 defined for the compounds of formula (I) according to the present invention,

[0157] A is defined for compound (I-A) and

[0158] R 4 and R 7are C1-C4 alkyl.

[0159] Preferably, in the compound of formula (I-A7) of the present invention

[0160] R 1 is methyl,

[0161] R 2 and R 3 are hydrogen, a halogen such as fluorine, or methyl,

[0162] R 4 and R 7 are methyl,

[0163] R 8 and R 9 are hydrogen, hydroxy, methoxy, difluoromethoxy, 2,2-difluoroethoxy or 2,2,2-trifluoroethoxy,

[0164] A is defined for compound (I-A) and

[0165] Z 1 defined for the compounds of formula (I) according to the present invention.

[0166] In another embodiment of this embodiment of the present invention, the compound of formula (I-A) may be a compound of formula (I-A8), wherein B 2 represents CH and R 4 , R 5 , R 6 , R 7 , R 8 and R 9 represent hydrogen:

[0167]

[0168] where

[0169] B 1 represents CR 10 , And

[0170] R 1 , R 2 , R 3 , R 10 and Z 1 defined for the compounds of formula (I) according to the present invention, and

[0171] A is defined for compound (I-A).

[0172] Preferably, in the compound of formula (I-A8) of the present invention

[0173] R 1 is methyl,

[0174] R 2 and R 3 independently of each other represent hydrogen, a halogen such as fluorine, or methyl,

[0175] R 10 is a halogen such as fluorine, methyl, trifluoromethyl, methoxy or phenyl,

[0176] A is defined for compound (I-A) and

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

[0178] In another embodiment of this embodiment of the present invention, the compound of formula (I-A) may be a compound of formula (I-A9), wherein B 1 represents CH and R 4 , R 5 , R 6 , R 7 , R 8 and R 9 represent hydrogen:

[0179]

[0180] where

[0181] B 2 represents CR 11 , And

[0182] R 1 , R 2 , R 3 , R 11 n Z 1 defined for the compounds of formula (I) according to the present invention, and

[0183] A is defined for compound (I-A).

[0184] Preferably, in the compound of formula (I-A9) of the present invention

[0185] R 1 is methyl,

[0186] R 2 and R 3 independently of each other represent hydrogen, a halogen such as fluorine, or methyl,

[0187] R11 is a halogen such as fluorine, methyl, trifluoromethyl, methoxy or phenyl,

[0188] A is defined for compound (I-A) and

[0189] Z 1 defined for compounds of formula (I) according to the present invention. In another embodiment of this embodiment of the present invention, the compound of formula (I-A) may be a compound of formula (I-A10), wherein B 1 is CH, B 2 represents N and R 4 , R 5 , R 6 , R 7 , R 8 and R 9 represent hydrogen:

[0190]

[0191] where R 1 , R 2 , R 3 and Z 1 defined for the compounds of formula (I) according to the present invention and

[0192] A is defined for compound (I-A).

[0193] Preferably, in the compound of formula (I-A10) of the present invention

[0194] R 1is methyl,

[0195] R 2 and R 3 independently of each other represent hydrogen, a halogen such as fluorine, or methyl,

[0196] A is defined for compound (I-A) and

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

[0198] The presence of one or more possible asymmetric carbon atoms in any of the compounds of formula (I), (I-A) and (I-A1) to (I-A10) according to the present invention means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms.

[0199] More preferably, the compound of formula (I) according to the present invention is selected from the compounds listed in any one of Tables A-1 to A-32 or Table T1.

[0200] 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, with the proviso that the compound of formula (I) is not

[0201] connection with ID 119105753 in PubChem;

[0202] connection with ID 119105755 in PubChem;

[0203] connection with ID 119105758 in PubChem;

[0204] connection with ID 119105768 in PubChem;

[0205] connection with ID 121022987 in PubChem;

[0206] connection with ID 121023008 in PubChem;

[0207] connection with ID 121198339 in PubChem;

[0208] , compound ID 121198395 in PubChem;

[0209] , compound ID 121198398 in PubChem;

[0210] , compound ID 121198478 in PubChem;

[0211] , compound ID 121198479 in PubChem;

[0212] , compound ID 121198480 in PubChem;

[0213] , compound ID 121198481 in PubChem;

[0214] , compound ID 121198482 in PubChem;

[0215] , compound ID 121198502 in PubChem;

[0216] , compound ID 121198515 in PubChem;

[0217] , compound ID 129530178 in PubChem;

[0218] , compound ID 129530183 in PubChem;

[0219] , connection with ID 129530240 in PubChem;

[0220] , connection with ID 129530241 in PubChem;

[0221] , compound ID 129530774 in PubChem;

[0222] , connection with ID 129530780 in PubChem;

[0223] , compound ID 129530918 in PubChem;

[0224] , compound ID 129530919 in PubChem;

[0225] , compound ID 129530931 in PubChem;

[0226] , compound ID 129530933 in PubChem;

[0227] , compound ID 129531203 in PubChem;

[0228] connection with ID 129531204 in PubChem;

[0229] or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof.

[0230] The PubChem compound ID listed for the above rejected compounds refers to the identification number of each compound on the PubChem website https: / / pubchem.ncbi.nlm.nih.gov / .

[0231] In one embodiment, in the compound of formula (I) according to the present invention

[0232] R 1 represents hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl or C3-C6 cycloalkyl;

[0233] R 2 represents 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 alkylcarbonimidoyl, N-hydroxy-C-C1-C4 alkylcarbonimidoyl or C1-C4 alkoxycarbonyl;

[0234] R3 and R 4 independently of each other represent hydrogen, halogen or C1-C4 alkyl;

[0235] R 5 and R 6 independently of each other represent hydrogen or C1-C4 alkyl;

[0236] R 7 represents hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkylcarbonimidoyl, N-hydroxy-C-C1-C4 alkylcarbonimidoyl, C1-C4 alkoxycarbonyl, N-methoxy-N-methylcarbonyl, 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 said phenyl, 5- or 6-membered heteroaryl, and C3-C6 cycloalkyl is optionally substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4alkyl, C1-C4haloalkyl and C1-C4alkoxy;

[0237] B 1 represents CR 10 or N;

[0238] B 2represents CR 11 or N;

[0239] R 8 , R 9 , R 10 and R 11 independently of one another are 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 alkylcarbonimidoyl, N-hydroxy-C-C1-C4 alkylcarbonimidoyl, 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 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 and C1-C4 alkoxy;

[0240] A 1 , A 2 and A 3independently of each other represent CR 12 , N, NR 13 , O and S, provided that at least one of A 1 , A 2 and A 3 selected from N, O and S and that no more than one of A 1 , A 2 and A 3 represents O or S;

[0241] R 12 represents hydrogen, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl;

[0242] R 13 represents hydrogen, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl; and

[0243] 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 is 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,

[0244] provided that said compound of formula (I) is not any of the above-rejected compounds with the following identification numbers: compound with PubChem ID 119105753, compound with PubChem ID 119105755, compound with PubChem ID 119105758, compound with PubChem ID 119105768, compound with PubChem ID 121022987, compound with PubChem ID 121023008, compound with PubChem ID 121198339, compound with PubChem ID 121198395, compound with PubChem ID 121198398, compound with PubChem ID 121198478, compound with PubChem ID 121198479 in PubChem, compound ID 121198480 in PubChem, compound ID 121198481 in PubChem, compound ID 121198482 in PubChem, compound ID 121198502 in PubChem, compound ID 121198515 in PubChem, compound ID 129530178 in PubChem, compound ID 129530183 in PubChem, compound ID 129530240 in PubChem, compound ID 129530241 in PubChem, compound ID 129530774 in PubChem, compound ID 129530780 in PubChem,compound with ID 129530918 in PubChem, compound with ID 129530919 in PubChem, compound with ID 129530931 in PubChem, compound with ID 129530933 in PubChem, compound with ID 129531203 in PubChem, compound with ID 129531204 in PubChem.,

[0245] In one embodiment, in the compound of formula (I) according to the present invention

[0246] R 1 represents hydrogen, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl or C3-C6 cycloalkyl;

[0247] R 2 represents 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 alkylcarbonimidoyl, N-hydroxy-C-C1-C4 alkylcarbonimidoyl or C1-C4 alkoxycarbonyl;

[0248] R 3 and R 4 independently of each other represent hydrogen, halogen or C1-C4 alkyl;

[0249] R 5 and R 6 independently of each other represent hydrogen or C1-C4 alkyl;

[0250] R 7represents hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkylcarbonimidoyl, N-hydroxy-C-C1-C4 alkylcarbonimidoyl, C1-C4 alkoxycarbonyl, N-methoxy-N-methylcarbonyl, 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 said phenyl, 5- or 6-membered heteroaryl, and C3-C6 cycloalkyl is optionally substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4alkyl, C1-C4haloalkyl and C1-C4alkoxy;

[0251] B 1 represents CR 10 or N;

[0252] B 2 represents CR 11 or N;

[0253] R 8 , R 9 , R 10 and R 11independently of one another are 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 alkylcarbonimidoyl, N-hydroxy-C-C1-C4 alkylcarbonimidoyl, 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 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 and C1-C4 alkoxy;

[0254] A 1 , A 2 and A 3 independently of each other represent CR 12 , N, NR 13, O and S, provided that at least one of A 1 , A 2 and A 3 selected from N, O and S and that no more than one of A 1 , A 2 and A 3 represents O or S; R 12 represents hydrogen, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl;

[0255] R 13 represents hydrogen, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl; and

[0256] Z 1 is 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 is 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,

[0257] provided that said compound of formula (I) is not any of the above-rejected compounds with the following identification numbers: compound with PubChem ID 119105753, compound with PubChem ID 119105755, compound with PubChem ID 119105758, compound with PubChem ID 119105768, compound with PubChem ID 121022987, compound with PubChem ID 121023008, compound with PubChem ID 121198339, compound with PubChem ID 121198395, compound with PubChem ID 121198398, compound with PubChem ID 121198478, compound with PubChem ID 121198479 in PubChem, compound ID 121198480 in PubChem, compound ID 121198481 in PubChem, compound ID 121198482 in PubChem, compound ID 121198502 in PubChem, compound ID 121198515 in PubChem, compound ID 129530178 in PubChem, compound ID 129530183 in PubChem, compound ID 129530240 in PubChem, compound ID 129530241 in PubChem, compound ID 129530774 in PubChem, compound ID 129530780 in PubChem,compound with ID 129530918 in PubChem, compound with ID 129530919 in PubChem, compound with ID 129530931 in PubChem, compound with ID 129530933 in PubChem, compound with ID 129531203 in PubChem, compound with ID 129531204 in PubChem.,

[0258] In another embodiment, in the compound of formula (I) according to the present invention

[0259] R 1 is C1-C4 alkyl,

[0260] R 2 represents hydrogen, halogen, C1-C4 alkyl, C1-C4 alkylcarbonyl or N-C1-C4 alkoxy-C-C1-C4 alkylcarbonimidoyl,

[0261] R 3 and R 4 independently of each other represent hydrogen or C1-C4 alkyl,

[0262] R 5 and R 6 represent hydrogen or C1-C4 alkyl,

[0263] R 7 represents hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, M-C1-C4 alkoxy-C-C1-C4 alkylcarbonimidoyl or phenyl,

[0264] B 1 represents CR 10 or N;

[0265] B 2 represents CR 11 or N;

[0266] R 8 and R 11 independently of each other represent hydrogen, halogen or C1-C4 alkyl,

[0267] R 9 and R 10 independently of one another are hydrogen, halogen, hydroxy, C1-C3 alkyl, C1-C2 haloalkyl, C1-C3 haloalkoxy, C1-C4 alkoxy, C1-C3 alkoxycarbonyl, cyano or phenyl,

[0268] A 1 and A 2 independently of each other represent CR 12 , N and O and A 3 represents CR 12 , N, O or S, provided that at least one of A 1 , A 2 and A 3 represents N or O and that no more than one of A 1 , A 2 and A 3 represents O;

[0269] R 12 represents hydrogen or C1-C4 alkyl and

[0270] 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 is 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.

[0271] In one embodiment, in the compound of formula (I) according to the present invention

[0272] R 1 represents hydrogen or C1-C4 alkyl,

[0273] R 2 represents hydrogen, halogen, C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkylcarbonimidoyl or N-hydroxy-C1-C4 alkylcarbonimidoyl,

[0274] R 3 and R 4 independently of each other represent hydrogen, halogen or C1-C4 alkyl,

[0275] R 5 and R6 independently of each other represent hydrogen, methyl or ethyl,

[0276] R 7 represents hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, N-C1-C4 alkoxy-C1-C4 alkylcarbonimidoyl, N-hydroxy-C1-C4 alkylcarbonimidoyl, C1-C4 alkoxycarbonyl, N-methoxy-N-methylcarbonyl, phenyl, 4-cyanophenyl, cyclopropyl and 1-cyanocyclopropyl,

[0277] B 1 represents CR 10 ;

[0278] B 2 represents CR 11 ,

[0279] R 8 and R 11 independently of each other represent hydrogen, halogen or C1-C4 alkyl, R 9 and R 10independently of one another are hydrogen, chlorine, fluorine, 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,

[0280] 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-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 independently of each other represent CR 12, N or O and A 3 represents CR 12 , N, O or S, provided that at least one of A 1 , A 2 and A 3 represents N or O and that no more than one A 1 , A 2 and A 3 represents O,

[0281] R 12 represents hydrogen or methyl,

[0282] Z 1 is 1-methylpyrazol-4-yl, 2,3,4-trifluorophenyl, 2,3-difluorophenyl, 3,4-difluorophenyl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2-fluoro-4-methoxyphenyl, 2-fluoro-4-methylsulfonylphenyl, 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-fluorophenyl, 4-fluoro-2-methoxyphenyl, cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, n-propyl or phenyl.

[0283] In another embodiment, in the compound of formula (I) according to the present invention

[0284] R 1 is C1-C4 alkyl,

[0285] R 2 represents hydrogen, halogen, C1-C4 alkyl, C1-C4 alkylcarbonyl or N-C1-C4 alkoxy-C-C1-C4 alkylcarbonimidoyl,

[0286] R 3 and R 4 independently of each other represent hydrogen or C1-C4 alkyl,

[0287] R 5 and R 6 represent hydrogen or C1-C4 alkyl,

[0288] R 7 represents hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkylcarbonimidoyl or phenyl,

[0289] B 1 represents CR 10 or N;

[0290] B 2 represents CR 11 or N;

[0291] R 8 and R 11 independently of each other represent hydrogen, halogen or C1-C4 alkyl,

[0292] R 9 and R 10independently of one another are hydrogen, halogen, hydroxy, C1-C3 alkyl, C1-C2 haloalkyl, C1-C3 haloalkoxy, C1-C4 alkoxy, C1-C3 alkoxycarbonyl, cyano or phenyl,

[0293] A 1 and A 2 independently of each other represent CR 12 , N and O and A 3 represents CR 12 , N, O or S, provided that at least one of A 1 , A 2 and A 3 represents N or O and that no more than one of A 1 , A 2 and A 3 represents O;

[0294] 12 represents hydrogen or C1-C4 alkyl and

[0295] 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 is 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.

[0296] In one embodiment, the compound of formula (I) may be compound (IB), wherein B 1 represents CR 10 , and B 2 represents CR 11 ; And

[0297] where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11correspond to the same definitions as those given for the compounds of formula (I) according to the present invention. Preferably, in compound (IB)

[0298] R 1 is C1-C4 alkyl,

[0299] R 2 represents hydrogen, halogen, C1-C4 alkyl, C1-C4 alkylcarbonyl or N-C1-C4 alkoxy-C-C1-C4 alkylcarbonimidoyl,

[0300] R 3 and R 4 independently of each other represent hydrogen or C1-C4 alkyl,

[0301] R 5 and R 6 represent hydrogen or C1-C4 alkyl,

[0302] R 7 represents hydrogen, C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, N-C1-C4 alkoxy-C-C1-C4 alkylcarbonimidoyl or phenyl,

[0303] R 8 and R 11 independently of each other represent hydrogen, halogen or C1-C4 alkyl,

[0304] R 9 and R 10independently of one another are hydrogen, halogen, hydroxy, C1-C3 alkyl, C1-C2 haloalkyl, C1-C3 haloalkoxy, C1-C4 alkoxy, C1-C3 alkoxycarbonyl, cyano or phenyl,

[0305] A 1 and A 2 independently of each other represent CR 12 , N and O and A 3 represents CR 12 , N, O or S, provided that at least one of A 1 , A 2 and A 3 represents N or O and that no more than one of A 1 , A 2 and A 3 represents O;

[0306] R 12 represents hydrogen or C1-C4 alkyl and

[0307] 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 is 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.

[0308] In one embodiment, the compound of formula (I) may be compound (IB), wherein B 1 represents CR 10 , and B 2 represents CR 11 , and where R 5 and R 6 represent hydrogen; and

[0309] where R 1 , R 2 , R 3 , R 4 , R 7 , R 8 , R 9 , R 10 and R 11correspond to the same definitions as those given for the compounds of formula (I) according to the present invention.

[0310] Preferably in conjunction (IB)

[0311] R 1 is C1-C4 alkyl,

[0312] R 2 represents hydrogen, halogen or C1-C4 alkyl,

[0313] R 3 and R 4 independently of each other represent hydrogen or C1-C4 alkyl,

[0314] R 7 represents hydrogen or C1-C4 alkyl and

[0315] R 8 , R 9 , R 10 , R 11 , A 1 , A 2 , A 3 , R 12 , R 13 and Z 1 defined for the compounds of formula (I) according to the present invention.

[0316] In another embodiment, the compound of formula (I) may be compound (IB), wherein B 1 represents CR 10 , and B 2 represents CR 11 , and where R 4 , R5 , R 6 and R 7 represent hydrogen; and

[0317] where R 1 , R 2 , R 3 , R 8 , R 9 , R 10 and R 11 correspond to the same definitions as those given for the compounds of formula (I) according to the present invention.

[0318] Preferably in conjunction (IB)

[0319] R 1 is C1-C4 alkyl,

[0320] R 2 represents hydrogen, halogen or C1-C4 alkyl,

[0321] R 3 represents hydrogen or C1-C4 alkyl and

[0322] R 8 , R 9 , R 10 , R 11 , A 1 , A 2 , A 3 , R 12 , R 13 and Z 1 defined for the compounds of formula (I) according to the present invention.

[0323] In another embodiment, the compound of formula (I) may be compound (IB), wherein B 1 represents CR10 , and B 2 represents CR 11 , and where R 7 is methyl; and

[0324] where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 and R 11 correspond to the same definitions as those given for the compounds of formula (I) according to the present invention.

[0325] Preferably in conjunction (IB)

[0326] R 1 is C1-C4 alkyl,

[0327] R 2 represents hydrogen, halogen or C1-C4 alkyl,

[0328] R 3 and R 4 independently of each other represent hydrogen or C1-C4 alkyl,

[0329] R 5 and R 6 represent hydrogen and

[0330] R 8 , R 9 , R 10 , R 11 , A 1 , A 2 , A 3 , R 12 , R 13 and Z 1defined for the compounds of formula (I) according to the present invention.

[0331] 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 a composition, intended for use in agriculture, may further comprise at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

[0332] According to a fifth aspect of the present invention, there is provided an intermediate compound of formula (III) or a salt thereof:

[0333]

[0334] where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , IN 1 and B 2correspond to the same definitions as those given for the compounds of formula (I) according to the present invention. The intermediate compounds of formula (III) have the same definitions for R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , IN 1 and B 2 , as given for the compounds of formula (I) according to the present invention and their respective preferences.

[0335] In one embodiment, the intermediate compound of formula (III) may be compound (III-c), wherein B 1 represents CR 10 , and B 2 represents CR 11 ; And

[0336] where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11correspond to the same definitions as those given for the compounds of formula (I) according to the present invention. The presence of one or more possible asymmetric carbon atoms in a compound of formula (III) according to the present invention means that the compounds can occur in chiral isomeric forms, i.e. enantiomeric or diastereomeric forms.

[0337] According to a sixth aspect of the present invention, there is provided an intermediate compound of formula (IV):

[0338]

[0339] where R 1 , R 2 , R 3 , R 5 , R 7 , R 8 , R 9 , B 1 and B 2 correspond to the same definitions as those given for the compounds of formula (I) according to the present invention.

[0340] 12 3

[0341] The intermediates of formula (IV) have the same definitions for R 1 , R 2 , R 3 , R 5 , R7 , R 8, R 9 B 1 and B 2 , as given for the compounds of formula (I) according to the present invention and their respective preferences.

[0342] In one embodiment, the intermediate compound of formula (IV) may be a compound (IV-a), wherein B 1 represents CR 10 , and B 2 represents CR 11 ; And

[0343] where R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 correspond to the same definitions as those given for the compounds of formula (I) according to the present invention.

[0344] The presence of one or more possible asymmetric carbon atoms in the compound of formula (IV) according to the present invention means that the compounds may occur in chiral isomeric forms, i.e. enantiomeric or diastereomeric forms.

[0345] According to a seventh aspect of the present invention, there is provided an intermediate compound of formula (XVIII):

[0346]

[0347] where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , IN 1 and B 2 correspond to the same definitions as those given for the compounds of formula (I) according to the present invention.

[0348] The intermediates of formula (XVIII) have the same definitions for R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , IN 1 and B2, as given for the compounds of formula (I) according to the present invention and their respective preferences. In one embodiment, the intermediate compound of formula (XVIII) may be compound (XVIII-a), where B 1represents CR 10 , and B 2 represents CR 11 ; And

[0349] where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 correspond to the same definitions as those given for the compounds of formula (I) according to the present invention.

[0350] The presence of one or more possible asymmetric carbon atoms in the compound of formula (XVIII) according to the present invention means that the compounds can occur in chiral isomeric forms, i.e. enantiomeric or diastereomeric forms.

[0351] According to an eighth aspect of the present invention, there is provided an intermediate compound of formula (XIX):

[0352]

[0353] where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8, R 9 , IN 1 and B 2 correspond to the same definitions as those given for the compounds of formula (I) according to the present invention.

[0354] The intermediates of formula (XIX) have the same definitions for R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , IN 1 and B 2 , as given for the compounds of formula (I) according to the present invention and their respective preferences. In one embodiment, the intermediate compound of formula (XIX) may be compound (XIX-a), where B 1 represents CR 10 , and B 2 represents CR 11 ; And

[0355] where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11correspond to the same definitions as those given for the compounds of formula (I) according to the present invention. In one embodiment, the intermediate compound of formula (XIX) may be compound (XIX-b)

[0356] , where R 4 is hydrogen, B 1 represents CR 10 , and B 2 represents CR 11 ; And

[0357] where R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 correspond to the same definitions as those given for the compounds of formula (I) according to the present invention. The presence of one or more possible asymmetric carbon atoms in a compound of formula (XIX) according to the present invention means that the compounds can occur in chiral isomeric forms, i.e. enantiomeric or diastereomeric forms.

[0358] According to a ninth aspect of the present invention, there is provided an intermediate compound of formula (XX):

[0359]

[0360] where R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , B 1 and B 2 correspond to the same definitions as those given for the compounds of formula (I) according to the present invention.

[0361] The intermediates of formula (XX) have the same definitions for R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , IN 1 and B2, as given for the compounds of formula (I) according to the present invention and their respective preferences.

[0362] In one embodiment, the intermediate compound of formula (XX) may be a compound (XX-a), wherein B 1 represents CR 10 , and B2 represents CR 11 ; And

[0363] where R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 correspond to the same definitions as those given for the compounds of formula (I) according to the present invention. The presence of one or more possible asymmetric carbon atoms in a compound of formula (XX) according to the present invention means that the compounds can occur in chiral isomeric forms, i.e. enantiomeric or diastereomeric forms.

[0364] Certain intermediate compounds described in the above schemes are novel and in themselves form a further aspect of the present invention.

[0365] The compounds of formula (I) according to the present invention can be prepared as shown in the following schemes 1-12, in which, unless otherwise indicated, the definition of each variable is as defined above for the compound of formula (I). In particular, the compounds of formula (I), where R 4 and R 6 represent hydrogen and R 5 represents hydrogen or methyl, can be prepared as shown in the following schemes 1-7, in which, unless otherwise indicated, the definition of each variable is as defined above for the compound of formula (I). In any of schemes 1-12 below, the presence of one or more possible asymmetric carbon atoms in a compound of formula (I) according to the present invention means that the compounds may occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms.

[0366] Compounds of formula (I) can be prepared by a person skilled in the art according to known methods. More specifically, compounds of formula (I) can be prepared from compounds of formula (III) or a salt thereof, where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , IN 1 and B 2 defined above for a compound of formula (I), by reaction with a compound of formula (II), where A 1 , A 2 , A 3 and Z 1 defined above for the compound of formula (I). This reaction is shown in Scheme 1.

[0367]

[0368] In Scheme 1, compounds of formula (II), where A 1 , A 2 , A 3 and Z 1defined above for the compound of formula (I), are 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), where X 0 is a halogen, are formed by treating compounds of formula (II) with, for example, oxalyl chloride or thionyl chloride in the presence of catalytic amounts of N,N-dimethylformamide (DMF) in inert solvents such as methylene dichloride or tetrahydrofuran (THF) at temperatures from 20°C to 100°C, preferably at 25°C. By treating compounds of formula (IIa) with compounds of formula (III), where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , IN 1 and B 2defined above for the compound of formula (I), optionally in the presence of a base, for example triethylamine or pyridine, to obtain compounds of formula (I). Alternatively, compounds of formula (I) can be prepared by treating compounds of formula (II) with dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) or 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxidehexafluorophosphate (HATU) to obtain an activated compound of formula (IIa), where X 0 represents X 01 , X 02 or X 03 , set out below, in an inert solvent, such as pyridine, DMF, acetonitrile, CH2Cl2 or THF, optionally in the presence of a base, such as triethylamine, at temperatures from 30° to 180°C. Finally, the compound of formula (II) can also be activated by reaction with a coupling reagent, such as propanephosphonic anhydride (PPA), to obtain compounds of formula (IIa), where X 0represents X 04 , as described below, for example, in Synthesis 2013, 45, 1569. Further reaction with an amine (or its salt) of the compound of formula (III) leads to the preparation of compounds of formula (I).

[0369]

[0370] Compounds of formula (IIIa), where R 4 and R 6 represent hydrogen, R 5 represents hydrogen or methyl and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , IN 1 and B 2 defined above for the compound of formula (I), can be prepared by a person skilled in the art according to known methods.

[0371] For example, compounds of formula (IIIa), where R 4 and R 6 represent hydrogen, R 5 represents hydrogen or methyl and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , IN 1 and B 2defined above for the compound of formula (I), can be prepared from compounds of formula (IVa), where R 4 and R 6 represent hydrogen, R 5 represents hydrogen or methyl and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , B 1 and B 2defined above for a compound of formula (I), by treatment with a reducing agent such as NaBH3CN and an acid, for example hydrochloric acid or acetic acid, in a protic solvent such as methanol or ethanol, etc. Such reactions are widely known in the literature and similar reactions have been described, for example, in Deng, Zepmg et al., CN 103772278, 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 diphosphine [1,2-bis(diphenylphosphino)eztane (dppe), 1,3-bis(diphenylphosphino)propane (dppp) or 1,4-bis(diphenylphosphino)butane (dppb)]. Similar reactions have been described, for example, in Reaction Kinetics and Catalysis Letters (2007), 92, 99–104. This reaction is shown in Scheme 2.

[0372]

[0373] Alternatively, compounds of formula (IIIa) can be prepared as shown in Scheme 4.

[0374] As shown in Scheme 3, compounds of formula (IIIb), where R 4 , R 6 and R 7 represent hydrogen, R 5 represents hydrogen or methyl and R 1 , R 2 , R 3 , R 8 , R 9 , B 1 and B 2 defined above for the compound of formula (I), can be converted into compounds of formula (V), where R 4 , R 6 and R 7 represent hydrogen, R 5 represents hydrogen or methyl and R 1 , R 2 , R 3 , R 8 , R 9 , IN 1 and B 2 defined above for the compound of formula (I), by treating compounds of formula (IIIb) with a compound of formula (VI), where X 0 is a leaving group such as halogen, and R 0is C1-C4 alkyl, by methods known to those skilled in the art and the methods described in Scheme 1. Alternatively, compounds of formula (V) can be prepared by treatment with an anhydride of formula (R 0 CO)2O, where R 0 is C1-C4 alkyl, in an inert solvent such as methylene chloride, THF or 2-methyl-TEP, optionally in the presence of a base such as triethylamine or dimethylaminopyridine, at temperatures from 0°C to 60°C. The compounds of formula (V) are then subjected to a metalation reaction with a base, for example an alkyl metal base such as tert-butyl lithium, and an additive such as N,N,N',N'-tetramethylethylenediamine (TMEDA) at low temperature, for example at a temperature from -78°C to room temperature, in an inert polar solvent such as THF or 2-methyl-TNA. Subsequent treatment of the anion of formula (V) formed under such conditions with an electrophile of formula R X -X 0 , where X 0defined earlier and R X represents C1-C4 alkyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, N-methoxy-N-methylcarbonyl, C1-C4 alkylaminocarbonyl, di(C1-C4 alkylamino)carbonyl or C3-C6 cycloalkyl, wherein C3-C6 cycloalkyl is optionally substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl and C1-C4 alkoxy, resulting in compounds of formula (Va), where R 4 and R 6 represent hydrogen, R 5 represents hydrogen or methyl, R 0 represents C1-C4 alkyl and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , IN 1 and B 2 defined above for the compound of formula (I). This reaction is shown in Scheme 3.

[0375]

[0376] Compounds of formula (Va) can be converted into compounds of formula (IIIa), where R 4 and R 6 represent hydrogen, R5 represents hydrogen or methyl and R 1 , R 2 , R 3 , R 7 ,R 8 , R 9 , B 1 and B 2 defined above for the compound of formula (I), by methods known to those skilled in the art. For example, compounds of formula (Va), where R 0 is tert-butyl, can be treated with an organic or inorganic acid, such as trifluoroacetic acid or HCl, to give compounds of formula (IIIa). This reaction is shown in Scheme 4.

[0377]

[0378] Compounds of formula (IVa), where R 4 and R 6 represent hydrogen, R 5 represents hydrogen or methyl and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , IN 1 and B 2defined above for the compound of formula (I), can be obtained by reacting compounds of formula (VIII), where R 1 , R 2 and R 3 defined above for the compound of formula (I) and X 0 is a halogen, preferably chlorine, bromine or iodine, with compounds of formula (VII), where R 5 represents hydrogen or methyl and R 7 , R 8 , R 9 , IN 1 and B 2 defined above for the compound of formula (I), by a C-C bond formation reaction, typically under palladium-catalyzed (alternatively nickel-catalyzed) cross-coupling conditions. This reaction is shown in Scheme 5.

[0379]

[0380] Suzuki-Miyaura cross-coupling reactions between compounds of formula (VIII) and a compound of formula (VH) are well known to those skilled in the art and are typically carried out in the presence of a palladium catalyst such as tetrakis(triphenylphosphine)-palladium(0) or [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane complex and a base such as sodium or potassium carbonate in a solvent such as N,N-dimethylformamide, dioxane or dioxane-water mixtures at temperatures from room temperature to 160°C, optionally under microwave heating and preferably under an inert atmosphere. Such reactions have been discussed, for example, in J. Organomet. Chem. 576, 1999, 147-168. It will also be clear to one skilled in the art that the reaction can be reversed, i.e., by reacting a compound of formula (X), where R 1 , R 2 and R 3defined above for the compound of formula (I), with the compound of formula (IX), where R 5 represents hydrogen or methyl, R 7 , R 8 , R 9 , IN 1 and B 2 defined above for the compound of formula (I) and X 0 is a halogen, preferably chlorine, bromine or iodine, to obtain a compound of formula (IVa), where R 4 and R 6 represent hydrogen, R 5 represents hydrogen or methyl and R 1 , R 2 , R 3 , R 5 , R 7 , R 9 , B 1 and B 2 defined above for the compound of formula (I). This reaction is shown in Scheme 6.

[0381]

[0382] Additional cross-coupling chemistry, namely C-H activation, can also be used to prepare compounds of formula (IVa), where R 4 and R 6 represent hydrogen, R 5represents hydrogen or methyl and R 1 , R 2 , R 3 , R 7 , R 8 , R 9 , IN 1 and B 2 defined above for the compound of formula (I). This reaction is shown in Scheme 7.

[0383]

[0384] As shown in Scheme 7, compounds of formula (IX), where R 5 represents hydrogen or methyl, R 7 , R 8 , R 9 , IN 1 and B2 are defined above for the compound of formula (I) and X 0 is a halogen, preferably chlorine, bromine or iodine, is reacted with compounds of formula (XI), where R 1 , R 2 and R 3defined above for the compound of formula (I), in the presence of a palladium catalyst, typically palladium acetate Pd(OAc)-, a suitable ligand, for example 1,10-phenanthrolene, in the presence of a base such as cesium carbonate or potassium carbonate, in inert solvents such as chlorobenzene, toluene or xylene, at temperatures from room temperature to 180°C, optionally under microwave heating, preferably under an inert atmosphere. Similar reactions have been described in the literature, for example, in Chemical Science (2013), 4, 2374-2379.

[0385] Compounds of formula (III) can also be prepared from compounds of formula (XVI). This reaction is shown in Scheme S.

[0386]

[0387] As shown in Scheme 8, the compounds of formula (III) can be prepared by a person skilled in the art through a reaction of removing the carbamate protecting group of compounds of formula (XVI), where R 1 , R 2 , R3 , R 4 , R 3 , R 6 , R 7 , R 8 , R 9 , IN 1 and B2 are defined above for the compound of formula (1) and R 01 may be a member of a general substituent of a carbamate protecting group, such as methyl, tert-butyl, allyl, 2,2,2-trichloroethyl, or benzyl. For example, if R 01 is methyl, a suitable solvent such as dichloromethane and a suitable reagent such as iodotrimethylsilane can be used for the preparation, with heating at temperatures from room temperature to 200°C, preferably from 20°C to the boiling point of the reaction mixture, as described, for example, in Journal of the American Chemical Society 1992, 114, 5959. Compounds of formula (III) obtained in this way are converted to compounds of formula (I), as shown in Scheme 1. Compounds of formula (XVI), where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R9 , IN 1 and B 2 defined above for the compound of formula (1) and where R01 is described above, can be formed by means of the Pictet-Spengler reaction between an aldehyde (including formaldehyde in its various forms) of formula (XV), where R 7 defined above for the compound of formula (I), and the compound of formula (XIV), where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , IN 1 and B 2 defined above for the compound of formula (I) and where R 01 described above, by combining with an acid in a suitable solvent, for example as described in Tetrahedron 1987, 43, 439. This reaction is shown in Scheme 9.

[0388]

[0389] Compounds of formula (XIV), where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , IN 1 and B 2defined above for the compound of formula (I) and where R 01 described above, can be obtained by reaction between amines of formula (XIII), where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , IN 1 and B 2 defined above for the compound of formula (I), and a suitable protecting reagent such as methyl chloroformate, optionally in the presence of a base such as triethylamine or pyridine, in a suitable solvent such as dichloromethane, at temperatures from -20°C to the boiling point of the mixture, as described, for example, in Organic & Biomolecidar Chemistry 201614, 6853. This reaction is shown in Scheme 10.

[0390]

[0391] Compounds of formula (XIII) or their salts, where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , IN 1 and B 2defined above for the compound of formula (I), can be prepared by a person skilled in the art by reaction between nitriles of formula (XII), where R 1 , R 2 , R 3 , R 4 , R 8 , R 9 , B1 and B2 are as defined above for the compound of formula (I), and a suitable nucleophile such as (dimethyl sulfide)dihydroborone (BMS), in a suitable aprotic solvent such as tetrahydrofuran, for example as described in The Journal of Organic Chemistry 1981 47, 3153. Alternatively, Grignard reagents, R 5 MgBr or R 6 MgBr, where R 5 and R 6defined above for the compound of formula (I), can be added as nucleophiles to compounds of formula (XII), sequentially or simultaneously, to provide amines of formula (XIII) with a higher degree of substitution. Such Grignard additions to nitriles are carried out in an inert solvent such as diethyl ether, tert-butyl methyl ether and cyclopentyl methyl ether, in the presence of a Lewis acid such as Ti(O- i Pr)4(see Spnlett (2007), (4), 652–654). This reaction is shown in Scheme 11.

[0392]

[0393] Compounds of formula (XII), where R 1 , R 2 , R 3 , R 4 , R 8 , R 9 , IN 1 and B 2defined above for the compound of formula (I), can be prepared by a person skilled in the art according to known methods. More specifically, compounds of formula (XII) in which intermediates can be prepared from compounds of formula (XVII), as shown in Scheme 12.

[0394]

[0395] For example, compounds of formula (XII), where R 1 , R 2 , R 3 , R 8 , R 9 , IN 1 and B 2 defined above for the compound of formula (I) and R 4 is other than hydrogen, can be obtained by a person skilled in the art by deprotonating a compound of formula (XIIa), where R 4 represents hydrogen and R 1 , R 2 , R 3 , R 8 , R 9 , IN 1 and B 2defined above for the compound of formula (I), using a strong base such as n-butyl lithium or sodium hydride at cryogenic temperatures in an inert solvent such as tetrahydrofuran, followed by the addition of a suitable alkylating agent R 4 -X, where X is a halogen, such as iodomethane.

[0396] Compounds of formula (XIIa), where R 4 represents hydrogen and R 1 , R 2 , R 3 , R 8 , R 9 , IN 1and B as defined above for the compound of formula (I), can 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 from 0°C to the boiling point of the reaction mixture. Such transformations are widely known in the literature under various conditions, for example as described in Organic Letters 2008 10, 4570, and the references cited therein. This reaction is shown in Scheme 12.

[0397] Alternatively, compounds of formula (III), wherein R 1 , R 2 , R 3 , R 4 , R 8 , R 9 , B 1 and B 2 defined above for the compound of formula (I), can be prepared from compounds of formula (XVIII), compounds of formula (XIX) or a compound of formula (XX), as shown in Scheme 13.

[0398]

[0399] The intermediate compounds of formulas (XVIII), (XIX), and (XX) are novel and in themselves form a further aspect of the present invention. Compounds of formula (III) can be prepared by treating compounds of formula (XVIII), where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , IN 1 and B 2 correspond to the same definitions as those given for the compounds of formula (I) according to the present invention, a strong acid. For example, compounds of formula (III), where B 1 represents CR 10 , IN 2 represents CR 11 , R 1 is C1-C4 alkyl, R 2 represents hydrogen, halogen or C1-C4 alkyl, R 3 represents hydrogen, R 4 , R 5 , R 6 R 7 represent hydrogen or C1-C4 alkyl and R 8 , R 9 , R 10 and R11 defined earlier in formula (I), namely, compounds of formula (III-c) can be obtained by treating compounds of formula (XVIII-a)

[0400]

[0401] where R 1 is C1-C4 alkyl, R 2 represents hydrogen, halogen or C1-C4 alkyl, R 3 represents hydrogen, R 4 represents hydrogen or C1-C4 alkyl, R 5 , R 6 , R 7 represent hydrogen or C1-C4 alkyl and R 8 , R 9 , R 10 and R 11defined previously in formula (I), with strong acids, such as sulfuric, hydrochloric, hydrobromic, trifluoroacetic, trifluoromethanesulfonic or methanesulfonic acids, etc., or Lewis acids such as aluminum chloride or bismuth(III) triflate, in an inert solvent such as chlorobenzene, nitrobenzene, at a temperature from 0°C to 180°C to obtain compounds of formula (IIIc). Such compounds are converted to compounds of formula (I) as previously described vide supra.

[0402] One skilled in the art will appreciate that such cyclization procedures can be carried out using intermediate compounds such as compounds of formula (XIX). For example, compounds of formula (III-c), where B 1 represents CR 10 , IN 2 represents CR 11 , R 1 is C1-C4 alkyl, R 3 represents hydrogen, halogen, or C1-C4 alkyl, R represents hydrogen, R 4 , R 5, R 6 R 7a represent hydrogen or C1-C4 alkyl and R 8 , R 9 , R 10 and R 11 defined previously in formula (I) can be prepared by a cyclization procedure using intermediate compounds such as compounds of formula (XIX-a), where R 1 is C1-C4 alkyl, R 2 represents hydrogen, halogen or C1-C4 alkyl, R 3 represents hydrogen, R 4 represents hydrogen or C1-C4 alkyl, R 5 , R 6 , R 7 represent hydrogen or C1-C4 alkyl and R 8 , R 9 , R 10 and R 11 defined earlier in formula (I).

[0403]

[0404] Alternatively, compounds of formula (III), where R 4 is methyl and R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , IN1 and B 2 correspond to the same definitions as those given for compounds of formula (I), can be obtained by treating compounds of formula (XVIII), where R 4 is methyl and R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , IN 1 and B 2 correspond to the same definitions as those given for the compounds of formula (I) according to the present invention, by treatment with a strong acid, and such a cyclization procedure can be carried out using intermediates such as compounds of formula (XX), where R 4 is methyl and R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , IN 1 and B 2correspond to the same definitions as those given for the compounds of formula (I) according to the present invention. For example, compounds of formula (III-c), where B 1 represents CR 10 , IN 2 represents CR 11 , R 1 is C1-C4 alkyl, R 2 represents hydrogen, halogen or C1-C4 alkyl, R 3 represents hydrogen, R 4 is methyl, R 5 , R 6 R 7a represent hydrogen or C1-C4 alkyl and R 8 , R 9 , R 10 and R 11 defined previously in formula (I) can be prepared using intermediate compounds such as compounds of formula (XX-a), where R 1 is C1-C4 alkyl, R 2 represents hydrogen, halogen or C1-C4 alkyl, R 3 represents hydrogen, R 4 is C1-methyl, R 5 , R 6 , R 7represent hydrogen or C1-C4 alkyl and R 8 , R 9 , R 10 and R 11 defined earlier in formula (I),

[0405]

[0406] and where are the R substituents 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 in such compounds have been described previously.

[0407] Depending on the reaction conditions, such intermediates can be further isolated and / or converted directly to compounds of formula (III). One skilled in the art will also appreciate that if R 7 is a C1-C4 alkyl, mixtures of the racemic-(syn-IIIc) and racemic-(anti-IIIc) diastereoisomers can be prepared in ratios that can be controlled to directly preferentially form one isomer over the other (Scheme 13).

[0408] Compounds (XVIII), (XIX) and (XX), where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , IN 1 and B 2 correspond to the same definitions as those given for the compounds of formula (I) according to the present invention, can be obtained from compounds of formula (XXI), which can be easily obtained or commercially available from persons skilled in the art.

[0409] For example, compounds of formula (XVIII-a) and (XIX-a), where R 1 is C1-C4 alkyl, R 2 represents hydrogen, halogen or C1-C4 alkyl, R 3 represents hydrogen, R 4 represents hydrogen or C1-C4 alkyl, R 5 , R 6 , R 7 represent hydrogen or C1-C4 alkyl and R 8 , R 9 , R 10 and R 11defined previously in formula (I), can be prepared as shown in the following scheme 14, by Friedel-Crafts acylation followed by a Grignard reaction and cyclization, and as described in the experimental section. Alternatively, compounds of formula (XVIII-b) and (XIX-b), where R 1 is C1-C4 alkyl, R is hydrogen, halogen, or C1-C4 alkyl, R 3 represents hydrogen, R 4 represents hydrogen, R 5 , R 6 , R 7 represent hydrogen or C1-C4 alkyl and R 8 , R 9 , R 10 and R 11 defined previously in formula (I) can be prepared by Friedel-Crafts acylation followed by reduction using a hydride source such as sodium borohydride and by cyclization as shown in the following Scheme 14 and as described in the experimental section.

[0410]

[0411] As shown in Scheme 14, benzylamine has formula (XXI), where R 7 , R 8 , R 9 , R 10 and R 11correspond to the same definitions as those given for the compounds of formula (I) according to the present invention, are used to alkylate a compound of formula (XXII) in the presence of a base such as triethylamine (Et3N) in an inert solvent such as DMF or DMA. Compound (XXIII) obtained in this manner can be isolated or treated directly with BOC anhydride (Boc2-O) in situ to give a compound of formula (XXIV). Compound of formula XXIV can be reduced using a hydride source such as sodium tetrahydroborate (NaBH4) in MeOH / THF to give the target molecule (XVIII-b), which can then be cyclized, for example with an acid, for example camphorsulfonic acid (CSA), in a solvent such as ethyl acetate (EtOAc), to give compounds of formula (XIX-b). Alternatively, compounds of formula (XXIV) can be reacted with a Grignard reagent, R 4 MgBr, where R 4is C1-C4 alkyl, in an inert ether solvent such as THF 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 represents hydrogen, halogen or C1-C4 alkyl, R 4 represents hydrogen or C1-C4 alkyl, R 5 , R 6 and R 7 represent hydrogen or C1-C4 alkyl and R 8 , R 9 , R 10 and R 11 defined earlier in formula (I).

[0412] An additional aspect of this Friedel-Crafts reaction should be mentioned. If the chemical reaction is carried out starting from a chiral amine (XXI-a), where R 7 represents C1-C4 alkyl and R 8 , R 9 , R 10 and R 11correspond to the same definitions as those given for the compounds of formula (I) according to the present invention, the stereochemistry in compound (III-d) is preserved, where R 7 represents 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 correspond to the same definitions as those given for compounds of formula (I) and also for the final compounds of formula (I). This is illustrated below in Scheme 15 for the case when R 7 is methyl.

[0413]

[0414] Compounds of formula (II) are commercially available or are readily prepared from 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 are readily prepared by those skilled in the art or are commercially available.

[0415] Salts of the compounds of formula (I) can be prepared in a manner known per se. Thus, for example, acid addition salts of the compounds of formula (I) are prepared by treatment with a suitable acid or a suitable ion exchange reagent, and salts with bases are prepared by treatment with a suitable base or a suitable ion exchange reagent.

[0416] Salts of compounds of formula (I) can be converted in a standard manner into free compounds (I), acid addition salts, for example, by treatment with a suitable basic compound or a suitable ion exchange reagent, and salts with bases, for example, by treatment with a suitable acid or a suitable ion exchange reagent.

[0417] Salts of the compounds of formula (I) can be converted in a manner known per se into other salts of the compounds of formula (I), acid addition salts, for example into other acid addition salts, for example by treating a salt of an inorganic acid, such as a hydrochloride, with a suitable metal salt of the acid, such as a sodium, barium or silver salt, for example silver acetate, in a suitable solvent in which the inorganic salt that is formed, for example silver chloride, is insoluble and thus precipitates from the reaction mixture. Depending on the procedure or reaction conditions, compounds of formula (I) that have salt-forming properties can be obtained in free form or in the form of salts.

[0418] The compounds of formula (I) and, where applicable, the tautomers thereof, in each case in free form or in salt form, may be present in the form of one of the possible isomers or as a mixture thereof, for example, in the form of pure isomers, such as antipodes and / or diastereomers, or as mixtures of isomers, such as mixtures of enantiomers, for example racemates, mixtures of diastereomers or mixtures of racemates, depending on the number, absolute and relative configuration of the asymmetric carbon atoms present in the molecule and / or depending on the configuration of the non-aromatic double bonds present in the molecule; the present invention relates to pure isomers as well as to all possible mixtures of isomers, and is to be understood in each case above and below herein in this sense, even if the stereochemical details have not been specifically mentioned in each case.

[0419] Diastereomeric mixtures or racemic mixtures of compounds of formula (I) in free form or in salt form, which can be obtained depending on which starting materials and procedures have been chosen, can be separated in a known manner into pure diastereomers or racemates on the basis of physicochemical differences of the components, for example, by fractional crystallization, distillation and / or chromatography.

[0420] Enantiomeric mixtures, such as racemates, which can be obtained in a similar manner, can be separated into optical antipodes by known methods, for example, by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example, by high performance liquid chromatography (HPLC) on cellulose acetate, by suitable microorganisms, by cleavage with specific immobilized enzymes, by forming inclusion compounds, for example, using chiral crown ethers, wherein only one enantiomer participates in the formation of a complex, or by conversion into diastereomeric salts, for example, by reacting a racemate of the major end product with an optically active acid, such as a carboxylic acid, for example, camphoric, tartaric, or malic acid, or a sulfonic acid, for example, camphorsulfonic acid, and separating the mixture of diastereomers that can be obtained by so in a way,for example, by fractional crystallization based on their different solubilities to produce diastereomers from which the desired enantiomer can be liberated by the action of suitable means, such as basic agents.

[0421] Pure diastereomers or enantiomers can be obtained according to the present invention not only by separating suitable mixtures of isomers, but also by well-known methods of diastereoselective or enantioselective synthesis, for example, by carrying out the method according to the present invention with starting materials of the appropriate stereochemical configuration. It is advantageous to isolate or synthesize in each case the biologically more effective isomer, for example, an enantiomer or diastereomer, or a mixture of isomers, for example, a mixture of enantiomers or a mixture of diastereomers, if the individual components are characterized by different biological activities.

[0422] As an example, compounds with more than one asymmetric carbon atom may exist in diastereomeric forms, which can optionally be separated using, for example, supercritical fluid chromatography (SFC) or chromatography using chiral columns. 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 illustrated in the scheme below (Scheme 16).

[0423]

[0424] The compounds of formula (I) and, where appropriate, its tautomers, in each case in free form or in salt form, may also be obtained, if desired, in the form of hydrates and / or may contain other solvents, such as those that could be used for the crystallization of the compounds present in solid form.

[0425] As already mentioned, it has now been unexpectedly discovered that the compounds of formula (I) according to the present invention are characterized, in terms of practical expediency, by a very effective level of biological activity for protecting plants from diseases caused by fungi. The compounds of formula (I) according to the present invention can be used in agriculture and related fields, for example, as active ingredients for the control of plant pests or on non-living materials for the control of spoilage microorganisms or organisms potentially harmful to humans. The new compounds are characterized by excellent activity at low application rates, while they are well tolerated by plants and are safe for the environment. They are characterized by very useful therapeutic, prophylactic and systemic properties, and they can be used to protect a variety of cultivated plants.Compounds of formula (I) can be used to suppress or destroy pests that occur on plants or parts of plants (fruits, flowers, leaves, stems, tubers, roots) of various agricultural crops of useful plants, while simultaneously protecting those parts of plants that develop later, for example, from phytopathogenic microorganisms.

[0426] The present invention further relates to a method for controlling or preventing the infestation of plants or plant propagation material and / or harvested food crops susceptible to attack 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 present invention is applied to the plants, their parts or their growing site. Also, the compound of formula (I) according to the present invention can be used as a fungicide. The term "fungicide" as used herein means a compound that controls, modifies or prevents the growth of fungi.The term "fungicidally effective amount," when used, means the amount of a compound or combination of compounds capable of producing an effect on fungal growth. Controlling or modifying effects include all deviations from natural development, such as destruction, growth inhibition, etc., and prevention includes a barrier or other protective formation in or on a plant to prevent infection caused by fungi.

[0427] The compounds of formula (I) according to the present invention can also be used as dressing agents for treating plant propagation material, such as seeds, for example fruits, tubers, or grains, or plant shoots, to protect against infections caused by fungi, as well as against phytopathogenic fungi found in the soil. The propagation material can be treated with a composition containing a compound of formula (I) before planting: the seed, for example, can be dressed before sowing. The active compounds of formula (I) can also be applied to grains (coating), either by impregnating the seeds with a liquid composition or by coating them with a solid composition. The composition can also be applied to the planting site when planting the propagation material, for example, to the seed furrow when sowing.The present invention also relates to such methods for treating plant propagation material and to the plant propagation material treated in this manner. Furthermore, the compounds of formula (I) according to the present invention can be used to control fungi in related fields, for example, in the protection of technical materials, including wood and wood-related technical products, in the storage of food products, and in the organization of sanitization. Furthermore, the present invention can be used to protect non-living materials from fungal attack, for example, lumber, cladding boards, and paint. The compounds of formula (I) according to the present invention are, for example, effective against fungi and fungal disease vectors, as well as against phytopathogenic bacteria and viruses. These fungi and fungal disease vectors, as well as phytopathogenic bacteria and viruses, are, for example,

[0428] Absidia corymbifera, Alternaria spp., including Alternaria solani, Aphanomyces spp., Ascochyta spp., Aspergillus spp., including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terms, Aureobasidium spp., including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lattucae, Botryosphaeria spp., including B. dothidea, V. obtusa, Botryotinia fuckeliana, Botrytis spp., including Botrytis cinerea, Candida spp., including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans, Ceratocystis spp., Cercospora spp., including Cercospora arachidicola, Cercospora kikuchii, Cercospora sojina, Cercosporidium personatum, Cladosporium spp., including Cladosporium cucumerinum, Claviceps purpurea, Coccidioides immitis, Cochliobolus spp., Colletotrichum spp., including Colletotrichum musae, Colletotrichum asianum, Corynespora cassiicola, Cryptococcus neoformans, Diaporthe spp., Didymella spp., including Didymella bryoniae, Drechslera spp., Elsinoe spp., Epidermophyton spp., Erwinia amylovora, Erysiphe spp., including Erysiphe cichoracearum, Eutypa lata, Fusarium spp., including Fusarium culmorum, Fusarium graminearum, Fusarium langsethiae, Fusarium moniliforme, Fusarium oxysporum, Fusarium proliferatum, Fusarium subglutinans, 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, Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp., including Mycosphaerella graminicola, Mycosphaerella pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp., Penicillium spp., including P. digitatum, P.italicum, Petriellidium spp., Peronosclerospora spp., including P. maydis, P. philippinensis and P. sorghi, Peronospora spp., Phaeosphaeria nodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp., Phoma spp., Phomopsis viticola, Phytophthora spp., including 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, P. humuli, Pseudopeziza tracheiphila, Puccinia spp., including Puccinia hordei, Puccinia recondita, Puccinia striiformis, Puccinia triticina, Pyrenopeziza spp., Pyrenophora spp., including Pyrenophora teres, Pyricularia spp., including 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., Septoria spp., including Septoria nodorum, Septoriatritici, 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, T. viride, Trichophyton spp., Typhula spp., Uncinula necator, Urocystis spp., Ustilago spp., Venturia spp., including Venturia inaequalis, Verticillium spp. and Xanthomonas spp. The compounds of formula (I) according to the present invention can be used, for example, in relation to turf, ornamental plants such as flowers, shrubs, broad-leaved trees or evergreen plants such as conifers, and also for injection into trees, pest control, etc.

[0429] Within the scope of the present invention, target crops and / or useful plants to be protected typically include perennial and annual crops such as berry plants, such as varieties of blackberries, blueberries, cranberries, raspberries and strawberries; cereals, such as barley, maize (corn), millet, oats, rice, rye, sorghum, triticale and wheat; fiber plants, such as cotton, flax, hemp, jute and sisal; field crops, such as sugar beet, fodder beet, coffee tree, hops, mustard, oilseed rape (canola), poppy, sugarcane, sunflower, tea bush and tobacco; Fruit trees such as apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear, and plum; Grasses such as Bermuda grass, Kentucky bluegrass, bentgrass, Eremochloa serpentina, fescue, ryegrass, St. Augustine's grass, and Zoysia japonica;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; Palm trees 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, onions, peppers, potatoes, pumpkins, rhubarb, spinach, and tomatoes; as well as grape crops, such as grape varieties.;

[0430] The term "useful plants" shall be understood to also include useful plants that have been rendered tolerant to herbicides like bromoxynil or to classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors such as primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen oxidase) inhibitors) as a result of conventional breeding methods or genetic engineering. An example of an agricultural crop that has been rendered tolerant to imidazolinones, such as imazamox, by conventional breeding methods (mutagenesis) is Clearfield® rapeseed (canola).Examples of crops that have been genetically engineered to be tolerant to herbicides or classes of herbicides include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I*, and LibertyLink®.

[0431] The term "useful plants" shall be understood to also include useful plants that have been transformed by the use of recombinant DNA techniques in such a way that they have become capable of synthesizing one or more selectively acting toxins, such as those known, for example, from toxin-forming bacteria, in particular bacteria of the genus Bacillus.

[0432] Examples of such plants are: YieldGard* (maize variety expressing CryIA(b) toxin); YieldGard Rootworm* (maize variety expressing CryIIIB(b1) toxin); YieldGard Plus* (maize variety expressing CryIA(b) toxin and CryIIIB(b1) toxin); Starlink* (maize variety expressing Cry9(c) toxin); Herculex I* (maize variety expressing CryIF(a2) toxin and phosphinothricin N-acetyltransferase (PAT) enzyme to provide tolerance to the herbicide glufosinate ammonium); NuCOTN 33B* (cotton variety expressing CryIA(c) toxin); Bollgard I* (cotton variety expressing CryIA(c) toxin); Bollgard II® (cotton variety expressing CryIA(c) toxin and CryIIA(b) toxin); VIPCOT* (cotton variety expressing VIP toxin); NewLeaf* (potato variety expressing CryIIIA toxin);Nature-Gard* Agrisure® GT Advantage (GA21 with glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 with resistance to European corn borer (CB)), Agrisure® RW (with resistance to western corn rootworm) and Protecta*. The term "crops" shall be understood to also include crop plants that have been transformed by recombinant DNA techniques so that they have become capable of synthesizing one or more selectively acting toxins, such as those known, for example, from toxin-producing bacteria, in particular bacteria of the genus Bacillus.

[0433] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins of Bacillus cereus or Bacillus popilliae; or insecticidal proteins of 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 of bacteria colonizing nematodes, for example, Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome inactivating proteins (RIPs), such as ricin, maize RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP glycosyltransferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA reductase, ion channel blockers such as sodium or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, dibenzyl synthase, chitinases and glucanases.Furthermore, in the context of the present invention, 5-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), such as Vip1, Vip2, Vip3 or Vip3A, are to be understood to include in particular also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly using a new combination of different domains of such proteins (see, for example, WO 02 / 15701). Truncated toxins are known, such as truncated Cry1Ab. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid substitutions, sequences recognized by proteases that are not present in the natural toxin are preferably introduced into the toxin, as, for example, in the case of Cry3A055, a sequence recognized by cathepsin G is introduced into the Cry3A toxin (see WO 03 / 018810).Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-A-0374753, WO93 / 07278, W095 / 34656, EP-A-0427529, EP-A-451878 and WO 03 / 052073.

[0434] Methods for producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their production are known, for example, from WO 95 / 34656, EP-A-0367474, EP-A-0401979 and WO 90 / 13651.

[0435] A toxin contained in transgenic plants confers tolerance to harmful insects. These insects can belong to any taxonomic group of insects, but are particularly common among beetles (Coleoptera), dipterans (Diptera), and butterflies (Lepidoptera). Transgenic plants containing one or more genes encoding insect resistance and expressing one or more toxins are known, some of which are commercially available.Examples of such plants are the following: YieldGard* (maize variety expressing the Cry1Ab toxin); YieldGard Rootworm* (maize variety expressing the Cry3Bb1 toxin); YieldGard Plus* (maize variety expressing the Cry1Ab and Cry3Bb1 toxin); Starlink* (maize variety expressing the Cry9C toxin); Herculex I* (maize variety expressing the Cry1Fa2 toxin and the phosphinothricin M-acetyltransferase (PAT) enzyme, achieving tolerance to the herbicide glufosinate ammonium); NuCOTN 33B* (cotton variety expressing the Cry1Ac toxin); Bollgard I* (cotton variety expressing the Cry1Ac toxin); Bollgard II® (cotton variety expressing the Cry1Ac and Cry2Ab toxins); VipCot* (cotton variety expressing Vip3A toxin and Cry1Ab); NewLeaf* (potato variety expressing Cry3A toxin); Nature-Gard*, Agrisure® GT Advantage (GA21 with glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 with European corn borer (CB) resistance trait), and Protecta*.Additional examples of such transgenic crops include the following.

[0436] 1. Bt11 maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified Zea mays rendered resistant to European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. Btl 1 maize also transgenically expresses the PAT enzyme to confer tolerance to the herbicide glufosinate ammonium.

[0437] 2. Maize Btl76 from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified Zea mays, which was given resistance to infestation by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) through transgenic expression of the Cry1Ab toxin. Maize Bt176 also transgenically expresses the PAT enzyme, providing tolerance to the herbicide glufosinate ammonium.

[0438] 3. Maize MIR604 from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. Maize conferred insect resistance through transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin G protease recognition sequence. The production of such transgenic maize plants is described in WO 03 / 018810.

[0439] 4. Maize MON 863 from Monsanto Europe SA 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses the Cry3Bb1 toxin and has resistance to certain insects from the order Coleoptera.

[0440] 5. Cotton IPC 531 from Monsanto Europe SA 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0441] 6. Maize 1507 from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Genetically modified maize expressing the Cry1F protein to achieve resistance to certain insects from the order Lepidoptera and the PAT protein to achieve tolerance to the herbicide glufosinate ammonium.

[0442] 7. Maize NK603 × MON 810 from Monsanto Europe SA 270-272 Avenue de Tervuren, B 1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. Consists of hybrid maize varieties conventionally bred by crossing the genetically modified varieties NK603 and MON 810. Maize NK603 × MON 810 transgenically expresses the CP4 EPSPS protein obtained from Agrobacterium sp., strain CP4, which confers tolerance to the herbicide Roundup® (contains glyphosate), as well as the Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki, which confers tolerance to certain representatives of the order Lepidoptera, including the European corn borer.

[0443] The compounds of formula (I) according to the present invention can be used in the control or prevention of phytopathogenic diseases, especially those caused by phytopathogenic fungi such as Alternaria solani, Blumeria graminis, Botryotinia fuckeliana, Botrytis cinerea, Cercospora arachidicola, Cercospora kikuchii, Cercospora sojina, Cladosporium cucumerinum, Colletotrichum lagenarium, Corynespora cassiicola, Didymella bryoniae, Fusarium spp, Glomerella lagenarium, Leptosphaeria spp, Leveillula taurica, Microdochium nivale, Plasmopara viticola, Puccinia recondita, Pyrenophora teres, Pyricularia oryzae, Rhizoctonia solani, Sclerotinia sclerotiorum, Septoria nodorum, Septoriatritici, Sphaerotheca fuliginea, Uncinula necator and Venturia inaequalis. In one embodiment of the present invention, the compounds of formula (I) according to the present invention can be used in the control or prevention of phytopathogenic diseases, especially those caused by phytopathogenic fungi,such as Septoria tritici, Pyrenophora teres, Puccinia recondita and Blumeria graminis in cereals; Cercospora arachidicola and Sclerotinia sclerotiorum in field crops; Alternaria solani in fruits and vegetables, such as tomatoes and potato varieties; Botrytis cinerea in fruits, vegetables and field crops, such as strawberry varieties, tomatoes, sunflowers, legumes and grape varieties; Glomerella lagenarium in vegetables, such as cucumbers; Uncinula necator in vegetables, such as grape varieties; Venturia inaequalis in fruits, such as apples; Rhizoctonia solani in vegetables, such as potato varieties; Cladosporium cucumerinum, Didymella bryoniae, and Sphaerotheca fuliginea in vegetables such as cucumbers; Leveillula taurica in cucumbers and nightshade vegetables; Fusarium spp in cereals and vegetables; Leptosphaeria spp in cereals.

[0444] The term "growing place" as used herein means fields in or on which plants are grown, or where the seeds of cultivated plants are sown, or where the seeds will be placed in the soil. It includes soil, seeds and seedlings, as well as established vegetation. The term "plants" means all physical parts of a plant, including seeds, seedlings, shoots, roots, tubers, stems, petioles, leaves, and fruits. The term "plant propagation material" is understood to mean the generative organs of a plant, such as seeds, which can be used for propagation, and vegetative material, such as sprouts or tubers, for example, of potatoes. In this case, mention may be made, for example, of seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes, and parts of plants. Also mentioned may be germinated plants and young plants that need to be transplanted after germination or after emerging from the soil.These young plants can be protected before replanting by complete or partial immersion treatment. Preferably, "plant propagation material" should be understood to mean seeds.

[0445] The compounds of formula (I) according to the present invention can be used in unmodified form or, preferably, together with auxiliaries conventionally used in the field of formulation. In this regard, for the sake of convenience, they can be formulated using a known method into emulsifiable concentrates, pastes applied as coatings, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granules, as well as encapsulated forms, for example, in polymeric substances. As in the case of the type of composition, the application methods, such as spraying, fine spraying, dusting, scattering, coating or pouring, are selected in accordance with the intended purposes and the prevailing conditions.The compositions may also contain additional auxiliary substances such as stabilizers, antifoaming agents, viscosity regulators, binders or tackifiers, as well as fertilizers, microelement donors or other compounds to achieve special effects.

[0446] Suitable carriers and auxiliaries, for example for agricultural use, can be solid or liquid and are substances useful in formulation technology, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are described, for example, in WO 97 / 33890. Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations include anti-settling agents and dispersing agents and may additionally include a wetting agent to enhance activity, as well as an anti-foaming agent and a crystal growth inhibitor. When used, these concentrates are diluted with water and typically applied as a spray to the area to be treated.The amount of active ingredient can vary from 0.5% to 95% concentrate.

[0447] Wettable powders are finely divided particles that disperse readily in water or other liquid carriers. The particles contain the active ingredient held in a solid matrix. Typical solid matrices include fuller's earth, kaolin clays, silica varieties, and other readily wettable organic or inorganic solids. Wettable powders typically contain from 5% to 95% active ingredient plus a small amount of wetting, dispersing, or emulsifying agent. Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or another liquid and may consist entirely of the active compound with a liquid or solid emulsifying agent or may also contain a liquid carrier such as xylene, aromatic-containing heavy naphthas, isophorone and other non-volatile organic solvents.When applied, these concentrates are dispersed in water or another liquid and typically applied as a spray to the area to be treated. The amount of active ingredient can vary from 0.5% to 95% of the concentrate.

[0448] Granular formulations include both extrudates and relatively large particles and are generally applied undiluted to the area to be treated. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite, calcium carbonate, sandstone, pumice, pyrophyllite, kaolin, dolomite, gypsum, wood flour, ground corn cobs, ground peanut hulls, sugars, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesium oxide, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate, and other organic or inorganic materials that absorb the active compound or that can be coated with it.Granular formulations typically contain between 5% and 25% active ingredients, which may include surface-active agents such as aromatic-containing heavy naphthas, kerosene and other petroleum fractions or vegetable oils, and / or adhesives such as dextrins, glue or synthetic resins.

[0449] Powders are free-flowing mixtures of the active ingredient with finely divided solids such as talc, clays, fine powders, and other organic and inorganic solids that act as dispersants and carriers. Microcapsules typically consist of droplets or granules of the active ingredient enclosed in an inert porous shell that allows the enclosed materials to be released into the surrounding medium at controlled rates. The diameter of encapsulated droplets typically ranges from 1 to 50 microns. The enclosed liquid typically accounts for 50 to 95% of the capsule's weight and may include a solvent in addition to the active compound. Encapsulated granules are generally porous granules with porous membranes sealing the pore openings of the granules, trapping the active ingredients in liquid form within the pores of the granules.Granule diameters typically range from 1 millimeter to 1 centimeter, and are preferably between 1 and 2 millimeters. Granules are formed by extrusion, agglomeration, or pelletizing, or they are natural. Examples of such materials include vermiculite, sintered clay, kaolin, attapulgite clay, sawdust, and granulated carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes, and starch xanthates.

[0450] Other suitable formulations for agrochemical applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the required concentration, such as acetone, alkylated naphthalenes, xylene, and other organic solvents. Pressurized sprayers can also be used, where the active ingredient is dispersed in a finely divided form by evaporation of the low-boiling dispersant carrier solvent.

[0451] Suitable agriculturally useful auxiliary substances and carriers that are useful in formulating the compositions of the present invention into the previously described types of formulations are well known to those skilled in the art.

[0452] Liquid carriers that can be used include, for example, water, toluene, xylene, ligroin, 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, alkylpyrrolidinone, 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, glycerin, diacetate glycerol, glycerol monoacetate, glycerol triacetate,Hexadecane, Hexylene Glycol, Isoamyl Acetate, Isobornyl Acetate, Isooctane, Isophorone, Isopropyl Benzene, Isopropyl Myristate, Lactic Acid, Laurylamine, Mesityl Oxide, Methoxypropanol, Methyl Isoamyl Ketone, Methyl Isobutyl Ketone, Methyl Laurate, Methyl Octanoate, Methyl Oleate, Methylene Chloride, m-Xylene, n-Hexane, n-Octylamine, Octadecanoic Acid, Octylamine Acetate, Oleic Acid, Oleylamine, o-Xylene, Phenol, Polyethyleneglycol (PEG 400), Propionic Acid, Propylene Glycol, Propylene Glycol Monomethyl Ether, p-Xylene, Toluene, Triethyl Phosphate, Triethylene Glycol, Xylene Sulfonic Acid, Paraffin, Mineral Oil, Trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol and high molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerin and N-methyl-2-pyrrolidinone. Generally, the best carrier for diluting concentrates is water.

[0453] 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 shell flour and lignin.

[0454] A wide range of surfactants are successfully used in both the liquid and solid formulations mentioned above, particularly those intended for dilution with a carrier prior to use. When used, such substances typically comprise from 0.1% to 15% by weight of the formulation. They can be anionic, cationic, nonionic, or polymeric in nature and can be used as emulsifying agents, wetting agents, suspending agents, or for other purposes.Typical surfactants include alkyl sulfate salts such as diethanolammonium lauryl sulfate; alkyl aryl sulfonate salts such as calcium dodecylbenzenesulfonate; alkyl phenol-alkylene oxide addition products such as nonylphenol C18 ethoxylate; alcohol-alkylene oxide addition products such as tridecyl alcohol C16 ethoxylate; soaps such as sodium stearate; alkyl naphthalene sulfonate salts such as sodium dibutyl naphthalene sulfonate; dialkyl esters of sulfosuccinate salts such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitan 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.

[0455] Other auxiliary substances commonly used in compositions used in agriculture include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, antifoaming agents, light blocking agents, compatibilizers, defoamers, complexing agents, neutralizing agents and buffers, corrosion inhibitors, dyes, aromatic substances, spreading agents, penetration promoters, microelements, softening agents, lubricants, adhesion promoting agents. In addition, other biocidally active ingredients or compositions can also be combined with the compositions of the present invention and used in the methods of the present invention, and used simultaneously or sequentially with the compositions of the present invention.When used simultaneously, these additional active ingredients can be formulated together with the compositions of the present invention or mixed, for example, in a sprayer tank. These additional biologically active ingredients can be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides, and / or plant growth regulators.

[0456] Pesticide products referred to in this document by their common name are known, for example, from "The Pesticide Manual", 15th Ed., British Crop Protection Council 2009.

[0457] Furthermore, the compositions of the present invention can also be used with one or more inducers of systemic acquired resistance (SAR inducer). SAR inducers are known and described, for example, in U.S. Patent No. US 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.

[0458] The compounds of formula (I) according to the present invention are generally used in the form of agrochemical compositions and can be applied to the crop area or plant to be treated, simultaneously or sequentially with additional compounds. Such additional compounds can be, for example, fertilizers or micronutrient donors or other preparations that affect plant growth. They can also be selective herbicides or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if necessary, together with additional carriers, surfactants or application auxiliaries commonly used in the field of formulation.The compounds of formula (I) according to the present invention can be used in the form of (fungicidal) compositions for the control or protection against phytopathogenic microorganisms, containing as an active ingredient at least one compound of formula (I) or at least one preferred individual compound defined herein, in free form or in the form of an agrochemically applicable salt and at least one of the above-mentioned auxiliary substances.

[0459] Therefore, the present invention provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I) according to the present invention, an agriculturally acceptable carrier, and optionally an auxiliary substance. The agriculturally acceptable carrier is, for example, a carrier that is suitable for agricultural use. Agricultural carriers are well known in the art. Preferably, said composition may contain at least one or more pesticidally active compounds, for example an additional fungicidally active ingredient, in addition to the compound of formula (I).

[0460] The compound of formula (I) according to the present invention may be the sole active ingredient of the composition or, if necessary, it may be mixed with one or more additional active ingredients, such as a pesticide, fungicide, synergist, herbicide, or plant growth regulator. The additional active ingredient may, in some cases, lead to unexpected synergistic activities.

[0461] Examples of suitable additional active ingredients include the following: acycloamino acid group fungicides, aliphatic nitrogen-containing compound group fungicides, amide group fungicides, anilide group fungicides, antibiotic group fungicides, aromatic compound group fungicides, arsenic-containing fungicides, arylphenyl ketone group fungicides, benzamide group fungicides, benzanilide group fungicides, benzimidazole group fungicides, benzothiazole group fungicides, plant fungicides, bridged biphenyl group fungicides, carbamate group fungicides, carbanilate group fungicides, conazole group fungicides, copper-containing fungicides, dicarboximide group fungicides, dinitrophenol group fungicides, dithiocarbamates, dithiolane group fungicides, furamide group fungicides, furanilide group fungicides, hydrazide group fungicides, imidazole group fungicides, mercury-containing fungicides, morpholine group fungicides,organophosphorus fungicides, organotin fungicides, oxathiine fungicides, oxazole fungicides, phenylsulfamide fungicides, polysulfide fungicides, pyrazole fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungicides, quinone fungicides, quinoxaline fungicides, strobilurin fungicides, sulfonanilide fungicides, thiadiazole fungicides, thiazole fungicides, thiazolidine fungicides, thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, valineamide fungicides and zinc-containing fungicides.

[0462] Examples of suitable additional active ingredients include the following: petroleum oils, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenylbenzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylacetamide, 4-chlorophenylphenylsulfone, acetoprole, aldoxycarb, amidithione, amidothioate, amiton, amiton hydroxalate, amitraz, aramit, arsenic oxide, azobenzene, azotoate, benomyl, benoxafos, benzyl benzoate, bixafen, bromelain, bromocyclen, bromophos, bromopropylate, buprofezin, butocarboxim, butoxycarboxim, butylpyridaben, calcium polysulfide, camphechlor, carbonolate, Carbophenothione, Cimiazole, Chinomethionate, Chlorbenzide, Chlordimeform, Chlordimeform Hydrochloride, Chlorphenethol, Chlorfensone, Chlorphensulfide, Chlorobenzilate, Chloromebuform, Chloromethiuron, Chlorpropylate, Chlorthiophos, Cinerin I, Cinerin II, Cinerins, Closantel, Coumaphos, Crotamiton, Crotoxyfos, Cufraneb, Cyanthoate, DCPM, DDT, Demethion, Demethion-O, Demethion-S, Demeton-methyl, Demeton-O, Demeton-O-methyl, Demeton-S, Demeton-S-methyl,demeton-S-methylsulfone, dichlorofluanid, dichlorvos, diclifos, dienochlor, dimefox, dinex, dinex-diklexin, dinocap-4, dinocap-6, dinoctone, dinopentone, dinosulfone, dinoterbone, dioxathion, diphenylsulfone, disulfiram, DNOC, dofenapine, doramectin, endothion, eprinomectin, etoate-methyl, etrimphos, fenazaflor, fenbutatin oxide, phenothiocarb, fenpyrad, fenpyroximate, fenpyrazamine, phenzone, fentriphanil, flubenzimine, flucycloxuron, fluenethyl, fluorobenzide, FMC 1137, formetanate, formetanate hydrochloride, formparanate, gamma-NSN, gliodin, galfenprox, hexadecyl-cyclopropanecarboxylate, isocarbofos, jasmoline I, jasmoline II, iodofenphos, lindane, malonoben, mecarbam, mephospholane, mesulfen, metacryphos, methyl bromide, metolcarb, mexacarbate, milbemycin oxime, mipafox, monocrotophos, morphothion, moxidectin, naled, 4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one, nifluridide, nikkomycins, nitrilacarb, nitrilacarb and zinc chloride complex 1:1, omethoate, oxideprofos, oxidisulfoton,pp'-DDT, parathion, permethrin, fenkapton, phosalone, phospholane, phosphamidon, polychloroterpenes, polynactins, proclonol, promacil, propoxur, protidathion, protoate, pyrethrin I, pyrethrin II, pyrethrins, pyridafenthion, pyrimitate, quinalfos, quinthiofos, R-1492, phosglycine, rotenone, shradan, sebufos, selamectin, sofamid, SSI-121, sulfiram, sulfluramide, sulfotep, seru, difluvidazine, tau-fluvalinate, TERP, terbam, tetradifon, tetrasul, thiafenox, thiocarboxim, thiophanox, thiomethon, thioquinox, thuringiensin, triamiphos, triaraten, triazophos, triazuron, trifenofos, trinactin, vamidothion, vaniliprole, betoxazin, copper dioctanoate, copper sulfate, cybutryn, dichlon, dichlorophen, endothal, fentin, slaked lime, nabam, quinoclamine, quinonamide, simazine, triphenyltin acetate, triphenyltin hydroxide, crufomate, piperazine, thiophanate, chloralose, fenthion, pyridin-4-amine, strychnine, 1-hydroxy-1H-pyridine-2-thione, 4-(quinoxalin-2-ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, copper hydroxide, cresol,Dipyrithione, Dodicin, Fenaminosulf, Formaldehyde, Hydrargaphene, Kasugamycin, Kasugamycin Hydrochloride Hydrate, Nickel Bis(Dimethyldithiocarbamate), Nitrapyrin, Octhilinone, Oxolinic Acid, Oxytetracycline, Potassium Hydroxyquinoline Sulfate, Probenazole, Streptomycin, Streptomycin Sesquisulfate, Tecloftalam, Thiomersal, Adoxophyes orana GV, Agrobacterium radiobacter, Amblyseius spp., Anagrapha falcifera NPV, Anagrus atomus, Aphelinus abdominalis, Aphidius colemani, Aphidoletes aphidimyza, Autographa californica NPV, Bacillus sphaericus Neide, Beauveria brongniartii, Chrysoperla camea, Cryptolaemus montrouzieri, Cydia pomonella GV, Dacnusa sibirica, Diglyphus isaea, Encarsia formosa, Eretmocerus eremicus, Heterorhabditis bacteriophora and H. megidis, Hippodamia convergens, Leptomastix dactylopii, Macrolophus caliginosus, Mamestra brassicae NPV, Metaphycus helvolus, Metarhizium anisopliae var. acridum, Metarhizium anisopliae var. anisopliae, Neodiprion sertifer NPV and N. lecontei NPV, Onus 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, afolate, bisazire, busulfan, dimatif, chemel, hempu, metepu, methiotepu, methylafolat, morside, penfluron, tepu, thiochempu, thiotepu, tretamin, uredepu, (E)-dec-5-en-1-yl acetate with (E)-dec-5-en-1-ol, (E)-tridec-4-en-1-ylacetate, (E)-6-methylhept-2-en-4-ol, (E,Z)-tetradeca-4,10-dien-1-ylacetate, (Z)-dodec-7-en-1-ylacetate, (Z)-hexadec-11-enal, (7)-hexadec-11-en-1-ylacetate, (Z)-hexadec-13-en-11-yne-1-ylacetate, (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)-tetradeca-9,11-dien-1-yl acetate, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate, 14-methyloctadec-1-ene, 4-methylnonan-5-ol with 4-methylnonan-5-one,alpha-multistriatin, brevicomine, codlelur, codlemone, quelur, disparlur, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodeca-8, 10-dien-1-yl acetate, dominicalur, ethyl 4-methyloctanoate, eugenol, frontalin, grandlur, grandlur I, grandlur II, grandlur III, grandlur IV, hexalur, ipsdienol, ipsenol, japonilur, lineatin, litlur, luplur, medlur, megatomoic acid, methyleugenol, muscalure, octadeca-2,13-dien-1-yl acetate, octadeca-3,13-dien-1-yl acetate, orfralur, orictalur, ostramon, siglur, sordidin, sulcatol, tetradec-11-en-1-ylacetate, trimedlur, trimedlur A, trimedlur B1, trimedlur B2, trimedlur C, trunc-call, 2-(octylthio)ethanol, butopyronoxyl, butoxy(polypropylene glycol), dibutyl adipate, dibutyl phthalate, dibutyl succinate, diethyltoluamide, dimethyl carbate, dimethyl phthalate, ethylhexanediol, hexamide, methoquin-butyl, methylneodecanamide, 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-Dichlorophenyl)ethyl acetate, 2,2-dichlorovinyl-2-ethylsulfinylethyl methyl phosphate, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate, 2-(2-butoxyethoxy)ethyl thiocyanate, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate, 2-(4-chloro-3,5-xylyloxy)ethanol, 2-chlorovinyl diethyl phosphate, 2-imidazolidone, 2-isovalerylindane-1,3-dione, 2-methyl(prop-2-ynyl)aminophenyl methylcarbamate, 2-thiocyanatoethyl laurate, 3-bromo-1-chloroprop-1-ene, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate, 4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate, 5,5-dimethyl-3-oxocyclohex-1-enylmethylcarbamate, acetion, acrylonitrile, aldrin, allosamidine, allixicarb, alpha-ecdysone, aluminum phosphide, aminocarb, anabasine, atidathion, azamethiphos, Bacillus thuringiensis delta-endotoxins, barium hexafluorosilicate, barium polysulfide, bartrin, Bayer 22 / 190, Bayer 22408, beta-cyfluthrin, beta-cypermethrin, bioethanomethrin, biopermethrin, bis(2-chloroethyl) ether, borax, bromfenvinphos, bromo-DDT, bufencarb, butacarb, butathiophos, butonate, arsenate calcium, calcium cyanide,Carbon disulfide, tetrachloromethane, carboxymethyl sulfoxide, cevadin, chlorbicyclen, chlordane, chlordecone, chloroform, chloropicrin, chlorphoxime, chlorprazophos, cis-resmethrin, cismethrin, clocitrin, copper acetoarsenite, copper arsenate, copper oleate, cumitoate, cryolite, CS 708, cyanofenphos, cyanophos, cicletrin, cythioate, d-tetramethrin, DAEP, dazomet, decarbofuran, diamidefos, dicapton, dichlorfenthion, dicresyl, dicyclanil, dieldrin, diethyl-5-methylpyrazol-3-yl phosphate, dilor, dimefluthrin, dimethane, dimethrine, dimethylvinphos, dimethylane, dinoprop, dinosam, dinoseb, Diofenolan, Dioxabenzophos, Dithicrophos, DSP, Ecdysterone, EI 1642, EMPC, EPBP, Etafos, Ethifencarb, Ethyl Formate, Ethylene Dibromide, Ethylene Dichloride, Ethylene Oxide, EXD, Fenchlorvos, Fenetacarb, Fenitrothion, Fenoxacrim, Fenpyritrin, Fensulfothion, Fenthion-ethyl, Flucofuron, Fosmethylan, Fospirate, Fosthiethane, Furathiocarb, Furethrin, Guazatine, Guazatine Acetates, Sodium Tetrathiocarbonate, Halfenprox, HCH, HEOD, Heptachlor, Heterophos, HHDN, Hydrogen Cyanide, Hiquincarb, IPSP,Isazophos, Isobenzan, Isodrin, Isofenphos, Isolan, Isoprothiolane, Isoxathion, Juvenile Hormone I, Juvenile Hormone II, Juvenile Hormone III, Kelevan, Kinoprene, Lead Arsenate, Leptophos, Lirimfos, Lithidathion, M-Cumenyl Methylcarbamate, Magnesium Phosphide, Mazidox, Mecarfone, Menazon, Mercuric Chloride, Mesulfenfos, Metam, Metam Potassium, Metam Sodium, Methanesulfonyl Fluoride, Metocrotophos, Methoprene, Methotrin, Methoxychlor, Methyl Isothiocyanate, Methyl Chloroform, Methylene Chloride, Methoxadiazone, Mirex, Naphthalofos, Naphthalene, NC-170, Nicotine, Nicotine Sulfate, Nithiazine, Nornicotine, O-5-dichloro-4-iodophenyl-O-ethylethylphosphonothioate, O,O-diethyl-O-4-methyl-2-oxo-2H-chromen-7-ylphosphorothioate, O,O-diethyl-O-6-methyl-2-propylpyrimidin-4-ylphosphorothioate, O,O,O',O'-tetrapropyldithiopyrophosphate, oleic acid, para-dichlorobenzene, parathion-methyl, pentachlorophenol, pentachlorophenyl laurate, pH 60-38, phencapton, phosnichlor, phosphine, phoxim-methyl, pyrimethafos, polychlorodicyclopentadiene isomers, potassium arsenite, potassium thiocyanate, precocene I,Precocen II, Precocen III, Primidofos, Profluthrin, Promecarb, Prothiophos, Pyrazophos, Pyresmethrin, Quassia, Quinalfos-methyl, Quinothion, Rafoxanide, Resmethrin, Rotenone, Cadetrin, Ryania, Ryanodine, Sabadilla), Shradane, Sebufos, SI-0009, Tiapronil, Sodium Arsenite, Sodium Cyanide, Sodium Fluoride, Sodium Hexafluorosilicate, Sodium Pentachlorophenoxide, Sodium Selenate, Sodium Thiocyanate, Sulcofuron, Sulcofuron-Sodium, Sulfuryl Fluoride, Sulprofos, Tar Oils, Tazimcarb, TDE, Tebupirimphos, Temephos, Theralletrin, Tetrachloroethane, Thicrophos, Thiocyclam, Thiocyclam Hydroxalate, thionazine, thiosultap, thiosultap sodium, tralomethrin, transpermethrin, triazamate, trichlormetaphos-3, trichloronate, trimethacarb, tolprocarb, triclopiricarb, triprene, veratridine, veratrine, CMS, zetamethrin, zinc phosphide, zolaprofos and meperfluthrin, tetramethylfluthrin, bis(tributyltin oxide), bromoacetamide, ferrous 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, benclothiase, cytokinins, DCIP, furfural, isamidophos, kinetin, Myrothecium verrucaria-based composition, tetrachlorothiophene, xylenols, zeatin, potassium ethyl xanthate, acibenzolar, acibenzolar-S-methyl, Reynoutria sachalinensis extract, alpha-chlorohydrin, anthus, barium carbonate, bisthiosemi, brodifacoum, bromadiolone, Bromethalin, chlorophacinone, cholecalciferol, coumachlor, coumafuril, coumatetralyl, crimidine, difenacoum, difethialone, diphacinone, ergocalciferol, flocoumafen, fluoroacetamide, flupropadine, flupropadine hydrochloride, norbormide, fosacetim, phosphorus, pindone, pyrinuron, scilliroside, sodium fluoroacetate, thallium sulfate, warfarin, 2-(2-butoxyethoxy)ethyl piperonylate, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, farnesol with nerolidol, verbutin, MGK 264, piperonyl butoxide, piprotal, propyl isomer, S421,sesamex, sesamolin, sulfoxide, anthraquinone, copper naphthenate, copper oxychloride, dicyclopentadiene, thiram, zinc naphthenate, ciram, imanine, ribavirin, mercuric oxide, thiophanate-methyl, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxyconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, furametpyr, 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, etirimol, dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph, cyprodinil, mepanipyrim, pyrimethanil, fenpiclonil, fludioxonil, benalaxyl, furalaxyl, metalaxyl, R- metalaxyl, ofuras, oxadixyl, carbendazim, debacarb, fuberidazole, thiabendazole, clozolinate, diclozolin, myclozolin, procymidone, vinclozolin, boscalid,Carboxin, Fenfuram, Flutolanil, Mepronil, Oxycarboxin, Penthiopyrad, Thifluzamide, Dodine, Iminoctadine, Azoxystrobin, Dimoxystrobin, Enestroburin, Fenaminstrobin, Flufenoxystrobin, Fluoxastrobin, Kresoxim-methyl, Metominostrobin, Trifloxystrobin, Orisastrobin, Picoxystrobin, Pyraclostrobin, Pyramethostrobin, Pyraoxystrobin, Ferbam, Mancozeb, Maneb, Metiram, Propineb, Zineb, Captafol, Captan, Fluorimide, Folpet, Tolylfluanid, Bordeaux Mixture, Copper Oxide, Mancopper, Copper Oxine, Nitrothal-Isopropyl, Edifenphos, Iprobenfos, Fosdifen, Tolclofos-methyl, Anilazine, benthiavalicarb, blasticidin-S, chloroneb, chlorothalonil, cyflufenamide, cymoxanil, cyclobutrifluram, diclocymet, diclomezine, dicloran, diethofencarb, dimethomorph, flumorph, dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, ferimzone, fluazinam, fluopicolide, flusulfamide, fluxapyroxad, fenhexamide, fosetyl-aluminum, himexazole, iprovalicarb, cyazofamid, metasulfocarb, metrafenone, pencycuron, phthalide, polyoxins,propamocarb, pyribencarb, proquinazid, pyroquilone, pyriophenone, quinoxyfen, quintozene, tiadinil, triazoxide, tricyclazole, triforine, validamycin, valiphenalate, zoxamide, mandipropamide, flubeneteram, isopyrazam, sedaxan, benzovindiflupyr, pidiflumetofen, (3',4',5'-trifluorobiphenyl-2-yl)amide 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid, isoflucipram, isothianil, 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-dimethylindan-4-yl]pyridine-3-carboxamide, 4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine-3-carbonitrile, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-2,5-dimethylpyrazol-3-amine, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, fluindapyr, cumethoxystrobin (jiaxiangjunzhi), luibengymixianan, dichlobenthiazox, mandestrobin, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone,2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol, oxathiapiproline, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenylmethylene]amino]oxymethyl]-2-pyridyl]carbamate, pyraziflumide, inpirfluxam, trolprocarb, mefentrifluconazole, ipfentrifluconazole, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethylindan-4-yl]pyridine-3-carboxamide, N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylformamidine, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethylphenyl]-N-ethyl-N-methylformamidine, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chlorophenyl]methanesulfonate, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)phenylmethylene]amino]oxymethyl]-2-pyridyl]carbamate, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methylphenyl]methyl]carbamate, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine, pyridachloromethyl, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazol-4-carboxamide,1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methylphenyl]-4-methyltetrazol-5-one, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one, aminopyrifen, amethoctradine, amisulbrom, penflufen, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethylpent-3-enamide, florylpicoxamide, fenpicoxamide, tebufloquine, ipflufenoquine, quinofumelin, isofetamide, N-[2-[2,4-dichlorophenoxy]phenyl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide, benzothiostrobin, fenamacryl, zinc salt of 5-amino-1,3,4-thiadiazole-2-thiol (2:1), fluopyram, flutianil, fluopimamide, pyrapropone, picarbutrazox, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethylindan-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, methyltetraprole,2-(difluoromethyl)-N-((311)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidinemethanol, 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, kumoxystrobin, zhongshenmycin, copper thiodiazole, zinc thiazole, amectotractin, iprodione, N-octyl-N'-[2-(octylamino)ethyl]ethane-1,2-diamine, N'-[5-bromo-2-methyl-6-[(18)-1-methyl-2-propoxyethoxy]-3-pyridyl]-N-ethyl-N-methylformamidine, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxyethoxy]-3-pyridyl]-N-ethyl-N-methylformamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-ethyl-N-methylformamidine,N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-ethyl-N-methylformamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-isopropyl-N-methylformamidine (such compounds can be prepared by the methods described in WO 2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methylformamidine (such compound can be prepared by the methods described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenylethyl)phenyl]-N-methylformamidine, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxyethyl)-5-methoxy-2-methylphenyl]-N-isopropyl-N-methylformamidine (such compounds can be prepared using the methods described in WO 2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methylformamidine, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methylformamidine (such compounds can be prepared using the methods described in WO 2018 / 228896);described in WO 2019 / 110427); N-[(1R)-1-benzyl-3-chloro-1-methylbut-3-enyl]-8-fluoroquinoline-3-carboxamide, N-[(1S)-1-benzyl-3-chloro-1-methylbut-3-enyl]-8-fluoroquinoline-3-carboxamide, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methylpropyl]-8-fluoroquinoline-3-carboxamide, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methylpropyl]-8-fluoroquinoline-3-carboxamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoroquinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethylbutyl]-7,8-difluoroquinoline-3-carboxamide, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethylbutyl]quinoline-3-carboxamide, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethylbutyl]quinoline-3-carboxamide, N-[(1R)-1-benzyl-1,3-dimethylbutyl]-8-fluoroquinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethylbutyl]-8-fluoroquinoline-3-carboxamide, N-((1R)-1-benzyl-3-chloro-1-methylbut-3-enyl)-8-fluoroquinoline-3-carboxamide, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoroquinoline-3-carboxamide (such compounds can be prepared using the methods described in WO 2017 / 153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethylisoquinoline, 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-methylpyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethylisoquinoline (such compounds can be prepared using the methods described in WO 2017 / 025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethylisoquinoline, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline, 4,4-difluoro-1-(5-fluoro-4-methylbenzimidazol-1-yl)-3,3-dimethyl-isoquinoline, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole (such compounds can be prepared using the methods described in WO 2016 / 156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine (such compounds can be prepared using 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 (such a compound can be obtained using 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 (such a compound can be obtained using the methods described in WO 2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile (such a compound can be prepared using the methods described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile (such a compound can be prepared using the methods described in WO 2016 / 156290); (4-phenoxyphenyl)methyl 2-amino-6-methylpyridine-3-carboxylate (such a compound can be prepared using the methods 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)-tetron (such a compound can be obtained using methodsdescribed in WO 2011 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethylpent-3-enamide (such a compound can be prepared using the methods described in WO 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methyl-formamidine; N'-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylformamidine (such a compound can be prepared using the methods described in WO 2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethylindan-4-yl]pyridine-3-carboxamide (such a compound can be prepared using the methods 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 (such compounds can be prepared using the methods described in WO 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide (such a compound can be prepared using the methods described in WO 2018 / 065414); ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate (such a compound can be prepared using the methods described in WO 2018 / 158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[N-methoxy-C-methylcarbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (such compounds can be prepared using the methods described in WO 2018 / 202428).,

[0463] The compositions according to the present invention may also contain additional solid or liquid auxiliary substances, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example, epoxidized coconut oil, rapeseed oil or soybean oil), antifoaming agents, for example silicone oil, preservatives, viscosity regulators, binders and / or tackifiers, fertilizers or other active ingredients to provide specific effects, for example bactericides, fungicides, nematicides, plant growth activators, molluscicides or herbicides.

[0464] The compositions according to the present invention are prepared by a method known per se, in the absence of auxiliary agents, for example, by grinding, sifting and / or pressing the solid active ingredient, and in the presence of at least one auxiliary agent, for example, by thoroughly mixing and / or grinding the active ingredient with the auxiliary agent(s). Such methods for preparing compositions and the use of compounds (I) for preparing such compositions are also an object of the present invention.

[0465] Another aspect of the present invention relates to the use of a compound of formula (I) according to the present invention or a preferred single compound as defined herein above, a composition comprising at least one compound of formula (I) or at least one preferred single compound as defined herein above, or a fungicidal or insecticidal mixture comprising at least one compound of formula (I) or at least one preferred single compound as defined herein above, in admixture with other fungicides or insecticides as described herein above, for controlling or preventing infestation of plants, such as useful plants such as agricultural crops, propagation material thereof, such as seeds, harvested crops, such as harvested food crops, or non-living materials by insects or phytopathogenic microorganisms, preferably fungal organisms.A further aspect of the present invention relates to a method for controlling or preventing the infestation of plants, for example useful plants such as agricultural crops, their propagation material such as seeds, harvested crops such as harvested food crops, or non-living materials by phytopathogenic or spoilage microorganisms, or organisms potentially harmful to humans, especially fungal organisms, which comprises using a compound of formula (I) according to the present invention or a preferred single compound as defined herein above as an active ingredient in relation to plants, parts of plants or their locus of growth, their propagation material, or any part of the non-living materials.

[0466] Control or prevention means reducing the degree of infestation by insects or phytopathogenic or spoilage microorganisms or organisms potentially harmful to humans, especially fungal organisms, to a level where improvement occurs.

[0467] A preferred method for controlling or preventing the infestation of agricultural crops by phytopathogenic microorganisms, in particular fungal organisms, or insects, which involves the use of a compound of formula (I) according to the present invention or an agrochemical composition containing at least one of said compounds of formula (I), is foliar application. The frequency of application and the application rate will depend on the risk of infestation by the respective pathogen or insect. However, the compounds of formula (I) according to the present invention can also penetrate the plant from the soil through the roots (systemic action) by irrigating the growing site of the plant with a liquid formulation or by applying the compounds in solid form to the soil, for example in granular form (soil application). In the case of crops such as water rice, these granules can be applied to a flooded rice field.The compounds of formula (I) can also be applied to seeds (coating) either by impregnating the seeds or tubers with a liquid formulation of the fungicide or by coating them with a solid formulation. A formulation, for example a composition, containing a compound of formula (I) according to the present invention and, if necessary, a solid or liquid auxiliary substance or monomers for encapsulating the compound of formula (I) can be prepared in a known manner, typically by thoroughly mixing and / or grinding the compound with excipients, such as solvents, solid carriers and, optionally, surface-active compounds (surfactants).

[0468] The preferred application rates are generally 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably 10g to 1kg⋅a.i. / ha, and most preferably 20g to 600g⋅a.i. / ha. When used as a seed dressing, suitable dosages are 10mg to 1g of active ingredient per kg of seed.

[0469] If the combinations of the present invention are used for seed treatment, then rates of 0.001 to 50 g of the compound of formula (I) per kg of seed, preferably 0.01 to 10 g per kg of seed, are generally sufficient. Accordingly, the composition containing the compound of formula (I) according to the present invention is used either for preventive purposes, which means application before the development of the disease, or for therapeutic purposes, which means application after the development of the disease.

[0470] The compositions of the present invention can be used in any conventional form, such as twin pack, dry seed treatment powder (DS), seed treatment emulsion (ES), seed treatment flowable concentrate (FS), seed treatment solution (LS), water-dispersible seed treatment powder (WS), seed treatment capsule suspension (CF), seed treatment gel (GF), emulsion concentrate (EC), suspension concentrate (SC), suspoemulsion (SE), capsule suspension (CS), water-dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsion (EO), oil-in-water emulsion (EW), microemulsion (ME), oil dispersion (OD), oil-miscible flowable (OF), oil-miscible liquid (OL), soluble concentrate (SL), ultra-low volume suspension (SU), liquid ultra-low volume (UL), technical concentrate (TC), dispersible concentrate (DC),wettable powder (WP) or any technically feasible formulation in combination with agriculturally acceptable excipients.

[0471] Such compositions can be prepared in a conventional manner, for example by mixing the active ingredients with appropriate inert formulation components (diluents, solvents, fillers, and optionally other formulation ingredients such as surfactants, biocides, antifreeze additives, adhesives, thickeners, and compounds that provide auxiliary properties). If prolonged action is intended, conventional slow-release formulations can also be used. In particular, formulations used in spray form, such as water-dispersible concentrates (e.g., EC, SC, DC, OD, SE, EW, EO, etc.)), wettable powders and granules, may contain surface-active agents such as wetting and dispersing agents and other compounds that provide auxiliary properties, such as a condensation product of formaldehyde with naphthalene sulfonate, alkyl aryl sulfonate, lignin sulfonate, alkyl fatty acid sulfate, as well as ethoxylated alkyl phenol and ethoxylated fatty alcohol.

[0472] The seed dressing composition is applied by a method known per se for seeds, using a combination of the present invention and a diluent in a suitable seed dressing composition form, for example, as an aqueous suspension or in the form of a dry powder, characterized by good adhesion to the seeds. Such seed dressing compositions are known in the art. The seed dressing compositions may contain individual active ingredients or a combination of active ingredients in encapsulated form, for example, in the form of slow-release capsules or microcapsules.

[0473] In general, the formulations comprise from 0.01 to 90% by weight of the active agent, from 0 to 20% of an agriculturally acceptable surfactant and from 10 to 99.99% of solid or liquid inert substances for formulation and auxiliary substance(s), wherein the active agent consists of at least a compound of formula (I) according to the present invention, optionally together with other active agents, in particular microbiocides or preservatives or the like. Concentrated forms of the compositions typically contain from about 2 to 80%, preferably from about 5 to 70% by weight of the active agent. Usable forms of the formulation may, for example, contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of the active agent. Since commercial products will preferably be formulated as concentrates, the end user will in most cases use diluted formulations.

[0474] Because commercial products are preferably formulated as concentrates, the end user will in most cases use diluted formulations. The disclosure of the present application allows for any and all combinations of the embodiments disclosed herein.

[0475] The compounds according to Tables A-1 to A-32 below can be prepared according to the methods described above. The following examples are presented to illustrate the present invention and show preferred compounds of formula (I). In any of Tables A-1 to A-32 below, the presence of one or more possible asymmetric carbon atoms in a compound of formula (I) according to the present invention means that the compounds can occur in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms.

[0476] Table A This table discloses 12 compounds of formula (Ia) according to the present invention:

[0477]

[0478] where G has the formula , defined below:

[0479]

[0480] The following compounds are specific compounds of formula (Ia) described in Tables A-1 to A-32, wherein G is defined in Table A. For example, compound A-1.G1 is a compound of formula (Ia), where R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and B 2 are defined in Table A-1 and G is G1 defined in Table A.

[0481] Table A-1. This table presents 12 compounds A-1.G1 - A-1.G12 of formula (Ia), where R 2 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 represent H, B 2 is CH and G is defined in Table A. For example, compound A-1.G9 is characterized by the following structure:

[0482]

[0483] Table A-2. This table presents 12 compounds A-2.G1 - A-2.G12 of formula (Ia), where R 2 is CH3, R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 represent H, B represents CH, and G is defined in Table A. For example, compound A-2.G1 is characterized by the following structure:

[0484]

[0485] Table A-3. This table presents 12 compounds A-3.G1 - A-3.G12 of formula (Ia), where R 2 represents F, R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 represent H, B 2 represents CH and G is defined in Table A.

[0486] Table A-4. This table presents 12 compounds A-4.G1 - A-4.G12 of formula (Ia), where R 2 represents Cl, R 4 , R5 , R 6 , R 7 , R 8 , R 9 , R 10 represent H, B represents CH and G is defined in Table A.

[0487] Table A-5. This table presents 12 compounds A-5.G1 - 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 represent H, B 2 represents CH and G is defined in Table A.

[0488] Table A-6. This table presents 12 compounds A-6.G1 - 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 represent H, B represents CH and G is defined in Table A.

[0489] Table A-7. This table presents 12 compounds A-7.G1 - A-7.G12 of formula (Ia), where R 2is C=N(OCH3)CH3, R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 represent H, B represents CH and G is defined in Table A.

[0490] Table A-8. This table presents 12 compounds A-8.G1 - A-8.G12 of formula (Ia), where R 2 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 represent H, R 4 is CH3, B 2 is CH and G is defined in Table A. For example, compound A-8.G1 is characterized by the following structure:

[0491]

[0492] Table A-9. This table presents 12 compounds A-9.G1 - A-9.G12 of formula (Ia), where R 5 , R 6 , R 7 , R 8 , R 9 , R 10 represent H, R 2 and R 4 represent CH3, B 2represents CH and G is defined in Table A.

[0493] Table A-10. This table presents 12 compounds A-10.G1 - A-10.G12 of formula (Ia), where R 5 , R 6 , R 7 , R 8 , R 9 , R 10 represent H, R 2 and R 4 represent CH3, B 2 represents N and G is defined in Table A.

[0494] Table A-11. This table presents 6 compounds A-11.G1, A-11.G2, A-11.G5, A-11.G6, A-11.G9 and A-11.G10 of formula (Ia), where R 2 , R 4 and R 7 represent CH3, R 5 , R 6 , R 8 , R 9 , R 10 represent H, B 2 is CH and G is defined in Table A. For example, compound A-11.G5 is characterized by the following structure:

[0495]

[0496] Table A-12. This table presents 6 compounds A-12.G1, A-12.G2, A-12.G5, A-12.G6, A-12.G9 and A-12.G10 of formula (Ia), where R 2 represents F, R 4 and R 7 represent CH3, R 5 , R 6 , R 8 , R 9 , R 10 represent H, B 2 represents CH and G is defined in Table A.

[0497] Table A-13. This table presents 6 compounds A-13.G1, A-13.G2, A-13.G5, A-13.G6, A-13.G9 and A-13.G10 of formula (Ia), where R 2 represents Cl, R 4 and R 7 represent CH3, R 5 , R 6 , R 8 , R 9 , R 10 represent H, B 2 represents CH and G is defined in Table A.

[0498] Table A-14. This table presents 6 compounds A-14.G1, A-14.G2, A-14.G5, ​​A-14.G6, A-14.G9 and A-14.G10 of formula (Ia), where R 2 is cyclopropyl, R 4and R 7 represent CH3, R 5 , R 6 , R 8 , R 9 , R 10 represent H, B 2 represents CH and G is defined in Table A.

[0499] Table A-15. This table presents 6 compounds A-15.G1, A-15.G2, A-15.G5, A-15.G6, A-15.G9 and A-15.G10 of formula (Ia), where R 2 , R 4 and R 7 represent CH3, R 5 , R 6 , R 8 , R 9 , R 10 represent H, B 2 represents N and G is defined in Table A.

[0500] Table A-16. This table shows 6 compounds A-16.G1, A-16.G2, A-16.G5, A-16.G6, A-16.G9 and A-16.G10 of formula (Ia), where R 2 , R 4 and R 7 represent CH3, R 5 , R 6 , R 9 , R 10 represent H, R 8 is OCH3, B 2 represents CH and G is defined in Table A.

[0501] Table A-17. This table presents 6 compounds A-17.G1, A-17.G2, A-17.G5, A-17.G6, A-17.G9 and A-17.G10 of formula (Ia), where R 2 , R 4 and R 7 represent CH3, R 5 , R 6 , R 8 , R 10 represent H, R 9 is OCH3, B 2 represents CH and G is defined in Table A.

[0502] Table A-18. This table presents 6 compounds A-18.G1, A-18.G2, A-18.G5, A-18.G6, A-18.G9 and A-18.G10 of formula (Ia), where R 2 , R 4 and R 7 represent CH3, R 5 , R 6 , R 8 , R 10 represent H, R 9 represents OH, B 2 represents CH and G is defined in Table A.

[0503] Table A-19. This table presents 6 compounds A-19.G1, A-19.G2, A-19.G5, A-19.G6, A-19.G9 and A-19.G10 of formula (Ia), where R 2 , R 4 and R 7represent CH3, R 5 , R 6 , R 8 , R 10 represent H, R 9 is CF3, B 2 represents CH and G is defined in Table A.

[0504] Table A-20. This table presents 6 compounds A-20.G1, A-20.G2, A-20.G5, A-20.G6, A-20.G9 and A-20.G10 of formula (Ia), where R 2 , R 4 and R 7 represent CH3, R 5 , R 6 , R 8 , R 10 represent H, R 9 represents CN, B 2 represents CH and G is defined in Table A.

[0505] Table A-21. This table presents 6 compounds A-21.G1, A-21.G2, A-21.G5, A-21.G6, A-21.G9 and A-21.G10 of formula (Ia), where R 2 , R 4 and R 7 represent CH3, R 5 , R 6 , R 8 , R 9 represent H, R 10 is OCH3, B 2represents CH and G is defined in Table A.

[0506] Table A-22. This table presents 6 compounds A-22.G1, A-22.G2, A-22.G5, A-22.G6, A-22.G9 and A-22.G10 of formula (Ia), where R 2 , R 4 and R 7 represent CH3, R 5 , R 6 , R 8 , R 9 represent H, R 10 represents OH, B 2 represents CH and G is defined in Table A.

[0507] Table A-23. This table presents 6 compounds A-23.G1, A-23.G2, A-23.G5, A-23.G6, A-23.G9 and A-23.G10 of formula (Ia), where R 2 , R 4 and R 7 represent CH3, R 5 , R 6 , R 8 , R 9 represent H, R 10 is CF3, B 2 represents CH and G is defined in Table A.

[0508] Table A-24. This table presents 6 compounds A-24.G1, A-24.G2, A-24.G5, ​​A-24.G6, A-24.G9 and A-24.G10 of formula (Ia), where R 2 , R 4 and R 7 represent CH3, R 5 , R 6 , R 8 , R 9 represent H, R 10 represents CN, B 2 represents CH and G is defined in Table A.

[0509] Table A-25. This table presents 6 compounds A-25.G1, A-25.G2, A-25.G5, A-25.G6, A-25.G9 and A-25.G10 of formula (Ia), where R 2 , R 4 and R 7 represent CH3, R 5 , R 6 , R 8 represent H, R represents OCH3, R represents CF3, B represents CH and G is defined in Table A.

[0510] Table A-26. This table presents 6 compounds A-26.G1, A-26.G2, A-26.G5, A-26.G6, A-26.G9 and A-26.G10 of formula (Ia), where R 2 , R 4 and R 7 represent CH3, R5 , R 6 , R 8 represent H, R 9 is OCH3, R 10 represents CN, B 2 represents CH and G is defined in Table A.

[0511] Table A-27. This table presents 6 compounds A-27.G1, A-27.G2, A-27.G5, A-27.G6, A-27.G9 and A-27.G10 of formula (Ia), where R 2 , R 4 and R 7 represent CH3, R 5 , R 6 , R 8 represent H, R 9 is CF3, R 10 represents OCH3, B represents CH and G is defined in Table A.

[0512] Table A-28. This table presents 6 compounds A-28.G1, A-28.G2, A-28.G5, A-28.G6, A-28.G9 and A-28.G10 of formula (Ia), where R 2 , R 4 and R 7 represent CH3, R 5 , R 6 , R 8 represent H, R 9 represents CN, R 10 is OCH3, B 2represents CH and G is defined in Table A.

[0513] Table A-29. This table presents 6 compounds A-29.G1, A-29.G2, A-29.G5, A-29.G6, A-29.G9 and A-29.G10 of formula (Ia), where R 2 , R 5 , R 6 and R 7 represent CH3, R 4 , R 8 , R 9 , R 10 represent H, B represents CH and G is defined in Table A.

[0514] Table A-30. This table presents 6 compounds A-30.G1, A-30.G2, A-30.G5, A-30.G6, A-30.G9 and A-30.G10 of formula (Ia), where R 2 , R 4 , R 5 , R 6 and R 7 represent CH3, R 8 , R 9 , R 10 represent H, B 2 represents CH and G is defined in Table A.

[0515] Table A-31. This table presents 6 compounds A-31.G1, A-31.G2, A-31.G5, A-31.G6, A-31.G9 and A-31.G10 of formula (Ia), where R 2 , R 4 and R 7represent CH3, R 5 , R 6 , R 9 , R 10 represent H, R 8 represents F, B 2 represents CH and G is defined in Table A.

[0516] Table A-32. This table presents 6 compounds A-32.G1, A-32.G2, A-32.G5, A-32.G6, A-32.G9 and A-32.G10 of formula (Ia), where R 2 , R 4 and R 7 represent CH3, R 5 , R 6 , R 8 , R 9 , R 10 represent H, B 2 represents CF and G is defined in Table A.

[0517] EXAMPLES

[0518] The following examples serve to illustrate the present invention and are not intended to limit the present invention in any way. The compounds of the present invention can be distinguished from known compounds by their higher efficacy at low application rates, which can be verified by one skilled in the art using the experimental procedures set forth in the examples, using lower application rates, if necessary, such as 60 ppm, 20 ppm, or 2 ppm.Compounds of formula (I) may have a number of advantages, including, inter alia, advantageous levels of biological activity for protecting plants from diseases caused by fungi, or superior properties for use as agrochemical active ingredients (e.g., higher biological activity, advantageous spectrum of activity, improved safety profile (including improved crop tolerance), improved physicochemical properties, or increased biodegradability).

[0519] Throughout this description, temperatures are given in degrees Celsius, and "mp" refers to melting point. LC-MS refers to liquid chromatography with mass spectrometry, and the apparatus and methods are described as follows. 1H NMR measurements were recorded on a Brucker 400 MHz spectrometer; chemical shifts are reported in ppm according to the TMS standard. Spectra were measured in the indicated deuterated solvents. Compounds were characterized using any of the LC-MS methods described below. The characteristic LC-MS values ​​obtained for each compound were the retention time ("Rt", recorded in minutes) and the measured molecular ion content (M+H). + or (M-N) - .

[0520] Method A.

[0521] The 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 ions), capillary voltage: 0.8-3.00 kV, cone voltage: 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 an Acquity UPLC from Waters Corporation: two-component pump, heated column compartment, diode array detector, and ELSD. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, temp.: 60°C, wavelength range DAD (nm): 210-400, analysis time: 1.5 min; solvents: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; flow rate (ml / min) 0.85, gradient: 10% B isocratic for 0.2 min, then 10-100% B for 1.0 min, 100% B isocratic for 0.2 min, 100-10% B for 0.05 min., 10% B isocratic for 0.05 min.

[0522] 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 ions, capillary voltage: 3.0 kV, cone voltage: 30 V, extractor voltage: 3.00 V, source temperature: 150 °C, desolvation temperature: 400 °C, cone gas flow: 60 L / h, desolvation gas flow: 700 L / h, mass range: 140-800 Da), and an ACQUITY UPLC from Waters Corporations with a solvent degasser, a two-component pump, a heated column compartment, and a diode array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30×2.1 mm, temp.: 60°C, wavelength range DAD (nm): from 210 to 400, solvent gradient: A = water / methanol 9:1 + 0.1% formic acid, B = acetonitrile + 0.1% formic acid, gradient: 0-100% B in 2.5 min.; flow rate (ml / min.) 0.75.

[0523] Method C.

[0524] Equipment:

[0525] Mass Spectrometer: Waters Acquity QDA Mass Spectrometer

[0526] HPLC: UPLC 'H' class

[0527] Optimized mass parameter:

[0528] Ionization method: electrospray (ESI)

[0529] Polarity: Positive and negative polarity switch

[0530] Scan Type: Full Scan

[0531] Capillarity (kV): 0.8

[0532] Cone Voltage (V): 25.00

[0533] Source temperature (°C): 120

[0534] Desolvation gas flow rate (L / h): 1000

[0535] Desolvation temperature (°C): 600

[0536] Gas flow in cone (l / h): 50

[0537] Weight range: 110 to 850 Da

[0538] PDA wavelength range: 230 to 400 nm

[0539] Optimized chromatographic parameter:

[0540] Gradient conditions:

[0541] Solvent A: water with 0.1% formic acid: acetonitrile: 95:5 v / v,

[0542] Solvent B: Acetonitrile with 0.05% formic acid.

[0543]

[0544] Column: AcquityUPLC HSS T3 C18

[0545] Column length: 30mm

[0546] Column inner diameter: 2.1mm

[0547] Particle size: 1.8 μm

[0548] Column thermostat temperature: 40°C.

[0549] Method D. Equipment:

[0550] Mass Spectrometer: Waters Acquity SQD Mass Spectrometer

[0551] HPLC: UPLC 'H' class

[0552] Optimized mass parameter:

[0553] Ionization method: electrospray (ESI)

[0554] Polarity: Positive and negative polarity switch

[0555] Scan Type: Full Scan

[0556] Capillarity (kV): 3.00

[0557] Cone Voltage (V): 41.00

[0558] Source temperature (°C): 150

[0559] Desolvation gas flow rate (L / h): 1000

[0560] Desolvation temperature (°C): 500

[0561] Gas flow in cone (l / h): 50

[0562] Mass range: 110-800 Da;

[0563] PDA wavelength range: 210 to 400 nm

[0564] Optimized chromatographic parameter:

[0565] Gradient conditions:

[0566] Solvent A: water with 0.1% formic acid: acetonitrile: 95:5 v / v,

[0567] Solvent B: Acetonitrile with 0.05% formic acid.

[0568]

[0569] Column: AcquityUPLC HSS T3 C18

[0570] Column length: 30mm

[0571] Column inner diameter: 2.1mm

[0572] Particle size: 1.8 μm

[0573] Column thermostat temperature: 40°C.

[0574] Method E.

[0575] Equipment:

[0576] Mass Spectrometer: Agilent Technologies 6410 Triple Quadrupole Mass Spectrometer

[0577] HPLC: Agilent 1200 Series HPLC

[0578] Optimized mass parameter:

[0579] Ionization method: electrospray (ESI)

[0580] Polarity: Positive and negative polarity switch

[0581] Scan Type: MS2 Scan

[0582] Capillarity (kV): 4.00

[0583] Fragmenter (B): 100.00

[0584] Gas temperature (°C): 350

[0585] Gas flow (L / min): 11

[0586] Atomizer Gas (psi): 40

[0587] Weight range: 110-1000 Yes

[0588] Detection (VWD): at 254 nm

[0589] Optimized chromatographic parameter:

[0590] Gradient conditions:

[0591] Solvent A: water with 0.1% formic acid: acetonitrile: 95:5 v / v,

[0592] Solvent B: Acetonitrile with 0.1% formic acid.

[0593]

[0594] Column: KINETEX EVO C18

[0595] Column length: 50mm

[0596] Column inner diameter: 4.6mm

[0597] Particle size: 2.6 microns

[0598] Column thermostat temperature: 40°C.

[0599] EXAMPLES OF RECEIPT

[0600] The compounds of formula (I) according to the present invention can be prepared using the synthetic procedures described above and below in this document.

[0601] 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)

[0602]

[0603] Step 1. Preparation of 4-(1-methylpyrazol-4-yl)isoquinoline

[0604]

[0605] In a microwave heating vial, 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) was degassed with argon for several minutes, and 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 for 1 hour under microwave heating. 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.

[0606] 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 (eluting with ethyl acetate in cyclohexane) afforded the title compound as a brown oil (115 mg, 0.550 mmol).

[0607] LC-MS (method A): retention time 0.41 min, m / z 210 [M+H+].

[0608] 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).

[0609] Step 2. Preparation of 4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline hydrochloride

[0610]

[0611] To a solution of 4-(1-methylpyrazol-4-yl)isoquinoline (prepared as described in step 1 above, 115 mg, 0.550 mmol) in methanol (5.5 mL) was added sodium cyanoborohydride (218 mg, 3.30 mmol, 6.00 equiv.) at room temperature. 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 for 30 min at room temperature, 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 2 M 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.

[0612] 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)

[0613]

[0614] To a solution of 4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline hydrochloride (prepared as described in step 2 above, 200 mg, 0.664 mmol) in DMF (6.6 mL) 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.) at room temperature, followed by the addition of 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 completion of the reaction, confirmed 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 dimethyl sulfoxide (DMSO) (3 mL) and acidified with a few drops of formic acid before purification by reverse phase chromatography (acetonitrile 30% to 100%) to afford the desired product as a white solid (222 mg, 0.528 mmol).

[0615] LC-MS (method A): retention time 1.04 min, m / z 421 [M+H+].

[0616] 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)

[0617]

[0618] Step 1. Preparation of (1-methylpyrazol-4-yl)phenylmethanol

[0619]

[0620] A single-neck round-bottomed flask equipped with a magnetic stirrer was charged with 1-methyl-1H-pyrazole-4-carbaldehyde (2.20 g, 19.2 mmol) and THF (40 mL). 1 M phenylmagnesium bromide in THF (21 mL, 21.1 mmol) was added dropwise to the colorless solution at 0-5 °C under argon atmosphere over 15 min. After the 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 saturated NH4Cl solution (40 mL) and extracted with ethyl acetate (2×40 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 chromatography on CombiFlash (silica gel, gradient: ethyl acetate in cyclohexane) to give the desired product (1-methylpyrazol-4-yl)phenylmethanol as a colorless oil.

[0621] LC-MS (Method A): 189 [M+H]+; retention time: 0.62 min.

[0622] 1 H NMR (400 MHz, 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).

[0623] Step 2. Preparation of 2-(1-methylpyrazol-4-yl)-2-phenylacetonitrile

[0624]

[0625] A round-bottomed flask equipped with a magnetic stirrer and a condenser was charged with (1-methylpyrazol-4-yl)phenylmethanol (prepared as described above in step 1, 3.45 g, 15.6 mmol) and dichloromethane (156 mL). Then, lithium carbonate (0.23 g, 3.1 mmol), trimethylsilyl cyanide (9.0 mL), and iodine (7.23 g, 28.0 mmol) were added sequentially at room temperature. The mixture was stirred at 35 °C for 1 hour. The reaction mixture was then cooled to room temperature and poured into a saturated 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 chromatography on CombiFlash (silica gel, gradient: ethyl acetate in cyclohexane) to give the desired title compound as a yellow oil.

[0626] LC-MS (Method A): 198 [M+H]+; retention time: 0.78 min.

[0627] 1 H NMR (400 MHz, CDCl3) δ ppm 3.87 (s, 3H) 5.09 (s, 1H) 7.32 (s, 1H) 7.33-7.43 (m, 6H).

[0628] Step 3. Preparation of 2-(1-methylpyrazol-4-yl)-2-phenylpropanenitrile

[0629]

[0630] A 250 mL 3-necked flask equipped with a magnetic stirrer and a condenser was charged with 2-(1-methylpyrazol-4-yl)-2-phenylacetonitrile (prepared as described in step 2 above, 3.22 g, 16.3 mmol) and THF (65 mL). A solution of n-butyl lithium in hexane (7.8 mL, 19.6 mmol) was added dropwise at -70 °C under a nitrogen atmosphere. The orange solution was stirred at this temperature for 30 minutes before adding iodomethane (1.54 mL, 24.5 mmol) dropwise at -70 °C. The resulting yellow solution was stirred at -78 °C for 5 minutes and then allowed to warm to ambient temperature and stirred for 30 minutes. 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 yield the crude product as an orange oil.It was purified by chromatography on CombiFlash (silica gel, gradient: ethyl acetate in cyclohexane) to give the title compound as a yellow oil.

[0631] LC-MS (Method A): 211 [M+H]+; retention time: 0.84 min.

[0632] 1 H NMR (400 MHz, CDCl3) δ ppm 2.04 (s, 3H) 3.88 (s, 3H) 7.28–7.49 (m, 7H).

[0633] Step 4. Preparation of 2-(1-methylpyrazol-4-yl)-2-phenylpropan-1-amine

[0634]

[0635] A 250 mL 3-necked flask equipped with a magnetic stirrer was charged with 2-(1-methylpyrazol-4-yl)-2-phenylpropanenitrile (obtained as described in Step 3 above, 2.82 g, 13.3 mmol) and THF (40 mL). Borane dimethyl sulfide complex (4.0 mL, 40.0 mmol) was added dropwise to the yellow solution at room temperature under an argon atmosphere, and the resulting colorless mixture was stirred at 65 °C for 2 hours. The reaction mixture was cooled to 0 °C before hydrochloric acid (8.9 mL, 53.7 mmol) was added dropwise (strong gas evolution), and the mixture was stirred at 65 °C for 1 hour and left to stand overnight at room temperature. 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 without further purification in the next step.

[0636] LC-MS (Method A): 216 [M+H]+; retention time: 0.39 min.

[0637] Step 5. Preparation of methyl N-[2-(1-methylpyrazol-4-yl)-2-phenylpropyl]carbamate

[0638]

[0639] 2-(1-methylpyrazol-4-yl)-2-phenylpropan-1-amine (prepared as described in step 4 above, 3.01 g, 11.2 mmol) and dichloromethane (45 mL) were charged into a sealed tube equipped with a magnetic stirrer. Methyl chloroformate (1.1 mL, 13.4 mmol) and then triethylamine (4.7 mL, 33.6 mmol) were added dropwise at 0-10 °C under an argon atmosphere. The ice bath was removed and the mixture was stirred at room temperature for 1 h. The reaction mixture was poured into water and the organic phase was separated. The aqueous phase was extracted twice with ethyl acetate. The combined organic layers were dried over sodium sulfate and concentrated in vacuo. The crude material was purified by chromatography on CombiFlash (silica gel, gradient: ethyl acetate in cyclohexane) to give the title compound as a colorless gum.

[0640] LC-MS (Method A): 274 [M+H]+; retention time: 0.80 min.

[0641] Step 6. Preparation of methyl 4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinoline-2-carboxylate

[0642]

[0643] A single-neck round-bottom flask equipped with a magnetic stirrer was charged with methyl N-[2-(1-methylpyrazol-4-yl)-2-phenylpropyl]carbamate (prepared as described in step 5 above, 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, at which time the reaction was complete by LC-MS analysis. The reaction mixture was slowly poured into water (30 mL), neutralized with NaHCO3, and extracted with ethyl acetate (3×20 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 such without further purification.

[0644] LC-MS (Method A): 286 [M+H]+; retention time: 0.87 min.

[0645] Step 7. Preparation of 4-methyl-4-(1-methylpyrazol-4-yl)-2,3-dihydro-1H-isoquinoline

[0646]

[0647] A single-neck round-bottom flask equipped with a magnetic stirrer was charged with methyl 4-methyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinoline-2-carboxylate (prepared as described in Step 6 above, 3.86 g, 13.5 mmol), 1,2-dichloropentane (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, and LC-MS analysis showed the reaction to be complete. 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.

[0648] LC-MS (Method A): 228 [M+H]+; retention time: 0.61 min.

[0649] 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)

[0650]

[0651] To a solution of 4-methyl-4-(1-methylpyrazol-4-yl)-2,3-dihydro-1H-isoquinoline (obtained as described in Step 7 above, 1.50 g, 6.60 mmol) in ethyl acetate (27 mL) were 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. T3P (7.56 g, 7.07 mL, 11.9 mmol) was added to this solution, 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 x 20 mL). The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated in vacuo. The crude product was purified by chromatography on a CombiFlash (12 g SiO2 cartridge, eluting with an EtOAc / cyclohexane gradient) to afford the title compound as a colorless gum.

[0652] LC-MS (Method A): 435 [M+H]+; retention time: 1.06 min.

[0653] 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)

[0654]

[0655] 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 chiral HPLC using supercritical fluid chromatography (SFC).

[0656] SFC analytical method:

[0657] SFC: Waters Acquity UPC 2 / QDa

[0658] PDA Detector Waters Acquity UPC 2

[0659] Column: Daicel SFC CHIRALPAK ® IA, 3 µm, 0.3 cm × 10 cm, 40°C

[0660] Mobile phase: A: CO2 B: EtOH isocratic mode: 20% B for 4.8 min.

[0661] ABPR: 1800 psi

[0662] Flow rate: 2.0ml / min.

[0663] Detection: at 257 nm

[0664] Sample concentration: 1 mg / mL in acetonitrile

[0665] Injection volume: 1 μL

[0666] Method of preparative SFC:

[0667] Column: Daicel CHIRALPAK ® AY, 5 µm, 2.0 cm × 25 cm

[0668] Mobile phase: A: CO2B: MeOH, isocratic mode: 30% B

[0669] Back pressure: 150 bar

[0670] Flow rate: 60 ml / min

[0671] GLS Pump: -

[0672] Detection: at UV 257nm

[0673] Sample concentration: 80 mg in 2 ml acetonitrile

[0674] Injection volume: 500μL

[0675] Two peaks were identified.

[0676] Peak 1: 21 mg, white crystals; retention time (min.) 3.55; chemical purity (% area at 257 nm)>99%; enantiomeric excess (%)>99%.

[0677] Peak 2: 21 mg, white solid; retention time (min) ~2.72; chemical purity (% area at 245 nm) >99%; enantiomeric excess (%) >99%.

[0678] It was demonstrated that peak 1 was characterized by the absolute (R)-configuration according to the X-ray analysis, and it was demonstrated that peak 2 was characterized by the absolute (S)-configuration according to the X-ray analysis.

[0679] The (S)-enantiomer (compound P48, Table T1) was found to be more fungicidally active than the (R)-isomer (compound P49, Table T1).

[0680] 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)

[0681]

[0682] Step 1. Preparation of tert-butyl 4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxylate

[0683]

[0684] To a suspension of 4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline hydrochloride (prepared as described above in Example P1, Step 2, 200 mg, 0.698 mmol) in dichloromethane (3.5 mL) were 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) at room temperature. The reaction mixture was stirred at room temperature overnight. The reaction mixture was diluted with saturated ammonium chloride solution and extracted with dichloromethane (×3). 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 (eluting with ethyl acetate in cyclohexane) gave the title product as a colourless oil.

[0685] LC-MS (Method A): 314 [M+H]+; retention time: 1.01 min.

[0686] Step 2. Preparation of tert-butyl 1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxylate

[0687]

[0688] To a solution of tert-butyl 4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxylate (obtained as described in Step 1 above, 50 mg, 0.16 mmol) and N,N,N',N'-tetramethylethylenediamine (0.073 ml, 0.48 mmol) in tetrahydrofuran (1.6 ml), tert-butyl lithium (1.7 M in pentane, 0.19 ml, 0.32 mmol) was added dropwise at -78°C. The reaction mixture was stirred at the same temperature for 30 minutes. After this time, 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 min at the same temperature. The reaction mixture was allowed to reach room temperature, diluted with saturated ammonium chloride solution, and extracted with dichloromethane (×3). The combined organic layers were dried over sodium sulfate, filtered, and concentrated in vacuo to yield the desired product, which was used without further purification.

[0689] LC-MS (Method A): 328 [M+H]+; retention time: 1.05 min.

[0690] Step 3. Preparation of 1-methyl-4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinolin-2-ium trifluoroacetate salt

[0691]

[0692] To a solution of tert-butyl 1-methyl-4-(1-methylpyrazol-4-yl)-3,4-dihydro-1H-isoquinoline-2-carboxylate (prepared as described in Step 2 above, 150 mg, 0.229 mmol) in dichloromethane (1.1 mL) was added 2,2,2-trifluoroacetic acid (0.23 mL) at room temperature. The reaction mixture was stirred for 1 hour at room temperature. The reaction mixture was then concentrated under reduced pressure to obtain the product, which was used without further purification.

[0693] LC-MS (Method A): 228 [M+H]+; retention time: 0.43 min.

[0694] 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)

[0695]

[0696] A solution of 1-methyl-4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinolin-2-ium trifluoroacetate salt (prepared as described 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 overnight at room temperature. The reaction mixture was quenched with saturated NH4Cl solution and then extracted with dichloromethane (× 3). The combined organic layers were dried over Na2SO4, filtered, and concentrated in vacuo. The crude product was purified by chromatography on a CombiFlash (24 g SiO2 cartridge, eluting with cyclohexane and ethyl acetate) to afford the title compound as a 3:1 diastereomeric mixture of anti- and syn-isomers.

[0697] LC-MS (Method A): 435 [M+H]+; retention time: 1.72 min.

[0698] 1 H NMR (600 MHz, DMSO-d6) δ ppm 1.24 (s, 2H); 1.40 (s, 5H); 1.55 (s, 2H); 1.57 (d, J=6.7 Hz, 10H); 1.63 (d, J=6.9 Hz, 2H); 1.69 (d, J=6.7 Hz, 1H); 1.91 (s, 1H); 2.52-2.55 (m, 5H); 3.58 (br d, J=9.3 Hz, 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, 3.5 Hz, 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=6.7 Hz, 1H); 5.76-5.80 (m, 3H); 6.12 (d, J=3.1 Hz, 3H); 6.85(s, 3H); 6.92 (br d, J=7.7 Hz, 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,.7=1.1 Hz, 1H); 7.32-7.37 (m, 7H); 7.41 (d, J=7.8 Hz, 3H); 7.44(s, 1H); 7.56-7.61 (m, 5H); 8.02 (td, J=8.7, 6.4 Hz, 3H); 8.06-8.12 (m, 2H).

[0699] 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

[0700]

[0701] Step 1. Preparation of methyl 1,4-dimethyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinoline-2-carboxylate

[0702]

[0703] A 50 mL 3-necked round-bottomed flask equipped with a magnetic stirrer was charged with methyl N-[2-(1-methylpyrazol-4-yl)-2-phenylpropyl]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). 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. It was used in the next step without further purification.

[0704] LC-MS standard: 300 [M+H]+; retention time: 0.91 min.

[0705] Step 2. Preparation of 1,4-dimethyl-4-(1-methylpyrazol-4-yl)-2,3-dihydro-1H-isoquinoline

[0706]

[0707] Methyl 1,4-dimethyl-4-(1-methylpyrazol-4-yl)-1,3-dihydroisoquinoline-2-carboxylate (prepared as described in step 1 above, 1.1 g, 3.3 mmol), 1,2-dichloroethane (16 mL), and iodotrimethylsilane (1.4 mL, 9.7 mmol) were charged into a single-necked round-bottomed flask equipped with a magnetic stirrer. The mixture was stirred at 60°C under argon atmosphere for 1 h. Then, the reaction mixture was cooled to room temperature and slowly poured 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 as such in the next step. LC-MS standard: 242 [M+H]+; retention time: 0.54 min.

[0708] Step 3. Preparation of 5-(2,4-difluorophenyl)isoxazole-3-carbonyl chloride

[0709]

[0710] A suspension of 5-(2,4-difluorophenyl)isoxazole-3-carboxylic acid (1.00 g, 4.3 mmol) in tetrahydrofuran (22 mL) was treated at room temperature with one drop of DMF, followed by oxalyl chloride (0.38 mL, 4.3 mmol). The light yellow solution was stirred at ambient temperature under a nitrogen atmosphere for 14 h, and then the solvent was removed in vacuo to give the title compound as a yellow solid.

[0711] LC-MS (quenched with MeOH) of ester: 240 [M+H]+, retention time: 0.97.

[0712] 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

[0713]

[0714] A solution of 1,4-dimethyl-4-(1-methylpyrazol-4-yl)-2,3-dihydro-1H-isoquinoline (prepared as described in step 2 above, 0.24 g, 1.0 mmol) in tetrahydrofuran (2.4 mL) was transferred into a Supelco vial under argon atmosphere. To this solution were added 5-(2,4-difluorophenyl)isoxazole-3-carbonyl chloride (0.40 g, 1.0 mmol) and then triethylamine (0.42 mL, 3.0 mmol). The reaction mixture was stirred at room temperature for 17 h and then poured into an aqueous NaHCO3 solution and diluted with ethyl acetate. After layer separation, the aqueous phase was back extracted with ethyl acetate, and the combined organic phases were washed with water and brine. The organic layer was dried over sodium sulfate, filtered, and concentrated in vacuo. The crude material was purified by chromatography on CombiFlash (silica gel, gradient: ethyl acetate in cyclohexane) to afford the title compound as a brown gum.

[0715] LC-MS standard: 449 (M+H)+; retention time: 1.07 min.

[0716] NMR analysis demonstrated that the compound is an approximately 1:1 mixture of syn- and anti-isomers.

[0717] 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 chiral HPLC using supercritical fluid chromatography (SFC).

[0718] SFC analytical method:

[0719] SFC: Waters Acquity UPC 2 / QDa

[0720] PDA Detector Waters Acquity UPC 2

[0721] Column: Daicel SFC CHIRALPAK ® IH, 3 µm, 0.46 cm × 10 cm, 40°C

[0722] Mobile phase: A: CO2B: MeOH, isocratic mode: 15% B for 10 min.

[0723] ABPR: 1800 psi

[0724] Flow rate: 2.0 ml / min.

[0725] Detection: at 255nm

[0726] Sample concentration: 1 mg / mL in dichloromethane / acetonitrile

[0727] Injection volume: 1 μL

[0728] Method of preparative SFC:

[0729] Sepiatec Prep SFC 100

[0730] Column: Daicel Chiralpak ® IG, 5 µm, 2.0 cm × 25 cm

[0731] Mobile phase: A: CO2 B: IPA isocratic mode: 12% B

[0732] Back pressure: 150 bar

[0733] Flow rate: 90ml / min.

[0734] GLS Pump: -

[0735] Detection: UV at 255nm

[0736] Sample concentration: 260 mg in 2 ml dichloroethane / acetonitrile

[0737] Injection volume: 350 µl

[0738] Four peaks were identified.

[0739] Peak 1: 46 mg, brown gum; retention time (min) 1.88 min; chemical purity (% area at 255 nm) >93%; enantiomeric excess (%) ~98%.

[0740] Peak 2: 38 mg, brown gum; retention time (min) 2.09 min; chemical purity (% area at 255 nm) >96%; enantiomeric excess (%) ~98%.

[0741] Peak 3: 43 mg, brown gum; retention time (min.) 2.56 min; chemical

[0742] Purity (Area% at 255 nm)>98%; Enantiomeric Excess (%) ~98%.

[0743] Peak 4: 46 mg, brown gum; retention time (min.) 2.09 min; chemical

[0744] Purity (Area% at 255nm)>99%; Enantiomeric Excess (%) ~99%.

[0745] By analysis 1 H NMR showed that peaks 1 and 2 have identical NMR spectra and are characterized by the relative positions of the anti-methyl and pyrazole as determined by ROSY 2D NMR, see below:

[0746]

[0747] Peaks 3 and 4 also had identical NMR spectrum, but different from the NMR spectrum of peaks 1 and 2. Using NMR analysis, in particular ROSY 2D NMR, nOe are shown, which confirm that the methyl and pyrazole groups are characterized by a syn- arrangement, see below:

[0748]

[0749] 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).

[0750] 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).

[0751] 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).

[0752] 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).

[0753] The compound of peak 1 (compound P9, Table T1) was shown to be more fungicidally active than the compound of peak 2 (compound P8, Table T1). The compound of peak 4 (compound P6, Table T1) was also shown to be more fungicidally active than the compound of peak 3 (compound P7, Table T1).

[0754] Example P7. Preparation of rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-1,2,3,4-tetrahydroisoquinopine

[0755]

[0756] Step 1. Preparation of methyl N-[2-(1,5-dimethylpyrazol-4-yl)-2-phenylethyl-1carbamate

[0757]

[0758] 2-(1,5-Dimethylpyrazol-4-yl)-2-phenylethanamine (3.5 g, 16 mmol), ethyl acetate (65 mL), and triethylamine (6.8 mL, 49 mmol) were charged into a three-necked flask equipped with a mechanical stirrer. Then, methyl chloroformate (1.5 mL, 20 mmol) was added dropwise at 0 °C under argon atmosphere over 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 vacuo. The crude material was purified by FCC (80 g SiO2, EtOAc / cyclohexane gradient) to give methyl N-[2-(1,5-dimethylpyrazol-4-yl)-2-phenylethyl]carbamate.

[0759] LC-MS (method A): retention time 0.76 min, 274 (M+H)

[0760] 1 H NMR (400 MHz, CDCl3) δ ppm 2.03-2.13 (m, 3H) 3.62-3.74 (m, 5H) 3.77 (s, 3H) 3.94-4.05 (m, 1H) 4.72 (brs, 1H) 7.21-7.26 (m, 3H) 7.27-7.34 (m, 2H) 7.38 (s, 1H)

[0761] Step 2. Preparation of rac-methyl [-(1S,4S)-4-([5-dimethylpyrazol-4-yl)-1-methyl-3,4-dihydro-1H-isoquinoline-2-carboxylate

[0762]

[0763] A single-neck round-bottom flask equipped with a magnetic stirrer was charged with methyl N-[2-(1,5-dimethylpyrazol-4-yl)-2-phenylethyl]carbamate (2.0 g, 7.3 mmol), hydrochloric acid (conc. 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), slowly neutralized with NaHC3 portionwise (strong gas evolution) to pH 8. The mixture was extracted with EtOAc (3×50 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-carboxylates as one syn-diastereoisomer 1 H NMR

[0764] LC-MS (method A): retention time 0.87 min, 300 (M+H)

[0765] 1 H NMR (400 MHz CDCl3) δ ppm: 1.56 (d, J=6.90 Hz, 3H); 2.18 (br s, 3H); 3.02-3.27 (m, 1H); 3.76 (br s, 3H); 3.83 (s, 3H); 3.97-4.09 (m, 1H); 4.09-4.37 (m, 1H); 5.18-5.45 (m, 1H); 6.86-7.02 (m, 1H); 7.04-7.24 (m, 4H).

[0766] Step 3. Preparation of rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-1,2,3,4-tetrahydroisoquinoline

[0767]

[0768] A 100 mL single-neck round-bottom flask equipped with a magnetic stirrer was charged with rac-methyl (13,43)-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 argon atmosphere. The reaction mixture was cooled to rt, then 22 mL of 10% aqueous HCl was added to the reaction mixture 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 yield rac-(1S,4S)-4-(1,5-dimethylpyrazol-4-yl)-1-methyl-1,2,3,4-tetrahydroisoquinoline, which was pure enough to be used without further purification.

[0769] LC-MS (method A): retention time 0.35 min, 242 (M+H)

[0770] 1H NMR (600 MHz, CHLOROFORM-d) δ ppm 1.86 (d, J=6.9 Hz, 3H) 2.23 (s, 3H) 3.27 (dd, J=12.5, 10.8 Hz, 1H) 3.59 (dd, J=12.8, 5.6 Hz, 1H) 3.83 (s, 3H) 4.58 (dd, J=10.6, 5.4 Hz, 1H) 4.80 (q, J=6.8 Hz, 1H) 7.00 (d, J=7.8 Hz, 1H) 7.11 (s, 1H) 7.16 (d, J=7.6 Hz, 1H) 7.18-7.22 (m, 1H) 7.25-7.28 (m, 1H)

[0771] Example P8. Preparation of 1,4-dimethyl-4-(1-methylpyrazol-4-yl)-2,3-dihydro-1H-isoquinoline

[0772]

[0773] Step 1. Preparation of tert-butyl N-[2-hydroxy-2-(1-methylpyrazol-4-yl)propyl]-N-(1-phenylethyl)carbamate

[0774]

[0775] Method 1. Step 1. Preparation of tert-butyl N-[2-(1-methylpyrazol-4-yl)-2-oxoethyl]-N-(1-phenylethyl)carbamate

[0776]

[0777] 2-Bromo-1-(1-methyl-1H-pyrazol-4-yl)ethanone (1 g, 4.72 mmol) and N,N-dimethylacetamide (23.6 mL) were charged into a three-necked flask equipped with a magnetic stirrer. The resulting mixture was cooled to 0 °C under an argon atmosphere, and then DL-alpha-methylbenzylamine (0.64 mL, 4.72 mmol) was slowly added (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-butyl pyrocarbonate (1.14 g, 5.2 mmol) dissolved in N,N-dimethylacetamide (23.6 mL) was added dropwise at 0°C under argon. The reaction mixture was allowed to warm to rt and stirred overnight. HCl was added to the reaction mixture (to adjust pH to 3), and the aqueous layer was then 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 silica gel chromatography with a cyclohexane / ethyl acetate gradient to give the title compound as a white solid.

[0778] LC-MS (method A): retention time 0.99 min, 344 (M+H)

[0779] 1 H NMR (400 MHz, CDCl3) δ ppm 1H NMR (400 MHz, Solvent) δ ppm 7.74-7.99 (m, 2H) 7.35 (br d, J=5.1 Hz, 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)

[0780] Method 1. Step 2. Preparation of tert-butyl N-[2-hydroxy-2-(1-methylpyrazol-4-yl)propyl 1-N-(1-phenylethyl)carbamate

[0781]

[0782] Tert-butyl N-[2-(1-methylpyrazol-4-yl)-2-oxoethyl]-N-(1-phenylethyl)carbamate (100 mg, 0.291 mmol) and tetrahydrofuran (1.5 mL) were charged into a round-bottomed flask equipped with a magnetic stirrer, and the resulting mixture was cooled to 0 °C under argon atmosphere. Then, 3 M methylmagnesium bromide solution (0.24 mL, 0.728 mmol) was added dropwise under argon atmosphere at 0 °C. After 1.5 h, the reaction mixture was warmed to rt. An additional portion of 3 M methylmagnesium bromide solution (0.24 mL, 0.728 mmol) was added at rt, and the mixture was stirred for 2.5 h at rt. and then 21 hours at 60°C. The reaction mixture was cooled and saturated aqueous NH4Cl was added.The aqueous layer was then extracted with ethyl acetate and the combined organic layers were washed with brine and 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 (ca. 70%) and tert-butyl N-[2-(1-methylpyrazol-4-yl)-2-oxoethyl]-N-(1-phenylethyl)carbamate (ca. 30%). The desired product was not isolated using an additional purification method.

[0783] LC-MS (method A): retention time 1.02 min, 360 (M+H)

[0784] Method 2. Step 1. Obtaining tert-butyl N-acetonyl N-(1-phenylethyl)carbamate

[0785]

[0786] 1-Chloropropan-2-one (0.86 mL, 10.27 mmol), N,N-dimethylacetamide (51 mL), and potassium iodide (1.705 g, 10.27 mmol) were charged into a three-necked flask equipped with a magnetic stirrer. The resulting mixture was cooled to 0 °C under an argon atmosphere, and then DL-alpha-methylbenzylamine (1.4 mL, 10.27 mmol) was slowly added. 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 because the starting material was still present. The resulting mixture was stirred for 3 h at 0°C to 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. The reaction mixture was warmed to rt and stirred overnight. HCl was then added to the mixture (to pH 3), and the aqueous layer was then 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 silica gel chromatography with a cyclohexane / ethyl acetate gradient to afford tert-butyl N-acetonyl N-(1-phenylethyl)carbamate as an orange / brown liquid.

[0787] LC-MS (method A): retention time 1.04 min, 300 (M+Na)

[0788] 1H NMR (400 MHz, 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, 12 H)

[0789] Method 2. Step 2. Preparation of tert-butyl N-[2-hydroxy-2-(1-methylpyrazol-4-yl)propyl 1-N-(1-phenylethyl)carbamate

[0790]

[0791] 4-iodo-1-methyl-1H-pyrazole (3.1 g, 14 mmol) and tetrahydrofuran (12 mL) were charged into a 100 mL three-necked flask, and the resulting mixture was cooled to 0 °C under an argon atmosphere. A solution of o-propyl magnesium chloride lithium chloride complex (1.3 mol / L) in THF (12 mL, 16 mmol) was slowly added thereto (over 15 min). The mixture was kept under stirring at 0 °C. Then, after 45 min, tert-butyl N-acetonyl-N-(1-phenylethyl)carbamag (1.6 g, 5.8 mmol) dissolved in tetrahydrofuran (12 mL) was added dropwise under an argon atmosphere at 0 °C. The reaction mixture was warmed to room temperature (a precipitate formed, yielding a yellow solution) and stirred overnight at room temperature. The reaction mixture was neutralized with saturated aqueous 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 yield the crude product as a yellow sticky oil.The crude mixture was purified by silica gel chromatography with a cyclohexane / ethyl acetate gradient to give tert-butyl N-[2-hydroxy-2-(1-methylpyrazol-4-yl)propyl]-N-(1-phenylethyl)carbamate.

[0792] LC-MS (method A): retention time 1.01 min, 361 (M+2H)

[0793] 1 H NMR (400 MHz, 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, 12 H)

[0794] Step 2. Preparation of 1,4-dimethyl-4-(1-methylpyrazol-4-yl)-2,3-dihydro-1H-isoquinoline

[0795]

[0796] Method 1.

[0797] Tert-butyl N-[2-hydroxy-2-(1-methylpyrazol-4-yl)propyl]-N-(1-phenylethyl)carbamate (50 mg, 0.139 mmol) was charged into a 5 mL vial 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 and at room temperature for 3 days and finally at 60 °C for 2 h. The reaction mixture was carefully poured into saturated sodium bicarbonate solution, 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- ~ 1:3)

[0798] LC-MS (method A): retention time 0.51 min, 242 (M+H)

[0799] 1H NMR (400 MHz, 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, 7.01 Hz, 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=6.54 Hz, 1H) 1.26 (t, J=7.08 Hz, 2H)

[0800] Method 2.

[0801] 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) were charged into a 5 mL vial under argon atmosphere at room temperature. The resulting mixture was stirred for 1 h at room temperature, 1 h at 50 °C and overnight at room temperature and finally for 3 h at 60 °C. 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, poured into saturated sodium bicarbonate solution, and then extracted with ethyl acetate, dried over sodium sulfate, filtered, and concentrated in vacuo to afford the crude title product. Analyses of the crude material were consistent with the product structure (a mixture of anti- and syn- diastereoisomers ~1:1).

[0802] LC-MS (method A): retention time 0.51 min, 242 (M+H)

[0803] 1 H NMR (400 MHz, 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, 7.01 Hz, 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=6.54 Hz, 1H) 1.26 (t, J=7.08 Hz, 2H)

[0804] Example P10. Preparation of 1-methyl-4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline

[0805]

[0806] Step 1. Preparation of tert-butyl N-[2-hydroxy-2-(1-methylpyrazol-4-yl)ethyl]-N-(1-phenylethyl)carbamate

[0807]

[0808] 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) were charged into a 25 mL flask at 0 °C. Then, the reaction mixture was allowed to warm to room temperature and stirred for 1.5 h. The reaction mixture was diluted with saturated ammonium chloride solution and ethyl acetate. After layer separation, the aqueous layer was extracted once with ethyl acetate. The combined organic layer was 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.

[0809] LC-MS (method A): retention time 0.98 min, 346 (M+H)

[0810] 1H NMR (400 MHz, CDCl3) δ ppm 7.10 (s, 6H) 6.95 (br d, J=0.73 Hz, 7H) 5.20-5.45 (m, 2H) 4.85 (br d, J=8.72 Hz, 1H) 4.16-4.31 (m, 1H) 3.85 (d, J=13.08 Hz, 6H) 3.31-3.65 (m, 2H) 2.91-3.15 (m, 2H) 1.59 (d, J=7.27 Hz, 3H) 1.44-1.51 (m, 12H) 1.59 (d, J=7.27 Hz, 3H)

[0811] Step 2. Preparation of 1-methyl-4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline

[0812]

[0813] Method 1.

[0814] 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, then 3.5 h at 40 °C. The reaction mixture was carefully quenched with saturated sodium bicarbonate solution and diluted with ethyl acetate. After separating 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 3:1 mixture of anti-:syn diastereoisomers.

[0815] LC-MS (method A): retention time 0.15-0.33 min, 228 (M+H)

[0816] 1H NMR (400 MHz, 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, 4.90 Hz, 1H) 3.11-3.37 (m, 1H) 3.03 (dd, J=12.90, 7.81 Hz, 1H) 2.79-2.98 (m, 2H) 1.47-1.58 (m, 4H) 2.79-2.98 (m, 2H)

[0817] Method 2. Step 1. Preparation of 5-(1-methylpyrazol-4-yl)-3-(1-phenylethyl)oxazolidin-2-one

[0818]

[0819] 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 saturated sodium bicarbonate solution. Then, it was diluted with ethyl acetate. After separating 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 vacuo. The crude material was purified by chromatography to afford 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)

[0820] Connection 1

[0821] LC-MS (method A): retention time 0.77 min, 272 (M+H)

[0822] 1H NMR (400 MHz, CDCl3) δ ppm 7.37 (d, J=2.18 Hz, 5H) 7.31 (s, 1H) 7.22 (s, 1H) 5.45 (dd, J=8.36, 6.90 Hz, 1H) 5.30 (q, J=7.15 Hz, 1H) 3.87 (s, 3H) 3.76-3.81 (m, 1H) 3.09 (dd, J=8.90, 6.72 Hz, 1H) 2.63-2.90 (m, 1H) 1.63 (d, J=7.27 Hz, 3H)

[0823] Connection 2

[0824] LC-MS (method A): retention time 0.79 min, 272 (M+H)

[0825] 1H NMR (400 MHz, CDCl3) δ ppm 7.52 (s, 1H) 7.47 (s, 1H) 7.30-7.42 (m, 5H) 5.40 (t, J=7.81 Hz, 2H) 5.21-5.34 (m, 2H) 3.95 (s, 3H) 335-3.52 (m, 3H) 2.91-3.13 (m, 1H) 1.60 (d, J=6.90 Hz, 3H)

[0826] Method 2. Step 2. Preparation of 1-methyl-4-(1-methylpyrazol-4-yl)-1,2,3,4-tetrahydroisoquinoline

[0827]

[0828] 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) were charged into a 5 mL vial under argon atmosphere at rt. Then, aluminum chloride (0.06144 g, 0.460 mmol) was 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 saturated sodium bicarbonate solution, and the mixture was diluted with ethyl acetate. After separating 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 3:2 anti / syn mixture of diastereoisomers.

[0829] LC-MS (method A): retention time 0.34 min, 22S (M+H)

[0830] Further examples of the synthesized compounds of formula (I) are shown in Table T1.

[0831]

[0832]

[0833]

[0834]

[0835]

[0836]

[0837]

[0838]

[0839]

[0840]

[0841]

[0842]

[0843]

[0844]

[0845]

[0846]

[0847]

[0848]

[0849]

[0850]

[0851]

[0852]

[0853]

[0854]

[0855]

[0856]

[0857]

[0858]

[0859]

[0860]

[0861]

[0862]

[0863]

[0864]

[0865]

[0866]

[0867]

[0868]

[0869]

[0870]

[0871]

[0872]

[0873]

[0874]

[0875]

[0876]

[0877]

[0878]

[0879]

[0880]

[0881]

[0882]

[0883]

[0884]

[0885]

[0886]

[0887] BIOLOGICAL EXAMPLES

[0888] Example B1. Treatment of leaf disc / tomato / Alternaria solani I (early blight)

[0889] The leaf discs of the Baby tomato cultivar were placed on agar in multi-well plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf discs were inoculated with the fungal spore suspension 2 days after application. The inoculated leaf discs were incubated at 23°C / 21°C (day / night) and 80% relative humidity under a 12 h / 12 ​​h (light / dark) light regime in a climate chamber, and the compound activity was evaluated as a percentage of disease control compared to the untreated material when the corresponding degree of disease damage appeared on the untreated leaf discs, which represented the control discs (5-7 days after application).

[0890] The following compounds provided at least 80% control of Alternaria solani at 200 ppm compared to the untreated control, which showed extensive disease development under the same conditions:

[0891] Р-2, Р-6, Р-10, Р-11, Р-13, Р-18, Р-38, Р-42, Р-45, Р-46, Р-48, Р-51, Р-52, Р-53, Р-55, Р-56, Р-63, Р-64, Р-65, Р-92, Р-100, R-104, R-105, R-108, R-109, R-110, R-115, R-118, R-119, R-120, R-124, R-126, R-127, R-131, R-133, R-134, R-136, R-140, R-141, R-142, R-143, R-146, R-148, R-151, R-158, R-163, R-165, R-168, R-180, R-181, R-182, R-191, R-207, R-208, R-225, and R-228

[0892] Example B2. Treatment of liquid culture of Botryotinia fuckeliana (Botrytis cinerea) I (gray mold)

[0893] Fungal conidia from cryogenic storage were directly mixed with nutrient broth (Vogel's broth). After adding the test compound solution in DMSO to a 96-well microtiter plate, nutrient broth containing fungal spores was added. The plates containing the test compound were incubated at 24°C, and growth inhibition was determined photometrically 3-4 days after application.

[0894] The following compounds provided at least 80% control of Botryotinia fuckeliana at 20 ppm compared to the untreated control, which showed extensive disease development under the same conditions:

[0895] Р-1, Р-6, Р-11, Р-16, Р-38, Р-42, Р-45, Р-47, Р-48, Р-49, Р-52, Р-53, Р-63, Р-64, Р-65, Р-100, Р-105, Р-108, Р-109, Р-110, R-119, R-120, R-135, R-140, R-141, R-142, R-143, R-146, R-151, R-152, R-154, R-158, R-159, R-162, R-163, R-180, R-192, R-207, R-208, R-209, R-212, R-215, R-216, R-218, R-223, R-224, and R-227

[0896] Example B3. Cercospora kikuchii (soybean leaf spot)

[0897] Fungal conidia collected from cryogenic storage were mixed directly with nutrient broth (potato dextrose broth). A solution of test compounds (in DMSO) was added to a 96-well microtiter plate, and nutrient broth containing fungal spores was added. The plates containing the test compound were incubated at 24°C, and after 3-4 days, growth inhibition was determined photometrically at 620 nm.

[0898] The following compounds provided at least 80% control of Glomerella lagenarium at 20 ppm compared to the untreated control, which showed extensive disease development under the same conditions:

[0899] Р-38, Р-53, Р-65, Р-140 and Р-180.

[0900] Example B4. Cercospora sojina (selenophorous leaf spot of soybean)

[0901] Fungal conidia taken from cryogenic storage were mixed directly with nutrient broth (potato dextrose broth). A solution of test compounds (in DMSO) was added to a 96-well microtiter plate, and nutrient broth containing fungal spores was added. The plates containing the test compound were incubated at 24°C, and after 3-4 days, growth inhibition was determined photometrically at 620 nm.

[0902] The following compounds provided at least 80% control of Cercospora sojina at 20 ppm compared to the untreated control, which showed extensive disease development under the same conditions:

[0903] Р-38, Р-53, Р-65, Р-140 and Р-180.

[0904] Example B5. Glomerella lagenarium (Colletotrichum lagenarium) I liquid culture (anthracnose)

[0905] Fungal conidia taken from cryogenic storage were mixed directly with nutrient broth (potato dextrose broth). After adding a solution of the test compound in DMSO to a 96-well microtiter plate, the nutrient broth containing the fungal spores was added.

[0906] Test compound plates were incubated at 24°C and growth inhibition was measured photometrically 3-4 days after application.

[0907] The following compounds provided at least 80% control of Glomerella lagenarium at 20 ppm compared to the untreated control, which showed extensive disease development under the same conditions:

[0908] Р-1, Р-6, Р-10, Р-11, Р-14, Р-16, Р-18, Р-38, Р-45, Р-47, Р-48, Р-49, Р-50, Р-51, Р-52, Р-53, Р-56, Р-58, Р-62, Р-63, Р-64, R-65, R-76, R-92, R-97, R-100, R-104, R-105, R-108, R-109, R-110, R-111, R-117, R-119, R-120, R-121, R-124, R-126, R-138, R-139, R-140, R-141, R-142, R-143, R-149, R-151, R-152, R-154, R-155, R-158, R-162, R-163, R-165, R-166, R-169, R-180, R-181, R-187, R-188, R-190, R-191, R-192, R-194, R-205, R-206, R-207, R-208, R-209, R-212, R-215, R-216, R-223, R-224, R-225, R-226, R-227, R-228, R-229, R-231, R-232, and R-234

[0909] Example B6. Corynesyora cassiicola (target spot of tomato leaf)

[0910] Fungal conidia taken from cryogenic storage were mixed directly with nutrient broth (potato dextrose broth). A solution of test compounds (in DMSO) was added to a 96-well microtiter plate, and nutrient broth containing fungal spores was added. The plates with the test compound were incubated at 24°C, and after 3-4 days, growth inhibition was determined photometrically at 620 nm. The following compounds provided at least 80% control of Corynespora cassiicola at 20 ppm compared to the untreated control, which showed extensive disease development under the same conditions:

[0911] Р-38, Р-53, Р-65, Р-140 and Р-180.

[0912] Example B7. Treatment to prevent leaf disc infection / wheat / Blumeria sraminis f. sp.tritici (Erysiphe sraminis f. sp.tritici) l (powdery mildew of wheat)

[0913] Kanzler wheat leaf segments were placed on agar in a multi-well plate (24-well format) and sprayed with the formulated test compound diluted in water. Leaf discs were inoculated by shaking powdery mildew-infected plants over the test compound plates 1 day after application. The inoculated leaf discs were incubated at 20°C and 60% relative humidity under a 24-h light / dark followed by 12-h light / 12-h dark cycle in a climate chamber, and the compound activity was assessed as an indicator of disease control, expressed as a percentage, compared to untreated material by showing the corresponding degree of disease damage on untreated control leaf segments (6-8 days after application). The following compounds provided at least 80% control of Blumeria graminisf. sp.tritici at 200 ppm compared to an untreated control, which showed extensive disease development under the same conditions:.

[0914] Р-11, Р-63, Р-65, Р-104, Р-108, Р-109, Р-140, Р-141, Р-151, Р-207, and Р-208.

[0915] Example B8. Fusarium culmorum I culture in liquid medium (fusarium)

[0916] Fungal conidia collected from cryogenic storage were mixed directly with nutrient broth (potato dextrose broth). After adding a solution of the test compound in DMSO to a 96-well microtiter plate, nutrient broth containing fungal spores was added. The plates containing the test compound were incubated at 24°C, and growth inhibition was determined photometrically 3-4 days after application. The following compounds provided at least 80% control of Fusarium culmorum at 20 ppm compared to the untreated control, which showed extensive disease development under the same conditions:

[0917] Р-38, Р-52, Р-64, Р-65, Р-108, Р-119, Р-140, Р-212, and Р-223.

[0918] Example B9. Treatment to prevent leaf disc infection / wheat / (Septoria nodorum) I (septoria leaf spot)

[0919] Kanzler wheat leaf segments were placed on agar in a 24-well multiwell plate and sprayed with the formulated test compound diluted in water. Leaf discs were inoculated with a fungal spore suspension 2 days after application. The inoculated test leaf discs were incubated at 20°C and 75% relative humidity under a 12-hour light / 12-hour dark regime in a climate chamber. The compound activity was evaluated as a percentage of disease control compared to untreated material when the corresponding degree of disease damage was observed on untreated control leaf discs (5-7 days after application).

[0920] The following compounds provided at least 80% control of Phaeosphaeria nodorum at 200 ppm compared to the untreated control, which showed extensive disease development under the same conditions:

[0921] Р-2, Р-6, Р-10, Р-11, Р-13, Р-38, Р-40, Р-42, Р-45, Р-46, Р-48, Р-49, Р-51, Р-52, Р-53, Р-56, Р-62, Р-63, Р-64, Р-65, Р-100, R-104, R-105, R-108, R-109, R-110, R-117, R-119, R-120, R-136, R-140, R-141, R-142, R-143, R-146, R-151, R-180, R-204, R-208, R-221 and R-248

[0922] Example B10. Liquid culture treatment (Microdochium nivale) / (root rot of cereals)

[0923] Fungal conidia taken from cryogenic storage were mixed directly with nutrient broth (potato dextrose broth). After adding the test compound solution in DMSO to a 96-well microtiter plate, nutrient broth containing fungal spores was added. The plates containing the test compound were incubated at 24°C, and growth inhibition was determined photometrically 4-5 days after application.

[0924] The following compounds provided at least 80% control of Monographella nivalis at 20 ppm compared to the untreated control, which showed extensive disease development under the same conditions:

[0925] Р-1, Р-2, Р-6, Р-9, Р-11, Р-13, Р-14, Р-16, Р-17, Р-18, Р-30, Р-33, Р-34, Р-36, Р-38, Р-39, Р-40, Р-42, Р-45, Р-46, Р-47, Р-48, R-49, R-51, R-52, R-53, R-56, R-58, R-62, R-63, R-64, R-65, R-74, R-92, R-100, R-104, R-105, R-108, R-109, R-110, R-111, R-117, R-119, R-120, R-121, R-124, R-125, R-126, R-127, R-133, R-134, R-135, R-136, R-138, R-140, R-141, R-142, R-143, R-146, R-149, R-151, R-152, R-154, R-155, R-156, R-158, R-159, R-160, R-162, R-163, R-164, R-165, R-166, R-169, R-177, R-179, R-180, R-190, R-191, R-194, R-197, R-205, R-206, R-207, R-208, R-209, R-212, R-215, R-216, R-218, R-219, R-221, R-222, R-223, R-224, R-225, R-227, R-228, R-234, R-236, R-246, and R-248

[0926] Example B11. Liquid culture treatment / (Cercosyora arachidicola) (early leaf spot)

[0927] Fungal conidia collected from cryogenic storage were mixed directly with nutrient broth (potato dextrose broth). After adding a solution of the test compound in DMSO to a 96-well microtiter plate, the nutrient broth containing the fungal spores was added.

[0928] Tablets containing the test compound were incubated at 24°C and growth inhibition was determined photometrically 4-5 days after application.

[0929] The following compounds provided at least 80% control of Mycosphaerella arachidis at 20 ppm compared to the untreated control, which showed extensive disease development under the same conditions:

[0930] Р-1, Р-2, Р-6, Р-11, Р-14, Р-16, Р-18, Р-26, Р-30, Р-33, Р-34, Р-35, Р-38, Р-39, Р-40, Р-42, Р-45, Р-46, Р-47, Р-48, Р-50, R-51, R-52, R-53, R-63, R-64, R-65, R-92, R-100, R-104, R-105, R-108, R-109, R-110, R-114, R-117, R-118, R-119, R-120, R-121, R-123, R-124, R-125, R-126, R-133, R-134, R-135, R-137, R-138, R-139, R-140, R-141, R-142, R-143, R-146, R-148, R-151, R-152, R-154, R-155, R-158, R-159, R-162, R-163, R-165, R-166, R-172, R-176, R-179, R-180, R-181, R-182, R-188, R-191, R-194, R-205, R-207, R-208, R-209, R-212, R-215, R-218, R-220, R-221, R-222, R-223, R-224, R-227, R-228, R-229, R-231, R-232, R-234, R-236, R-239, R-241, R-247, and R-248

[0931] Example B12. Treatment to prevent leaf disc infection / grapes / Plasmoyara viticola (late blight)

[0932] Leaf discs of cultivated grapes were placed on an aqueous agar solution in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf discs were inoculated with a suspension of fungal spores 1 day after application. The undosed leaf discs were incubated at 19°C and 80% relative humidity under a 12-hour light / 12-hour dark regime in a climate chamber. The compound activity was evaluated as an indicator of disease control, expressed as a percentage, compared with untreated material, based on the corresponding degree of disease damage on untreated control leaf discs (6-8 days after application).

[0933] The following compounds provided at least 80% control of Plasmopara viticola at 200 ppm compared to the untreated control, which showed extensive disease development under the same conditions:

[0934] P-146 and P-147.

[0935] Example B13. Treatment after leaf disc infection / wheat / Puccinia recondita f. sp. tritici (brown rust)

[0936] Kanzler wheat leaf segments were placed on agar in multiwell plates (24-well format). The leaf segments were inoculated with a fungal spore suspension. The plates were stored in the dark at 19°C and 75% relative humidity. The formulated test compound diluted in water was used 1 day after inoculation. The leaf segments were incubated at 19°C and 75% relative humidity under a 12-hour light / 12-hour dark regime in a climate chamber, and the compound activity was assessed as an indicator of disease control, expressed as a percentage, compared to untreated material by showing a corresponding degree of disease damage on untreated control leaf segments (6-8 days after application). The following compounds provided at least 80% control of Puccinia recondita f. sp.tritici at 200 ppm compared to the untreated control, which under the same conditions showed extensive disease development:

[0937] R-47, R-104, R-140, and R-234

[0938] Example B14. Treatment to prevent leaf disc infection / wheat / Puccinia recondita f. sp. tritici I (brown rust)

[0939] Kanzler wheat leaf segments were placed on agar in 24-well multiwell plates and sprayed with the formulated test compound diluted in water. Leaf discs were inoculated with a fungal spore suspension 1 day after application. The inoculated leaf segments were incubated at 19°C and 75% relative humidity under a 12-hour light / 12-hour dark regime in a climate chamber. The compound activity was evaluated as a percentage of disease control compared to untreated material when the corresponding degree of disease damage was observed on untreated control leaf segments (7-9 days after application).

[0940] The following compounds provided at least 80% control of Puccinia recondita f. sp.tritici at 200 ppm compared to the untreated control, which showed extensive disease development under the same conditions:

[0941] Р-31, Р-34, Р-104, Р-109, Р-133, Р-171, Р-194 and Р-206.

[0942] Example B15. Treatment to prevent leaf disc infection / rice / Magnaporthe grisea (Pyricularia oryzae) (rice blast)

[0943] Ballila rice leaf segments were placed on agar in a 24-well multiwell plate and sprayed with the formulated test compound diluted in water. The leaf segments were inoculated with a fungal spore suspension 2 days after application. The inoculated leaf segments were incubated at 22°C and 80% relative humidity under a 24-hour light / dark cycle followed by 12-hour light / 12-hour dark in a climate chamber. The compound activity was evaluated as a percentage of disease control compared to untreated material when the corresponding degree of disease damage occurred on untreated control leaf segments (5-7 days after application).

[0944] The following compounds provided at least 80% control of Magnaporthe grisea at 200 ppm compared to the untreated control, which showed extensive disease development under the same conditions:

[0945] Р-81, Р-108, Р-110, Р-117, Р-154 and Р-194.

[0946] Example B16. Treatment to prevent leaf disc infection / barley / Pyrenophora teres (net spot)

[0947] Leaf segments of the Hasso barley cultivar were placed on agar in a 24-well multiwell plate and sprayed with the formulated test compound diluted in water. The leaf segments were inoculated with a fungal spore suspension 2 days after application. The inoculated leaf segments were incubated at 20°C and 65% relative humidity under a 12-hour light / 12-hour dark regime in a climate chamber. The compound's activity as an indicator of disease control was evaluated compared to untreated material by the appearance of a corresponding degree of disease-induced damage on untreated control leaf segments (5-7 days after application).

[0948] The following compounds provided at least 80% control of Pyrenophora teres at 200 ppm compared to the untreated control, which showed extensive disease development under the same conditions:

[0949] Р-2, Р-6, Р-14, Р-18, Р-38, Р-45, Р-48, Р-51, Р-52, Р-53, Р-54, Р-56, Р-63, Р-64, Р-65, Р-100, Р-104, Р-105, Р-108, Р-109, R-110, R-117, R-119, R-120, R-124, R-126, R-136, R-140, R-141, R-143, R-151, R-180, R-208, R-216, R-225, and R-228

[0950] Example B17. Treatment of liquid culture of Thanatephorus cucumeris (Rhizoctonia solani) (root rot, damping off)

[0951] Mycelial fragments from a freshly grown fungal culture in liquid medium were directly mixed with nutrient broth (potato dextrose broth). After adding the test compound solution (in DMSO) to a 96-well microtiter plate, nutrient broth containing the fungal material was added. The plates with the test compound were incubated at 24°C, and growth inhibition was determined photometrically 3-4 days after application. The following compounds provided at least 80% control of Thanatephorus cucumeris at 20 ppm compared to the untreated control, which showed extensive disease development under the same conditions:

[0952] P-109 and P-140.

[0953] Example B18. Treatment of liquid culture of Sclerotinia sclerotiorum (white rot

[0954] Mycelial fragments from a freshly grown fungal culture in liquid medium were directly mixed with nutrient broth (potato dextrose broth). After adding a solution of the test compound in DMSO to a 96-well microtiter plate, nutrient broth containing the fungal material was added. The plates with the test compound were incubated at 24°C, and growth inhibition was determined photometrically 3-4 days after application. The following compounds provided at least 80% control of Sclerotinia sclerotiorum at 20 ppm compared to the untreated control, which showed extensive disease development under the same conditions:

[0955] Р-48, Р-65, Р-100, Р-109, Р-140, Р-143, Р-180, Р-207, Р-208, Р-212, и Р-223

[0956] Example B19. Treatment of liquid culture of Mycosphaerella graminicota (Septoria tritici) (septoria leaf spot)

[0957] Fungal conidia taken from cryogenic storage were mixed directly with nutrient broth (potato dextrose broth). After adding the test compound solution in DMSO to a 96-well microtiter plate, nutrient broth containing fungal spores was added. The plates containing the test compound were incubated at 24°C, and growth inhibition was determined photometrically 4-5 days after application.

[0958] The following compounds provided at least 80% control of Mycosphaerella graminicola at 20 ppm compared to the untreated control, which showed extensive disease development under the same conditions:

[0959] R-1, R-2, R-6, R-7, R-9, R-10, R-11, R-13, R-14, R-16, R-17, R-18, R-20, R-21, R-26, R-27, R-28, R-29, R-30, R-33, R-34, R-35, R-36, R-37, R-38, R-39, R-40, R-41, R-42, R-43, R-45, R-46, R-47, R-48, R-49, R-50, R-51, R-52, R-53, R-54, R-55, R-56, R-58, R-59, R-61, R-62, R-63, R-64, R-65, R-66, R-68, R-69, R-83, R-84, R-88, R-90, R-92, R-100, R-103, R-104, R-105, R-108, R-109, R-110, R-111, R-112, R-113, R-114, R-115, R-116, R-117, R-118, R-119, R-120, R-121, R-123, R-124, R-125, R-126, R-127, R-128, R-129, R-131, R-133, R-134, R-135, R-136, R-137, R-138, R-139, R-140, R-141, R-142, R-143, R-144, R-146, R-147, R-148, R-149, R-150, R-151, R-152, R-154, R-155, R-156, R-158, R-159, R-160, R-161, R-162, R-163, R-164, R-165, R-166, R-167, R-168, R-169, R-172, R-176, R-177, R-179, R-180, R-181, R-182, R-184, R-187, R-188, R-190, R-191, R-192, R-194, R-195, R-197, R-201, R-202, R-204, R-205, R-206, R-207, R-208, R-209, R-212, R-215, R-216, R-217, R-218, R-219, R-220, R-221, R-222, R-223,R-224, R-225, R-226, R-227, R-228, R-229, R-231, R-232, R-233, R-234, R-235, R-236, R-237, R-239, R-241, R-242, R-244, R-245, R-246, R-247, and R-248.,

Claims

1. Compound of formula (I-A): characterized by the fact that R 1 selected from C1-C4 alkyl; R 2 selected from hydrogen, halogen and C1-C4 alkyl; R 3 and R 4 independently selected from the group of hydrogen, halogen and C1-C4 alkyl; R 5 and R 6 independently selected from the group of hydrogen and C1-C4 alkyl; R 7 selected from hydrogen, C1-C4 alkyl and C3-C6 cycloalkyl; B 1 represents CR 10 ; B 2 represents CR 11 ; R 8 , R 9 , R 10 and R 11 independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfonyl, C1-C4 alkoxy-C1-C4 alkyl, C1-C4 alkoxycarbonyl, hydroxy or cyano A is selected from A1, A4, A6, A7, A9, A10, A13 or A15: Where denotes the bond with the C(=O) group and the arrow denotes the bond with the Z group 1 ; And Z 1 selected from phenyl and a 5- or 6-membered heteroaryl, wherein the 5- or 6-membered heteroaryl contains one heteroatom individually selected from N, O and S, and wherein any of said phenyl and 5- or 6-membered heteroaryl is unsubstituted or 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 C1-C4 alkynyl; provided that said compound of formula (I-A) is not: , compound ID 119105768 in PubChem; , compound ID 121023008 in PubChem; , compound ID 121198339 in PubChem; , compound ID 121198502 in PubChem; , compound ID 121198515 in PubChem; , compound ID 129530178 in PubChem; , compound ID 129530183 in PubChem; , compound ID 129530918 in PubChem; , compound with GO 129530919 in PubChem.

2. The compound according to item 1, where R 1 is methyl.

3. The compound according to item 1 or item 2, where R 2 represents hydrogen or methyl.

4. The connection according to any one of paragraphs 1-3, where R 3 and R 4 independently selected from hydrogen and methyl.

5. The connection according to any one of paragraphs 1-4, where R 5 and R 6 represent hydrogen.

6. A connection according to any one of paragraphs 1-5, where R 7 represents hydrogen, methyl or cyclopropyl.

7. A connection according to any one of paragraphs 1-6, where R 8 and R 11 independently selected from hydrogen, halogen and C1-C4 alkyl.

8. A connection according to any one of paragraphs 1-7, where R 9 and R 10independently selected from hydrogen, halogen, hydroxy, C1-C3 alkyl, C1-C2 haloalkyl, C1-C3 haloalkoxy, C1-C4 alkoxy, C1-C4 alkoxycarbonyl and cyano.

9. The connection according to any of paragraphs 1-8, where Z 1 selected from the group of 2,3,4-trifluorophenyl, 2,3-difluorophenyl, 3,4-difluorophenyl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2-fluoro-4-methoxyphenyl, 2-fluoro-4-methylsulfonylphenyl, 2-25 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-fluorophenyl, 4-fluoro-2-methoxyphenyl, and phenyl.

10. A method for controlling or preventing infection of useful plants by phytopathogenic fungi, wherein a fungicidally effective amount of a compound of formula (IA) specified in any of claims 1-9, or a composition containing a compound of formula (IA) specified in any of claims 1-9, is applied to plants, their parts or their growing site.

11. A fungicidal composition comprising a fungicidally effective amount of a compound of formula (IA) specified in any one of claims 1 to 9 and suitable carriers or excipients.

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