Microbicidal Bicyclic Heterocyclic Derivatives

Abstract

Compounds of formula (I) which can be used as fungicides: JPEG2025503432000135.jpg58159, wherein the substituents are as defined in claim 1, and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of these compounds are provided.

Description

[Technical field]

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

[0002] According to a first aspect of the present invention, there is provided a compound of formula (I): [ka] (In the formula, R 1 is hydrogen, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl, C 2 ~C 4 Alkynyl and C 3 ~C 6 cycloalkyl; R 2 is hydrogen, halogen, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl, C 2 ~C 4 Alkynyl, C 1 ~C 4 Haloalkyl, C 3 ~C 6 Cycloalkyl, C 1 ~C 4 Alkylcarbonyl, NC 1 ~C 4 Alkoxy-CC1 ~C 4 Alkyl-Carbonimidoyl, N-Hydroxy-CC 1 ~C 4 Alkyl-carbonimidoyl and C 1 ~C 4 alkoxycarbonyl; R 3 is hydrogen, halogen and C 1 ~C 4 selected from the group consisting of alkyl; R 4 is hydrogen, halogen and C 1 ~C 4 selected from the group consisting of alkyl; R 5 and R 6 is hydrogen and C 1 ~C 4 independently selected from the group consisting of alkyl; R 7 is hydrogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Alkylcarbonyl, NC 1 ~C 4 Alkoxy-CC 1 ~C 4 Alkyl-Carbonimidoyl, N-Hydroxy-CC 1 ~C 4 Alkyl-carbonimidoyl, C 1 ~C 4 Alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C 1 ~C 4 Alkylaminocarbonyl, di(C 1 ~C 4 alkylamino)carbonyl, phenyl, 5- or 6-membered heteroaryl and C 3 ~C 6 cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S, and wherein the phenyl, 5- or 6-membered heteroaryl, and C 3 ~C 6-Cycloalkyl is any of halogen, cyano, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl or C 1 ~C 4 optionally substituted with 1, 2, or 3 substituents independently selected from alkoxy; Z 1 is C 1 ~C 4 Alkyl, phenyl, 5- or 6-membered heteroaryl and C 3 ~C 6 -cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3 or 4 heteroatoms individually selected from N, O and S, and wherein the phenyl, 5- or 6-membered heteroaryl and C 3 ~C 6 -Cycloalkyl is any of halogen, cyano, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl, C 1 ~C 4 Alkoxy, C 1 ~C 4 Haloalkoxy, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl or C 2 ~C 4 optionally substituted with 1, 2, or 3 substituents independently selected from alkynyl; X 1 , X 2 and X 3 is R 8 , N and S, where X 1 , X 2 and X 3 One of them is S; R 8 is hydrogen, halogen and C 1 ~C 4 selected from the group consisting of alkyl; A 1 , A 2 and A 3 CR 9 , N, N.R. 10 , O and S, with the proviso that A 1 , A 2 and A 3 is selected from N, O and S, and A 1 , A 2 and A 3 at most one of is O or S; R 9 is hydrogen, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl and C 2 ~C 4 alkynyl; R 10 is hydrogen, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl and C 2 ~C 4 alkynyl) or an agrochemically acceptable salt, stereoisomer, enantiomer, tautomer or N-oxide thereof is provided.

[0003] It has now been surprisingly found that the compounds of formula (I) have in fact a highly advantageous level of biological activity for the protection of plants against diseases caused by fungi.

[0004] According to a second 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, which may further comprise at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

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

[0006] According to a fourth aspect of the present invention, there is provided the use of a compound of formula (I) according to the present invention as a bactericide or fungicide. According to this particular aspect of the present invention, this use may exclude methods of treatment of the human or animal body by surgery or therapy. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] As used herein, the term "halogen" or "halo" refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine.

[0008] As used herein, cyano refers to the group --CN.

[0009] As used herein, the terms "hydroxyl" or "hydroxy" refer to an --OH group.

[0010] As used herein, oxo refers to a =O group, such as a sulfinyl (-S(O)-) or sulfonyl (-S(O) 2 -) means oxygen.

[0011] As used herein, "C 1 ~C 4 The term "alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from 1 to 4 carbon atoms, and attached to the remainder of the molecule by a single bond. 1 ~C 3 Alkyl" and "C 1 ~C 2 The term "alkyl" should be construed accordingly. 1~C 4 Examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, 1-methylethyl (isopropyl), n-butyl, and 1,1-dimethylethyl (t-butyl). 1 ~C 4 An "alkylene" group is a C alkylene group, except that such a group is attached to the remainder of the molecule by two single bonds. 1 ~C 4 Refers to the corresponding definition of alkyl. 1 ~C 4 An example of an alkylene is -CH 2 - and -CH 2 CH 2 -It is.

[0012] As used herein, "C 2 ~C 4 The term "alkenyl" refers to a straight or branched hydrocarbon chain radical group composed solely of carbon and hydrogen atoms, containing at least one double bond which may be in the (E) or (Z) configuration, having 2 to 4 carbon atoms and attached to the remainder of the molecule by a single bond. 3 ~C 4 The term "alkenyl" should be construed similarly. 2 ~C 4 Examples of alkenyl include, but are not limited to, ethenyl and prop-1-enyl.

[0013] As used herein, "C 2 ~C 4 The term "alkynyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having 2 to 4 carbon atoms, and attached to the rest of the molecule by a single bond. 3 ~C 4 The term "alkynyl" should be construed similarly. 3 ~C 4Examples of alkynyl include, but are not limited to, ethynyl, prop-1-ynyl, propargyl (prop-2-ynyl), but-1-ynyl, and 3-methyl-but-1-ynyl.

[0014] As used herein, "C 1 ~C n The term "-haloalkyl" refers to a linear or branched saturated alkyl group having 1 to n carbon atoms (as defined above) attached via any of the carbon atoms, in which some or all of the hydrogen atoms in these groups may be replaced by fluorine, chlorine, bromine and / or iodine, i.e., for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, ethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl, or nonafluorobutyl. 1 ~C 2 The term "fluoroalkyl" refers to a C alkyl group having 1, 2, 3, 4 or 5 fluorine atoms. 1 ~C 2The term "fluoro" refers to any one of the alkyl groups, for example, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, or pentafluoroethyl. 1 ~C n "-haloalkoxy" refers to C-haloalkoxy groups each substituted with one or more halo atoms which may be the same or different. 1 ~C n -refers to an alkoxyl group.

[0015] As used herein, "C 1 ~C 4 The term "alkoxy" refers to R a is generally defined as C 1 ~C 4 The formula R is an alkyl group. a It refers to the O- group. 1 ~C 3 Alkoxy" and "C 1 ~C 2 The term "alkoxy" should be construed similarly. 1 ~C 4 Examples of alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, iso-propoxy and t-butoxy.

[0016] As used herein, "C 1 ~C 4 Alkoxy-C 1 ~C 4 The term "alkyl" refers to R b is the general definition of C 1 ~C 4 is an alkyl group, and R a is the general definition of C 1 ~C 4 An alkylene group, formula R b -OR a - refers to the group.

[0017] As used herein, "C 1 ~C 4 The term "alkylcarbonyl" means a is the general definition of C 1 ~C 4 Alkyl groups of the formula -C(O)R a Refers to the group.

[0018] As used herein, "C 1 ~C 4 The term "alkoxycarbonyl" refers to R a is the general definition of C 1 ~C 4 An alkyl group of the formula -C(O)OR a Refers to the group.

[0019] As used herein, "C 1 ~C 4 The term "alkylaminocarbonyl" refers to R a is the general definition of C 1 ~C 4 An alkyl group of the formula -C(O)NHR a Refers to the group.

[0020] As used herein, “di(C 1 ~C 4 The term "alkylamino)carbonyl" refers to each R a are C, which may be the same or different, as generally defined above 1 ~C 4 An alkyl group of the formula -C(O)NR a (R a ) group.

[0021] As used herein, "C 2 ~C 4 The term "alkenyloxy" means a is the general definition of C 2 ~C 4 An alkenyl group of the formula -OR a Refers to the group.

[0022] As used herein, "C 2 ~C 4 The term "alkynyloxy" refers to a is the general definition of C 2 ~C 4 An alkynyl group of the formula -OR a Refers to the group.

[0023] As used herein, "C 1 ~C n -alkylthio" or "C 1 ~C n The term "-alkylsulfanyl" refers to a C-alkylsulfanyl group that is bonded through a sulfur atom. 1 ~C n -refers to an alkyl group.

[0024] As used herein, "C 1 ~C n The term "-alkylsulfinyl" refers to a C(-alkylsulfinyl) group bonded through the sulfur atom of the sulfinyl (or S(=O)-) group. 1 ~C n Refers to an alkyl group.

[0025] As used herein, "C 1 ~C n The term "-alkylsulfonyl" refers to sulfonyl (or S(=O) 2 -) group via the sulfur atom 1 ~C n Refers to an alkyl group.

[0026] As used herein, "NC 1 ~C 4 Alkoxy-CC 1 ~C 4 The term "alkyl-carbonimidoyl" refers to a is the general definition of C 1 ~C 4 is an alkyl group, and R b is the general definition of C 1 ~C 4The alkyl group of the formula -C(R a )=NO(R b ) group.

[0027] As used herein, "N-hydroxy-CC 1 ~C 4 The term "alkyl-carbonimidoyl" refers to a is the general definition of C 1- C 4 The alkyl group of the formula -C(R a )=NOH group.

[0028] As used herein, "C 3 ~C 6 The term "cycloalkyl" refers to a stable monocyclic ring radical that is saturated or partially saturated and contains 3 to 6 carbon atoms. 3 ~C 4 Cycloalkyl" and "C 3 ~C 5 The term "cycloalkyl" should be construed similarly. 3 ~C 6 Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopenten-1-yl, cyclopenten-3-yl, and cyclohexen-3-yl.

[0029] As used herein, "C 3 ~C 6 Cycloalkyl C 1 ~C 4 The term "alkyl" means any of the C 1 ~C 4 C, as defined above, attached to the remainder of the molecule by an alkylene group. 3 ~C 6 Refers to a cycloalkyl ring. 3 ~C 6 Cycloalkyl C 1 ~C 4Examples of alkyl include, but are not limited to, cyclopropyl-methyl, cyclobutyl-ethyl, and cyclopentyl-methyl.

[0030] Examples of 5- or 6-membered heteroaryl rings containing 1 to 4 heteroatoms independently selected from nitrogen, oxygen and sulfur include, but are not limited to, pyridyl, pyrimidyl, pyrrolyl, pyrazolyl, furyl, thienyl, imidazolyl, isoxazolyl, oxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, pyrazinyl, pyridazinyl and triazinyl.

[0031] The compounds of formula (I) or intermediate compounds of formula (III) and (IV) according to the invention, which have at least one basic centre, can be reacted with a strong inorganic acid, such as a mineral acid, such as perchloric acid, sulfuric acid, nitric acid, phosphoric acid or a hydrohalic acid, to produce unsubstituted or, for example, halogen-substituted C, such as acetic acid. 1 ~C 4 Alkane carboxylic acids, such as saturated or unsaturated dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, hydroxycarboxylic acids, such as ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or together with strong organic carboxylic acids, such as benzoic acid, or C carboxylic acids, which are unsubstituted or substituted, for example by halogens, such as methane- or p-toluenesulfonic acid. 1 ~C 4 For example, acid addition salts can be formed with organic sulfonic acids, such as -alkane- or arylsulfonic acids.

[0032] The compounds of formula (I) or intermediate compounds of formulae (III) and (IV) according to the invention having at least one acidic group can form salts with bases, for example inorganic salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or can form salts with ammonia or organic amines, such as morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower-alkylamines, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or mono-, di- or trihydroxy-lower-alkylamines, for example mono-, di- or triethanolamine.

[0033] The possible presence of one or more asymmetric carbon atoms in the compounds of formula (I) according to the invention means that the compounds can occur in chiral isomeric forms, i.e. enantiomeric or diastereomeric forms. Atropisomers can also occur as a result of restricted rotation about a single bond. Formula (I) is intended to include all of these possible isomeric forms and mixtures thereof. The invention includes all of these possible isomeric forms and mixtures thereof of the compounds of formula (I) according to the invention. Similarly, the compounds of formula (I) are intended to include all possible tautomers, if any, including lactam-lactim tautomers and keto-enol tautomers. The invention includes all possible tautomeric forms of the compounds of formula (I) according to the invention.

[0034] In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form as N-oxides, in covalently hydrated form or in salt form, for example in agriculturally usable or agrochemically acceptable salt form. N-oxides are the oxidized forms of tertiary amines or nitrogen-containing aromatic heterocyclic compounds. These are described, for example, in the book "Heterocyclic N-oxides", A. Albini and S. Pietra, CRC Press, Boca Raton 1991. The compounds of formula (I) according to the invention also include hydrates that may be formed during salt formation.

[0035] The following list refers to the compounds of formula (I) of the present invention and is intended to illustrate the substituent R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , Z 1 , A 1 , A 2 , A 3 , X 1 , X 2 and X 3 For any one of these substituents, any of the definitions set forth below may be combined with any of the definitions of any other substituents set forth below or elsewhere in this document.

[0036] In an embodiment of the present invention, R 1 is hydrogen, C 1 ~C 4 Alkyl or C 2 ~C 4 alkynyl. Preferably, R 1 is hydrogen, methyl, ethyl or isopropyl. More preferably, R 1 is methyl.

[0037] In an embodiment of the present invention, R 2 is hydrogen, halogen, C 1 ~C 4 Alkyl, C 3 ~C 6 Cycloalkyl, C 1 ~C 4 Alkylcarbonyl, NC 1 ~C 4 Alkoxy-CC 1 ~C 4 Alkyl-carbonimidoyl and N-hydroxy-CC 1 ~C 4 Preferably, R is selected from the group consisting of alkyl-carbonimidoyl. 2is hydrogen, halogen, methyl, ethyl, cyclopropyl, C 1 ~C 2 Alkylcarbonyl, NC 1 ~C 2 Alkoxy-CC 1 ~C 2 Alkyl-carbonimidoyl and N-hydroxy-CC 1 ~C 2 More preferably, R is selected from the group consisting of alkyl-carbonimidoyl. 2 is hydrogen, fluorine, chlorine, bromine, methyl, ethyl, cyclopropyl, acetyl, -C(CH 3 )=NOCH 3 , -C(CH 3 )=NOCH 2 CH 3 and -C(CH 3 Even more preferably, R 2 is selected from the group consisting of hydrogen, fluorine, chlorine and methyl.

[0038] In an embodiment of the present invention, R 3 is hydrogen, halogen and C 1 ~C 4 Preferably, R is selected from the group consisting of alkyl. 3 is selected from the group consisting of hydrogen, fluorine, chlorine, methyl and ethyl. More preferably, R 3 is selected from the group consisting of hydrogen and methyl.

[0039] In an embodiment of the present invention, R 4 is hydrogen, halogen and C 1 ~C 4 Preferably, R is selected from the group consisting of alkyl. 4 is selected from the group consisting of hydrogen, fluorine, chlorine, methyl, and ethyl. More preferably, R 4 is selected from the group consisting of hydrogen and methyl.

[0040] In an embodiment of the present invention, R 5 and R 6is independently selected from the group consisting of hydrogen, methyl and ethyl.

[0041] In another embodiment of the present invention, R 7 is hydrogen, C 1 ~C 4 Alkyl, C 1 ~C 4 Alkylcarbonyl, NC 1 ~C 4 Alkoxy-CC 1 ~C 4 Alkyl-Carbonimidoyl, N-Hydroxy-CC 1 ~C 4 Alkyl-carbonimidoyl, C 1 ~C 4 Preferably, R is selected from the group consisting of alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, phenyl, 4-cyanophenyl, cyclopropyl and 1-cyanocyclopropyl. 7 is hydrogen, methyl, acetyl, -C(CH 3 )=NOCH 3 , -C(CH 3 )=NOCH 2 CH 3 , -C(CH 3 )=NOH, methoxycarbonyl, ethoxycarbonyl, N-methoxy-N-methyl-carbonyl, phenyl and cyclopropyl. More preferably, R 7 is selected from the group consisting of hydrogen and methyl.

[0042] In an embodiment of the present invention, Z 1 is C 1 ~C 4 Alkyl, phenyl, 5- or 6-membered heteroaryl and C 3 ~C 6 -cycloalkyl, wherein the 5- or 6-membered heteroaryl contains 1, 2, 3, or 4 heteroatoms individually selected from N, O, and S, and wherein the phenyl and 5- or 6-membered heteroaryl are selected from the group consisting of halogen, cyano, C 1 ~C 4 Alkyl, C 1 ~C4 Haloalkyl, C 1 ~C 4 Alkoxy, C 1 ~C 4 Haloalkoxy, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkyl sulfinyl or C 1 ~C 4 alkylsulfonyl; and 3 ~C 6 -Cycloalkyl is halogen, cyano, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl or C 1 ~C 4 Optionally, Z is substituted with 1, 2 or 3 substituents independently selected from alkoxy. 1 is selected from the group consisting of methyl, n-propyl, cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3-methoxyphenyl, 4-ethynyl-2-fluoro-phenyl, 4-fluoro-2-methoxy-phenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 3,4-difluorophenyl, 2,3,4-trifluorophenyl, 2,4,6-trifluorophenyl, 2-fluoro-4-methoxy-phenyl, 2-fluoro-4-methylsulfonyl-phenyl, 2-furyl, 2-thienyl, 3-thienyl and 1-methylpyrazol-4-yl. More preferably, Z 1is selected from the group consisting of methyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylphenyl, 2-fluorophenyl, 4-fluorophenyl, 3-chlorophenyl, 4-fluoro-2-methoxy-phenyl, 2,4-difluorophenyl, 3,4-difluorophenyl, 2,4,6-trifluorophenyl, 2-furyl, 2-thienyl, 3-thienyl and 1-methylpyrazol-4-yl. Even more preferably, Z 1 is selected from the group consisting of methyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylphenyl, 2-fluorophenyl, 4-fluorophenyl, 3-chlorophenyl, 4-fluoro-2-methoxy-phenyl, 2,4-difluorophenyl, 3,4-difluorophenyl, 2,4,6-trifluorophenyl, 3,5-difluoro-2-pyridyl, 2-furyl, 2-thienyl, 3-thienyl and 1-methylpyrazol-4-yl. Even more preferably, Z 1 is selected from the group consisting of phenyl, 2-fluorophenyl, 4-fluorophenyl and 2,4-difluorophenyl. Even more preferably, Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, 4-fluorophenyl or phenyl.

[0043] In another embodiment, Z 1are 1-methylpyrazol-4-yl, 2,3,4-trifluorophenyl, 2,3-difluorophenyl, 3,4-difluorophenyl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 3,5-difluoro-2-pyridyl, 5-fluoro-2-pyridyl, 3-fluoro-2-pyridyl, 2-fluoro-4-methoxy-phenyl, 2-fluoro-4-methylsulfonyl-phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 3,5-difluoro-2-furyl, 3- Fluoro-2-furyl, 5-fluoro-2-furyl, 3,5-difluoro-2-thienyl, 3-fluoro-2-thienyl, 5-fluoro-2-thienyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3-methoxyphenyl, 4-ethynyl-2-fluoro-phenyl, 4-fluoro-2-methoxy-phenyl, cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl, n-propyl or phenyl. More preferably, Z 1 is selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2-chlorophenyl, 2-fluorophenyl, 3,5-difluoro-2-pyridyl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-fluorophenyl, 3-methylphenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, 4-methylphenyl, cyclobutyl, cyclohexyl, cyclopentyl, methyl or phenyl. Even more preferably, Z 1is selected from 1-methylpyrazol-4-yl, 2,4,6-trifluorophenyl, 3,5-difluoro-2-pyridyl, 2,4-difluorophenyl, 2-fluorophenyl, 2-furyl, 2-methylphenyl, 2-thienyl, 3,4-difluorophenyl, 3-chlorophenyl, 3-thienyl, 4-fluoro-2-methoxy-phenyl, 4-fluorophenyl, cyclobutyl, cyclohexyl, cyclopentyl or phenyl. Even more preferably, Z 1 is selected from the group consisting of methyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylphenyl, 2-fluorophenyl, 4-fluorophenyl, 3-chlorophenyl, 4-fluoro-2-methoxy-phenyl, 2,4-difluorophenyl, 3,4-difluorophenyl, 2,4,6-trifluorophenyl, 3,5-difluoro-2-pyridyl, 2-furyl, 2-thienyl, 3-thienyl and 1-methylpyrazol-4-yl. Even more preferably, Z 1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, 4-fluorophenyl or phenyl.

[0044] In an embodiment of the present invention, X 1 is S, and X 2 and X 3 CR 8 and N. In another embodiment of the present invention, X 2 is S, and X 1 and X 3 CR 8 and N. In another embodiment of the present invention, X 3 is S, and X 1 and X 2 CR 8 and N.

[0045] In an embodiment of the present invention, R 8 is selected from the group consisting of hydrogen, chlorine, bromine, methyl and ethyl. 8is selected from the group consisting of hydrogen, chlorine and methyl. More preferably, R 8 is hydrogen.

[0046] In an embodiment of the present invention, A 1 , A 2 and A 3 CR 9 , N, O, and S, with the proviso that A 1 , A 2 and A 3 is selected from N, O and S, and A 1 , A 2 and A 3 At most one of is O or S.

[0047] In an embodiment of the present invention, R 9 is hydrogen or C 1 ~C 4 It is alkyl, preferably hydrogen or methyl.

[0048] In an embodiment of the present invention, R 10 is hydrogen or C 1 ~C 4 It is alkyl, preferably hydrogen or methyl.

[0049] In an embodiment of the invention, the compound of formula (I) is a compound of formula (IA): [ka] wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X 1 , X 2 , X 3 and Z 1 is as defined for the compounds of formula (I) according to the invention, and A is A1~A36: [ka] wherein: [ka] indicates a bond to a C(=O) group, and the arrow indicates Z 1 is a bond to a group, and R 9a , R 9b , R 9c , R 10a , R 10b and R 10c is hydrogen, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl and C 2 ~C 4 alkynyl.

[0050] In an embodiment of the invention, in the compound of formula (IA), A is selected from A1, A4, A6, A7, A9, A10, A13 and A15: [ka] wherein: [ka] indicates a bond to a C(=O) group, and the arrow indicates Z 1 is a bond to a group, and R 9a , R 9b and R 9c is hydrogen, C 1 ~C 4 Alkyl, C 2 ~C 4 Alkenyl and C 2 ~C 4 alkynyl.

[0051] In another embodiment of the invention, in the compound of formula (IA), A is selected from A1, A4, A9, A10, A13 and A15: [ka] wherein: [ka] indicates a bond to a C(=O) group and the arrow indicates Z 1 is a bond to a group, 9a , R 9b and R 9c is hydrogen.

[0052] In another embodiment of the invention, in the compound of formula (IA), A is selected from A1, A4, A9 and A10: [ka] wherein: [ka] indicates a bond to a C(=O) group and the arrow indicates Z 1 is a bond to a group, 9c is hydrogen.

[0053] In another embodiment of the invention, in the compound of formula (IA), A is selected from A4, A6, A9 and A10: [ka] wherein: [ka] indicates a bond to a C(=O) group and the arrow indicates Z 1 The bond is to a group.

[0054] In one embodiment of the present invention, preferably, in the compound of formula (IA), A is selected from the group consisting of A4, A6, A9 and A10, and R 9c is hydrogen.

[0055] In another embodiment of the invention, in the compound of formula (IA), A is selected from A4, A9 and A10: [ka] wherein: [ka] indicates a bond to a C(=O) group and the arrow indicates Z 1 The bond is to a group.

[0056] In one embodiment of the present invention, preferably, in the compound of formula (IA), A is selected from the group consisting of A4, A9 and A10, and R 9c is hydrogen.

[0057] In another embodiment of the present invention, in the compound of formula (II), A is selected from A4, A7 and A9 [ka] wherein: [ka] indicates a bond to a C(=O) group and the arrow indicates Z 1 is a bond to a group, and R 7c is hydrogen.

[0058] More preferably, in the compound of formula (II), A is selected from the group consisting of A4, A7 and A9, and R 7c is hydrogen.

[0059] More preferably, in the compound of formula (II), A is A9 and R 7c is hydrogen.

[0060] In an embodiment of the present invention, R 9a , R 9b , R 9c , R 10a , R 10b and R 10c is independently hydrogen or methyl.

[0061] In another embodiment of the present invention, R 9a , R 9b , R 9c , R 10a , R 10b and R 10c is hydrogen.

[0062] In another embodiment of the present invention, R 9a , R 9b , R 9c , R 10a , R 10b and R 10c is methyl.

[0063] In an embodiment of the invention, the compound of formula (I) is X 1 Compounds of formula (II-A) where is S: [ka] wherein X 2 and X 3 CR 8 and N, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , A 1 , A 2 , A 3 and Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0064] Preferably, in the compound of formula (II-A) of the present invention, X 2 is CR 8 and X 3 is CR 8 or X 2 is N, and X 3 is CR 8 or X 2 is CR8 and X 3 is N, or X 2 is N, and X 3 is N, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , A 1 , A 2 , A 3 and Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0065] In another embodiment of the invention, the compound of formula (I) is X 2 Compounds of formula (II-B) where is S: [ka] wherein X 1 and X 3 CR 8 and N, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , A 1 , A 2 , A 3 and Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0066] Preferably, in the compound of formula (II-B) of the present invention, X 1 is CR 8 and X 3 is CR 8 or X 1 is N, and X 3 is CR 8 or X 1 is CR 8 and X 3 is N, or X 1 is N, and X 3 is N, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , A 1 , A 2 , A 3 and Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0067] In another embodiment of the invention, the compound of formula (I) is X 3 Compounds of formula (II-C) where: [ka] wherein X 1 and X 2 CR 8 and N, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , A 1 , A 2 , A 3 and Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0068] Preferably, in the compound of formula (II-C) of the present invention, X 1 is CR 8 and X 2 is CR 8 or X 1 is N, and X2 is CR 8 or X 1 is CR 8 and X 2 is N, or X 1 is N, and X 2 is N, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , A 1 , A 2 , A 3 and Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0069] More preferably, the compound of formula (I) is selected from compounds A.01, A.02, A.03, A.04, A.05, A.06, A.07, A.08, A.09, A.10, A.11 and A.12 as defined in Table A below, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , A 1 , A 2 , A 3 and Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0070] [Table 1]

[0071] Even more preferably, the compound of formula (I) is selected from compounds A.01, A.02, A.03, A.04, A.05, A.06, A.07, A.08, A.09, A.10, A.11 and A.12 as defined in Table A above, wherein R 8is selected from the group consisting of hydrogen, chlorine, bromine, methyl and ethyl, preferably R 8 is selected from the group consisting of hydrogen, chlorine and methyl, more preferably R 8 is hydrogen, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , A 1 , A 2 , A 3 and Z 1 is as defined for the compounds of formula (I) according to the present invention.

[0072] The possible presence of one or more asymmetric carbon atoms in any of the compounds of formula (I), (IA), (II-A), (II-B) and (II-C) according to the invention means that the compounds may occur in chiral isomeric, i.e. enantiomeric or diastereomeric forms.

[0073] More preferably, the compound of formula (I) according to the present invention is selected from the compounds listed in any one of Tables B-1 to B-10, C-1 to C-102 or the compounds (P-1) to (P-39) listed in Table T1.

[0074] Even more preferably, the compounds of formula (I) according to the invention are selected from the compounds (P-1) to (P-39) listed in Table T1.

[0075] According to a fifth aspect of the present invention, there is provided an intermediate compound of formula (III): [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X 1 , X 2 and X 3corresponds to the same definition as for the compounds of formula (I) according to the present invention) or a salt thereof is provided.

[0076] The intermediate compound of formula (III) is R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X 1 , X 2 and X 3 have the same definitions and corresponding preferences as in the compounds of formula (I) according to the present invention.

[0077] The possible presence of one or more asymmetric carbon atoms in the compounds of formula (III) according to the invention means that the compounds can occur in chiral isomeric forms, i.e. enantiomeric or diastereomeric forms.

[0078] According to a sixth aspect of the present invention, there is provided an intermediate compound of formula (IV): [ka] (In the formula, R 1 , R 2 , R 3 , R 5 , R 7 , X 1 , X 2 and X 3 corresponds to the same definition as for the compounds of formula (I) according to the present invention) is provided.

[0079] The intermediate compound of formula (IV) is R 1 , R 2 , R 3 , R 5 , R 7 , X 1 , X 2 and X 3 have the same definitions and corresponding preferences as in the compounds of formula (I) according to the present invention.

[0080] The possible presence of one or more asymmetric carbon atoms in the compounds of formula (IV) according to the invention means that the compounds can occur in chiral isomeric forms, i.e. enantiomeric or diastereoisomeric forms.

[0081] Compounds of formula (I) according to the present invention can be formed as shown in Schemes 1-12 below, where, unless otherwise specified, the definition of each variable is as defined above for compounds of formula (I).

[0082] In particular, R 4 and R 6 is hydrogen, and R 5 Compounds of formula (I), where is hydrogen or methyl, can be formed as shown in Schemes 1-7 below, where, unless otherwise specified, the definition of each variable is as defined above for compounds of formula (I).

[0083] In any of the following schemes 1 to 12, the possible presence of one or more asymmetric carbon atoms in the compound of formula (I) according to the invention means that this compound can occur in chiral isomeric forms, i.e. in enantiomeric or diastereomeric forms.

[0084] The compound of formula (I) can be prepared by a person skilled in the art according to known methods. More specifically, the compound of formula (I) can be prepared by a compound of formula (III) or a salt thereof, 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X 1 , X 2 and X 3 is as defined above for compounds of formula (I)) to a compound of formula (V), 1 , A 2 , A 3 and Z 1can be prepared by reaction of a cycloalkyl group with a cycloalkyl group, which is as defined above for compounds of formula (I). This reaction is shown in Scheme 1. [ka] Scheme 1

[0085] In Scheme 1, a compound of formula (V) 1 , A 2 , A 3 and Z 1 X is as defined above for compounds of formula (I) can be activated to compounds of formula (Va) by methods known to those skilled in the art and described, for example, in Tetrahedron 2005, 61(46), 10827-10852. For example, compounds of formula (Va) (wherein X 0 is halogen) is formed by treatment of compounds of formula (V) with, for example, oxalyl chloride or thionyl chloride in the presence of a catalytic amount of N,N-dimethylformamide (DMF) in an inert solvent such as dichloromethane or tetrahydrofuran (THF) at a temperature between 20° C. and 100° C., preferably 25° C. Optionally, compounds of formula (III) (wherein R is a halogen) can be ... 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X 1 , X 2 and X 3 Treatment of a compound of formula (Va) with toluene (wherein V is as defined above for compounds of formula (I)) provides a compound of formula (I). Alternatively, a compound of formula (I) can be prepared by elution with, for example, pyridine, DMF, acetonitrile, CH 2 Cl 2 or THF, optionally in the presence of a base, for example triethylamine, at a temperature between 30° C. and 180° C. 0 As described below, X 01 , X 02 Or X03 Compounds of formula (V) may be prepared by treatment with dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) or 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU) to give compounds of formula (Va), where X 0 As described below, X 04 Further reaction with a compound of formula (III) or a salt thereof can provide a compound of formula (I). [ka]

[0086] A compound of formula (IIIa) 4 and R 6 is hydrogen, and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , X 1 , X 2 and X 3 is as defined above for compounds of formula (I), may be prepared by those skilled in the art according to known methods.

[0087] For example, a compound of formula (IIIa) 4 and R 6 is hydrogen, and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , X 1 , X 2 and X 3is as defined above for compounds of formula (I), 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , X 1 , X 2 and X 3 is defined above for compounds of formula (I), from NaBH in a protic solvent such as methanol or ethanol, etc. 3 Compounds of formula (IIIa) can be prepared by treatment with a reducing agent such as CN and an acid such as hydrochloric acid or acetic acid. Such reactions are well known in the literature and similar reactions are described, for example, in Deng, Zeping et al, Chinese Patent No. CN103772278 and Synthesis 1979,4,281-3. Alternatively, compounds of formula (IIIa) can be prepared from compounds of formula (IV) by reduction with hydrogen in the presence of a suitable metal catalyst such as Pd, Ir, Rh, with a suitable ligand such as a diphosphine [1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp) or 1,4-bis(diphenylphosphino)butane (dppb)]. Similar reactions have been reported, for example, in Reaction Kinetics and Catalysis Letters 2007,92,99-104. This reaction is shown in Scheme 2. [ka] Scheme 2

[0088] Alternatively, compounds of formula (IIIa) may be prepared as shown in Scheme 4.

[0089] As shown in Scheme 3, a compound of formula (IIIb), 4 , R 6 and R 7 is hydrogen, and R 5 is hydrogen or methyl, and R 1 , R2 , R 3 , X 1 , X 2 and X 3 is as defined above for compounds of formula (I), can be converted to compounds of formula (VI), where X is a substituted or unsubstituted aryl group, by methods known to those skilled in the art and as described in Scheme 1. 0 is a leaving group such as a halogen, and R 0 is C 1 ~C 4 Treatment of a compound of formula (IIIb) with a phenyl group (R 1 ) provides a compound of formula (VII) 4 , R 6 and R 7 is hydrogen, and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , X 1 , X 2 and X 3 is as defined above for compounds of formula (I). Alternatively, compounds of formula (VII) can be converted to compounds of formula (R 0 CO) 2 O(wherein, R 0 is C 1 ~C 4 Compounds of formula (VII) can then be metallated with a base, for example an alkyl metal base, such as tert-butyllithium, and an additive, such as N,N,N',N'-tetramethylethylenediamine (TMEDA), in an inert polar solvent, such as THF or 2-methyl-THF, at low temperatures, for example from -78°C to room temperature. X -X 0 (wherein X 0 is as previously defined, and R X is C 1 ~C 4 Alkyl, C 1 ~C 4 Alkyl carbonyl, C1 ~C 4 Alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C 1 ~C 4 Alkylaminocarbonyl, di(C 1 ~C 4 Alkylamino)carbonyl or C 3 ~C 6 cycloalkyl, where C 3 ~C 6 -Cycloalkyl is halogen, cyano, C 1 ~C 4 Alkyl, C 1 ~C 4 Haloalkyl and C 1 ~C 4 Subsequent treatment of the anion of formula (VII) formed under such conditions with an anion of formula (VII) optionally substituted with 1, 2 or 3 substituents independently selected from alkoxy, gives a compound of formula (VIIa), 4 and R 6 is hydrogen, and R 5 is hydrogen or methyl, R 0 is C 1 ~C 4 alkyl, and R 1 , R 2 , R 3 , R 7 , X 1 , X 2 and X 3 is as defined above for compounds of formula (I), which is shown in Scheme 3. [ka] Scheme 3

[0090] Compounds of formula (VIIa) can be prepared by methods known to those skilled in the art from compounds of formula (IIIa), 4 and R 6 is hydrogen, and R 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , X1 , X 2 and X 3 is as defined above for compounds of formula (I). For example, a compound of formula (VIIa), 0 (Ilia) can be treated with an organic or inorganic acid, such as trifluoroacetic acid or HCl, to give compounds of formula (IIIa). This reaction is shown in Scheme 4. [ka] Scheme 4

[0091] A compound of formula (IVa) 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , X 1 , X 2 and X 3 is as defined above for compounds of formula (I), can be converted to compounds of formula (IX), typically by a C-C bond forming reaction under palladium-catalyzed (or alternatively nickel-catalyzed) cross coupling conditions, 1 , R 2 and R 3 is as defined above for compounds of formula (I), and X 0 is a halogen, preferably chlorine, bromine or iodine, with a compound of formula (VIII), 5 is hydrogen or methyl, and R 7 , X 1 , X 2 and X 3 can be prepared by reacting (as defined above for compounds of formula (I)) with (which is shown in Scheme 5). [ka] Scheme 5

[0092] The Suzuki-Miyaura cross-coupling reaction of compounds of formula (VIII) with compounds of formula (IX) is well known to those skilled in the art and is usually carried out in the presence of a palladium catalyst such as tetrakis(triphenylphosphine)-palladium(0) or [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane complex and a base such as sodium carbonate or potassium carbonate, in a solvent such as N,N-dimethylformamide, dioxane or a dioxane-water mixture, at a temperature between room temperature and 160°C, optionally under microwave heating conditions and preferably under an inert atmosphere. Such reactions are reviewed, for example, in J. Organomet. Chem. 1999,576,147-168. The skilled artisan will also appreciate that the reaction is reversible, i.e., the reaction of the compound of formula (XI) (wherein R 1 , R 2 and R 3 is as defined above for compounds of formula (I)) and a compound of formula (X) 5 is hydrogen or methyl, R 7 , X 1 , X 2 and X 3 is as defined above for compounds of formula (I), and X 0 is a halogen, preferably chlorine, bromine or iodine, to give a compound of formula (IVa), 5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , X 1 , X 2 and X 3 It will be appreciated that the reaction can result in a 2-amino-2-propanediol (as defined above for compounds of formula (I)). This reaction is shown in Scheme 6. [ka] Scheme 6

[0093] Further cross-coupling chemistry, i.e., C-H activation, can also be used to give compounds of formula (IVa),5 is hydrogen or methyl, and R 1 , R 2 , R 3 , R 7 , X 1 , X 2 and X 3 may also be used to prepare compounds of formula (I) (as defined above for compounds of formula (I)). This reaction is shown in Scheme 7. [ka] Scheme 7

[0094] As shown in Scheme 7, a compound of formula (X), 5 is hydrogen or methyl, R 7 , X 1 , X 2 and X 3 is as defined above for compounds of formula (I), and X 0 is a halogen, preferably chlorine, bromine or iodine, and is reacted with a palladium catalyst, typically palladium acetate Pd(OAc) 2 in the presence of a suitable ligand, for example 1,10-phenanthroline, in the presence of a base, such as cesium carbonate or potassium carbonate, in an inert solvent, such as chlorobenzene, toluene or xylene, at a temperature between room temperature and 180° C., optionally under microwave heating conditions, preferably under an inert atmosphere, to form a compound of formula (XII), 1 , R 2 and R 3 is reacted with (as defined above for compounds of formula (I)). Similar reactions have been reported in the literature, for example in Chemical Science 2013, 4, 2374-2379.

[0095] Compounds of formula (III) can also be prepared from compounds of formula (XIII), the reaction of which is shown in Scheme 8. [ka] Scheme 8

[0096] As shown in Scheme 8, a compound of formula (III) can be prepared by reacting a compound of formula (XIII), 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X 1 , X 2 and X 3 is as defined above for compounds of formula (I), and R 01 can be prepared by one skilled in the art by carbamate deprotection reaction of common carbamate protecting group substituents, such as methyl, tert-butyl, allyl, 2,2,2-trichloroethyl, or benzyl. For example, R 01 When is methyl, for example, a suitable solvent such as dichloromethane and a suitable reagent such as iodotrimethylsilane may be employed to obtain the product by heating at a temperature between room temperature and 200° C., preferably between 20° C. and the boiling point of the reaction mixture, as described in J. Am. Chem. Soc. 1992, 114, 5959. The compound of formula (III) thus obtained is converted to the compound of formula (I) as shown in Scheme 1.

[0097] A compound of formula (XIII) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X 1 , X 2 and X 3 is as defined above for compounds of formula (I), and 01 where R is as above), can be reacted with an aldehyde of formula (XV) (including formaldehyde in its various forms) (where R is as above), in combination with an acid, in a suitable solvent, as described, for example, in Tetrahedron 1987, 43, 439. 7is as defined above for compounds of formula (I)) and a compound of formula (XIV) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X 1 , X 2 and X 3 is as defined above for compounds of formula (I), and 01 can be formed by the Pictet-Spengler reaction with 2-(2-(2-phenylpropanediol)-2-propanediol), as shown in Scheme 9. [ka] Scheme 9

[0098] A compound of formula (XIV) 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X 1 , X 2 and X 3 is as defined above for compounds of formula (I), and 01 where R is as above), can be reacted with an amine of formula (XVI), where R is as above, optionally in the presence of a base, such as triethylamine or pyridine, in a suitable solvent, such as dichloromethane, at a temperature between −20° C. and the boiling point of the mixture, as described, for example, in Org. Biomolec. Chem. 2016, 14, 6853. 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X 1 , X 2 and X 3 can be prepared by reaction of a 2-aminopropyl ether (which is as defined above for compounds of formula (I)) with a suitable protecting reagent, such as methyl chloroformate. This reaction is shown in Scheme 10. [ka] Scheme 10

[0099] A compound of formula (XVI) or a salt thereof (wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X 1 , X 2 and X 3 is as defined above for compounds of formula (I), can be reacted with a nitrile of formula (XVII), where R 1 , R 2 , R 3 , R 4 , X 1 , X 2 and X 3 can be prepared by one skilled in the art by reaction of the Grignard reagent R (as defined above for compounds of formula (I)) with a suitable nucleophile such as (dimethylsulfide)dihydroboron (BMS). 5 MgBr or R 6 MgBr (wherein, R 5 and R 6 As defined above for compounds of formula (I), Ti(O-) can be added sequentially or simultaneously as a nucleophile to compounds of formula (XVII) to allow the preparation of more highly substituted amines of formula (XVI). Such Grignard additions to nitriles can be carried out in inert solvents such as diethyl ether, tert-butyl methyl ether and cyclopentyl methyl ether using Ti(O-) as a nucleophile. i Pr) 4 (See Synlett 2007, (4), 652-654.) This reaction is shown in Scheme 11. [ka] Scheme 11

[0100] A compound of formula (XVII) 1 , R 2 , R 3 , R 4 , X 1 , X 2 and X 3 (wherein X is as defined above for compounds of formula (I)) can be prepared by one skilled in the art according to known methods. More specifically, compounds of formula (XVII) and intermediates thereto can be prepared from compounds of formula (XVIII) as shown in Scheme 12. [ka] Scheme 12

[0101] For example, a compound of formula (XVII) 1 , R 2 , R 3 , R 4 , X 1 , X 2 and X 3 is as defined above for compounds of formula (I), and R 4 is different from hydrogen) can be prepared by the reaction of a compound of formula (XVIIa), where R 4 is hydrogen, and R 1 , R 2 , R 3 , X 1 , X 2 and X 3 is defined as above for compounds of formula (I), followed by the addition of a suitable alkylating agent R 4 -X, where X is a halogen.

[0102] A compound of formula (XVIIa), 4 is hydrogen, and R 1 , R 2 , R 3 , X 1 , X 2and X 3 (wherein is as defined above for compounds of formula (I)) may be prepared from alcohols of formula (XVIII) by treatment with cyanotrimethylsilane (TMSCN) in the presence of a base such as lithium carbonate, in a non-polar solvent such as dichloromethane, at temperatures between 0° C. and the boiling point of the reaction mixture. Such transformations are well known in the literature under a variety of conditions, for example as described in Org. Lett. 2008, 10, 4570 and references therein. This reaction is shown in Scheme 12.

[0103] Compounds of formula (III) are commercially available or easily prepared by compounds known in the art. Compounds of formula (XVIII) can be prepared by methods known to those skilled in the art.

[0104] Salts of compounds of formula (I) can be prepared in a manner known per se: thus, for example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or with a suitable ion exchange reagent, and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchange reagent.

[0105] The salts of the compounds of formula (I) can be converted in customary manner, for example into the free compounds I (acid addition salts) by treatment with a suitable basic compound or a suitable ion exchange reagent, and can also be converted into salts with bases, for example by treatment with a suitable acid or a suitable ion exchange reagent.

[0106] Salts of compounds of formula (I) can be converted into other salts (acid addition salts, e.g. other acid addition salts) of compounds of formula (I) in a manner known per se, for example by treating the salt of an inorganic acid, such as hydrochloric acid, with a suitable metal salt of the acid, such as a sodium, barium or silver salt (e.g. silver acetate), in a suitable solvent (in which inorganic salts forming, for example, silver chloride, are insoluble and therefore precipitate from the reaction mixture).

[0107] Depending on the procedure or reaction conditions, compounds of formula (I) having salt-forming properties may be available in the free form or in salt form.

[0108] The compounds of formula (I) and, where appropriate, their tautomers, in each free or salt form, can exist in the form of pure isomers, such as, for example, enantiomers and / or diastereomers, or as isomeric mixtures, such as enantiomeric mixtures, for example racemates, diastereomeric mixtures or racemic mixtures, depending on the number, absolute and relative configuration of asymmetric carbon atoms occurring in the molecule and / or depending on the configuration of non-aromatic double bonds occurring in the molecule; the invention relates to the pure isomers and also to all possible isomeric mixtures, and is to be understood in this sense above and below, respectively, even if details of the stereochemistry are not specifically stated in each case.

[0109] Diastereomeric or racemic mixtures of compounds of formula I, in free or salt form, obtained depending on which starting materials and procedures are selected, may be separated in known manner into the pure diastereomers or racemates on the basis of the physical chemical differences of the components, for example, by fractional crystallization, distillation and / or chromatography.

[0110] Enantiomeric mixtures, such as racemates, which can be obtained in a similar manner can be resolved into their optical antipodes by known methods, for example by recrystallization from optically active solvents; by chromatography in chiral adsorbents, for example by high performance liquid chromatography (HPLC) on cellulose acetate using suitable microorganisms; by cleavage by specific immobilized enzymes, via the formation of inclusion compounds, for example with chiral crown ethers, in which only one enantiomer is complexed; or by conversion into diastereomeric salts, for example by reacting the basic end-product racemate with an optically active acid, such as a carboxylic acid, for example camphoric acid, tartaric acid or malic acid, or a sulfonic acid, for example camphorsulfonic acid, and separating the diastereomeric mixtures which can be obtained thereby, for example by fractional crystallization according to their different solubilities, from which the desired enantiomer can be liberated by the action of a suitable agent, for example a basic agent.

[0111] Pure diastereomers or enantiomers can be obtained according to the invention not only by separating the appropriate isomeric mixture but also by diastereoselective or enantioselective synthesis, which is generally known in the art, e.g. by carrying out the process according to the invention using starting materials with the appropriate stereochemistry.

[0112] If the individual components have different biological activity, it may be advantageous to isolate or synthesize, in each case, the more biologically effective isomer, e.g., enantiomer or diastereomer, or a mixture of isomers, e.g., a mixture of enantiomers or diastereomers.

[0113] As an example, compounds with two or more asymmetric carbon atoms may exist in diastereoisomeric forms that are optionally separable using, for example, supercritical fluid chromatography (SFC) chromatography with a chiral column. Such diastereomers may exhibit different fungicidal activity profiles, but all isomers and diastereomers form part of the present invention.

[0114] The compounds of formula (I) of the present invention (also shown for compounds of formula (IA)) have three asymmetric carbon atoms, where an asterisk (*) indicates the asymmetric carbon atom, and therefore there are eight stereoisomers. These eight stereoisomers are composed of four pairs of enantiomers. [ka]

[0115] Formula (I) and Formula (IA) (wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X 1 , X 2 , X 3 , A and Z 1 It will be appreciated by those skilled in the art that the above diastereoisomers and enantiomers of (wherein R is as defined in formula (I)) are within the scope of the present invention.

[0116] A compound of formula (IA) 1 is methyl, R 2 , R 3 , R 4 , R 5 , R 6 is hydrogen, and R 7 is methyl and X 1 and X 2 is CH, and X 3 is S and A is A10) are shown below for the enantiomeric and diastereomeric relationships. [ka]

[0117] The compounds of formula (I) and, where appropriate, their tautomers may also be available in free or salt form, where appropriate, also in the form of hydrates and / or include other solvents, such as those that may have been used for the crystallization of compounds present in solid form.

[0118] As stated above, it has now surprisingly been found that the compounds of formula (I) according to the invention have a highly advantageous level of biological activity for practical purposes in protecting plants against diseases caused by fungi.

[0119] The compounds of formula (I) according to the invention can be used in the agricultural sector and related fields of use, for example as active ingredients for controlling plant pests or non-living materials, for controlling spoilage microorganisms or organisms potentially harmful to humans. The novel compounds are distinguished by their excellent activity at low application rates, their excellent tolerance by plants, and their safety for the environment. They have highly useful curative, preventive and systemic properties and can be used to protect numerous cultivated plants. The compounds of formula (I) can be used to inhibit or eliminate pests occurring on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time also protecting these parts of later-growing plants from, for example, phytopathogenic microorganisms.

[0120] The present invention further relates to a method for controlling or preventing infestation of susceptible plants or plant propagation material and / or harvested food crops by microorganisms by treating the plants or plant propagation material and / or harvested food crops, wherein an effective amount of a compound of formula (I) according to the invention is applied to the plant, its part or its habitat.

[0121] The compounds of formula (I) according to the present invention may also be used as fungicides. The term "fungicide" as used herein means a compound that controls, modifies or prevents fungal growth. The term "fungicidally effective amount" as used herein means the amount of such a compound or combination of such compounds that is capable of producing an effect on fungal growth. A controlling or modifier effect includes any deviation from natural development such as killing, retardation, etc., and prevention includes the formation of a barrier or other defense in the plant to prevent infection by fungi.

[0122] As used herein, the term "controlling" refers to reducing the number of pests, eradicating pests, and / or preventing further pest damage such that damage to plants or plant-derived products is reduced.

[0123] The term "preventing" when used in the context of infestation of plants or plant propagation material and / or harvested food crops refers to the avoidance of symptoms of microbial attack or fungal infection (fungal growth).

[0124] It may also be possible to use the compounds of formula (I) according to the invention as dressings for treating plant propagation material, for example seeds such as fruits, tubers or grains or plant cuttings, for protection against fungal infections occurring in the soil as well as against phytopathogenic fungi. The propagation material can be treated with a composition comprising a compound of formula (I) before planting: for example, seeds can be dressed before being sown. The active compounds of formula (I) can also be applied to grains (coating) by impregnating the seeds in a liquid formulation or coating the seeds with a solid formulation. The composition can also be applied to the planting site when the propagation material is planted, for example in the sowing furrow during sowing. The invention also relates to a method for treating such plant propagation material and to the plant propagation material thus treated.

[0125] Furthermore, the compounds of formula (I) according to the present invention can be used for controlling fungi in related fields such as the protection of industrial materials, including wood and wood-based industrial products, food storage and hygiene control.

[0126] In addition, the present invention can be used to protect non-living materials such as timber, wallboard and paint from fungal attack.

[0127] The compounds of formula (I) according to the invention are effective against, for example, fungi and fungal vectors involved in diseases, as well as phytopathogenic bacteria and viruses, such as, for example: Alternaria spp., including Absidia corymbifera, Alternaria solani, Aphanomyces spp., Ascochyta spp., Aspergillus spp., including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucae, lactucae, Aureobasidium spp., including B. dothidea, B. obtusa, Botryosphaeria spp., including Botryotinia fuckeliana, Botrytis spp., including Botrytis cinerea, C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, C. tropicalis, Candida spp., including Cephaloascus fragrans spp., Cercospora spp., including Ceratocystis spp., Cercospora arachidicola, Cercospora kikuchii, Cercospora sojina, and Cercospora personatum.), Cladosporium spp. spp., including Cladosporium cucumerinum, Claviceps purpurea, and Coccidioides immitis, Cochliobolus spp., Colletotrichum spp., including Colletotrichum musae, Colletotrichum asianum, Corynespora cassiicola, and Cryptococcus neoformans, Diaporthe spp., Didymella Didymella spp. including Erysiphe spp. bryoniae, Drechslera spp., Elsinoe spp., Epidermophyton spp., Erwinia amylovora, Erysiphe spp. including Erysiphe cichoracearum, Eutypa lata, Fusarium culmorum, Fusarium graminearum, Fusarium langsethiae, Fusarium moniliforme, Fusarium oxysporum Fusarium spp., including Fusarium oxysporum, Fusarium proliferatum, Fusarium subglutinans, and Fusarium solani.), Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate, Glomerella lagenarium, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium spp., Hemileia spp., Histoplasma spp. including H. capsulatum spp., Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp., Monilinia spp., Mucor spp., Mycosphaerella spp. including Mycosphaerella graminicola, Mycosphaerella spp. including Mycosphaerella pomi, Oncobasidium theobromaeon theobromaeon, Ophiostoma piceae, Paracoccidioides spp., Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp., P.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, spp., Plasmopara spp. including Plasmopara halstedii and Plasmopara viticola, Pleospora spp., Podosphaera spp. including P. leucotricha, Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp., Pseudoperonospora spp. including P. cubensis and P. humuli, spp.), Puccinia spp. including Pseudopeziza tracheiphila, 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. spp., Scedosporium spp., including S. apiospermum and S. prolificans, Schizothyrium pomi, Sclerotinia spp., including Sclerotinia sclerotiorum, Sclerotium spp., Septoria spp., including Septoria nodorum, Septoria tritici, Sphaerotheca macularis, Sphaerotheca fusca, Sphaerotheca fuliginea, Sphaerotheca fusca ... fuliginea), Sporothorix spp., Stagonospora nodorum, Stemphylium spp., Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia spp., T. harzianum, T.pseudokoningii (T. pseudokoningii), T. Trichoderma spp. including T. viride, Trichophyton spp., Typhula spp., Uncinula necator, Urocystis spp., Ustilago spp., Venturia spp. including Venturia inaequalis, Verticillium spp., and Xanthomonas spp.

[0128] The compounds of formula (I) according to the invention may be used, for example, on turf, ornamental plants such as flowers, shrubs, broadleaf or evergreen trees such as conifers, as well as for trunk injections, pest management and the like.

[0129] Within the scope of the present invention, the target crops and / or useful plants to be protected are typically berry plants, such as blackberries, blueberries, cranberries, raspberries and strawberries; cereals, such as barley, maize (corn), millet, oats, rice, rye, sorghum, triticale and wheat; fibre plants, such as cotton, flax, hemp, jute and sisal; agricultural crops, such as sugar and fodder beet, coffee, hops, mustard, oilseed rape (canola), poppy, sugarcane, sunflower, tea and tobacco; fruit trees, such as apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; and arable plants, such as bermuda grass, strawberry bush, bentgrass, centipede grass, fescue, ryegrass, lawn grass and wild grass. herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes such as beans, lentils, peas and soybeans; nuts such as almonds, cashews, peanuts, hazelnuts, peanuts, pecans, pistachios and walnuts; palms such as oil palm; ornamental plants such as flowers, shrubs and trees; other trees such as cocoa, coconut, olive and rubber; vegetables such as asparagus, eggplant, broccoli, cabbage, carrots, cucumber, garlic, lettuce, squash, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and perennial and annual crops such as vines, for example grapes.

[0130] The term "useful plants" should also be understood to include useful plants in which resistance to herbicides such as bromoxynil or to a class of herbicides (e.g. HPPD inhibitors, ALS inhibitors such as primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyroyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors, etc.) has been imparted by conventional breeding or genetic engineering methods. An example of a crop in which resistance to imidazolinones, e.g. imazamox, has been imparted by conventional breeding methods (mutagenesis) is Clearfield® summer rapeseed (canola). Examples of crops that have been rendered resistant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-tolerant corn varieties commercially available under the trade names RoundupReady®, Herculex I®, and LibertyLink®.

[0131] The term "useful plants" should also be understood to include useful plants which have been transformed by recombinant DNA techniques so as to be capable of synthesizing one or more selectively acting toxins, such as the known ones derived from toxin-producing bacteria, especially those belonging to the genus Bacillus.

[0132] Examples of such plants are YieldGard® (a corn variety expressing a CryIA(b) toxin); YieldGard Rootworm® (a corn variety expressing a CryIIIB(b1) toxin); YieldGard Plus® (a corn variety expressing CryIA(b) and CryIIIB(b1) toxins); Starlink® (a corn variety expressing a Cry9(c) toxin); Herculex I® (a corn variety expressing a CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety expressing a CryIA(c) toxin); Bollgard I® (a cotton variety expressing a CryIA(c) toxin); Bollgard II® (a cotton variety expressing CryIA(c) and CryIIA(b) toxins); VIPCOT® (a cotton variety expressing VIP toxin); NewLeaf® (a potato variety expressing CryIIIA toxin); Nature-Gard® Agrisure® GT Advantage (GA21 glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), Agrisure® RW (corn root-feeding nematode trait) and Protecta®.

[0133] The term "crop plant" should also be understood to include crop plants which have been transformed using recombinant DNA techniques so as to be capable of synthesizing one or more selectively acting toxins, such as those known from toxin-producing bacteria, particularly those belonging to the genus Bacillus.

[0134] Toxins which can be expressed by such transformed plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as d-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), for example Vip1, Vip2, Vip3 or Vip3A; or insecticidal proteins from Photorhabdus spp. or Xenorhabdus spp., for example Photorhabdus luminescens, Xenorhabdus nematophilus. spp.); toxins produced by animals such as scorpion toxins, spider toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi such as Streptomycete toxins, plant lectins such as pea lectin, barley lectin or snowdrop lectin; agglutinins; proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ricin, Ribosome-inactivating proteins (RIPs) such as maize-RIP, abrin, rufin, saporin or bryodin; steroid metabolic enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers such as sodium or calcium blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

[0135] Furthermore, in the context of the present invention, delta-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or trophic insecticidal proteins (Vip), such as Vip1, Vip2, Vip3 or Vip3A, are also to be understood as being especially hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by new combinations of different domains of these proteins (see, for example, WO 02 / 15701). Truncated toxins, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the natural toxin are replaced. In such amino acid substitutions, preferably a non-naturally occurring protease recognition sequence is inserted into the toxin, for example, in the case of Cry3A055, a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see WO 03 / 018810).

[0136] Examples of such toxins or transformed plants capable of synthesizing such toxins are disclosed, for example, in EP 0 374 753, WO 93 / 07278, WO 95 / 34656, EP 0 427 529, EP 451 878 and WO 03 / 052073.

[0137] The processes for the preparation of such transformed plants are generally known to those skilled in the art and are described, for example, in the above-mentioned publications. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP 0 367 474, EP 0 401 979 and WO 90 / 13651.

[0138] The toxins contained in the transformed plants confer resistance to harmful insects on the plants, which can be from any taxonomic group of insects, but are particularly commonly found among beetles (Coleoptera), two-winged insects (Diptera), and butterflies (Lepidoptera).

[0139] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known, and some are commercially available. Examples of such plants include: YieldGard® (a corn variety expressing Cry1Ab toxin); YieldGard Rootworm® (a corn variety expressing Cry3Bb1 toxin); YieldGard Plus® (a corn variety expressing Cry1Ab and Cry3Bb1 toxins); Starlink® (a corn variety expressing Cry9C toxin); Herculex I® (a corn variety expressing Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety expressing Cry1Ac toxin); Bollgard I® (a cotton variety expressing Cry1Ac toxin); Bollgard II® (a cotton variety expressing Cry1Ac and Cry2Ab toxins); VipCot® (a cotton variety expressing Vip3A and Cry1Ab toxins); NewLeaf® (a potato variety expressing Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), and Protecta®.

[0140] Further examples of such transformed crops are: 1. Bt11 maize, registration number C / FR / 96 / 05 / 10, manufactured by Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St.Sauveur, France. Genetically engineered maize (Zea mays) that is resistant to the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also achieves tolerance to the herbicide glufosinate ammonium by transgenic expression of the enzyme PAT.

[0141] 2. Bt176 maize, registration number C / FR / 96 / 05 / 10, manufactured by Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St.Sauveur, France. A genetically engineered maize (Zea mays) that is resistant to the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of the Cry1Ab toxin. Bt176 maize also achieves tolerance to the herbicide glufosinate ammonium by transgenic expression of the enzyme PAT.

[0142] 3. MIR604 maize, registration number C / FR / 96 / 05 / 10, from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France. Maize conferred insect resistance by transgenic expression of a modified Cry3A toxin. The toxin is Cry3A055 modified by the insertion of a cathepsin-G-protease recognition sequence. The preparation of such transformed maize plants is described in WO 03 / 018810.

[0143] 4. MON863 maize, registration number C / DE / 02 / 9, from Monsanto Europe SA 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium. MON863 expresses the Cry3Bb1 toxin and confers resistance to certain coleopteran insects.

[0144] 5. IPC531 Cotton made by Monsanto Europe SA 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0145] 6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Maize genetically engineered for expression of the protein Cry1F to achieve resistance to certain lepidopteran insects, and for expression of the PAT protein to achieve resistance to the herbicide glufosinate ammonium.

[0146] 7. NK603 x MON810 maize, registration number C / GB / 02 / M3 / 03, from Monsanto Europe SA 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium. It consists of a conventional hybrid maize variety by crossing the genetically engineered varieties NK603 and MON810. NK603 x MON810 maize transgenic expresses the protein CP4 EPSPS from the strain CP4 of Agrobacterium sp., which confers resistance to the herbicide Roundup® (containing glyphosate), and also transgenic expresses the Cry1Ab toxin from Bacillus thuringiensis subsp. kurstaki, which confers resistance to certain Lepidoptera, including the European corn borer.

[0147] The compounds of formula (I) according to the invention are useful in the control of phytopathogenic diseases, in particular Alternaria solani, Blumeria graminis, Botryotinia fuckeliana, Botrytis cinerea, Cercospora arachidicola, Cercospora kikuchii, Cercospora sojina, Cladosporium cucumerinum, Colletotrichum lagenarium, Corynespora cassiicola, Didymella bryoniae, Fusarium spp. spp., Glomerella lagenarium, Leptosphaeria spp., Leveillula taurica, Microdochium nivale, Plasmopara viticola, Puccinia recondita, Pyrenophora teres, Pyricularia oryzae, Rhizoctonia solani, Sclerotinia sclerotiorum, Septoria nodorum, Septoria tritici, Sphaerotheca fuliginea In some embodiments, the fungi may be used in the control or prevention of phytopathogenic fungi such as Pseudomonas fuliginea, Uncinula necator and Venturia inaequalis.In an embodiment of the invention, the compounds of formula (I) according to the invention are useful for the prevention and control of phytopathogenic diseases, in particular Septoria tritici, Pyrenophora teres, Puccinia recondita and Blumeria graminis in cereals; Cercospora arachidicola and Sclerotinia sclerotiorum in crops; Alternaria solani in fruits and vegetables, such as tomatoes and potatoes; Botrytis cinerea in fruits, vegetables and crops, such as strawberries, tomatoes, sunflowers, legumes and grapes; Glomerella lagenarium in vegetables, such as cucumbers; Uncinula necatr in vegetables, such as grapes. necator); Venturia inaequalis in fruits, e.g. apple; Rhizoctonia solani in vegetables, e.g. potato; Cladosporium cucumerinum, Didymella bryoniae and Sphaerotheca fuliginea in vegetables, e.g. cucumber; Leveillula taurica in cucumber and solanaceous vegetables; Fusarium spp. in cereals and vegetables; Leptosphaeria spp. in cereals.

[0148] As used herein, the term "habitat" refers to the field in which the plant is growing or in which the seeds of the cultivated plant have been sown or in which the seeds will be sown in the soil, including the soil, the seeds and seedlings, as well as the established vegetation.

[0149] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, seedlings, roots, tubers, stems, stalks, foliage and fruits.

[0150] The term "plant propagation material" is understood to refer to reproductive parts of plants, such as seeds, which can be used for their propagation, and vegetative bodies, such as cuttings or tubers, for example potatoes. For example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and plant parts may be mentioned. Also mentioned are sprouted plants and shoots that are to be transplanted after germination or emergence from the soil. These shoots may be protected by a complete or partial treatment by immersion before transplantation. Preferably, "plant propagation material" is understood to refer to seeds.

[0151] The compounds of formula (I) according to the invention can be used in their pure form or, preferably, together with auxiliaries that are conveniently employed in the field of formulation.For this purpose, they can be conveniently formulated in a known manner into emulsifiable concentrates, coating pastes, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and capsules, for example, in polymeric materials.As well as the type of composition, the application method, such as spraying, misting, dusting, scattering, coating, or pouring, is selected according to the intended purpose and the current situation.The composition may also contain further auxiliaries, such as stabilizers, defoamers, viscosity regulators, binders or adhesives, as well as fertilizers, sources of trace elements, or other compounds for obtaining special effects.

[0152] Suitable carriers and adjuvants, for example for use in agriculture, can be solid or liquid and are substances useful in formulation technology, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers. Such carriers are described, for example, in WO 97 / 33890.

[0153] Suspension concentrates are aqueous formulations in which fine solid particles of the active compound are suspended. Such formulations contain anti-settling and dispersing agents and may further contain wetting agents to enhance activity, as well as anti-foaming agents and crystal growth inhibitors. In use, these concentrates are diluted in water and usually applied by spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

[0154] Wettable powders are in the form of fine particles that disperse easily in water or other liquid carriers. These particles contain the active ingredient held in a solid matrix. Typical solid matrices include Fuller's earth, kaolin clay, silica and other easily wet organic or inorganic solids. Wettable powders usually contain 5% to 95% of the active ingredient and small amounts of wetting agents, dispersing agents or emulsifying agents.

[0155] Emulsifiable concentrates are homogeneous liquid compositions that are dispersible in water or other liquids and may consist solely of the active compound and a liquid or solid emulsifier, or may contain a liquid carrier such as xylene, high boiling aromatic naphtha, isophorone, and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and usually applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

[0156] Granular formulations include both extrudates and relatively coarse particles, and are usually applied undiluted to the area where treatment is required. Typical carriers for granular formulations include sand, Fuller's earth, attapulgite clay, bentonite clay, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, gypsum, wood flour, ground corn cobs, ground peanut shells, sugar, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate, and other organic or inorganic materials that can absorb or be coated with the active compound. Granular formulations usually contain 5% to 25% active ingredient, which may include surfactants such as high-boiling aromatic naphtha, kerosene and other petroleum fractions, or vegetable oils; and / or spreading agents such as dextrin, glue or synthetic resins.

[0157] Dusts are free-flowing admixtures of the active ingredient and finely divided solids such as talc, clays, powders and other organic and inorganic solids which act as dispersants and carriers.

[0158] Microcapsules are typically droplets or granules of active ingredient enclosed in an inert porous shell that allows the encapsulated material to be released into the environment at a controlled rate. The encapsulated droplets are typically 1-50 microns in diameter. The encapsulated liquid typically constitutes 50-95% of the capsule's weight and may contain a solvent in addition to the active compound. Encapsulated granules are generally porous granules with a porous membrane that seals the pore openings of the granule and retains the active species in liquid form within the pores of the granule. The granules are typically in the range of 1 millimeter to 1 centimeter in diameter, preferably 1-2 millimeters. Granules are formed by extrusion, agglomeration or prilling, or are natural. Examples of such materials are vermiculite, calcined clay, kaolin, attapulgite clay, sawdust, and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xandates.

[0159] Other useful formulations for agricultural chemical applications include simple solutions of the active ingredient in solvents such as acetone, alkylated naphthalenes, xylenes and other organic solvents in which complete dissolution at the desired concentration is achieved. Pressurized sprayers may also be used in which the active ingredient is dispersed in finely divided form as the low boiling dispersant solvent carrier evaporates.

[0160] Suitable agricultural adjuvants and carriers useful in formulating the compositions of the present invention in the formulation types described above are well known to those skilled in the art.

[0161] Liquid carriers that may be utilized include, for example, water, toluene, xylene, petroleum naphtha oil, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-Trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, kutadeca Examples of suitable solvents include ethyl acetate, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol, glycerin, and N-methyl-2-pyrrolidinone. For dilution of concentrates, water is the typical carrier of choice.

[0162] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, Kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, Fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut hulls, and lignin.

[0163] A wide range of surfactants may be advantageously utilized in both the liquid and solid compositions, particularly those designed to be diluted with a carrier prior to application. These surfactants, when used, typically comprise from 0.1% to 15% by weight of the formulation. They may be anionic, cationic, nonionic or polymeric in nature and may be utilized as emulsifying agents, wetting agents, suspending agents, or for other purposes. Typical surfactants include alkyl sulfates such as diethanolammonium lauryl sulfate; alkylaryl sulfonate salts such as calcium dodecylbenzene sulfonate; alkylphenol-alkylene oxide adducts such as nonylphenol-C.sub.18 ethoxylate; alcohol-alkylene oxide adducts such as tridecyl alcohol-C.sub.16 ethoxylate; soaps such as sodium stearate; alkylnaphthalene sulfonates such as sodium dibutylnaphthalene sulfonate; dialkyl esters of sulfosuccinates such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters such as sorbitol oleate; quaternary amines such as lauryl trimethyl ammonium chloride; polyethylene glycol esters of fatty acids such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and dialkyl phosphate esters.

[0164] Other adjuvants commonly utilized in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray size regulators, pigments, antioxidants, foaming agents, defoamers, light blocking agents, compatibilizers, antifoaming agents, sequestering agents, neutralizing and buffering agents, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, trace elements, emollients, lubricants and adhesives.

[0165] In addition, other biocidal active ingredients or compositions may be combined with the compositions of the present invention, used in the methods of the present invention, and applied simultaneously or sequentially with the compositions of the present invention. When applied simultaneously, these additional active ingredients may be formulated together with the compositions of the present invention or may be mixed together, for example, in a spray tank. These additional biocidal active ingredients may be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and / or plant growth regulators.

[0166] Pesticides are referred to herein using their common names as known, for example from “The Pesticide Manual”, 15th Ed., British Crop Protection Council 2009.

[0167] In addition, the compositions of the present invention may also be applied together with one or more systemic acquired resistance inducers ("SAR" inducers). SAR inducers are known and are described, for example, in U.S. Patent No. 6,919,298, and include, for example, salicylates and the commercially available SAR inducer acibenzolar-S-methyl.

[0168] The compounds of formula (I) according to the present invention are usually used in the form of agrochemical compositions and can be applied to the crop areas or plants to be treated simultaneously or sequentially with further compounds. These further compounds can be, for example, fertilizers or trace element donors or other preparations that affect plant growth. They can also be selective or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired with further carriers, surfactants or application-promoting adjuvants customarily used in the field of formulations.

[0169] The compounds of formula (I) according to the present specification may be used in the form of a (fungicidal) composition for the control or protection against phytopathogenic microorganisms, comprising at least one compound of formula (I) as active ingredient, or in the form of at least one preferred individual compound as defined herein, in free form or in the form of an agrochemically usable salt, and at least one of the abovementioned auxiliaries.

[0170] The present invention therefore provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I) according to the present invention, an agriculturally acceptable carrier, and optionally an adjuvant. An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural carriers are well known in the art. Preferably, the composition may comprise, in addition to the compound of formula (I), at least one or more pesticidal active compounds, for example an additional fungicidal or fungicidal active ingredient.

[0171] The compounds of formula (I) according to the present invention may be the sole active ingredient in the composition or, where appropriate, may be mixed with one or more additional active ingredients, such as pesticides, fungicides, synergists, herbicides or plant growth regulators, which may in some cases result in unexpected synergistic activity.

[0172] Examples of suitable additional active ingredients are the following: acyl amino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenic fungicides, aryl phenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, fungicides, bridged diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, furamide fungicides, furanilide fungicides, hydrazide fungicides, imidazole fungicides, mercury fungicides, Morpholine fungicides and fungicides, organophosphate fungicides and fungicides, organotin fungicides and fungicides, oxathiin fungicides and fungicides, oxazole fungicides and fungicides, phenylsulfamide fungicides and fungicides, polysulfide fungicides and fungicides, pyrazole fungicides and fungicides, pyridine fungicides and fungicides, pyrimidine fungicides and fungicides, pyrrole fungicides and fungicides, quaternary ammonium fungicides and fungicides, quinoline fungicides and fungicides, quinone fungicides and fungicides, quinoxaline fungicides These include fungicides, strobilurin fungicides, sulfonanilide fungicides, thiadiazole fungicides, thiazole fungicides, thiazolidine fungicides, thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, valinamide fungicides and zinc fungicides.

[0173] Examples of suitable additional active ingredients that may be selected include: petroleum, 1,1-bis(4-chloro-phenyl)-2-ethoxyethanol, 2,4-dichlorophenylbenzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylacetamide, 4-chlorophenylphenylsulfone, acetoprole, aldoxicarb, amidithione, amidothioate, amiton, amiton hydrogen oxalate, amitraz, aramite, arsenic oxide, azobenzene, azotoate, benomyl, benoxa-phos, benzoic acid. Benzil, bixafen, brofenvalerate, bromocyclen, bromophos, bromopropylate, buprofezin, butocarboxim, butoxycarboxim, butylpyridaben, calcium polysulfide, camphorchlor, carbanolate, carbophenothione, cymiazole, chinomethionate, chlorbenside, chlordimeform, chlordimeform hydrochloride, chlorphenetole, chlorfenson, chlorphenesulfide, chlorobenzilate, chloromebuform, chloromethiron, Chloropropylate, Chlorthiophos, Cinerin I, Cinerin II, Cinerin, Closantel, Coumaphos, Crotamiton, Crotoxifos, Cufraneb, Cyanthoate, DCPM, DDT, Demefion, Demefion-O, Demefion-S, Demeton-methyl, Demeton-O, Demeton-O-Methyl, Demeton-S, Demeton-S-Methyl, Demeton-S-Methyl Sulfone, Dichlofluanid, Dichlorvos, Diglifos, Dienochlor, Dimefox, Zinex, Zinex-Diclexin, Dioxin. JAP-4, Dinocap-6, Dinoctone, Dinopentone, Dinosulfone, Dinotervone, Dioxathion, Diphenylsulfone, Disulfiram, DNOC, Dofenapine, Doramectin, Endothion, Eprinomectin, Ethoate-methyl, Etrimphos, Fenazaflor, Fenbutatin Oxide, Fenothiocarb, Fenpyrad, Fenpyroximate, Fenpyrazamine, Fenson, Fentrifanil, Flubenzimine, Flucycloxuron, Fluentil, Fluorobenside, FMC 1137, Formetanate, Formetanate Hydrochloride, Forparanate, Gamma-HCH, Gliosin, Halfrenprox, Hexadecylcyclopropanecarboxylate,Isocarbophos, Jasmolin I, Jasmolin II, Iodofenphos, Lindane, Malonoben, Mecarbam, Mesfolan, Mesulfen, Methacrifos, Methyl Bromide, Metolcarb, Mexacarbate, Milbemycin Oxime, Mipafox, Monocrotophos, Morphothion, Moxidectin, Naled, 4-Chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one, Nifluridide, Nikkomycin, Nitrilacarb, Nitrilacarb 1:1 Zinc Chloride Complex, Omethoate , oxydeprophos, oxydisulfoton, pp'-DDT, parathion, permethrin, fencapton, phosalone, phospholane, phosphamidon, polychloroterpenes, polynactin, proclonol, promacyl, propoxur, prothidathion, protoate, pyrethrin I, pyrethrin II, pyrethrins, pyridaphenthion, pyrimitate, quinalphos, quinthiophos, R-1492, phosglycine, rotenone, shladan, cebufos, selamectin, sofamide, SSI-121, sulfiram, sulfuramide, sulfotep, sulfur, di Flovidazin, tau-fluvalinate, TEPP, terbam, tetradifon, tetrasul, thiafenox, thiocarboxim, thiofanox, thiometon, thioquinox, thuringensin, triamiphos, triaraten, triazophos, triazuron, tripenophos, trinactin, vamidothion, vaniliprole, bethoxazin, copper dioctanoate, copper sulfate, sibutrin, dichloron, dichlorophen, endothal, fentin, hydrated lime, nabam, quinoclamine, quinonamide, simazine, triphenyltin acetate, triphenylsulphate , crufomate, piperazine, thiophanate, chloralose, fenthion, pyridin-4-amine, strychnine, 1-hydroxy-1H-pyridine-2-thione, 4-(quinoxalin-2-ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, copper hydroxide, cresol, dipyrithione, dodysin, phenaminosulf, formaldehyde, hydralgafen, kasugamycin, kasugamycin hydrochloride hydrate, nickel bis(dimethyldithiocarbamate), nitropyrine, octhilinone, oxolinic acid,Oxytetracycline, Potassium Hydroxyquinoline Sulfate, Probenazole, Streptomycin, Streptomycin Sesquisulfate, Tecloftalam, Thiomersal, Adoxophyes Orana GV, Agrobacterium radiobacter, Amblyseius species, Anagrapha falcifera NPV, Anagrus atomus, Aphelinus abdominalis, Aphidius colemani, Aphidoletes aphidimyza, Autographa californica NPV, Bacillus sphaericus Neide, Beauveria brongniartii, Chrysoperla carnea, Cryptolaemus montrouzieri, Cydia pomonella GV, Dacnusa sibirica, Diglyphus isaea, Encarsia formosa, Eretmocerus eremicus, Heterorhabditis bacteriophora and H. megidis, Hippodamia convergens, Leptomastix dactylopii dactylopii, Macrolophus caliginosus, Mamestra brassicae NPV, Metaphycus helvolus,Metarhizium anisopliae var. acridum, Metarhizium anisopliae var. anisopliae, Neodiprion sertifer NPV and N. lecontei NPV, Orius spp., Paecilomyces fumosoroseus, Phytoseiulus persimilis, Steinernema bibionis, Steinernema carpocapsae, Steinernema feltiae, feltiae, Steinernema glaseri, Steinernema riobrave, Steinernema riobravis, Steinernema scapterisci, Steinernema spp., Trichogramma spp., Typhlodromus occidentalis, Verticillium lecanii), afolate, bisazir, busulfan, dimatif, hemel, hempa, metepa, methiotepa, methyl afolate, molzide, penfluron, tepa, thiohempa, thiotepa, toretamine, uredepa, (E)-tridec-4-en-1-yl acetate with (E)-dec-5-en-1-yl acetate, (E)-6-methylhept-2-en-4-ol, (E,Z)-tetradec-4,10-dien-1-yl acetate, (Z)-dodec-7-en-1-yl acetate, (Z)-hexadec-11-enal, (Z)-hexadec-11-en-1-yl acetate, (Z)-hexadec-13-en-11-yn-1-yl acetate,(Z)-icos-13-en-10-one, (Z)-tetradec-7-en-1-al, (Z)-tetradec-9-en-1-ol, (Z)-tetradec-9-en-1-yl acetate, (7E,9Z)-dodeca-7,9-dien-1-yl acetate, (9Z,11E)-tetradec-9,11-dien-1-yl acetate, (9Z,12E)-tetradec-9,12-dien-1-yl acetate, 14-methyloctadec-1-ene, 4-methylnonan-5-ol with 4-methylnonan-5-one, 4-methylnonan-5-ol with alpha-multistriatin, brevicomin, codramon, cudramon, disparlure, dodec-8-en-1-yl acetate, dodec-9-en-1-yl acetate, dodeca-8 ... -8,10-dien-1-yl acetate, dominical lure, ethyl 4-methyloctanoate, eugenol, frontalin, grand lure, grand lure I, grand lure II, grand lure III, grand lure IV, hexal lure, ipsdienol, ipsenol, japonil lure, lineatin, little lure, loop lure, medi lure, megaatomic acid, methyl eugenol, muscal lure, octadeca-2,13-dien-1-yl acetate, octadeca-3,13-dien-1-yl acetate, orfulla lure, orictal lure, ostramon, siglure, soldidin sulcatol, tetradec-11-en-1-yl acetate, trimedlure, trimedlure A, trimedlure B, 1 , Trimedrua B 2, trimedlure C, trunc-call, 2-(octylthio)ethanol, butyronoxyl, butoxy(polypropylene glycol), dibutyl adipate, dibutyl phthalate, dibutyl succinate, diethyl toluamide, dimethylcarbate, dimethyl phthalate, ethyl hexanediol, hexamide, methoquin-butyl, methyl neodecaneamide, oxamate, picaridin, 1-dichloro-1-nitroethane, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane, 1,2-dichloropropane 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 dimethyl carbamate, 2-(2-butoxyethoxy)ethyl thiocyanate, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methyl carbamate, 2-(4-chloro -3,5-xylyloxy)ethanol, 2-chlorovinyl diethyl phosphate, 2-imidazolidone, 2-isovalerilindane-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-xylyl methylcarbamate, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate, acetione, acrylonitrile, aldrin, allosamidin, alixalve, alpha-ecdysone, aluminum phosphide, aminocarb, anabasine, atidathion, azamethiphos, Bacillus thuringiensis delta endotoxin (Bacillusthuringiensis deltaendotoxins), barium hexafluorosilicate, barium polysulfide, bartholin, Bayer 22 / 190, Bayer 22408, beta-cyfluthrin, beta-cypermethrin, bioethanomethrin, bioethanomethrin, bis(2-chloroethyl)ether, borax, bromfenbufos, bromo-DDT, bufencarb, butacarb, butathiophos, butonate, calcium arsenate, calcium cyanide, carbon disulfide, carbon tetrachloride, cartap hydrochloride, sebazine, chlorbicyclen, chlordane, chlordecone, chloroform, chloropicrin, chlorphoxime, chlorprazophos, cis-resmethrin, simetryn, clocitrin, copper acetoarsenite, arsenic acid Copper, copper oleate, kumitoate, acrolite, CS708, cyanofenphos, cyanophos, ciclethrin, cithioate, d-tetramethrin, DAEP, dazomet, decarbofuran, diamidaphos, dicapton, diclofenthion, dicresyl, dicyclanil, dieldrin, diethyl 5-methylpyrazol-3-yl phosphate, dirol, dimefluthrin, dimethane, dimethyrin, dimethylvinphos, dimethyllan, dinoprop, dinosam, dinoseb, diofenolan, dioxabenzophos, dicyclophos, DSP, ecdysterone, EI1642, EMPC, EPBP, ethaphos, ethiofencarb, ethyl formate, ethylene dibromide, ethylene dichloride,Ethylene oxide, EXD, fenchlorphos, fenetacarb, fenitrothion, fenoxacrim, fenpyritrin, fenthion ethyl, flucofuron, fosmetiran, fospirate, fostietan, furathiocarb, fretrin, guazatine, guazatine acetate, sodium tetrathiocarbonate, halffenprox, HCH, HEOD, heptachlor, heterophos, HHDN, hydrogen cyanide, hikincarb, IPSP, isofunofos, isobenzan, isodrin, isofenphos, isoprothiolane, Isoxathion, juvenile hormone I, juvenile hormone II, juvenile hormone III, kereban, kinoprene, lead arsenate, leptophos, lilimphos, ritidathion, m-cumenylmethylcarbamate, magnesium phosphide, magidox, mecarfone, menazone, mercurous chloride, mesulfenphos, metam, meta-potassium, meta-sodium, methanesulfonyl fluoride, methoclotophos, methoprene, methotrin, methoxychlor, methyl isothiocyanate, methylchloroform, methylene chloride, methoxadiazone, mirex, naphthalophos, naphthalene, NC -170, nicotine, nicotine sulfate, nithiazine, nornicotine, O-5-dichloro-4-iodophenyl O-ethyl phosphonothioate, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate, O,O,O',O'-tetrapropyl dithiopyrophosphate, oleic acid, paradichlorobenzene, parathion-methyl, pentachlorophenol, pentachlorophenyl laurate, PH60-38, fenkaptone, Phosniclor, phosphine, phoxim-methyl, pyrimetaphos, polychlorodicyclopentadiene isomers, potassium arsenite, potassium thiocyanate, precocene I, precocene II, precocene III, primidophos, profluthrin, promecarb, prothiophos, pyrazophos, pyresmethrin, cassia, quinofos-methyl, quinothion, rafoxanide, resmethrin, rotenone, cadethrin, ryania, ryanodine, sabadila, shradan, cebufos, SI-0009, thiapronil, sodium arsenite, sodium cyanide, sodium fluoride,Sodium hexafluorosilicate, sodium pentachlorophenoxide, sodium selenate, sodium thiocyanate, sulcofuron, sulcofuron sodium, sulfuryl fluoride, sulprofos, tar oil, tajincarb, TDE, tebupirimfos, temephos, telalethrin, tetrachloroethane, cyclofos, thiocyclam, thiocyclam hydrogen oxalate, thionazine, thiosultap, thiosultap-sodium, tralomethrin, transpermethrin, triazamate, trichlorometaphos-3, trichloronate, trimethacarb, tolprocarb, triclopyricarb, triplen, veratridine, veratrine, XMC, zetamethrin, zinc phosphate, zolaprofos, meperfluthrin, tetramethylfluthrin, bis(tributyltin) oxide , Bromoacetamide, Ferric phosphate, Niclosamide-olamine, Tributyltin oxide, Pyrimorph, Trifenmorph, 1,2-Dibromo-3-chloropropane, 1,3-Dichloropropene, 3,4-Dichlorotetrahydrothiophene 1,1-dioxide, 3-(4-chlorophenyl)-5-methylrhodanine, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid, 6-Isopentenylaminopurine, Anicifluprine, Benclotiaz, Cytokinins, DCIP, Furfural, Isamidophos, Kinetin, Myrothecium verrucaria composition, Tetrachlorothiophene, Xylenols, Zeatin, Potassium ethylxanthinate, Acibenzolar, Acibenzolar-S-methyl, Reynoutria sakarinensis (Reynoutria sachalinensis) extract, alpha-chlorohydrin, antu, barium carbonate, bisthiosemi, brodifacoum, bromadiolone, bromethalin, chlorophacinone, cholecalciferol, coumachlor, coumafuryl, coumatetralyl, crimidine, difenacoum, difethialone, diphacinone, ergocalciferol, flocoumafen, fluoroacetamide, flupropazine, flupropazine hydrochloride, norbormide, phosacetin, phosphorus, pindone, pyrinuron, sciriloside, sodium fluoroacetate, thallium sulfate, warfarin, 2-(2-butoxyethoxy)ethyl piperonylate,5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone, farnesol with nerolidol, berubutin, MGK264, piperonyl butoxide, piperotal, propyl isomer, S421, sesamex, sesamolin, sulfoxide, anthraquinone, copper naphthenate, copper oxychloride, dicyclopentadiene, thiram, zinc naphthenate, ziram, imanin, ribavirin, chloroinconazide, mercuric oxide, thiophanate methyl, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazo ol, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, furamepyr, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, paclobutrazol, pefurazoate, penconazole, prothioconazole, pyrifenox, prochloraz, propiconazole, pyrisoxazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole, ancymidazole , fenarimol, nuarimol, bupirimate, dimethirimol, ethirimol, dodemorph, fenpropidin, fenpropimorph, spiroxamine, tridemorph, cyprodinil, mepanipyrim, pyrimethanil, fenpiclonil, fludioxonil, benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurase, oxadixyl, carbendazim, debacarb, fuberidazole, thiabendazole, chlozolinate, dichlozolin, mycozolin, procymidone, vinclozolin, boscalid, carboxin, fenfuram, furan Lutranil, mepronil, oxycarboxin, penthiopyrad, thifluzamide, dodine, iminoctadine, azoxystrobin, dimoxystrobin, enestrobulin, phenaminestrobin, flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, ferbam, mancozeb, maneb, metiram, propineb, zineb, captafol, captan, fluoroimide,Folpet, Tolylfluanid, Boldeax mixture, Copper oxide, Mancopper, Oxine copper, Nitrothalisopropyl, Edifenphos, Iprobenfos, Fosdifen, Tolclofos methyl, Anilazine, Benthiavalicarb, Blasticidin-S, Chloroneb, Chlorothalonil, Cyflufenamid, Cymoxanil, Cyclobutrifluram, Diclocymet, Diclomedine, Dicloran, Diethofencarb, Dimethomorph, Flumorph, Dithianon, Ethaboxam, Etridiazole, Famoxadone, Fenamidone, Fenoxanil, Fenoxanil, Limzone, fluazinam, flumethylsulfolim, fluopicolide, fluoxythioconazole, flusulfamide, fluxapyroxad, fenhexamid, fosetylaluminum, hymexazole, iprovalicarb, cyanofamide, methasulfocarb, metrafenone, pencycuron, phthalide, polyoxin, propamocarb, pyribencarb, proquinazid, pyroquilon, pyriophenone, quinoxyfen, quintozene, thiadinil, triazoxide, tricyclazole, triforine, validamycin, valifenalate, zoxamide, ma Dipropamide, fulveneram, isopyrazam, sedaxane, benzovindiflupyr, pydiflumetofen, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide, isoflucipram, isotianil, dipimethitrone, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide amide, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylidan-4-yl]pyrazole-4-carboxamide, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-1,3-dimethyl-1H-pyrazol-5-amine, fluindapyr,methoxystrobin (jiaxiangjunzhi) lvbenmixianan, diclobenziazox, mandestrubin, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone, 2-[, 2-Fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol, oxathiapiproline, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate, pyraziflumide, impirflusam, trolprocarb, mefentrifluconazole, ipfentrifluconazole, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine -3-Carboxamide, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl]methanesulfonate, but- 3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine, pyridaclomethyl, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4- Carboxamide, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one, aminopyrifen, amethoctrazine, amisulbrom, penflufen, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-Dimethyl-pent-3-enamide, florylpicoxamide, fenpicoxamide, methallylpicoxamide, tebufloquine, ipulfenoquine, quinofumelin, isofetamide, ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate (which may be prepared by the methods described in WO 2020 / 056090), ethyl 1-[[4-[[(Z)-2-ethoxy-3,3,3-trifluorophenyl]phenyl]methyl]pyrazole-3-carboxylate (which may be prepared by the methods described in WO 2020 / 056090), methyl N-[[4-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazole-4-yl]-2-methyl-phenyl]methyl]carbamate (which may be prepared by the methods described in WO 2020 / 097012); methyl N-[[4-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazole- 4-yl]-2-methyl-phenyl]methyl]carbamate (which may be prepared by the methods described in WO 2020 / 097012), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (which may be prepared by the methods described in WO 2020 / 109391), 6-chloro-N-[2-(2-chloro-4-methyl-phenyl)-2,2-difluoro-ethyl]- 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide (which may be prepared by the methods described in WO 2020 / 109391), N-[2-[2,4-Dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide, benzothiostrobin, phenamacryl, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1), fluopyram, flufenoxadiazam, flutianil, fluopimomide, pyrapropoin, picarbutrazox, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)-4-oxazolidine ... -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-((3R)-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, methyl (Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop-2-enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-(4-propyltriazol-2-yl)phenoxy]prop-2-enoate, methyl (Z)-2-[5-(3-isopropyl methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]prop-2-enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]prop-2-enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]prop-2-enoate (these compounds are described in WO 2020 / 079111 (which may be prepared by the method described in WO 2020 / 193387), methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate, methyl (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate (which may be prepared by the method described in WO 2020 / 193387), 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3- (1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-Triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, trinexapac, comoxystrobin, zhongshengmycin, copper thiodiazole, zinc thiazole, amethotractin, iprodione, sebocthylamine, N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-chloro-2-methyl-6-(1-methyl-2 -propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine (these compounds can be prepared from the method described in WO 2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (these compounds can be prepared from the method described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine (these compounds can be prepared according to the methods described in WO 2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine, N-ethyl-N'-[5-methoxy-2-methyl-4-[2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine (these compounds can be prepared according to the methods described in WO 2019 / 110427); N-[( 1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide (these compounds can be prepared according to the method described in WO 2017 / 153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro- 3,3-Dimethyl-isoquinoline, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 1-(6-chloro-7-methyl-pyrazolo 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline, 6-chloro-4,4-di ...1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline, 1-(4,5-dimethylbenzimidazol-1-yl) Fluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole (these compounds can be prepared according to the method described in WO 2016 / 156085);N-Methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 1-Methoxy-3-methyl-1-[[4-[5-(trifluoromethyl) 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, -yl]phenyl]methyl]-1,2,4-triazol-3-amine (these compounds can be prepared from the methods described in WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 093348 and WO 2017 / 118689); 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared from the methods described in WO 2017 / 029179);2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (this compound can be prepared from the method described in WO 2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile (this compound can be prepared from the method described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate (this compound can be prepared from the method described in WO 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone (this compound can be prepared from the method described in WO 201 N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide (which can be prepared from the method described in WO 2018 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (this compound can be prepared from the method described in WO 2018 / 153707); N'- (2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine; N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared from the method described in WO 2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (this compound can be prepared from the method described in WO 2014 / 095675);(5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone (these compounds can be prepared from the method described in WO 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide (this compound can be prepared from the method described in WO 2018 / 065414); ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate (this compound can be prepared from the method described in WO 2018 / 065414). , which can be prepared from the method described in WO 2018 / 158365;2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, N-[N-methoxy-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide (these compounds can be prepared from the method described in WO 2018 / 202428).

[0174] The compounds of the present invention may also be used in combination with anthelmintics. Such anthelmintics include compounds selected from the macrocyclic lactone class of compounds, such as ivermectin, avermectin, abamectin, emamectin, epirimectin, doramectin, selamectin, moxidectin, nemadectin and milbemycin derivatives, as described in EP 0357460, EP 0444964 and EP 0594291. Additional anthelmintics include semi-synthetic and biosynthetic avermectin / milbemycin derivatives, such as those described in U.S. Pat. No. 5,015,630, WO 9415944 and WO 9522552. Additional anthelmintics include benzimidazoles, such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxyfendazole, oxybendazole, parbendazole and other members of this class. Additional anthelmintics include imidazothiazoles and tetrahydropyrimidines such as tetramisole, levamisole, pyrantel pamoate, oxantel or morantel. Additional anthelmintics include fluoxamides such as triclabendazole and clorsulon and cestocides such as praziquantel and epsiprantel.

[0175] The compounds of the present invention may be used in combination with derivatives and analogues of the paraherquamide / marcfortine class of anthelmintics and antiparasitic oxazolines such as those disclosed in U.S. Pat. No. 5,478,855, U.S. Pat. No. 4,639,771 and German Patent No. 19520936.

[0176] The compounds of the invention may be used in combination with derivatives and analogues of the general class of dioxomorpholine antiparasitic agents described in WO 9615121, and in combination with anthelmintic active cyclic depsipeptides such as those described in WO 9611945, WO 9319053, WO 9325543, EP 0626375, EP 0382173, WO 9419334, EP 0382173 and EP 0503538.

[0177] The compounds of the invention may be used in combination with other ectoparasiticides; for example fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide; neonicotinoids such as imidacloprid.

[0178] The compounds of the present invention may be used in combination with terpene alkaloids, particularly those disclosed in WO 95 / 19363 or WO 04 / 72086.

[0179] Other examples of such biologically active compounds with which the compounds of the present invention may be used in combination include, but are not limited to, the following: Organophosphates: Acephate, Azamethiphos, Azinphos-ethyl, Azinphos-methyl, Bromophos, Bromophos-ethyl, Cadusafos, Chlorethoxyphos, Chlorpyrifos, Chlorfenvinphos, Chlormephos, Demeton, Demeton-S-methyl, Demeton-S-methylsulfone, Diarifos, Diazinon, Dichlorvos, Dicrotophos, Dimethoate, Disulfoton, Ethion, Ethoprophos, Etrimphos, Fanfur, Fenamiphos, Fenitrothion, Fensulfothion, Fenthion, Flupyrazophos, Fonophos, Formothion, Fosthiazate, Heptenophos, Isazophos, Isothioate, Isoxathioate , malathion, methacrifos, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, paraoxon, parathion, parathion-methyl, phenthoate, phosalone, phospholane, phosphocarb, phosmet, phosphamidon, phorate, phoxim, pirimiphos, pirimiphos-methyl, profenofos, propafos, proethamphos, prothiofos, pyraclofos, pyridapenthione, quinalphos, sulprofos, temephos, terbufos, tebupirimphos, tetrachlorvinphos, thimeton, triazophos, trichlorfon, vamidothion.

[0180] Carbamates: alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801, isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl (methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717.

[0181] Pyrethroids: acrinathin, allethrin, alphamethrin, 5-benzyl-3-furylmethyl (E)-(1R)-cis-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, beta-cyfluthrin, cyfluthrin, alpha-cypermethrin, beta-cypermethrin, bioallethrin, bioallethrin ((S)-cyclopentyl isomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin , cycythrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (D isomer), imiprothrin, cyhalothrin, λ-cyhalothrin, permethrin, fenothrin, prallethrin, pyrethrins (natural products), resmethrin, tetramethrin, transfluthrin, θ-cypermethrin, silafluofen, t-fluvalinate, tefluthrin, tralomethrin, ζ-cypermethrin.

[0182] Arthropod growth regulators: a) Chitin synthesis inhibitors: Benzoyl ureas: Chlorfluazuron, Diflubenzuron, Fluazuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novaluron, Teflubenzuron, Triflumuron, Buprofezin, Diofenolan, Hexythiazox, Etoxazole, Chlorfentadine; b) Ecdysone antagonists: Halofenozide, Methoxyfenozide, Tebufenozide; c) Juvenoids: Pyriproxyfen, Methoprene (including S-methoprene), Fenoxycarb; d) Lipid biosynthesis inhibitors: Spirodiclofen.

[0183] Other antiparasitic drugs: Acequinocyl, Amitraz, AKD-1022, ANS-118, Azadirachtin, Bacillus thuringiensis thuringiensis), bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidine, cyromazine, diacloride, diafenthiuron, DBI-3204, dinactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, etofenprox, fenazaquin, flumite, MTI-800, fenpyroximate, fluacrypyrim, flubenzimine, flubrocythrinate, fluphenzin, flufenprox, fluproxifen, halofenprox ofenprox), hydramethylnon, IKI-220, Kanemite, NC-196, Nimgard, Nidinolterfuran, Nitenpyram, SD-35651, WL-108477, pyridalyl, propargite, protrifenbut, pymethrozine, pyridaben, pyrimidifen, NC-1111, R-195, RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601, silafluofen, cyromazine, spinosad, tebufenpyrad, tetradifon, tetranactin, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad, triazamate, triethoxyspinosin, trinactin, belbutin, bertarek, YI-5301.

[0184] Biological agents: Bacillus thuringiensis ssp aizawai, kurstaki, Bacillus thuringiensis delta-endotoxin, baculovirus, entomopathogenic bacteria, viruses and fungi.

[0185] Fungicides: Chlortetracycline, oxytetracycline, streptomycin.

[0186] Other biological agents: Enrofloxacin, Febantel, Penethamate, Moroxicam, Cephalexin, Kanamycin, Pimobendan, Clenbuterol, Omeprazole, Tiamulin, Benazepril, Pyriprole, Cefquinome, Florfenicol, Buserelin, Cefovecin, Tulathromycin, Ceftiowol, Carprofen, Metaflumizone, Praziquarantel, Triclabendazole.

[0187] The following mixtures of compounds of formula (I) with active ingredients are preferred: The abbreviation "TX" means a compound of formula (I) selected from the group consisting of compounds of formula (I), (IA), (II-A), (II-B) and (II-C) and one compound represented in Table A, Tables B-1 to B-10, Tables C-1 to C-102 or one compound (P-1) to (P-39) listed in Table T1 (below).

[0188] Petroleum + TX, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX, 2,4-dichlorophenylbenzenesulfonate + TX, 2-fluoro-N-methyl-N-1-cinnamaldehyde + TX, 4-chlorophenyl phenylsulfone + TX, acetoprole + TX, aldoxicarb + TX, amidithione + TX, amidothioate + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, aramite + TX, arsenic trioxide + TX, azobenzene + TX, azotoate + TX, benomyl + TX, benoxafos + TX, ben Dilbenzoate + TX, Bixafen + TX, Brofenvalerate + TX, Bromocyclen + TX, Bromophos + TX, Bromopropylate + TX, Buprofezin + TX, Butocarboxim + TX, Butoxycarboxim + TX, Butylpyridaben + TX, Calcium polysulfate + TX, Camphechlor + TX, Carbanolate + TX, Carbophenothione + TX, Cymiazole + TX, Tinomethionate + TX, Chlorbeneside + TX, Chlordimeform + TX, Chlordimeform hydrochloride + TX, Chlorphenetole + TX, Chlorphenesone +TX, Chlorphenesulfide +TX, Chlorobenzilate +TX, Chlormebuform +TX, Chlormethiuron +TX, Chloropropylate +TX, Chlorthiophos +TX, Cinerin I +TX, Cinerin II +TX, Cinerins +TX, Closantel +TX, Coumaphos +TX, Crotamiton +TX, Crotoxyphos +TX, Kufraeb +TX, Cyanthoate +TX, DCPM +TX, DDT +TX, Demefion +TX, Demefion-O +TX, Demefion-S +TX, Demeton-Methyl +TX, Demeton-O +TX, Demeton-O-Methyl +T X, Demeton-S+TX, Demeton-S-methyl+TX, Demeton-S-methylsulfone+TX, Dichlofluanid+TX, Dichlorvos+TX, Dicrifos+TX, Dienochlor+TX, Dimefox+TX, Zinex+TX, Zinex-diclexin+TX, Dinocap-4+TX, Dinocap-6+TX, Dinocton+TX, Dinopenton+TX, Dinosulfone+TX, Dinotervone+TX, Dioxathion+TX, Diphenylsulfone+TX, Disulfiram+TX, DNOC+TX, Dofenapine+TX, Doramectin+TX, Endothion+TX,Epirinomectin + TX, Ethoate-methyl + TX, Etrimphos + TX, Fenazaflor + TX, Fenbutatin oxide + TX, Fenothiocarb + TX, Fenpyrad + TX, Fenpyroximate + TX, Fenpyrazamine + TX, Fenson + TX, Fentrifanil + TX, Flubenzimine + TX, Flucycloxuron + TX, Fluenethyl + TX, Fluorobenside + TX, FMC1137 + TX, Formetanate + TX, Formetanate hydrochloride + TX, Formetanate Rumparanate + TX, γ-HCH + TX, Gliodin + TX, Halfenprox + TX, Hexadecylcyclopropanecarboxylate + TX, Isocarbophos + TX, Jasmolin I + TX, Jasmolin II + TX, Jodofenphos + TX, Lindane + TX, Malonoben + TX, Mecarbam + TX, Mefosfolan + TX, Mesulfen + TX, Methacrifos + TX, Methyl bromide + TX, Metolcarb + TX, Mexacarbate + TX, Milbemycin oxime + TX, Mipafox + TX, Monocrotophos + TX, Morphothion + TX, Moxidectin + TX, Naled + TX, 4-Chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, Nifluridide + TX, Nikkomycin + TX, Nitrilacarb + TX, Nitrilacarb 1:1 zinc chloride complex + TX, Omethoate + TX, Oxydeprophos + TX, Oxydisulfoton + TX, pp'-DDT + TX, Parathion + TX, Permethrin + TX, Fencaptone + TX, Phosalone + TX, Phosphorane + TX, Phosphamidon + TX, Polychloroterpenes + TX, Poly Linactin+TX, Proclonol+TX, Promacyl+TX, Propoxur+TX, Protidathion+TX, Protoate+TX, Pyrethrin I+TX, Pyrethrin II+TX, Pyrethrin+TX, Pyridaphenthion+TX, Pirimitate+TX, Quinalphos+TX, Quinthiophos+TX, R-1492+TX, Phosglycine+TX, Rotenone+TX, Shladan+TX, Cebufos+TX, Selamectin+TX, Sofamido+TX, SSI-121+TX, Sulfiram+TX, Sulfuramide+TX, Sulfotep+TX, Sulfur+TX, Diflobidazin+TX, Tau-Fulvalinate+TX, TEPP+TX, Therbam+TX,Tetradifon+TX, Tetrasul+TX, Thiafenox+TX, Thiocarboxim+TX, Thiofanox+TX, Thiometon+TX, Thioquinox+TX, Thuringiensin+TX, Triamiphos+TX, Triaratene+TX, Triazophos+TX, Triazuron+TX, Trifenophos+TX, Trinactin+TX, Vamidothion+TX, Vaniliprole+TX, Bethoxazin+TX, Copper dioctanoate+TX , Copper sulfate + TX, Sibutrin + TX, Dichlorne + TX, Dichlorophen + TX, Endothal + TX, Fentin + TX, Hydrated lime + TX, Nabam + TX, Quinoclamine + TX, Quinoneamide + TX, Simazine + TX, Triphenyltin acetate + TX, Triphenyltin hydroxide + TX, Crufomate + TX, Piperazine + TX, Thiophanate + TX, Chloralose + TX, Fenthion + TX, Pyridin-4-amine + T X, strychnine + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide + TX, 8-hydroxyquinoline sulfate + TX, bronopol + TX, copper hydroxide + TX, cresol + TX, dipyrithione + TX, doditin + TX, phenaminosulf + TX, formaldehyde + TX, hydralgafen + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel bis(dimethyldithiocarbamate) + TX, nitrapyrin + TX, octhilinone + TX, oxolinic acid + TX, oxytetracycline + TX, potassium hydroxyquinoline sulfate + TX, probenazole + TX, streptomycin + TX, streptomycin sesquisulfate + TX, tecloftalam + TX, thiomersal + TX, Adoxophyes orana GV+TX, Agrobacterium radiobacter+TX, Amblyseius spp.+TX, Anagrapha falcifera NPV+TX, Anagrus atomus+TX, Aphelinus abdominalis+TX, Aphidius colemani+TX,Aphidoletes aphidimyza + TX, Autographa californica NPV + TX, Bacillus sphaericus Neide + TX, Beauveria brongniartii + TX, Chrysoperla carnea + TX, Cryptolaemus montrouzieri + TX, Cydia pomonella GV + TX, Dacnusa sibirica + TX, Diglyphus isaea + TX, Encarsia formosa + TX, Eretmocerus eremicus+TX, Heterorhabditis bacteriophora and H. megidis+TX, Hippodamia convergens+TX, Leptomastix dactylopii+TX, Macrolophus caliginosus+TX, Mamestra brassicae NPV+TX, Metaphycus helvolus+TX, Metarhizium anisopliae var. acridum+TX, Metarhizium anisopliae var. anisopliae+TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, Orius spp. + TX, Paecilomyces fumosoroseus + TX, Phytoseiulus persimilis + TX, Steinernema bibionis + TX,Steinernema carpocapsae+TX, Steinernema feltiae+TX, Steinernema glaseri+TX, Steinernema riobrave+TX, Steinernema riobravis+TX, Steinernema scapterisci+TX, Steinernema spp.+TX, Trichogramma spp.+TX, Typhlodromus occidentalis+TX, Verticillium lecanii)+TX, apholate+TX, visadil+TX, busulfan+TX, dimatif+TX, hemel+TX, hempa+TX, metepa+TX, methiotepa+TX, methyl apholate+TX, molzide+TX, penfluron+TX, tepa+TX, thiohempa+TX, thiotepa+TX, tretamine+TX, uredepa+TX, (E)-dec-5-en-1-yl acetate+(E)-dec-5-en-1-ol+TX, (E)-tridec-4-en-1-yl acetate+TX, (E)-6-methylhept-2-en-4-ol+TX, (E,Z)-tetradec-4,10-dien-1-yl acetate+TX, (Z)-dodec-7-en-1-yl acetate+TX, (Z) -Hexadec-11-enal + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-icos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradec-9,12-dien-1-yl acetate + TX, 14-methyloctadec-1-ene + TX, 4-Methylnonan-5-ol + 4-methylnonan-5-one + TX, α-Murtistriatin + TX, Brevicomin + TX, Codrellet + TX, Codremon + TX, Querle + TX, Disparlure + TX, Dodec-8-en-1-yl acetate + TX, Dodec-9-en-1-yl acetate + TX, Dodec-8 + TX, 10-dien-1-yl acetate + TX, Dominicalure + TX, Ethyl 4-methyloctanoate + TX, Eugenol + TX, Frontalin + TX, Grand Lure + TX, Grand Lure I + TX, Grand Lure II + TX, Grand Lure III + TX, Grand Lure IV + TX , Hexalure + TX, Ipsdienol + TX, Ipsenol + TX, Japonirure + TX, Lineatin + TX, Littlea + TX, Loupur + TX, Medurure + TX, Megatomoic acid + TX, Methyleugenol + TX, Muscalure + TX, Octadeca-2,13-dien-1-yl acetate + TX, Octadeca-3,13-dien-1-yl acetate + TX, Olfuralure + TX, Orictalure + TX, Ostramon + TX, Siglua + TX, Soldidin + TX, Sulcatol + TX, Tetradec-11-en-1-yl acetate + TX, Trimedurure + TX, Trimedurure A + TX, Trimedurure B 1 +TX, Trimedrua B 2+TX, trimedlure C +TX, trunc-call +TX, 2-(octylthio)ethanol +TX, butapyronoxyl +TX, butoxy(polypropylene glycol) +TX, dibutyl adipate +TX, dibutyl phthalate +TX, dibutyl succinate +TX, diethyl toluamide +TX, dimethylcarbate +TX, dimethyl phthalate +TX, ethyl hexanediol +TX, hexamide +TX, methoquin-butyl +TX, methyl neodecane amide +TX, oxamate +TX, picaridin +TX, 1-dichloro-1-nitroethane +TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane +TX, 1,2-dichloropropane +1,3-dichloropropene +TX, 1-bromo-2-chloroethane +TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)acetate +TX, 2,2-dichlorovinyl 2-ethylsulfinylethylmethylphosphate +TX, 2-(1,3-dithiolan-2-yl)phenyldimethylcarbamate +TX, 2-(2-butoxyethoxy)ethylthiocyanate 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenylmethylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyldiethyl phosphate + TX, 2-imidazolidone + TX, 2-isovalerylindan-1,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenylmethylcarbamate + TX, 2-thiocyanatoethyl laurate + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-methyl-1-phenylpyrazole-5 -yl dimethyl carbamate + TX, 4-methyl (prop-2-ynyl) amino-3,5-xylyl methyl carbamate + TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethyl carbamate + TX, acetione + TX, acrylonitrile + TX, aldrin + TX, allosamidin + TX, alixycarb + TX, α-ecdysone + TX, aluminum phosphide + TX, aminocarb + TX, anabasine + TX, atidathion + TX, azamethiphos + TX, Bacillus thuringiensis δ endotoxin + TX, barium hexafluorosilicate + TX,Barium polysulfide +TX, Bartholin +TX, Bayer 22 / 190 +TX, Bayer 22408 +TX, β-cyfluthrin +TX, β-cypermethrin +TX, bioethanomethrin +TX, biopermethrin +TX, bis(2-chloroethyl)ether +TX, sodium borate +TX, bromfenvinphos +TX, bromo-DDT +TX, bufencarb +TX, butacarb +TX, butathiophos +TX, butonate +TX, calcium arsenate +TX, calcium cyanide +TX, carbon disulfide +TX, carbon tetrachloride +TX, cartap hydrochloride +TX, sebazine +TX, chlorbicyclen +TX, chlordane +TX, chlordecone +TX, chloroform +TX, chloropicrin +TX, chlorphoxim +TX, chlorprazophos +TX, cis-resmethrin +TX, cismethrin +TX, clositol Phosphorus+TX, Copper acetoarsenite+TX, Copper arsenate+TX, Copper oleate+TX, Cumitoate+TX, Cryolite+TX, CS708+TX, Cyanofenphos+TX, Cyanophos+TX, Cicrethrin+TX, Cithioate+TX, d-Tetramethrin+TX, DAEP+TX, Dazomet+TX, Decarbofuran+TX, Diamidaphos+TX, Dikapton+TX, Dichlorophenthion+TX, Dicresyl+TX , dicyclanil+TX, dieldrin+TX, diethyl 5-methylpyrazol-3-yl phosphate+TX, dilol+TX, dimefluthrin+TX, dimethane+TX, dimethryn+TX, dimethylvinphos+TX, dimethyllan+TX, dinoprop+TX, dinosam+TX, dinoseb+TX, diofenolan+TX, dioxabenzophos+TX, dicyclophos+TX, DSP+TX, ecdysterone+TX, EI 1642+TX, EMPC+TX, EPBP+TX, Ethaphos+TX, Ethiofencarb+TX, Ethyl Formate+TX, Ethylene Dibromide+TX, Dichloroethane+TX, Ethylene Oxide+TX, EXD+TX, Fenchlorphos+TX, Fenetacarb+TX, Fenitrothion+TX, Fenoxacrim+TX, Fenpyritrin+TX, Fensulfothion+TX, Fenthion-Ethyl+TX, Flucofuron+TX, Fosmetilan+TX, Fospirate+TX, Fostietan+TX, Furathiocarb+TX, Frethrin+TX, Guazatine+TX, Guazatine Acetate+TX,Sodium tetrathiocarboxylate + TX, Halfenprox + TX, HCH + TX, HEOD + TX, Heptachlor + TX, Heterofos + TX, HHDN + TX, Hydrogen cyanide + TX, Hikincarb + TX, IPSP + TX, Isazophos + TX, Isobenzan + TX, Isodrin + TX, Isofenphos + TX, Isorane + TX, Isoprothiolane + TX, Isoxathion + TX, Juvenile hormone I + TX, Juvenile hormone II + TX, Juvenile hormone III + TX, Kereban + TX, Kinoprene + TX, Lead arsenate + TX, Leptophos + TX, Lilimphos + T X, ritidathion + TX, m-cumenyl methyl carbamate + TX, magnesium phosphide + TX, magidox + TX, mecarbone + TX, menazone + TX, mercurous chloride + TX, mesulfenphos + TX, metam + TX, metam-potassium + TX, metam-sodium + TX, methanesulfonyl fluoride + TX, methoclotophos + TX, methoprene + TX, methotrin + TX, methoxychlor + TX, methyl isothiocyanate + TX, methyl chloroform + TX, methylene chloride + TX, methoxadiazone + TX, mirex + TX, naphthalophos + TX, Naphthalene + TX, NC-170 + TX, Nicotine + TX, Nicotine sulfate + TX, Nithiazine + TX, Nornicotine + TX, O-5-Dichloro-4-iodophenyl O-ethyl ethyl phosphonothioate + TX, O,O-Diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate + TX, O,O-Diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate + TX, O,O,O',O'-Tetrapropyl dithiopyrophosphate + TX, Oleic acid + TX, para-Dichlorobenzene + TX, para Thione-methyl+TX, Pentachlorophenol+TX, Pentachlorophenyl laurate+TX, PH60-38+TX, Fenkapton+TX, Phosnichlor+TX, Phosphine+TX, Phoxim-methyl+TX, Pyrimetaphos+TX, Polychlorodicyclopentadiene isomers+TX, Potassium arsenite+TX, Potassium thiocyanate+TX, Precocene I+TX, Precocene II+TX, Precocene III+TX, Pyrimidophos+TX, Profluthrin+TX, Promecarb+TX, Prothiophos+TX, Pyrazophos+TX, Pyresmethrin+TX,Cassia + TX, Quinalphos-methyl + TX, Quinothione + TX, Rafoxanide + TX, Resmethrin + TX, Rotenone + TX, Cadetrin + TX, Riania + TX, Ryanodine + TX, Sabadila + TX, Shradan + TX, Cebufos + TX, SI-0009 + TX, Tiapronil + TX, Sodium arsenite + TX, Sodium cyanide + TX, Sodium fluoride + TX, Sodium hexafluorosilicate + TX, Sodium pentachlorophenoxide salt + TX, Sodium selenate + TX, Sodium thiocyanate + TX, Sulcofuron + T X, Sulfuron-sodium +TX, Sulfuryl fluoride +TX, Sulprofos +TX, Tar oil +TX, Thionazine +TX, TDE +TX, Tebupirimfos +TX, Temephos +TX, Telarethrin +TX, Tetrachloroethane +TX, Cyclofos +TX, Thiocyclam +TX, Thiocyclam hydrogen oxalate +TX, Thionazine +TX, Thiosultap +TX, Thiosultap-sodium +TX, Tralomethrin +TX, Transpermethrin +TX, Triazamate +TX, Trichlormethaphos-3 +TX, Trichloronathion +TX, Trimethaphos-2 +TX, Trimethaphos-1 ... Tacarb + TX, Tolprocarb + TX, Triclopyricarb + TX, Triplen + TX, Veratridine + TX, Veratrine + TX, XMC + TX, Zetamethrin + TX, Zinc phosphide + TX, Zolaprophos + TX, and Meperfluthrin + TX, Tetramethylfluthrin + TX, Bis(tributyltin) oxide + TX, Bromoacetamide + TX, Ferric phosphate + TX, Niclosamide-olamine + TX, Tributyltin oxide + TX, Pyrimorph + TX, Trifenmorph + TX, 1,2-Dibromo-3-chloropropane + TX, 1,3-Di Chloropropene + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, 2-fluoro-N-(3-methoxyphenyl)-9H-purin-6-amine + TX, benclothiaz + TX, cytokinin + TX, DCIP + TX, rufural + TX, isamidophos + TX, kinetin + TX, Myrothecium verrucaria composition + TX,Tetrachlorothiophene + TX, Xylenol + TX, Zeatin + TX, Potassium Ethylxanthate + TX, Acibenzolar + TX, Acibenzolar-S-methyl + TX, Reynoutria sachalinensis Extract + TX, α-Chlorohydrin + TX, Anth + TX, Barium Carbonate + TX, Bisthiosemi + TX, Brodifacoum + TX, Bromadiolone + TX, Bromethalin + TX, Chlorophacinone + TX, Cholecalciferol + TX, Coumachlor + TX, Coumafuryl + TX, Coumatetralyl + TX, Crimidine + TX, Difenacoum + TX, Difethialone + TX, Diphacinone + TX, Ergocalciferol + TX, Flocoumafen + TX, Fluoroacetamide +TX, flupropazine +TX, flupropazine hydrochloride +TX, norbormide +TX, fosacetim +TX, phosphorus +TX, pindone +TX, pyrinuron +TX, sciriloside +TX, sodium fluoroacetate +TX, thallium sulfate +TX, warfarin +TX, 2-(2-butoxyethoxy)ethyl piperonylate +TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone +TX, farnesol + nerolidol +TX, berubutin +TX, MG, K 264+TX, piperonyl butoxide+TX, piprotal+TX, propyl isomer+TX, S421+TX, sesamex+TX, sesamolin+TX, sulfoxide+TX, anthraquinone+TX, copper naphthenate+TX, copper oxychloride+TX, dicyclopentadiene+TX, thiram+TX, zinc naphthenate+TX, ziram+TX, imanin+TX, ribavirin+TX, mercury(II) oxide+TX, thiophanate-methyl+TX, azaconazole+TX, bitertanol+TX, bromuconazole+TX, cyproconazole+TX, difenoconazole ru+TX, diniconazole+TX, epoxiconazole+TX, fenbuconazole+TX, fluquinconazole+TX, flusilazole+TX, flutriafol+TX, furametpyr+TX, hexaconazole+TX, imazalil+TX, imibenconazole+TX, ipconazole+TX, metconazole+TX, myclobutanil+TX, paclobutrazol+TX, pefurazoate+TX, penconazole+TX, prothioconazole+TX, pyrifenox+TX, prochloraz+TX, propiconazole+TX, pyrisoxazole+TX, Simeconazole + TX, Tebuconazole + TX, Tetraconazole + TX, Triadimefon + TX, Triadimenol + TX, Triflumizole + TX, Triticonazole + TX, Ancymidol + TX, Fenarimol + TX, Nuarimol + TX, Bupirimate + TX, Dimethirimol + TX, Ethyrimol + TX, Dodemorph + TX, Fenpropidin + TX, Fenpropimorph + TX, Spiroxamine + TX, Tridemorph + TX, Cyprodinil + TX, Mepanipyrim + TX, Pyrimethanil + TX, Fenpiclonil + TX, Fludioxonil + TX, Benalaxyl + TX, Furalaxyl + TX, Metalaxyl- + TX, R-metalaxyl + TX, Ofrace + TX, Oxadixyl + TX, Carbendazim + TX, Debacarb + TX, Fuberidazole + TX, Thiabendazole + TX, Chlozolinate + TX, Diclozolin + TX, Myclozolin + TX, Procymidone + TX, Vinclozolin + TX, Boscalid + TX, Carboxin + TX, Fenfuram + TX, Flutolanil + TX, Mepronil + TX, Oxycarboxin + TX, Penthiopyrad + TX, Thifluzamide + TX, Dodine + TX,Iminoctadine+TX, Azoxystrobin+TX, Dimoxystrobin+TX, Enestrobulin+TX, Phenaminestrobin+TX, Flufenoxystrobin+TX, Fluoxastrobin+TX, Kresoxim-methyl+TX, Metominostrobin+TX, Trifloxystrobin+TX, Oryzastrobin+TX, Picoxystrobin+TX, Pyraclostrobin+TX, Pyrametstrobin+TX, Pyraoxystrobin+TX, Ferbam+TX, Mancozeb+TX, Maneb+TX, Metiram+TX, Propineb+TX, Zineb+TX , Captafol+TX, Captan+TX, Fluorimide+TX, Folpet+TX, Tolylfluanid+TX, Bordeaux mixture+TX, Copper oxide+TX, Mancopper+TX, Oxine copper+TX, Nitrothal-isopropyl+TX, Edifenphos+TX, Iprobenfos+TX, Phosdifen+TX, Turcophos-methyl+TX, Anilazine+TX, Benthiavalicarb+TX, Blasticidin-S+TX, Chloroneb+TX, Chlorothalonil+TX, Cyflufenamid+TX, Cymoxanil+TX, Cyclobutrifluram+TX, Diclocymet+T X, diclomedine + TX, dicloran + TX, diethofencarb + TX, dimethomorph + TX, flumorph + TX, dithianon + TX, ethaboxam + TX, etridiazole + TX, famoxadone + TX, fenamidone + TX, fenoxanil + TX, ferimzone + TX, fluazinam + TX, fluopicolide + TX, flusulfamide + TX, fluxapyroxad + TX, fenhexamid + TX, fosetyl-aluminum + TX, hymexazole + TX, iprovalicarb + TX, cyazofamid + TX, methasulfocarb + TX, metola Phenone + TX, Pencycuron + TX, Phthalide + TX, Polyoxin + TX, Propamocarb + TX, Pyribencarb + TX, Proquinazid + TX, Pyroquilon + TX, Pyriophenone + TX, Quinoxyfen + TX, Quintozene + TX, Tiadinil + TX, Triazoxide + TX, Tricyclazole + TX, Triforine + TX, Validamycin + TX, Valifenalate + TX, Zoxamide + TX, Mandipropamide + TX, Fluventeram + TX, Isopyrazam + TX, Sedaxane + TX, Benzobindiflupyr + TX, Pydiflumetofen + TX,3-Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, isoflucipram + TX, isotianil + TX, dipimethitrone + TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile + TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, 4-(2,6-difluorophenyl)-6 -Methyl-5-phenyl-pyridazine-3-carbonitrile + TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine + TX, Fluindapyr +TX, methoxystrobin (jiaxiangjunzhi) +TX, lvbenmixianan +TX, diclobenziazox +TX, mandestrobin +TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone +TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol +TX, oxathiapiproline +TX, tert-butyl N-[6-[[[(1- Methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, pyraziflumide + TX, impirfluxam + TX, tulorprocarb + TX, mefentrifluconazole + TX, ipfentrifluconazole + TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX,N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl]methanesulfonic acid + TX, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl] Carbamate + TX, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, pyridaclomethyl + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl Til-tetrazol-5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX, aminopyrifen + TX, amethoctrazine + TX, amisulbrom + TX, penflufen + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX, florylpicoxamide + TX, fenpicoxamide + TX, tebufloquine + TX, ipulfenoquine + TX, quinofumelin + TX, isofetamide + TX, N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, benzothiostrobin + TX, fenamacril + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, fluopyram + TX,Flutianil + TX, fluopimomide + TX, pyrapropoin + TX, picarbutrazox + TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]- 3-pyridyl]oxy]benzonitrile + TX, methyltetraprole + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidinemethanol + TX, fluoxapiproline + TX, enoxastrobin + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy- 3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX [1-[oxy]benzonitrile+TX, trinexapac+TX, cumoxystrobin+TX, zhongshengmycin+TX, copper thiodiazole+TX, zinc thiazole+TX, amethotractin+TX, iprodione+TX, N-octyl-N'-[2-(octylamino)ethyl]ethane-1,2-diamine+TX; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine+TX,N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-, 3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds can be prepared by the methods described in WO 2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX (these compounds can be prepared by the methods described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine + TX. N-ethyl-N'-[5-methoxy-2-methyl-4-[2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine+TX, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine+TX (these compounds can be prepared by the methods described in WO 2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine+TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine+TX (these compounds can be prepared by the methods described in WO 2019 / 110427);N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[( 1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, 8-fluoro-N-[(1R)-1-[ (3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]- N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX (these compounds can be prepared by the methods described in WO 2017 / 153380);1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin- 3-yl)isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX (these compounds were prepared by the method described in WO 2017 / 025510). 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline + TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole + TX (these compounds can be prepared by the methods described in WO 2016 / 156085);N-Methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N,2-Dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N-Ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX 1-Methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1,3-Dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 3-Ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2 ,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate + TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine + TX. The compounds in this paragraph may be prepared by the methods described in WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 093348 and WO 2017 / 118689; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound may be prepared by 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 + TX (this compound can be prepared by the method described in WO 2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); 3-[2- (1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate + TX (this compound can be prepared by the method described in WO 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5 ,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone + TX (this compound can be prepared by the method described in WO 2011 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide + TX; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy -2-Methoxyimino-N,3-dimethyl-pent-3-enamide + TX (this compound can be prepared by the method described in WO 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX; N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared by the method described in WO 2016 / 202742);2-(Difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX (this compound can be prepared by the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone +TX (these compounds can be prepared by the methods described in WO 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide +TX (this compound can be prepared by the methods described in WO 2018 / 065414); ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate +TX (this compound can be prepared by the methods described in WO 2018 / 065414). can be prepared by the method described in Publication No. 2018 / 158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[ A compound selected from the group of substances consisting of N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX (these compounds can be prepared by the method described in WO 2018 / 202428), chloroinconazide + TX, flumetylsulforim + TX, fluoxythioconazole + TX, flufenoxadiazam + TX, methallylpicoxamide + TX;

[0189] The reference in parentheses following the active ingredient, for example [3878-19-1], refers to the Chemical Abstracts Registry number. The above mixing partners are known. When the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual-A World Compendium; Thirteenth Edition; Editor: CDS TomLin; The British Crop Protection Council], they are listed therein under the section number shown in parentheses hereinabove for the particular compound; for example, the compound "Abamectin" is listed under section number (1). When "[CCN]" is added for a particular compound listed above, the compound in question is included in the "Compendium of Pesticide Common Names" accessible via the Internet at [A. Wood; Compendium of Pesticide Common Names, Copyright 1995-2004]; for example, the compound "acetoprole" is listed at the Internet address http: / / www.alanwood.net / pesticides / acetoprole.html.

[0190] In the above specification, most of the above active ingredients are referred to by using in individual cases the so-called "common name", the relevant "ISO common name" or other "common name". In the absence of a "common name" designation, the nature of the designation used instead is stated in parentheses for the particular compound; in this case, the IUPAC name, the IUPAC / Chemical Abstracts name, the "chemical name", the "conventional name", the "chemical compound name" or the "development code" is used, or, if none of these designations or the "common name" is used, an "alternative name" is adopted. "CAS Registry Number" means Chemical Abstracts Registry number.

[0191] The mixture of the compounds of formula (I), (IA), (II-A), (II-B) and (II-C) with one of the compounds shown in Table A, Table B-1 to B-10, Table C-1 to C-102 or one of the compounds (P-1) to (P-39) listed in Table T1 (below) is preferably a mixture ratio of 100:1 to 1:100, particularly 50:1 to 1:50, more particularly 20:1 to 1:20, more particularly 10:1 to 1:10, and even more preferably 2:1 to 1:2. These mixture ratios are by weight.

[0192] The mixtures described above can be used in methods of controlling pests, comprising the step of applying a composition comprising the mixture described above to the pest or its environment, excluding methods of treating the human or animal body by surgery or therapy, and diagnostic methods performed on the human or animal body.

[0193] Mixtures containing a compound of formula (I), (IA), (II-A), (II-B) and (II-C), or a compound of formula (I) selected from one of the compounds represented in Table A, Tables B-1 to B-10, Tables C-1 to C-102 or one of the compounds (P-1) to (P-39) listed in Table T1 (below), and one or more of the active ingredients described above, can be applied, for example, in a single "ready-mix" form, in a combination spray mixture composed of individual combinations of single active ingredient components, such as "tank mixes", and in combinations of single active ingredients when applied sequentially, i.e., one after the other within a fairly short period of time, such as a few hours or days. The order of application of the compounds of formula (I), (IA), (II-A), (II-B) and (II-C) or one of the compounds represented in Table A, Tables B-1 to B-10, Tables C-1 to C-102 or one of the compounds (P-1) to (P-39) listed in Table T1 (below) and the active ingredients described above is not critical for the implementation of the invention. The compositions according to the invention may also contain further solid or liquid auxiliaries such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soybean oil), antifoams, for example silicone oils, preservatives, viscosity regulators, binders and / or adhesives, fertilizers or other active ingredients for achieving a particular effect, for example fungicides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0194] The compositions according to the invention are prepared in a manner known per se in the absence of auxiliaries, for example by pulverizing, screening and / or compressing the solid active ingredient, and in the presence of at least one auxiliary, for example by intimately mixing and / or pulverizing the active ingredient with one or more auxiliary agents. These preparation processes of the compositions and the use of compound (I) for preparing these compositions are also the subject of the present invention.

[0195] Another aspect of the present invention relates to the use of a compound of formula (I) according to the present invention or a preferred individual compound as defined herein, a composition comprising at least one compound of formula (I) or at least one preferred individual compound as defined herein, or a fungicidal or insecticidal mixture comprising at least one compound of formula (I) or at least one preferred individual compound as defined herein, in admixture with other fungicides or insecticides as defined herein above, for controlling or preventing infestation on plants, e.g. useful plants, such as crop plants, their propagation products, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living material by phytopathogenic microorganisms, e.g. insects or preferably fungal organisms.

[0196] A further aspect of the present invention relates to a method for controlling or preventing infestation on plants, e.g. useful plants, such as crop plants, their propagation materials, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living material by phytopathogenic or spoilage microorganisms or organisms that are potentially harmful to humans, in particular fungal organisms, which method comprises the step of applying a compound of formula (I) according to the present invention or a preferred individual compound as defined herein as active ingredient to the plant, a part of the plant or its habitat, its propagation materials, or any part of the non-living material.

[0197] By control or prevention is meant reducing infestation by insects or spoilage microorganisms or organisms that are plant pathogenic or potentially harmful to humans, particularly fungal organisms, to a level that demonstrates improvement.

[0198] A preferred method for controlling or preventing infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, or insects, which involves the application of a compound of formula (I) according to the invention or an agrochemical composition containing at least one compound of formula (I), is foliar treatment. The frequency and amount of application will depend on the risk of infestation by the corresponding pathogen or insect. However, the compounds of formula (I) according to the invention can also be introduced into the plant by the roots via the soil (systemic action) by irrigating the plant habitat with a liquid formulation or by applying the compounds to the soil in solid form, for example in granular form (soil application). In the case of rice crops, such granules can be applied to flooded rice fields. The compounds of formula (I) can also be applied to seeds (coating) by impregnating the seeds or tubers with a liquid formulation of the fungicide or by coating them with a solid formulation.

[0199] Formulations, e.g. compositions containing the compounds of formula (I) according to the invention and, if desired, solid or liquid auxiliaries or monomers encapsulating the compounds of formula (I), can be prepared in a known manner, typically by homogeneously mixing and / or grinding the compounds together with extenders, e.g. solvents, solid carriers and optional surface-active compounds (surfactants).

[0200] Advantageous applications are usually from 5 g to 2 kg of active ingredient (ai) per hectare (ha), preferably from 10 g to 1 kg ai / ha, most preferably from 20 g to 600 g ai / ha.When used as a seed drench, a convenient dosage is from 10 mg to 1 g of active substance per kg of seeds.

[0201] When the combinations of the invention are used for seed treatment, an amount of 0.001 to 50 g of a compound of formula (I) per kg of seed, preferably 0.01 to 10 g per kg of seed, will generally be sufficient.

[0202] The term "g ai / ha" as used herein refers to the application rate in grams [g] of active ingredient [ai] per unit area [ha]. The hectare (symbol ha) is the unit of measurement for a square measuring 100 m on each side (1 hectare = 100 m). 2 ) or 10,000 square metres. The hectare is a commonly used unit of area in the metric system.

[0203] Preferably, the compositions comprising the compounds of formula (I) according to the present invention are applied prophylactically, meaning before the onset of a disease, or therapeutically, meaning after the onset of a disease.

[0204] The compositions of the present invention may be in any conventional form, such as, for example, two-part systems, dry seed treatment powders (DS), seed treatment emulsions (ES), seed treatment flowable concentrates (FS), seed treatment solutions (LS), seed treatment water dispersible powders (WS), seed treatment capsule suspensions (CF), seed treatment gels (GF), emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water dispersible granules (WG), emulsifiable granules (WG), sorbent granules (RM ... The present invention may be employed in the form of an emulsion, such as an EG, an emulsion, a water-in-oil (EO), an emulsion, an oil-in-water (EW), a microemulsion (ME), an oil dispersion (OD), an oil-miscible fluid (OF), an oil-miscible liquid (OL), a soluble concentrate (SL), a very low volume suspension (SU), a very low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), or any technically desirable formulation in combination with an agriculturally acceptable adjuvant.

[0205] Such compositions can be produced in a conventional manner, for example by mixing the active ingredient with suitable inert compounding agents (diluents, solvents, fillers, and any other compounding agents such as surfactants, biocides, antifreeze agents, spreading agents, thickeners, and compounds that provide adjuvant activity effects). Conventional slow-release formulations can also be employed when long-lasting efficacy is intended. In particular, formulations applied in spray form, such as water-dispersible concentrates (e.g., EC, SC, DC, OD, SE, EW, EO, etc.), wettable powders, and granules, may contain surfactants such as wetting and dispersing agents and other compounds that provide adjuvant effects, such as, for example, condensates of formaldehyde with naphthalene sulfonates, alkylaryl sulfonates, lignin sulfonates, fatty alkyl sulfates, and ethoxylated alkylphenols and ethoxylated fatty alcohols.

[0206] The seed dressing formulation is applied to the seed in a manner known per se, utilizing the combination and diluent of the present invention in a suitable seed dressing formulation form, such as an aqueous suspension or a dry powder form with good adhesion to the seed. Such seed dressing formulations are known in the art. The seed dressing formulation may contain a single active ingredient or a combination of active ingredients in encapsulated form, for example as a slow release capsule or microcapsule.

[0207] In general, the formulations contain 0.01-90% by weight of active agent, 0-20% of agriculturally acceptable surfactants and 10-99.99% of solid or liquid inert compounding agents and adjuvants, the active agent being at least a compound of formula (I) according to the invention, optionally together with other active agents, in particular microbicides, preservatives, etc. Concentrated forms of the composition generally contain about 2-80%, preferably about 5-70% by weight of active agent. Application forms of the formulations may contain, for example, 0.01-20% by weight, preferably 0.01-5% by weight of active agent. Commercial products will preferably be formulated as concentrates, but end users will usually utilize diluted formulations.

[0208] Although it is preferred to formulate commercial products as concentrates, end users will typically dilute the formulations when used.

[0209] A preferred formulation may have the following composition (by weight): Emulsifiable concentrate: Active ingredient: 1-95%, preferably 60-90% Surfactant: 1-30%, preferably 5-20% Liquid carrier: 1-80%, preferably 1-35%

[0210] Powder: Active ingredient: 0.1-10%, preferably 0.1-5% Solid carrier: 99.9-90%, preferably 99.9-99%

[0211] Suspension concentrates: Active ingredient: 5-75%, preferably 10-50% Water: 94-24%, preferably 88-30% Surfactant: 1-40%, preferably 2-30%

[0212] Wettable powder: Active ingredient: 0.5-90%, preferably 1-80% Surfactant: 0.5-20%, preferably 1-15% Solid carrier: 5-95%, preferably 15-90%

[0213] Granules: Active ingredient: 0.1-30%, preferably 0.1-15% Solid carrier: 99.5-70%, preferably 97-85%

[0214] The disclosure in this application makes available each and every combination of the embodiments disclosed herein.

[0215] The compounds according to the following Tables B-1 to B-10 can be prepared according to the above-mentioned methods. The following examples are intended to illustrate the present invention and to show preferred compounds of formula (I). In any of the following Tables B-1 to B-10, the possible presence of one or more asymmetric carbon atoms in the compound of formula (I) according to the present invention means that the compound can occur in chiral isomeric form, i.e., in enantiomeric or diastereomeric form.

[0216] Table B-1: This table is for X 2 and X 3 CR 8 and R 8 is hydrogen; [ka] The present invention discloses 102 compounds B-1.001 to B-1.102, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , A and Z 1 is as defined in Tables C-1 to C-102 below.

[0217] For example, compound B-1.003 has the following structure: [ka] has.

[0218] Table B-2: This table is for X 2 is CH, and X 3 is CCl, [ka] The present invention discloses 102 compounds B-2.001 to B-2.102, wherein R 1 , R 2 , R 3 , R 4 , R5 , R 6 , R 7 , A and Z 1 is as defined in Tables C-1 to C-102 below.

[0219] Table B-3: This table is for X 2 is CCl, and X 3 is CH; [ka] The present invention discloses 102 compounds B-3.001 to B-3.102, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , A and Z 1 is as defined in Tables C-1 to C-102 below.

[0220] Table B-4: This table is for X 2 and X 3 is CCl, [ka] The present invention discloses 102 compounds B-4.001 to B-4.102, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , A and Z 1 is as defined in Tables C-1 to C-102 below.

[0221] Table B-5: This table is for X 1 and X 3 CR 8 and R 8 is hydrogen, [ka] The present invention discloses 102 compounds B-5.001 to B-5.102, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , A and Z 1 is as defined in Tables C-1 to C-102 below.

[0222] Table B-6: This table is for X 1 and X 2 CR 8 and R 8 is hydrogen, [ka] The present invention discloses 102 compounds B-6.001 to B-6.102, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , A and Z 1 is as defined in Tables C-1 to C-102 below.

[0223] Table B-7: This table is for X 1 and CH and X 2 is CCl, [ka] The present invention discloses 102 compounds B-7.001 to B-7.102, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , A and Z 1 is as defined in Tables C-1 to C-102 below.

[0224] Table B-8: This table is for X 2 CR 8 and R 8 is hydrogen; [ka] The present invention discloses 102 compounds B-8.001 to B-8.102, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , A and Z 1 is as defined in Tables C-1 to C-102 below.

[0225] Table B-9: This table is for X 2 CR 8 and R 8 is chlorine; [ka] The present invention discloses 102 compounds B-9.001 to B-9.102, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , A and Z 1 is as defined in Tables C-1 to C-102 below.

[0226] Table B-10: This table shows the compounds of formula (Ii) according to the present invention: [ka] The present invention discloses 102 compounds B-10.001 to B-10.102, wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7, A and Z 1 is as defined in Tables C-1 to C-102 below.

[0227] Table C-1: This table shows the 1 is methyl and R 2 , R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A1, and Z 1 is 2,4-difluorophenyl.

[0228] Table C-2: This table is for 1 is methyl and R 2 , R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A4, and Z 1 is 2,4-difluorophenyl.

[0229] Table C-3: This table is for R 1 is methyl and R 2 , R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A9, and Z 1 is 2,4-difluorophenyl.

[0230] Table C-4: This table is for 1 is methyl and R 2 , R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A10, and Z 1 is 2,4-difluorophenyl.

[0231] Table C-5: This table is for R 1 is methyl and R2 is methyl and R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A1, and Z 1 is 2,4-difluorophenyl.

[0232] Table C-6: This table is for 1 is methyl and R 2 is methyl and R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A4, and Z 1 is 2,4-difluorophenyl.

[0233] Table C-7: This table is for R 1 is methyl and R 2 is methyl and R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A9, and Z 1 is 2,4-difluorophenyl.

[0234] Table C-8: This table is for R 1 is methyl and R 2 is methyl and R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A10, and Z 1 is 2,4-difluorophenyl.

[0235] Table C-9: This table is for 1 is methyl and R 2 is methyl and R 3 is methyl and R 4 , R 5 , R 6 and R7 is hydrogen, A is A1, and Z 1 is 2,4-difluorophenyl.

[0236] Table C-10: This table is for R 1 is methyl and R 2 is methyl and R 3 is methyl and R 4 , R 5 , R 6 and R 7 is hydrogen, A is A4, and Z 1 is 2,4-difluorophenyl.

[0237] Table C-11: This table is for R 1 is methyl and R 2 is methyl and R 3 is methyl and R 4 , R 5 , R 6 and R 7 is hydrogen, A is A9, and Z 1 is 2,4-difluorophenyl.

[0238] Table C-12: This table is for R 1 is methyl and R 2 is methyl and R 3 is methyl and R 4 , R 5 , R 6 and R 7 is hydrogen, A is A10, and Z 1 is 2,4-difluorophenyl.

[0239] Table C-13: This table is for R 1 is methyl and R 4 is methyl and R 2 , R 3 , R 5 , R 6 and R 7 is hydrogen, A is A1, and Z 1is 2,4-difluorophenyl.

[0240] Table C-14: This table is for R 1 is methyl and R 4 is methyl and R 2 , R 3 , R 5 , R 6 and R 7 is hydrogen, A is A4, and Z 1 is 2,4-difluorophenyl.

[0241] Table C-15: This table is for R 1 is methyl and R 4 is methyl and R 2 , R 3 , R 5 , R 6 and R 7 is hydrogen, A is A9, and Z 1 is 2,4-difluorophenyl.

[0242] Table C-16: This table is for R 1 is methyl and R 4 is methyl and R 2 , R 3 , R 5 , R 6 and R 7 is hydrogen, A is A10, and Z 1 is 2,4-difluorophenyl.

[0243] Table C-17: This table is for R 1 is methyl and R 7 is methyl and R 2 , R 3 , R 4 , R 5 and R 6 is hydrogen, A is A1, and Z 1 is 2,4-difluorophenyl.

[0244] Table C-18: This table is for R 1is methyl and R 7 is methyl and R 2 , R 3 , R 4 , R 5 and R 6 is hydrogen, A is A4, and Z 1 is 2,4-difluorophenyl.

[0245] Table C-19: This table is for R 1 is methyl and R 7 is methyl and R 2 , R 3 , R 4 , R 5 and R 6 is hydrogen, A is A9, and Z 1 is 2,4-difluorophenyl.

[0246] Table C-20: This table is for 1 is methyl and R 7 is methyl and R 2 , R 3 , R 4 , R 5 and R 6 is hydrogen, A is A10, and Z 1 is 2,4-difluorophenyl.

[0247] Table C-21: This table is for R 1 is methyl and R 4 is methyl and R 7 is methyl and R 2 , R 3 , R 5 and R 6 is hydrogen, A is A1, and Z 1 is 2,4-difluorophenyl.

[0248] Table C-22: This table is for R 1 is methyl and R 4 is methyl and R 7 is methyl and R 2 , R 3, R 5 and R 6 is hydrogen, A is A4, and Z 1 is 2,4-difluorophenyl.

[0249] Table C-23: This table is for R 1 is methyl and R 4 is methyl and R 7 is methyl and R 2 , R 3 , R 5 and R 6 is hydrogen, A is A9, and Z 1 is 2,4-difluorophenyl.

[0250] Table C-24: This table is for R 1 is methyl and R 4 is methyl and R 7 is methyl and R 2 , R 3 , R 5 and R 6 is hydrogen, A is A10, and Z 1 is 2,4-difluorophenyl.

[0251] Table C-25: This table is for R 1 is methyl and R 2 is chlorine, and R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A4, and Z 1 is 2,4-difluorophenyl.

[0252] Table C-26: This table is for R 1 is methyl and R 2 is chlorine, and R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A9, and Z 1is 2,4-difluorophenyl.

[0253] Table C-27: This table is for R 1 is methyl and R 2 is chlorine, and R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A10, and Z 1 is 2,4-difluorophenyl.

[0254] Table C-28: This table is for R 1 and R 4 is methyl and R 2 is chlorine, and R 3 , R 5 , R 6 and R 7 is hydrogen, A is A4, and Z 1 is 2,4-difluorophenyl.

[0255] Table C-29: This table is for R 1 and R 4 is methyl and R 2 is chlorine, and R 3 , R 5 , R 6 and R 7 is hydrogen, A is A9, and Z 1 is 2,4-difluorophenyl.

[0256] Table C-30: This table is for 1 and R 4 is methyl and R 2 is chlorine, and R 3 , R 5 , R 6 and R 7 is hydrogen, A is A10, and Z 1 is 2,4-difluorophenyl.

[0257] Table C-31: This table is for R 1 and R 7 is methyl and R 2 is chlorine, and R 3 , R 4 , R 5 and R 6 is hydrogen, A is A4, and Z 1 is 2,4-difluorophenyl.

[0258] Table C-32: This table is for R 1 and R 7 is methyl and R 2 is chlorine, and R 3 , R 4 , R 5 and R 6 is hydrogen, A is A9, and Z 1 is 2,4-difluorophenyl.

[0259] Table C-33: This table is for R 1 and R 7 is methyl and R 2 is chlorine, and R 3 , R 4 , R 5 and R 6 is hydrogen, A is A10, and Z 1 is 2,4-difluorophenyl.

[0260] Table C-34: This table is for R 1 , R 4 and R 7 is methyl and R 2 is chlorine, and R 3 , R 5 and R 6 is hydrogen, A is A4, and Z 1 is 2,4-difluorophenyl.

[0261] Table C-35: This table is for R 1 , R 4 and R 7 is methyl and R2 is chlorine, and R 3 , R 5 and R 6 is hydrogen, A is A9, and Z 1 is 2,4-difluorophenyl.

[0262] Table C-36: This table is for R 1 , R 4 and R 7 is methyl and R 2 is chlorine, and R 3 , R 5 and R 6 is hydrogen, A is A10, and Z 1 is 2,4-difluorophenyl.

[0263] Table C-37: This table is for R 1 is methyl and R 2 is fluorine, and R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A4, and Z 1 is 2,4-difluorophenyl.

[0264] Table C-38: This table is for R 1 is methyl and R 2 is fluorine, and R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A9, and Z 1 is 2,4-difluorophenyl.

[0265] Table C-39: This table is for R 1 is methyl and R 2 is fluorine, and R 3 , R 4 , R 5 , R 6 and R 7is hydrogen, A is A10, and Z 1 is 2,4-difluorophenyl.

[0266] Table C-40: This table is for R 1 and R 4 is methyl and R 2 is fluorine, and R 3 , R 5 , R 6 and R 7 is hydrogen, A is A4, and Z 1 is 2,4-difluorophenyl.

[0267] Table C-41: This table is for R 1 and R 4 is methyl and R 2 is fluorine, and R 3 , R 5 , R 6 and R 7 is hydrogen, A is A9, and Z 1 is 2,4-difluorophenyl.

[0268] Table C-42: This table is for R 1 and R 4 is methyl and R 2 is fluorine, and R 3 , R 5 , R 6 and R 7 is hydrogen, A is A10, and Z 1 is 2,4-difluorophenyl.

[0269] Table C-43: This table is for R 1 and R 7 is methyl and R 2 is fluorine, and R 3 , R 4 , R 5 and R 6 is hydrogen, A is A4, and Z 1 is 2,4-difluorophenyl.

[0270] Table C-44: This table is for R 1 and R 7 is methyl and R 2 is fluorine, and R 3 , R 4 , R 5 and R 6 is hydrogen, A is A9, and Z 1 is 2,4-difluorophenyl.

[0271] Table C-45: This table is for R 1 and R 7 is methyl and R 2 is fluorine, and R 3 , R 4 , R 5 and R 6 is hydrogen, A is A10, and Z 1 is 2,4-difluorophenyl.

[0272] Table C-46: This table is for R 1 , R 4 and R 7 is methyl and R 2 is fluorine, and R 3 , R 5 and R 6 is hydrogen, A is A4, and Z 1 is 2,4-difluorophenyl.

[0273] Table C-47: This table is for R 1 , R 4 and R 7 is methyl and R 2 is fluorine, and R 3 , R 5 and R 6 is hydrogen, A is A9, and Z 1 is 2,4-difluorophenyl.

[0274] Table C-48: This table is for R 1 , R4 and R 7 is methyl and R 2 is fluorine, and R 3 , R 5 and R 6 is hydrogen, A is A10, and Z 1 is 2,4-difluorophenyl.

[0275] Table C-49: This table is for R 1 and R 2 is methyl and R 4 is ethyl, and R 3 , R 5 and R 6 is hydrogen, A is A4, and Z 1 is 2,4-difluorophenyl.

[0276] Table C-50: This table is for 1 and R 2 is methyl and R 4 is ethyl, and R 3 , R 5 and R 6 is hydrogen, A is A9, and Z 1 is 2,4-difluorophenyl.

[0277] Table C-51: This table is for R 1 and R 2 is methyl and R 4 is ethyl, and R 3 , R 5 and R 6 is hydrogen, A is A10, and Z 1 is 2,4-difluorophenyl.

[0278] Table C-52: This table is for R 1 is methyl and R 4 is ethyl, and R 2 , R 3 , R 5 and R 6 is hydrogen, A is A4, and Z 1is 2,4-difluorophenyl.

[0279] Table C-53: This table is for R 1 is methyl and R 4 is ethyl, and R 2 , R 3 , R 5 and R 6 is hydrogen, A is A9, and Z 1 is 2,4-difluorophenyl.

[0280] Table C-54: This table is for R 1 is methyl and R 4 is ethyl, and R 2 , R 3 , R 5 and R 6 is hydrogen, A is A10, and Z 1 is 2,4-difluorophenyl.

[0281] Table C-55: This table is for R 1 is methyl and R 2 , R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A4, and Z 1 is 4-fluorophenyl.

[0282] Table C-56: This table is for R 1 is methyl and R 2 , R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A9, and Z 1 is 4-fluorophenyl.

[0283] Table C-57: This table is for R 1 is methyl and R 2 , R 3 , R4 , R 5 , R 6 and R 7 is hydrogen, A is A10, and Z 1 is 4-fluorophenyl.

[0284] Table C-58: This table is for R 1 is methyl and R 2 is methyl and R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A4, and Z 1 is 4-fluorophenyl.

[0285] Table C-59: This table is for R 1 is methyl and R 2 is methyl and R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A9, and Z 1 is 4-fluorophenyl.

[0286] Table C-60: This table is for 1 is methyl and R 2 is methyl and R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A10, and Z 1 is 4-fluorophenyl.

[0287] Table C-61: This table is for R 1 is methyl and R 2 is methyl and R 3 is methyl and R 4 , R 5 , R 6 and R 7 is hydrogen, A is A4, and Z 1is 4-fluorophenyl.

[0288] Table C-62: This table is for R 1 is methyl and R 2 is methyl and R 3 is methyl and R 4 , R 5 , R 6 and R 7 is hydrogen, A is A9, and Z 1 is 4-fluorophenyl.

[0289] Table C-63: This table is for R 1 is methyl and R 2 is methyl and R 3 is methyl and R 4 , R 5 , R 6 and R 7 is hydrogen, A is A10, and Z 1 is 4-fluorophenyl.

[0290] Table C-64: This table is for 1 is methyl and R 4 is methyl and R 2 , R 3 , R 5 , R 6 and R 7 is hydrogen, A is A4, and Z 1 is 4-fluorophenyl.

[0291] Table C-65: This table is for 1 is methyl and R 4 is methyl and R 2 , R 3 , R 5 , R 6 and R 7 is hydrogen, A is A9, and Z 1 is 4-fluorophenyl.

[0292] Table C-66: This table is for R 1is methyl and R 4 is methyl and R 2 , R 3 , R 5 , R 6 and R 7 is hydrogen, A is A10, and Z 1 is 4-fluorophenyl.

[0293] Table C-67: This table is for R 1 is methyl and R 7 is methyl and R 2 , R 3 , R 4 , R 5 and R 6 is hydrogen, A is A4, and Z 1 is 4-fluorophenyl.

[0294] Table C-68: This table is for R 1 is methyl and R 7 is methyl and R 2 , R 3 , R 4 , R 5 and R 6 is hydrogen, A is A9, and Z 1 is 4-fluorophenyl.

[0295] Table C-69: This table is for R 1 is methyl and R 7 is methyl and R 2 , R 3 , R 4 , R 5 and R 6 is hydrogen, A is A10, and Z 1 is 4-fluorophenyl.

[0296] Table C-70: This table is for R 1 is methyl and R 4 is methyl and R 7 is methyl and R 2 , R 3 , R 5 and R6 is hydrogen, A is A4, and Z 1 is 4-fluorophenyl.

[0297] Table C-71: This table is for R 1 is methyl and R 4 is methyl and R 7 is methyl and R 2 , R 3 , R 5 and R 6 is hydrogen, A is A9, and Z 1 is 4-fluorophenyl.

[0298] Table C-72: This table is for R 1 is methyl and R 4 is methyl and R 7 is methyl and R 2 , R 3 , R 5 and R 6 is hydrogen, A is A10, and Z 1 is 4-fluorophenyl.

[0299] Table C-73: This table is for R 1 is methyl and R 2 is chlorine, and R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A4, and Z 1 is 4-fluorophenyl.

[0300] Table C-74: This table is for R 1 is methyl and R 2 is chlorine, and R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A9, and Z 1 is 4-fluorophenyl.

[0301] Table C-75: This table is for R 1 is methyl and R 2 is chlorine, and R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A10, and Z 1 is 4-fluorophenyl.

[0302] Table C-76: This table is for R 1 and R 4 is methyl and R 2 is chlorine, and R 3 , R 5 , R 6 and R 7 is hydrogen, A is A4, and Z 1 is 4-fluorophenyl.

[0303] Table C-77: This table is for R 1 and R 4 is methyl and R 2 is chlorine, and R 3 , R 5 , R 6 and R 7 is hydrogen, A is A9, and Z 1 is 4-fluorophenyl.

[0304] Table C-78: This table is for R 1 and R 4 is methyl and R 2 is chlorine, and R 3 , R 5 , R 6 and R 7 is hydrogen, A is A10, and Z 1 is 4-fluorophenyl.

[0305] Table C-79: This table is for R 1 and R 7 is methyl and R2 is chlorine, and R 3 , R 4 , R 5 and R 6 is hydrogen, A is A4, and Z 1 is 4-fluorophenyl.

[0306] Table C-80: This table is for 1 and R 7 is methyl and R 2 is chlorine, and R 3 , R 4 , R 5 and R 6 is hydrogen, A is A9, and Z 1 is 4-fluorophenyl.

[0307] Table C-81: This table is for R 1 and R 7 is methyl and R 2 is chlorine, and R 3 , R 4 , R 5 and R 6 is hydrogen, A is A10, and Z 1 is 4-fluorophenyl.

[0308] Table C-82: This table is for R 1 , R 4 and R 7 is methyl and R 2 is chlorine, and R 3 , R 5 and R 6 is hydrogen, A is A4, and Z 1 is 4-fluorophenyl.

[0309] Table C-83: This table is for R 1 , R 4 and R 7 is methyl and R 2 is chlorine, and R 3 , R 5 and R 6is hydrogen, A is A9, and Z 1 is 4-fluorophenyl.

[0310] Table C-84: This table is for R 1 , R 4 and R 7 is methyl and R 2 is chlorine, and R 3 , R 5 and R 6 is hydrogen, A is A10, and Z 1 is 4-fluorophenyl.

[0311] Table C-85: This table is for R 1 is methyl and R 2 is fluorine, and R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A4, and Z 1 is 4-fluorophenyl.

[0312] Table C-86: This table is for 1 is methyl and R 2 is fluorine, and R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A9, and Z 1 is 4-fluorophenyl.

[0313] Table C-87: This table is for R 1 is methyl and R 2 is fluorine, and R 3 , R 4 , R 5 , R 6 and R 7 is hydrogen, A is A10, and Z 1 is 4-fluorophenyl.

[0314] Table C-88: This table is for R 1 and R 4 is methyl and R 2 is fluorine, and R 3 , R 5 , R 6 and R 7 is hydrogen, A is A4, and Z 1 is 4-fluorophenyl.

[0315] Table C-89: This table is for R 1 and R 4 is methyl and R 2 is fluorine, and R 3 , R 5 , R 6 and R 7 is hydrogen, A is A9, and Z 1 is 4-fluorophenyl.

[0316] Table C-90: This table is for 1 and R 4 is methyl and R 2 is fluorine, and R 3 , R 5 , R 6 and R 7 is hydrogen, A is A10, and Z 1 is 4-fluorophenyl.

[0317] Table C-91: This table is for R 1 and R 7 is methyl and R 2 is fluorine, and R 3 , R 4 , R 5 and R 6 is hydrogen, A is A4, and Z 1 is 4-fluorophenyl.

[0318] Table C-92: This table is for R 1 and R 7 is methyl and R 2is fluorine, and R 3 , R 4 , R 5 and R 6 is hydrogen, A is A9, and Z 1 is 4-fluorophenyl.

[0319] Table C-93: This table is for R 1 and R 7 is methyl and R 2 is fluorine, and R 3 , R 4 , R 5 and R 6 is hydrogen, A is A10, and Z 1 is 4-fluorophenyl.

[0320] Table C-94: This table is for R 1 , R 4 and R 7 is methyl and R 2 is fluorine, and R 3 , R 5 and R 6 is hydrogen, A is A4, and Z 1 is 4-fluorophenyl.

[0321] Table C-95: This table is for R 1 , R 4 and R 7 is methyl and R 2 is fluorine, and R 3 , R 5 and R 6 is hydrogen, A is A9, and Z 1 is 4-fluorophenyl.

[0322] Table C-96: This table is for R 1 , R 4 and R 7 is methyl and R 2 is fluorine, and R 3 , R 5 and R 6is hydrogen, A is A10, and Z 1 is 4-fluorophenyl.

[0323] Table C-97: This table is for R 1 and R 2 is methyl and R 4 is ethyl, and R 3 , R 5 and R 6 is hydrogen, A is A4, and Z 1 is 4-fluorophenyl.

[0324] Table C-98: This table is for R 1 and R 2 is methyl and R 4 is ethyl, and R 3 , R 5 and R 6 is hydrogen, A is A9, and Z 1 is 4-fluorophenyl.

[0325] Table C-99: This table is for R 1 and R 2 is methyl and R 4 is ethyl, and R 3 , R 5 and R 6 is hydrogen, A is A10, and Z 1 is 4-fluorophenyl.

[0326] Table C-100: This table is for R 1 is methyl and R 4 is ethyl, and R 2 , R 3 , R 5 and R 6 is hydrogen, A is A4, and Z 1 is 4-fluorophenyl.

[0327] Table C-101: This table is for R 1 is methyl and R 4 is ethyl, and R2 , R 3 , R 5 and R 6 is hydrogen, A is A9, and Z 1 is 4-fluorophenyl.

[0328] Table C-102: This table is for R 1 is methyl and R 4 is ethyl, and R 2 , R 3 , R 5 and R 6 is hydrogen, A is A10, and Z 1 is 4-fluorophenyl. EXAMPLES

[0329] The examples which follow are intended to illustrate the invention and are not intended to limit it in any way.

[0330] The compounds of the present invention are distinguishable from known compounds by their high efficacy at low application rates, which can be verified by one skilled in the art using the experimental procedures outlined in the examples, and where necessary, low application rates, for example 60 ppm, 20 ppm or 2 ppm.

[0331] The compounds of formula (I) may have any number of benefits including, inter alia, an advantageous level of biological activity for protecting plants against diseases caused by fungi, or superior properties for use as an agrochemical active ingredient (e.g., high biological activity, an advantageous spectrum of activity, an enhanced safety profile (including improved crop tolerance), improved physico-chemical properties, or enhanced biodegradability).

[0332] Throughout this specification temperatures are given in degrees Celsius and "MP" means melting point. LC-MS means liquid chromatography mass spectrometry, with a description of the equipment and methods as follows.

[0333] 1 H NMR and19 F NMR measurements were recorded on a Bruker 400 MHz spectrometer, and chemical shifts were expressed as TMS ( 1 H) and CFCl3( 19 F) are given in ppm relative to standard. Spectra were run in deuterated solvents as specified. Compounds were characterized using one of the following LCMS methods. Characteristic LCMS values ​​obtained for each compound were retention time ("Rt", recorded in minutes) and molecular ion (M+H). + or (MH) - were the measured values.

[0334] The following HPLC-MS methods were used for the analysis of the compounds. Method A: Spectra were recorded on a Waters mass spectrometer (SQD, SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ion, capillary: 3.00 kV, cone range: 30 V, extractor: 2.00 V, source temperature: 150° C., desolvation temperature: 350° C., cone gas flow: 50 l / h, desolvation gas flow: 650 l / h, mass range: 100-900 Da) and a Waters Acquity UPLC: binary pump, heated column compartment, diode-array detector and ELSD detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm; Temperature: 60 °C; DAD wavelength range (nm): 210–500; Solvent gradient: A = water + 5% MeOH + 0.05% HC(O)OH, B = acetonitrile + 0.05% HC(O)OH; Gradient: 10 to 100% B in 1.2 min; Flow (ml / min): 0.85.

[0335] Method B: Spectra were recorded on a Waters ACQUITY mass spectrometer (SQD or SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative, capillary: 3.0 kV, cone: 30 V, extractor: 3.00 V, source temperature: 150° C., desolvation temperature: 400° C., cone gas flow: 60 L / hr, desolvation gas flow: 700 L / hr, mass range: 140-800 Da) and a Waters Corporations ACQUITY UPLC with solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm; Temperature: 60 °C; DAD wavelength range (nm): 210–400; Solvent gradient: A = water / methanol 9:1 + 0.1% formic acid, B = acetonitrile + 0.1% formic acid; Gradient: 0 to 100% B in 2.5 min; Flow rate (ml / min): 0.75.

[0336] Method C: Spectra were recorded on a Waters ZQ Mass Spectrometer (single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative, capillary: 3.00 kV, cone: 30.00 V, extractor: 2.00 V, source temperature: 100° C., desolvation temperature: 250° C., cone gas flow: 50 L / Hr, desolvation gas flow: 400 L / Hr, mass range: 100-900 Da) and a Waters Acquity UPLC (solvent degasser, binary pump, heated column compartment and diode-array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm, temperature: 60 °C, flow rate 0.85 mL / min; DAD wavelength range (nm): 210-500) Solvent gradient: A = HO + 5% MeOH + 0.05% HC(O)OH, B = acetonitrile + 0.05% HC(O)OH) Gradient: 0 min 10% B; 0-2.7 min 100% B; 2.7-3.0 min 100% B.

[0337] Method D: device: Mass spectrometer: Acquity QDA mass spectrometer manufactured by Waters HPLC: UPLC 'H' class Optimal mass parameters: Ionization method: Electrospray (ESI) Polarity: Anode and cathode switch Scan Type: Full Scan Capillary (kV): 0.8 Cone voltage (V): 25.00 Source temperature (℃): 120 Desolvation gas flow rate (L / Hr): 1000 Desolvation temperature (℃): 600 Gas flow @ cone (L / Hr): 50 Mass range: 110-850 Da PDA wavelength range: 230~400nm Optimal chromatographic parameters: Gradient conditions: Solvent A: Water + 0.1% formic acid:acetonitrile: 95:5 v / v Solvent B: Acetonitrile + 0.05% formic acid

[0338] [Table 2]

[0339] Column: Acquity UPLC HSS T3 C18 Column length: 30mm Column inner diameter: 2.1 mm Particle size: 1.8μ Column oven temperature: 40℃

[0340] Method E: device: HPLC system: UFLC Shimadzu Nexera X2 / Agilent HPLC 1200 Location: Kilo Analytical Lab Optimal chromatographic parameters: Gradient conditions: Solvent A: Water + 0.05% formic acid Solvent B: 100% acetonitrile + 0.1% formic acid

[0341] [Table 3]

[0342] Column: KINETEX-EVO C18 Column length: 50mm Column inner diameter: 4.6mm Particle size: 2.6μ Column oven temperature: 40℃

[0343] Method F: device: Mass spectrometer: Waters Acquity SQD mass spectrometer HPLC: UPLC 'H' class Optimal mass parameters: Ionization method: Electrospray (ESI) Polarity: Anode and cathode switch Scan Type: Full Scan Capillary (kV): 3.00 Cone voltage (V): 41.00 Source temperature (℃): 150 Desolvation gas flow rate (L / Hr): 1000 Desolvation temperature (℃): 500 Gas flow @ cone (L / Hr): 50 Mass range: 110-800 Da PDA wavelength range: 210~400nm Optimal chromatographic parameters: Gradient conditions: Solvent A: Water + 0.1% formic acid:acetonitrile: 95:5 v / v Solvent B: Acetonitrile + 0.05% formic acid

[0344] [Table 4]

[0345] Column: Acquity UPLC HSS T3 C18 Column length: 30mm Column inner diameter: 2.1 mm Particle size: 1.8μ Column oven temperature: 40℃

[0346] [Table 5]

[0347] The complex is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill to obtain a wettable powder which can be diluted with water to obtain a suspension of the desired concentration.

[0348] [Table 6]

[0349] The complex is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to obtain a powder which can be directly used as a seed treatment.

[0350] emulsifiable concentrate Active ingredient 10% Octylphenol polyethylene glycol ether (4-5 mol ethylene oxide) 3% Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (35 mol ethylene oxide) 4% Cyclohexanone 30% Xylene Mixture 50%

[0351] Emulsions of any required dilution which can be used in plant protection are obtained from this concentrate by dilution with water.

[0352] [Table 7]

[0353] Ready-to-use dusts are obtained by mixing the complex with a carrier and grinding the mixture in a suitable mill. Such dusts can also be used for dry dressing of seeds.

[0354] Extrusion Granules Active ingredient 15% Sodium Lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 82%

[0355] The composite is mixed with the auxiliary and ground, the mixture is moistened with water, the mixture is extruded and then dried in a stream of air.

[0356] Coated Granules Active ingredient: 8% Polyethylene glycol (200 mol wt) 3% Kaolin 89%

[0357] The finely ground compound is evenly applied to kaolin moistened with polyethylene glycol in a mixer, in this way a non-dusty coated granule is obtained.

[0358] Suspension concentrate Active ingredient 40% Propylene glycol 10% Nonylphenol polyethylene glycol ether (15 mol ethylene oxide) 6% Sodium Lignosulfonate 10% Carboxymethylcellulose 1% Silicone oil (in the form of a 75% emulsion in water) 1% water 32%

[0359] The finely ground composite can be thoroughly mixed with adjuvants to obtain a suspension concentrate which can be diluted with water to obtain a suspension of any desired dilution. Such dilutions can be used to treat and protect living plants and plant propagation material against microbial infestation by spraying, pouring, or immersion.

[0360] Seed treatment flowable concentrate Active ingredient 40% Propylene glycol 5% Copolymer butanol PO / EO 2% Tristyrene phenol + 10-20 mole EO 2% 1,2-Benzisothiazolin-3-one (in the form of a 20% aqueous solution) 0.5% Monoazo pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2% Water 45.3%

[0361] The finely ground composite can be thoroughly mixed with adjuvants to obtain a suspension concentrate which can be diluted with water to obtain a suspension of any desired dilution. Such dilutions can be used to treat and protect living plants and plant propagation material against microbial infestation by spraying, pouring, or immersion.

[0362] Slow-release capsule suspension 28 parts of the complex are mixed with 2 parts of aromatic solvent and 7 parts of toluene diisocyanate / polymethylene-polyphenylisocyanate mixture (8:1). The mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of defoamer and 51.6 parts of water until the desired particle size is achieved. A mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water is added to the emulsion. The mixture is stirred until the polymerization reaction is complete. The resulting capsule suspension is stabilized by adding 0.25 parts of thickener and 3 parts of dispersant. The capsule suspension formulation contains 28% active ingredient. The diameter of the medium-sized capsules is 8-15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for this purpose.

[0363] Formulation types include emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water dispersible granules (WG), emulsifiable granules (EG), emulsions, water in oil (EO), emulsions, oil in water (EW), microemulsions (ME), oil dispersions (OD), oil miscible flowables (OF), oil miscible liquids (OL), soluble concentrates (SL), ultra low volume suspensions (SU), ultra low volume liquids (UL), technical concentrates (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG) or any technically preferred formulation in combination with agriculturally acceptable adjuvants.

[0364] Abbreviation CDCl 3 Deuterated chloroform DCC Dicyclohexylcarbodiimide DMF Dimethylformamide DMSO Dimethyl sulfoxide DMSO-d6 Deuterated dimethyl sulfoxide EDC 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide EtOAc Ethyl acetate HATU 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate HCl Hydrochloric acid h / hrs hours / hours LC-MS Liquid Chromatography Mass Spectrometry (LC-MS or LCMS) nOe Nuclear Overhauser effect rh Relative humidity rt room temperature Rt retention time ssp. subspecies THF Tetrahydrofuran

[0365] Preparation Example The compounds of formula (I) according to the invention may be prepared using the synthetic techniques described both above and below.

[0366] The syn- and anti-isomers can be distinguished using high field NMR techniques such as ROESY 2D NMR. For example: [ka] (anti-isomer, compound P-9 in Table T1) [ka] (syn-isomer, compound P-8 in Table T1)

[0367] Example 1: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4R,7R)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]methanone (compound P-17, Table T1) and [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]methanone (compound P-14, Table T1). [ka] (Compound P-17, Table T1) [ka] (Compound P-14, Table T1)

[0368] Step A: Preparation of (1-methylpyrazol-4-yl)-(3-thienyl)methanol [ka] A one-necked round bottom flask equipped with a magnetic stir bar was charged with 4-iodo-1-methyl-1h-pyrazole (7.37 g, 33.6 mmol) and tetrahydrofuran (92 mL). Isopropylmagnesium chloride lithium chloride complex (1.3 mol / L) in THF (35 mL) was added dropwise at 0° C. under argon atmosphere (white suspension). The mixture was stirred at 0° C. for 45 min. Then, 3-thiophenecarboxaldehyde (3.50 g, 30.6 mmol) was added dropwise to the previous mixture at 0° C. under argon atmosphere. The mixture was stirred at this temperature for 10 min, then warmed to room temperature and stirred for 1 h. The reaction mixture was then poured into water (100 mL) and extracted with ethyl acetate (2×80 mL). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo to give the title compound. LC-MS (Method A): Retention time 0.56 min, 195(M+H).

[0369] Step B: Preparation of 2-(1-methylpyrazol-4-yl)-2-(3-thienyl)acetonitrile [ka] A sealed test tube equipped with a magnetic stir bar was charged with (1-methylpyrazol-4-yl)-(3-thienyl)methanol (5.94 g, 30.6 mmol) and dichloromethane (245 mL). To this solution was added, sequentially, lithium carbonate (0.456 g, 6.12 mmol), trimethylsilyl cyanide (18.7 mL, 138 mmol) and iodine (14.2 g, 55.0 mmol) at room temperature. After stirring at 35° C. for 1 h, the reaction mixture was cooled to room temperature and added with Na 2 S 2 O 3 (80 mL) and extracted with dichloromethane (2×60 mL). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo. The crude material was purified by chromatography on silica gel (20 g SiO 2 , ethyl acetate / cyclohexane gradient) to give the title compound. LC-MS (Method A): Retention time 0.75 min, 204(M+H). 1 H NMR (400MHz, CDCl3) δ ppm 3.92(s,3H)5.13-5.22(m,1H)7.00-7.08(m,1H)7.29-7.30(m,1H)7.36-7.40(m,2H)7.42-7.47(m,1H).

[0370] Step C: Preparation of 2-(1-methylpyrazol-4-yl)-2-(3-thienyl)ethanamine [ka] A one-necked round bottom flask equipped with a magnetic stir bar was charged with 2-(1-methylpyrazol-4-yl)-2-(3-thienyl)acetonitrile (1.78 g, 8.76 mmol) in tetrahydrofuran (26 mL). To this solution, borane dimethylsulfide complex (2.65 mL, 26.3 mmol) was added dropwise at room temperature under an argon atmosphere, and the mixture was then stirred at 65° C. for 1 h. The reaction mixture was cooled to 0° C., after which hydrochloric acid (6 mol / L, 5.87 mL, 35.2 mmol) was added dropwise, and the mixture was subsequently heated to 65° C. for 1 h. The mixture was diluted with water (20 mL), basified (pH 12) with NaOH 6M, cooled, 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 2-(1-methylpyrazol-4-yl)-2-(3-thienyl)ethanamine. LC-MS (Method A): Retention time 0.25 min, 208(M+H). 1 H NMR (400 MHz, CDCl 3 )δ ppm 7.30-7.44(m,2H)7.06-7.27(m,3H)7.00(br d,J=4.7Hz,1H)4.06-4.30(m,1H)3.87(s,3H)3.57-3.78(m,1H)3.21(br s,2H).

[0371] Step D: Preparation of N-[2-(1-methylpyrazol-4-yl)-2-(3-thienyl)ethyl]acetamide [ka] A one-necked round bottom flask equipped with a magnetic stir bar was charged with 2-(1-methylpyrazol-4-yl)-2-(3-thienyl)ethanamine (1.80 g, 8.68 mmol) and saturated aqueous sodium bicarbonate (43 mL). Acetyl chloride (0.71 mL, 9.55 mmol) in ethyl acetate (43 mL) was added dropwise at room temperature with vigorous stirring. The mixture was stirred at room temperature for 15 minutes. The reaction mixture was then extracted with ethyl acetate (2×20 mL) and the combined organic layers were washed with brine, dried over sodium sulfate, and concentrated in vacuo to give N-[2-(1-methylpyrazol-4-yl)-2-(3-thienyl)ethyl]acetamide. LC-MS (Method A): Retention time 0.25 min, 234(M+H). 1 H NMR(400MHz,CDCl3)δ ppm 7.37-7.41(m,1H)7.33(dd,J=5.1,2.9Hz,1H)7.21(s,1H)7.06(dd,J=1.5,0.7Hz,1H)6.99(dd,J=4.9,1.3Hz,1H)5.50(br s,1H)4.21(t,J=7.4Hz,1H)3.89(s,3H)3.73(td,J=7.9,6.0Hz,2H)1.94(s,3H).

[0372] Step E: Preparation of 7-methyl-4-(1-methylpyrazol-4-yl)-4,5,6,7-tetrahydrothieno[2,3-c]pyridine and 4-methyl-7-(1-methylpyrazol-4-yl)-4,5,6,7-tetrahydrothieno[3,4-c]pyridine [ka] Step 1 A one-necked round-bottom flask equipped with a magnetic stir bar was charged with N-[2-(1-methylpyrazol-4-yl)-2-(3-thienyl)ethyl]acetamide (1.73 g, 6.94 mmol) and phosphoryl chloride (7 mL). The mixture was stirred at 60° C. for 1 h. The reaction mixture was cooled to room temperature and added with Na 2 CO 3(20 mL) at 0° C. (gas evolution and exotherm!). The mixture was extracted with ethyl acetate (3×20 mL) and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo to give the title product mixture, which was used in the next step without further purification.

[0373] Step 2 A one-necked round bottom flask equipped with a magnetic stir bar was charged with the product from step 1 above (913 mg, 3.947 mmol) and methanol (12 mL). To this solution was added sodium borohydride (0.233 g, 5.92 mmol) at room temperature (gas evolution) and the mixture was then stirred at room temperature for 1 h. The reaction mixture was poured into water (20 mL) and the mixture was 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 7-methyl-4-(1-methylpyrazol-4-yl)-4,5,6,7-tetrahydrothieno[2,3-c]pyridine as a mixture with 4-methyl-7-(1-methylpyrazol-4-yl)-4,5,6,7-tetrahydrothieno[3,4-c]pyridine. LC-MS (Method A): Retention time 0.25 min, 234(M+H).

[0374] Step F: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4R,7R)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]methanone (compound P-17, Table T1) and [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]methanone (compound P-14, Table T1). [ka] (Compound P-17, Table T1) [ka] (Compound P-14, Table T1) A one-necked round bottom flask equipped with a magnetic stir bar was charged with 7-methyl-4-(1-methylpyrazol-4-yl)-4,5,6,7-tetrahydrothieno[2,3-c]pyridine (117 mg, 0.265 mmol, mixture from Example 1, step 2, step E) in mixture with 4-methyl-7-(1-methylpyrazol-4-yl)-4,5,6,7-tetrahydrothieno[3,4-c]pyridine, ethyl acetate (17 mL), N,N-diisopropylethylamine (0.88 mL, 5.14 mmol) and 5-(2,4-difluorophenyl)isoxazole-3-carboxylic acid (0.4378 g, 1.88 mmol). Propylphosphonic anhydride (1.82 mL, 3.08 mmol) was then added dropwise at room temperature and the mixture was stirred at room temperature. After 1 h, the reaction mixture was poured into water (20 mL). The mixture was extracted with ethyl acetate (2×20 mL) and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo. The crude material was purified by preparative HPLC (Preparative HPLC method: Waters Autopurification System: 2767 sample manager, 2489 UV / Visible Detector, 2545 Quaternary Gradient Module. MS-RP2: SQDII single quadrupole mass spectrometer with electrospray source. Column: BC: Phenomenex Gemini NX C18, 5 micron particle size, 110 Angstroms, 100×50 mm. Solvent: A: water; Solvent: B: acetonitrile; Modifier: formic acid, gradient: 40% B to 60% B, run time: 10 min) to give [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4R,7R)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]methanone as the first eluting product. LC-MS (Method A): Retention time 1.05 min, 441(M+H).

[0375] The second eluted product was isolated as [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]methanone. LC-MS (Method A): Retention time 1.08 min, 441(M+H). 1 H NMR(400MHz,CDCl3)δ ppm 7.88-8.09(m,1H)7.30-7.49(m,2H)7.04-7.19(m,2H)6.95-7.04(m,2H)6.67(d,J=5.1Hz,1H)5.68-6 .06(m,1H)4.53-4.98(m,1H)4.14-4.31(m,1H)3.84-4.02(m,3H)3.00-3.47(m,1H)1.67-1.83(m,3H).

[0376] Example 2: Preparation of [5-(2,4-difluorophenyl)-1,3,4-thiadiazol-2-yl]-[rac-(4R,7R)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]methanone (compound P-16, Table T1) and [5-(2,4-difluorophenyl)-1,3,4-thiadiazol-2-yl]-[rac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]methanone (compound P-15, Table T1) [ka] (Compound P-16, Table T1) [ka] (Compound P-15, Table T1) A one-necked round bottom flask equipped with a magnetic stir bar was charged with a mixture of 7-methyl-4-(1-methylpyrazol-4-yl)-4,5,6,7-tetrahydrothieno[2,3-c]pyridine and 4-methyl-7-(1-methylpyrazol-4-yl)-4,5,6,7-tetrahydrothieno[3,4-c]pyridine (117 mg, 0.265 mmol, mixture from Example 1, Step 2, Step E) (468 mg, 2.006 mmol) and toluene (8 mL). Trimethylaluminum (2.01 mL, 4.01 mmol) was added in several portions at room temperature under an argon atmosphere. The reaction was stirred at room temperature for 20 minutes, after which ethyl 5-(2,4-difluorophenyl)-1,3,4-thiadiazole-2-carboxylate (0.5964 g, 2.207 mmol) was added, diluted dropwise in toluene (8 mL) at room temperature, and the mixture was stirred at 90° C. for 24 hours. The reaction mixture was cooled to 0° C. and quenched by careful addition of HCl 1M (1 mL). The mixture was diluted with NaHCO 3 (20 mL) and extracted with ethyl acetate (3×20 mL). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The crude material was purified by preparative HPLC (Preparative HPLC Method: Waters Autopurification System: 2767 sample manager, 2489 UV / Visible Detector, 2545 Quaternary Gradient Module, MS-RP2: SQDII Single Quadrupole Mass Spectrometer with Electrospray Source, Column: MC: Phenomenex Gemini NX C18, 4 microns). Particle size, 80 Angstroms, 75×30 mm. Solvent: A: water; Solvent: B: acetonitrile; Denaturant: formic acid. Gradient: 40% B to 50% B, run time: 10 min) to give [5-(2,4-difluorophenyl)-1,3,4-thiadiazol-2-yl]-[rac-(4R,7R)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]methanone (compound P-16, Table T1) as the first eluting product. LC-MS (Method A): Retention time 1.13 min, 458(M+H).

[0377] The second eluting product was [5-(2,4-difluorophenyl)-1,3,4-thiadiazol-2-yl]-[rac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]methanone (compound P-15, Table T1). LC-MS (Method A): Retention time 1.18 min, 458(M+H). 1 H NMR(400MHz,CDCl3)δ ppm 8.39-8.58(m,1H)7.31-7.58(m,2H)6.95-7.21(m,3H)6.65-6.73(m,1H)5.84-6.66(m,1H) 4.79-5.56(m,1H)4.18-4.46(m,1H)3.87-4.03(m,3H)3.12-3.49(m,1H)1.64-1.89(m,3H).

[0378] Example 3: Preparation of [5-(2,4-difluorophenyl)-1,3,4-thiadiazol-2-yl]-[(4S,7R)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]methanone (compound P-1, Table T1) and 5-(2,4-difluorophenyl)-1,3,4-thiadiazol-2-yl]-[(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]methanone (compound P-2, Table T1) [ka] (Compound P-1, Table T1) [ka] (Compound P-2, Table T1) The racemic mixture [5-(2,4-difluorophenyl)-1,3,4-thiadiazol-2-yl]-[rac-(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]methanone was resolved into its enantiomers by preparative SFC HPLC.

[0379] Preparative SFC method: Sepiatec Preparative SFC 100, Column: Daicel CHIRALPAK® IB, 5 μm, 2.0 cm x 25 cm. Mobile phase: A: CO2-B: MeOH Isocratic: 10% B. Back pressure: 150 bar, Flow rate: 60 ml / min, GLS pump: Detection: UV 285 nm, Sample concentration: 97 mg in 3 ml MeOH, Injection: 500 microliters.

[0380] The following elution peaks were obtained: [5-(2,4-difluorophenyl)-1,3,4-thiadiazol-2-yl]-[(4S,7R)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]methanone Retention time (min) approx. 2.88 Chemical purity (area % at 285 nm) >99 Enantiomeric excess (%)>98.8% [5-(2,4-difluorophenyl)-1,3,4-thiadiazol-2-yl]-[(4R,7S)-7-methyl-4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]methanone Holding time (min) approx. 3.30 Chemical purity (area % at 285 nm) >99 Enantiomeric excess (%)>95.3%

[0381] Example 4: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4S,7S)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3-c]pyridin-6-yl]methanone (compound P-13, Table T1) and [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4S,7R)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3-c]pyridin-6-yl]methanone (compound P-12 Table T1) [ka] (Compound P-13, Table T1) [ka] (Compound P-12, Table T1)

[0382] Step A: Preparation of 2-(1-methylpyrazol-4-yl)-2-(3-thienyl)propanenitrile [ka] A sealed test tube equipped with a magnetic stir bar and temperature probe was charged with 2-(1-methylpyrazol-4-yl)-2-(3-thienyl)acetonitrile (2.32 g, 11.4 mmol) and tetrahydrofuran (46 mL). To this solution was added n-butyllithium (2.5 mol / L, 5.5 mL, 13.7 mmol) dropwise at -70°C under an argon atmosphere. The mixture was stirred at this temperature for 30 minutes, after which iodomethane (1.08 mL, 17.1 mmol) was added dropwise at -78°C. The reaction was stirred at -78°C for 5 minutes and then at room temperature for 30 minutes. The reaction mixture was poured into water (60 mL) and extracted with ethyl acetate (2 x 50 mL). The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated in vacuo to give 2-(1-methylpyrazol-4-yl)-2-(3-thienyl)propanenitrile. LC-MS (Method A): Retention time 0.81 min, 218(M+H). 1H NMR (400MHz, CDCl3) δ ppm 2.04(s,3H)3.91(s,3H)7.02-7.08(m,1H)7.24-7.30(m,1H)7.31-7.34(m,1H)7.34-7.39(m,1H)7.42-7.46(m,1H).

[0383] Step B: Preparation of 2-(1-methylpyrazol-4-yl)-2-(3-thienyl)propan-1-amine [ka] A one-necked round bottom flask equipped with a magnetic stir bar was charged with 2-(1-methylpyrazol-4-yl)-2-(3-thienyl)propanenitrile (2.48 g, 11.4 mmol) and tetrahydrofuran (34 mL). Borane dimethylsulfide complex (3.45 mL, 34.2 mmol) was added dropwise at room temperature under argon atmosphere and the mixture was stirred at 65° C. for 1 h. The reaction mixture was cooled to 0° C., after which hydrochloric acid (6 mol / L, 7.65 mL, 45.9 mmol) was added dropwise (strong gas evolution) and the mixture was stirred at 65° C. for 1 h. The mixture was diluted with water (30 mL), basified with NaOH 6M (pH 12) 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 2-(1-methylpyrazol-4-yl)-2-(3-thienyl)propan-1-amine. LC-MS (Method A): Retention time 0.28 min, 222(M+H). 1 H NMR(400MHz,CDCl3)δ ppm 7.36(d,J=0.7Hz,1H)7.29(s,1H)7.17(s,1H)7.04(dd,J=2.9,1.5Hz,1H)6.99(dd,J=5.1,1.5Hz,1H)3.88(s,3H)3.16(s,2H)1.65(s,3H).

[0384] Step C: Preparation of N-[2-(1-methylpyrazol-4-yl)-2-(3-thienyl)propyl]acetamide [ka] A one-necked round bottom flask equipped with a magnetic stir bar was charged with 2-(1-methylpyrazol-4-yl)-2-(3-thienyl)propan-1-amine (1.54 g, 6.96 mmol) and saturated aqueous sodium bicarbonate (35 mL). Acetyl chloride (0.573 mL, 7.65 mmol) was then dissolved in ethyl acetate (35 mL) and added dropwise with vigorous stirring at room temperature. The mixture was stirred at room temperature for 15 minutes. The reaction mixture was extracted with ethyl acetate (2×20 mL) and the combined organic layers were washed with brine, dried over sodium sulfate, and concentrated in vacuo to give N-[2-(1-methylpyrazol-4-yl)-2-(3-thienyl)propyl]acetamide. LC-MS (Method A): Retention time 0.68 min, 264(M+H). 1 H NMR(400MHz,CDCl3)δ ppm 7.29-7.36(m,2H)7.18(s,1H)7.05(dd,J=2.9,1.5Hz,1H)6.99(dd,J=4.9,1.3Hz,1H )5.22-5.38(m,1H)3.89(s,3H)3.77(dd,J=5.8,5.1Hz,2H)1.93(s,3H)1.61(s,3H).

[0385] Step D: Preparation of 4,7-dimethyl-4-(1-methylpyrazol-4-yl)-6,7-dihydro-5H-thieno[2,3-c]pyridine [ka] A one-necked round-bottom flask equipped with a magnetic stir bar was charged with N-[2-(1-methylpyrazol-4-yl)-2-(3-thienyl)propyl]acetamide (1.46 g, 5.54 mmol) and phosphoryl chloride (5.5 mL). The reaction mixture was stirred at 60° C. for 1 h, cooled to room temperature, and poured slowly into water (30 mL) at 45° C. The mixture was diluted with Na 2 CO 3The mixture was basified with (9) 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 4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5H-thieno[2,3-c]pyridine, which was diluted with methanol (9 mL) and treated with sodium borohydride (0.1728 g, 4.384 mmol) in several portions at room temperature. The reaction mixture was stirred for 30 min and poured into water (20 mL). The mixture was extracted with ethyl acetate (3×20 mL) and the combined organic layers were washed with brine, dried over sodium sulfate, and concentrated in vacuo to give 4,7-dimethyl-4-(1-methylpyrazol-4-yl)-6,7-dihydro-5H-thieno[2,3-c]pyridine. LC-MS (Method A): Retention time 0.41 min, 248(M+H).

[0386] Step E: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4S,7S)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3-c]pyridin-6-yl]methanone (compound P-13, Table T1) and [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4S,7R)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3-c]pyridin-6-yl]methanone (compound P-12, Table T1). [ka] (Compound P-13, Table T1) [ka] (Compound P-12, Table T1) A one-necked round bottom flask equipped with a magnetic stir bar was charged with 4,7-dimethyl-4-(1-methylpyrazol-4-yl)-6,7-dihydro-5H-thieno[2,3-c]pyridine (0.210 g, 0.848 mmol), ethyl acetate (9 mL), N,N-diisopropylethylamine (0.437 mL, 2.54 mmol) and 5-(2,4-difluorophenyl)isoxazole-3-carboxylic acid (0.216 g, 0.933 mmol). Propylphosphonic anhydride (0.900 mL, 1.528 mmol) was then added dropwise at room temperature. The reaction mixture was stirred at room temperature for 1 h and poured into water (20 mL). The aqueous layer was extracted with ethyl acetate (2×20 mL) and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The crude material was purified by preparative HPLC (Preparative HPLC Method: Waters Autopurification System: 2767 sample manager, 2489 UV / Visible Detector, 2545 Quaternary Gradient Module. MS-RP2: SQDII single quadrupole mass spectrometer with electrospray source. Column: MC: Phenomenex Gemini NX C18, 4 micron particle size, 80 Angstroms, 75×30 mm. Solvent: A: water; Solvent: B: acetonitrile; Modifier: formic acid. Gradient: 40% B to 50% B. Run time: 10 min) to give [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4S,7S)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3-c]pyridin-6-yl]methanone as the first eluting product. LC-MS (Method A): Retention time 1.14 min, 455(M+H). 1 H NMR (600MHz, CDCl 3d)δ ppm 1.61(s,3H)1.67(d,J=6.7Hz,3H)1.69-1.70(m,1H)1.70(s,1H)3.20(d,J=12.9Hz,1H)3.58(d ,J=13.6Hz,1H)3.72(s,3H)3.82(s,1H)3.90(d,J=15.6Hz,1H)4.41(d,J=13.6Hz,1H)4.92(d,J =12.9Hz,1H)5.84(q,J=6.6Hz,1H)6.09(q,J=6.7Hz,1H)6.24(d,J=3.7Hz,1H)6.63(s,1H)6.83 (d,J=5.1Hz,1H)6.86(d,J=3.7Hz,1H)6.99(s,1H)7.03-7.10(m,2H)7.24(d,J=5.1Hz,1H)7.88 -8.05(m,1H).

[0387] The second eluting product was [5-(2,4-difluorophenyl)isoxazol-3-yl]-[rac-(4S,7R)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothieno[2,3-c]pyridin-6-yl]methanone (compound P-12, Table T1). LC-MS (Method A): Retention time 1.16 min, 455(M+H). 1 H NMR (600MHz, CDCl 3 )δ ppm 1.56(s,5H)1.59(s,3H)1.68(d,J=6.6Hz,5H)1.76(d,J=6.6Hz,4H)3.26(d,J=13.2H z,1H)3.58(d,J=13.8Hz,2H)3.90(s,4H)3.94(s,3H)4.53(d,J=13.8Hz,1H)4.74(d,J =13.1Hz,1H)5.82(q,J=6.5Hz,1H)5.99(q,J=6.6Hz,1H)6.62(d,J=5.1Hz,1H)6.66(d ,J=5.1Hz,1H)7.14(d,J=5.1Hz,2H)7.25(s,1H)7.30(s,1H)7.36(s,1H)7.40(s,1H).

[0388] Example 5: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-(1,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thieno[3,2-c]pyridin-5-yl]methanone (compound P-33, Table T1) [ka] (Compound P-33, Table T1)

[0389] Step A: Preparation of 7-(1,5-dimethylpyrazol-4-yl)thieno[3,2-c]pyridine [ka] To a mixture of 7-bromothieno[3,2-c]pyridine (2.00 g, 9.34 mmol, CAS [1535297-40-5]), 1,5-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazole (4.93 g, 22.2 mmol) and potassium carbonate (2.25 g, 16.28 mmol) in a microwave vial, toluene (37.0 mL) and methanol (3.70 mL) were added. The resulting suspension was degassed with argon for several minutes, followed by the addition of tetrakis(triphenylphosphine)palladium(0) (0.86 g, 0.74 mmol). The vial was sealed and the reaction mixture was heated to 100° C. and stirred under microwave irradiation for 1 h. After cooling to room temperature, the reaction mixture was partitioned between a saturated solution of ammonium chloride and ethyl acetate. The aqueous layer was back-extracted twice with ethyl acetate and 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 (ethyl acetate ethanol 0-30%) afforded the title compound as a brown solid. 1 H NMR (400 MHz, CDCl 3 )δ ppm:2.39(s,3H)3.93(s,3H)7.54(2d,2H)7.81(s,1H)8.35(s,1H)9.08(s,1H).

[0390] Step B: Preparation of 7-(1,5-dimethylpyrazol-4-yl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine [ka] To a solution of 7-(1,5-dimethylpyrazol-4-yl)thieno[3,2-c]pyridine (intermediate prepared as described in step a above, 1.70 g, 7.72 mmol) in methanol (74 mL) was added sodium cyanoborohydride (2.9 g, 46.3 mmol) in portions. The reaction mixture was stirred at room temperature until LC-MS indicated the reaction was complete. The reaction was then treated with hydrochloric acid (44.0 mL 1.25 M in methanol) until the pH reached 3-4. After stirring at room temperature for 2 hours, the reaction mixture was then diluted with water and basified with 2N sodium hydroxide. The methanol was evaporated under reduced pressure and the remaining aqueous layer was extracted three times with ethyl acetate. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. The resulting brown oil was purified by flash chromatography on silica gel (ethyl acetate ethanol 0-30%) to the title compound, which was used without further purification. LC-MS (Method A): Retention time 0.26 min, m / z234[M+H + ].

[0391] Step C: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-(1,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thieno[3,2-c]pyridin-5-yl]methanone (compound P-33, Table T1) [ka] (Compound P-33, Table T1) To a solution of 7-(1,5-dimethylpyrazol-4-yl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine (intermediate prepared as described in step B above, 150 mg, 0.64 mmol) and 5-(2,4-difluorophenyl)isoxazole-3-carboxylic acid (145 mg, 0.64 mmol) in ethyl acetate (1.3 mL) at room temperature was added propylphosphonic anhydride as a 50% solution in ethyl acetate (1.02 g, 1.60 mmol), followed by N,N-diisopropylethylamine (430 mg, 3.20 mmol). The reaction mixture was stirred at room temperature overnight, then the reaction mixture was partitioned between water and ethyl acetate. The aqueous layer was back-extracted twice with ethyl acetate, and 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 (cyclohexane ethyl acetate 10-100%) afforded the title compound as a white solid, mp 160-161° C. 1 H NMR (400 MHz, CDCl 3 )δ ppm:2.20 + 2.29(2s,3H)3.33-3.42 + 3.68-3.72(2m,1H)3.75 1 3.85(2s,3H)4.28-4.32 + 4.34-4.38(2m,1H)4.43-4.48 + 4.75-4.80(2m,1H)4.71-4.76 + 4.82-4.87(2m,1H)5.20-5.25 + 5.30-5.35(2m,1H)6.78-6.81(m,1H)6.90-6.92(m,1H)6.94-7.13(m,3H)7.19-7.28(m,2H)7.93-8.14(m,1H).

[0392] Example 6: This example illustrates the preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-(1,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thiadiazolo[4,5-c]pyridin-5-yl]methanone (compound P-27, Table T1). [ka] (Compound P-27, Table T1)

[0393] Step A: Preparation of 3-bromo-4-chloro-5-nitro-pyridine [ka] A mixture of phosphoryl chloride (21.5 ml, 228 mmol) and 3-bromo-5-nitro-pyridin-4-ol (10.0 g, 45.6 mmol) in toluene (20 mL) was heated to 90° C. for 12 h. The progress of the reaction was monitored by LC-MS. The reaction mass was cooled to room temperature and phosphoryl chloride was removed under reduced pressure. The reaction was quenched with ice water, extracted with ethyl acetate (3 times) and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuum to give 3-bromo-4-chloro-5-nitro-pyridine as a solid. 1 H NMR (400MHz, DMSO-d6) δ ppm 9.20(s,1H),9.17(s,1H).LC-MS (Method D): Retention time 1.08 min, 237(M+H).

[0394] Step B: Preparation of 3-bromo-5-nitro-pyridine-4-thiol [ka] To a solution of 3-bromo-4-chloro-5-nitro-pyridine (2.0 g, 8.42 mmol) in methanol (20 mL) was added sodium hydrosulfide (0.96 g, 16.8 mmol). The reaction mixture was stirred at room temperature for 2 h. The reaction was monitored by TLC and LC-MS. After completion, the reaction mixture was concentrated in vacuum to give crude 3-bromo-5-nitro-pyridine-4-thiol (1.80 g, 6.90 mmol), which was used directly in the next step. LC-MS (Method D): Retention time 0.51 min, 235(M+H).

[0395] Step C: Preparation of 3-amino-5-bromo-pyridine-4-thiol [ka] To a solution of 3-bromo-5-nitro-pyridine-4-thiol (2.0 g, 8.50 mmol) in hydrochloric acid (8 mL) was added stannous chloride (3.24 g, 17.0 mmol) in water (8 mL). The reaction mixture was stirred at room temperature for 3 hours. After the reaction was completed, the reaction mixture was filtered and the filtrate was concentrated in vacuum to give crude 3-amino-5-bromo-pyridine-4-thiol (2 g), which was used directly in the next step. LC-MS (Method D): Retention time 0.19 min, 205(M+H).

[0396] Step D: Preparation of 7-bromothiadiazolo[4,5-c]pyridine [ka] A solution of sodium nitrite (0.52 g, 7.60 mmol) in water (20 mL) was added dropwise to a mixture of 3-amino-5-bromo-pyridine-4-thiol (2.0 g, 5.85 mmol) in hydrochloric acid (2 M) (60 mL, 708 mmol) at 0° C. The mixture was maintained at this temperature for 12 h. The reaction progress was monitored by LC-MS and upon completion, it was quenched with sodium bicarbonate, extracted with ethyl acetate (3 times), the combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo. The crude residue obtained was purified by chromatography on silica gel using a cyclohexane / ethyl acetate eluent system to give 7-bromothiadiazolo[4,5-c]pyridine. 1 H NMR (400 MHz, CDCl 3 )δ ppm 9.90(s,1H)8.84(s,1H). LC-MS (Method D): Retention time 1.05 min, 216(M+H).

[0397] Step E: Preparation of 7-(1,5-dimethylpyrazol-4-yl)thiadiazolo[4,5-c]pyridine [ka] A mixture of 7-bromothiadiazolo[4,5-c]pyridine (0.9 g, 4.16 mmol), 1,5-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazole (1.46 g, 6.24 mmol) and sodium carbonate (1.32 g, 12.5 mmol) in 1,4 dioxane (9 mL) and water (2 mL) was degassed with nitrogen for 5 minutes. To this solution, XPhos-Pd-G2 (0.16 g, 0.20 mmol, CAS [1310584-14-5]) was added and the reaction mixture was heated to 80° C. for 12 h. The reaction mass was then diluted with water and extracted twice with ethyl acetate. The combined organic layers were washed with water, brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude residue obtained was purified by trituration with pentane to give 7-(1,5-dimethylpyrazol-4-yl)thiadiazolo[4,5-c]pyridine. 1 H NMR (400MHz, DMSO-d6) δ ppm 9.98 (s, 1H), 8.76 (s, 1H), 7.79 (s, 1H), 3.87 (s, 3H), 2.40 (s, 3H). LC-MS (Method D): Retention time 0.88 min, 232(M+H).

[0398] Step F: Preparation of 7-(1,5-dimethylpyrazol-4-yl)-4,5,6,7-tetrahydrothiadiazolo[4,5-c]pyridine [ka] A solution of 7-(1,5-dimethylpyrazol-4-yl)thiadiazolo[4,5-c]pyridine (0.17 g, 0.73 mmol) in methanol (11 mL) was treated with sodium cyanoborohydride (0.48 g, 7.35 mmol) and hydrochloric acid (1.25 M in ethanol, 7.35 mL, 9.19 mmol) was added at room temperature. The resulting reaction mixture was stirred at room temperature for 12 hours. The reaction was monitored by TLC and LC-MS and, once complete, was concentrated in vacuum to give crude 7-(1,5-dimethylpyrazol-4-yl)-4,5,6,7-tetrahydrothiadiazolo[4,5-c]pyridine (0.21 g). The crude compound was used directly in the next step. LC-MS (Method D): Retention time 0.17 min, 236(M+H).

[0399] Step G: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-(1,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thiadiazolo[4,5-c]pyridin-5-yl]methanone (compound P-27, Table T1) [ka] (Compound P-27, Table T1) To a solution of 5-(2,4-difluorophenyl)isoxazole-3-carboxylic acid (0.17 g, 0.75 mmol) in acetonitrile (5 mL / mmol) was added N,N-diisopropylethylamine (0.66 mL, 3.77 mmol) followed by 1-propanephosphonic anhydride (1.12 mL, 1.88 mmol). The resulting solution was stirred under nitrogen atmosphere for 5 minutes and the resulting reaction mass was then transferred to another reaction flask containing 7-(1,5-dimethylpyrazol-4-yl)-4,5,6,7-tetrahydrothiadiazolo[4,5-c]pyridine (0.21 g, 0.90 mmol) dissolved in 1 mL of acetonitrile. The reaction mixture was stirred overnight at room temperature (monitored by TLC and LC-MS). After completion, the reaction mixture was diluted with water and extracted with ethyl acetate (3 times) and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated in reduced pressure. The crude residue obtained was purified by silica gel chromatography (eluting with cyclohexane / ethyl acetate) to give [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-(1,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thiadiazolo[4,5-c]pyridin-5-yl]methanone as a solid. LC-MS (Method D): Retention time 1.08 min, 443.2 (M+H). Melting point: 98℃~100℃.

[0400] Example 7: Preparation of [4-(1,5-dimethylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]-[5-(4-fluorophenyl)isoxazol-3-yl]methanone (compound P-30, Table T1) [ka] (Compound P-30, Table T1)

[0401] Step A: Preparation of methyl 4-bromothieno[2,3-c]pyridine-2-carboxylate [ka] To a stirred solution of 3,5-dibromopyridine-4-carbaldehyde (1.15 g, 4.12 mmol) in N,N-dimethylacetamide (17.3 mL) cooled to 0° C., potassium carbonate (0.62 g, 4.54 mmol) and methyl 2-sulfanylacetate (0.46 g, 4.33 mmol) were added under nitrogen atmosphere. After 30 min, the reaction mixture turned yellowish in color and the resulting solution was stirred at room temperature and monitored by LC-MS. After the reaction was complete, the mixture was diluted with water (20 mL) and then extracted with ethyl acetate (3 times). The combined organic phases were dried over sodium sulfate and concentrated in vacuum. The crude residue obtained was purified by silica gel chromatography (eluted with cyclohexane / ethyl acetate) to give methyl 4-bromothieno[2,3-c]pyridine-2-carboxylate as a white solid. 1 H NMR (400 MHz, CDCl 3 )δ=9.10(s,1H),8.67(s,1H),8.18(s,1H),4.03(s,3H). LC-MS (Method E): Retention time 1.47 min, 272(M+H).

[0402] Step B: Preparation of 4-bromothieno[2,3-c]pyridine [ka] To a solution of methyl 4-bromothieno[2,3-c]pyridine-2-carboxylate (2.4 g, 8.40 mmol) in 1-methyl-2-pyrrolidinone (42 mL) was added piperazine (3.6 g, 42 mmol) and the mixture was stirred at 160° C. while monitoring the progress of the reaction by LC-MS. After completion, the reaction mass was cooled to room temperature and the reaction mixture was carefully diluted with water and extracted with ethyl acetate (3 times). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuum. The crude residue obtained was purified by silica gel chromatography (cyclohexane / ethyl acetate) to give 4-bromothieno[2,3-c]pyridine (1.5 g, 6.7 mmol) as a solid. 1 H NMR (400 MHz, CDCl 3 )δ=9.08(s,1H),8.61(s,1H),7.83(d,J=5.5Hz,1H),7.53(dd,J=0.7,5.4Hz,1H). LC-MS (Method E): Retention time 1.29 min, 214(M+H).

[0403] Step C: Preparation of 4-(1,5-dimethylpyrazol-4-yl)thieno[2,3-c]pyridine [ka] To a degassed mixture of 4-bromothieno[2,3-c]pyridine (0.50 g, 2.34 mmol), 1,5-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazole (1.04 g, 4.67 mmol) and potassium carbonate (0.71 g, 5.13 mmol) in toluene (5.6 mL) and methanol (0.58 mL) in a microwave vial, tetrakis(triphenylphosphaniumyl)palladium (0.13 g, 0.12 mmol) was added and the mixture was then heated to 120° C. After completion of the reaction, the reaction mass was diluted with water and extracted with ethyl acetate (3 times). The combined organic layers were dried over sodium sulfate and concentrated in reduced pressure. The crude residue was purified by silica gel chromatography (elution with cyclohexane / ethyl acetate) to afford 4-(1,5-dimethylpyrazol-4-yl)thieno[2,3-c]pyridine as a white solid. 1 H NMR (400 MHz, CDCl 3 )δ ppm 9.10(s,1H),8.36(s,1H),7.72(d,J=5.50Hz,1H),7.64(s,1H),7.39(d,J=5.38Hz,1H),3.92(s,3H),2.32(s,3H). LC-MS (Method D): Retention time 0.2 min, 230 (M+H).

[0404] Step D: Preparation of 4-(1,5-dimethylpyrazol-4-yl)-4,5,6,7-tetrahydrothieno[2,3-c]pyridin-6-ium chloride [ka] A sample of 4-(1,5-dimethylpyrazol-4-yl)thieno[2,3-c]pyridine (0.11 g, 0.47 mmol) and chlorobis(cyclooctene)iridium(I) dimer (0.043 g, 0.047 mmol) in a microwave vial under nitrogen atmosphere was treated with diethylsilane (0.93 mL, 7.02 mmol) and the mixture was heated to 55° C. under microwave irradiation for 2 h. The reaction mixture was cooled and then diluted with 1,4-dioxane (1.2 mL). This mixture was transferred to a reaction flask under nitrogen atmosphere and then 4 M hydrochloric acid in 1,4-dioxane (2.26 mL) was added slowly dropwise (an exotherm was observed accompanied by gas evolution). The solution was stirred for 1 h and the solvent was removed in vacuo to give 4-(1,5-dimethylpyrazol-4-yl)-4,5,6,7-tetrahydrothieno[2,3-c]pyridin-6-ium; chloride, which was used in the next step without further purification.

[0405] Step E: Preparation of [4-(1,5-dimethylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]-[5-(4-fluorophenyl)isoxazol-3-yl]methanone (compound P-30, Table T1) [ka] (Compound P-30, Table T1) To a two-necked round-bottom flask containing 4-(1,5-dimethylpyrazol-4-yl)-4,5,6,7-tetrahydrothieno[2,3-c]pyridine (0.064 g, 0.27 mmol) dissolved in acetonitrile (1.15 mL) under argon atmosphere was added 5-(4-fluorophenyl)isoxazole-3-carboxylic acid (0.05 g, 0.23 mmol), followed by 1-propanephosphonic anhydride (0.34 mL, 0.57 mmol) and N,N-diisopropylethylamine (0.2 mL, 1.12 mmol). The solution was stirred overnight at room temperature, then the reaction mixture was diluted with water and extracted with ethyl acetate (3 times). The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated in vacuo. The crude product was purified by silica gel chromatography (eluting with cyclohexane / ethyl acetate) to give [4-(1,5-dimethylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]-[5-(4-fluorophenyl)isoxazol-3-yl]methanone as a gummy mass. LC-MS (Method E): Retention time 1.50 min, 423(M+H).

[0406] Example 8: Preparation of [5-(2,4-difluorophenyl)-1,3,4-thiadiazol-2-yl]-[4-(1,5-dimethylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]methanone (compound P-25, Table T1) [ka] (Compound P-25, Table T1) To a solution of ethyl 5-(2,4-difluorophenyl)-1,3,4-thiadiazole-2-carboxylate (0.10 g, 0.33 mmol, prepared as described in OPRD, 2020, 24, 228-234) in toluene (1 mL), 4-(1,5-dimethylpyrazol-4-yl)-4,5,6,7-tetrahydrothieno[2,3-c]pyridin-6-ium; chloride (0.10 g, 0.39 mmol, prepared as described in Example 7) was added, followed by bis(trimethylaluminum)-1,4-diazabicyclo[2.2.2]octane adduct (0.13 g, 0.49 mmol) at 0° C. The resulting mixture was heated to 70° C. under microwave irradiation for 3 h. The reaction was not complete after this time, therefore, an additional portion of bis(trimethylaluminum)-1,4-diazabicyclo[2.2.2]octane adduct (0.10 g, 0.39 mmol) was added and the reaction mixture was heated to 70° C. under microwave irradiation until the reaction was complete. The reaction mixture was cooled to 0° C., quenched with water, and extracted with ethyl acetate (3 times). The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated in vacuo. The crude product was purified by chromatography on silica gel eluting with cyclohexane / ethyl acetate to give [5-(2,4-difluorophenyl)-1,3,4-thiadiazol-2-yl]-[4-(1,5-dimethylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]methanone as a pale yellow solid. LC-MS (Method E): Retention time 1.44 min, 458.1 (M+H). Melting point: 169~171℃.

[0407] Example 9: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-(1,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thiazolo[4,5-c]pyridin-5-yl]methanone (compound P-28, Table T1) [ka] (Compound P-28, Table T1)

[0408] Step A: Preparation of 7-bromothiazolo[4,5-c]pyridine [ka] A solution of 3-amino-5-bromo-pyridine-4-thiol (1.5 g, 4.40 mmol, prepared as described in Example 6) in formic acid (12 mL) was treated with zinc (0.14 g, 2.20 mmol) and the reaction mixture was heated to 100° C. After the reaction was complete, it was concentrated in vacuo and the crude product was purified by silica gel chromatography (eluting with cyclohexane / ethyl acetate) to give 7-bromothiazolo[4,5-c]pyridine. 1 H NMR (400MHz, DMSO-d6) δ ppm 9.60 (s, 1H), 9.35 (s, 1H), 8.70 (s, 1H). LC-MS (Method E): Retention time 1.09 min, 214.8 (M+H).

[0409] Step B: Preparation of 7-(1,5-dimethylpyrazol-4-yl)thiazolo[4,5-c]pyridine [ka] A mixture of 7-bromothiazolo[4,5-c]pyridine (1.0 g, 4.64 mmol) and 1,5-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrazole (1.63 g, 6.97 mmol) in 1,4 dioxane (10 mL) and water (2 mL) was degassed with nitrogen for 15 min, followed by the addition of sodium carbonate (1.47 g, 13.9 mmol) and XPhos-Pd-G2 (0.18 g, 0.23 mmol, CAS [1310584-14-5]). The reaction mixture was heated to 80° C. for 12 h, then diluted with water and extracted with ethyl acetate (3 times). The combined organic layers were washed with water, brine, dried over sodium sulfate, filtered and concentrated in vacuo. The crude product was purified by washing with pentane to give 7-(1,5-dimethylpyrazol-4-yl)thiazolo[4,5-c]pyridine as a solid. 1H NMR (400MHz, DMSO-d6) δ ppm 9.57 (s, 1H), 9.29 (s, 1H), 8.49 (s, 1H), 7.75 (s, 1H), 3.86 (s, 3H), 2.36 (s, 3H). LC-MS (Method D): Retention time 0.17 min, 231.1 (M+H).

[0410] Step C: Preparation of 7-(1,5-dimethylpyrazol-4-yl)-4,5,6,7-tetrahydrothiazolo[4,5-c]pyridinium chloride [ka] To a solution of 7-(1,5-dimethylpyrazol-4-yl)thiazolo[4,5-c]pyridine (0.25 g, 1.08 mmol) in methanol (16 mL) was added sodium cyanoborohydride (0.71 g, 10.8 mmol) and hydrochloric acid (1.25 M in ethanol, 10.8 mL) at room temperature. The reaction mixture was stirred at room temperature for 12 hours. The reaction mixture was concentrated in vacuo to give the crude title compound, which was used in the next step without further purification. LC-MS (Method D): Retention time 0.20 min, 235.2 (M+H).

[0411] Step D: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-(1,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thiazolo[4,5-c]pyridin-5-yl]methanone (compound P-28, Table T1) [ka] (Compound P-28, Table T1) To 5-(2,4-difluorophenyl)isoxazole-3-carboxylic acid (0.25 g, 1.11 mmol) and 7-(1,5-dimethylpyrazol-4-yl)-4,5,6,7-tetrahydrothiazolo[4,5-c]pyridine (0.31 g, 1.33 mmol) in acetonitrile (5.5 mL) was added 1-propanephosphonic anhydride solution (1.65 mL, 2.77 mmol, T3P 50% in ethyl acetate) and N,N-diisopropylethylamine (0.97 mL, 5.55 mmol). The reaction mixture was stirred at room temperature for 12 hours. The reaction was monitored by TLC and LC-MS. After completion, the reaction mixture was diluted with water and extracted with ethyl acetate, the organic layer was washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The crude residue obtained was purified by silica gel chromatography (cyclohexane / ethyl acetate) to give [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-(1,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thiazolo[4,5-c]pyridin-5-yl]methanone (0.045 g, 0.096 mmol). LC-MS (Method D): Retention time 1.07 min, 442.2 (M+H).

[0412] Example 10: Preparation of [5-(2,4-difluorophenyl)-1,3,4-thiadiazol-2-yl]-[4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]methanone (compound P-24, Table T1) [ka] (Compound P-24, Table T1)

[0413] Step A: Preparation of 4-(1-methylpyrazol-4-yl)thieno[2,3-c]pyridine [ka] A microwave vial containing a stirred solution of 4-bromothieno[2,3-c]pyridine (0.47 g, 2.19 mmol, prepared as described in Example 7), 1-methyl-1H-pyrazole-4-boronic acid (0.42 g, 3.29 mmol) and sodium carbonate (0.69 g, 6.58 mmol) in 1,4-dioxane (4.7 mL) and water (4.3 mL) was degassed with nitrogen for 5 minutes. To this solution was added chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2'-amino-1,1'-biphenyl)]palladium(II) (0.088 g, 0.10 mmol) and the mixture was heated to 120° C. under microwave irradiation. The reaction mixture was quenched with ammonium chloride solution, diluted with water and extracted twice with ethyl acetate. The combined organic layers were washed with water, brine, dried over anhydrous sodium sulfate and concentrated in vacuo. The product was purified by silica gel chromatography (eluted with cyclohexane / ethyl acetate) to give 4-(1-methylpyrazol-4-yl)thieno[2,3-c]pyridine as a solid. 1 H NMR (400 MHz, chloroform-d); δ = 8.99 (s, 1H), 8.44 (s, 1H), 7.78 (s, 1H), 7.67-7.70 (m, 1H), 7.64-7.66 (m, 1H), 7.53 (d, J = 5.50 Hz, 1H), 3.96 (s, 3H). LC-MS (Method D): Retention time 0.26 min, 216.1 (M+H).

[0414] Step B: Preparation of 4-(1-methylpyrazol-4-yl)-4,5,6,7-tetrahydrothieno[2,3-c]pyridin-6-ium chloride [ka] In a microwave vial, 4-(1-methylpyrazol-4-yl)thieno[2,3-c]pyridine (0.1 g, 0.46 mmol), chlorobis(cyclooctane)iridium(I) dimer (0.42 g, 0.046 mmol) and diethylsilane (0.91 mL, 6.967 mmol) were added under nitrogen atmosphere. The reaction mass was heated to 58° C. under microwave irradiation for 2 hours. The reaction mass was diluted with 1,4-dioxane (1 mL) and then transferred to a round bottom flask under nitrogen atmosphere, then hydrochloric acid (4 mol / L) in 1,4-dioxane (2 mL, 8 mmol) was slowly added dropwise and the mixture was stirred for 1 hour. The volatiles were then removed in vacuo to give crude 4-(1-methylpyrazol-4-yl)-4,5,6,7-tetrahydrothieno[2,3-c]pyridin-6-ium chloride, which was used directly in the next step. LC-MS (Method E): Retention time 0.31 min, 220.1 (M+H).

[0415] Step C: Preparation of [5-(2,4-difluorophenyl)-1,3,4-thiadiazol-2-yl]-[4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]methanone (compound P-24, Table T1) [ka] (Compound P-24, Table T1) Ethyl 5-(2,4-difluorophenyl)-1,3,4-thiadiazole-2-carboxylate (0.10 g, 0.37 mmol) in toluene (1 mL) was treated with 4-(1-methylpyrazol-4-yl)-4,5,6,7-tetrahydrothieno[2,3-c]pyridin-6-ium chloride (0.12 g, 0.44 mmol) in a microwave vial and the resulting reaction mixture was cooled to 0° C. To this mixture was added (bis(trimethylaluminum)-1,4-diazabicyclo[2.2.2]octane (0.38 g, 1.48 mmol), and then the reaction mixture was subjected to microwave heating at 70° C. for 3 h. The reaction mixture was quenched with ice water and extracted with ethyl acetate (three times). The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, and concentrated in vacuo. The resulting crude product was purified by silica gel chromatography to give [5-(2,4-difluorophenyl)-1,3,4-thiadiazol-2-yl]-[4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl]methanone as a solid. LC-MS (Method E): Retention time 1.35 minutes, 444.1 (M+H). Melting point: 73~75℃.

[0416] Example 11: This example illustrates the preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-isothiazolo[5,4-c]pyridin-6-yl]methanone (compound P-26, Table T1). [ka] (Compound P-26, Table T1)

[0417] Step A: Preparation of 3-bromo-5-fluoro-pyridine-4-carbaldehyde [ka] To a solution of 3-bromo-5-fluoro-pyridine (12.0 g, 68.1 mmol) in tetrahydrofuran (120 mL) cooled to -78°C, lithium diisopropylamide (75 mL, 150 mmol) was added dropwise at -78°C (the reaction mixture turned brown), and the resulting reaction mixture was stirred at this temperature for 45 min. To the reaction mixture, ethyl formate (56 mL, 681 mmol) was added over 15 min, and the reaction mixture was stirred at -78°C for another 1.5 h. After the reaction was complete (monitored by TLC and GCMS), the reaction mixture was quenched with a saturated solution of ammonium chloride, and the resulting mixture was extracted with ethyl acetate (3 times). The combined organic layers were washed with brine, dried, and concentrated in vacuum to give a brown residue, which was subjected to combiflash chromatography using cyclohexane / ethyl acetate as eluent. This gave 3-bromo-5-fluoro-pyridine-4-carbaldehyde as a light yellow solid. 1 H NMR (400 MHz, CDCl 3 )δ ppm 10.35(s,1H),8.74(s,1H),8.60(s,1H).

[0418] Step B: Preparation of 3-bromo-5-tert-butylsulfanyl-pyridine-4-carbaldehyde [ka] A mixture of 3-bromo-5-fluoro-pyridine-4-carbaldehyde (6.8 g, 30 mmol), potassium carbonate (5.1 g, 36 mmol) and 2-methyl-2-propanethiol (3.0 mL, 30 mmol) in dry N,N-dimethylformamide (20 mL) was placed in a Teflon container and heated to 110° C. in a sealed test tube for 32 h. The reaction was cooled to room temperature, water was added and the mixture was extracted with ethyl acetate (3 times). The combined organic fractions were washed with water, dried over sodium sulfate, filtered and concentrated in vacuo to give the crude title compound, which was purified using combiflash chromatography using ethyl acetate / cyclohexane as eluent to give 3-bromo-5-tert-butylsulfanyl-pyridine-4-carbaldehyde as a yellow oil. 1 H NMR (400 MHz, CDCl 3 )δ ppm 10.5(s,1H),8.85(s,1H),8.73(s,1H),1.34(s,9H).

[0419] Step C: Preparation of 4-bromoisothiazolo[5,4-c]pyridine [ka] A mixture of 3-bromo-5-tert-butylsulfanyl-pyridine-4-carbaldehyde (3.8 g, 12.0 mmol) and hydroxylamine hydrochloride (4.4 g, 62.0 mmol) in isopropanol (160 mL) and water (33 mL) was heated to 90° C. for 16 h. The reaction mixture was cooled and 2-propanol was removed in vacuum. Water was added to the residue followed by saturated aqueous sodium bicarbonate until the pH was about 8. The mixture was extracted with ethyl acetate (3 times) and the combined organic fractions were dried over sodium sulfate, filtered and concentrated in vacuum to give the crude title compound, which was used in the next step without further purification. The resulting crude oxime was then suspended in polyphosphoric acid (15 mL) and heated to 110° C. for 2 h. The reaction mixture was cooled to room temperature, extracted with ethyl acetate, dried over sodium sulfate and concentrated in vacuum. The crude residue was subjected to combiflash purification using ethyl acetate / cyclohexane as eluent to give pure 4-bromoisothiazolo[5,4-c]pyridine as a white solid. 1 H NMR (400 MHz, CDCl 3 )δ ppm 9.29(s,1H),9.09(d,J=0.61Hz,1H),8.69(s,1H). LC-MS (Method D): Retention time 0.98 min, 215(M+H).

[0420] Step D: Preparation of 4-(1-methylpyrazol-4-yl)isothiazolo[5,4-c]pyridine [ka] A microwave vial was charged with 4-bromoisothiazolo[5,4-c]pyridine (0.17 g, 0.79 mmol), 1-methyl-1H-pyrazole-4-boronic acid (0.15 g, 1.18 mmol), sodium carbonate (0.25 g, 2.37 mmol), 1,4-dioxane (1.7 mL) and water (1.6 mL). The reaction mixture was degassed with nitrogen for 5.0 min, then XPhos-Pd-G2 (0.031 g, 0.039 mmol) was added and the mixture was heated to 120° C. under microwave irradiation for 2 h. After the reaction was completed (monitored by TLC and LC-MS), the reaction mixture was filtered through Celite, washed with ethyl acetate, and the filtrate was concentrated in vacuo to give a brown residue, which was purified by combiflash using an ethyl acetate / cyclohexane eluent system to give pure 4-(1-methylpyrazol-4-yl)isothiazolo[5,4-c]pyridine as a white solid. 1 H NMR (400 MHz, CDCl 3 )δ ppm 9.26(s,1H),9.19(s,1H),8.62(s,1H),7.92(s,1H),7.81(s,1H),4.07(s,3H). LC-MS (Method D): Retention time 0.55 min; 217.1 (M+H).

[0421] Step E: Preparation of 4-(1-methylpyrazol-4-yl)-4,5,6,7-tetrahydroisothiazolo[5,4-c]pyridine [ka] A round bottom flask equipped with a magnetic stir bar was charged with 4-(1-methylpyrazol-4-yl)isothiazolo[5,4-c]pyridine (0.15 g, 0.69 mmol) and methanol (10.4 mL) to obtain a clear solution. To this solution, sodium cyanoborohydride (0.45 g, 6.93 mmol) was added in portions at 0° C. Then, methanolic hydrochloric acid (6.9 mL, 20.8 mmol, 3 mol / L) was added dropwise at room temperature (gas evolution was observed) and the mixture was stirred at room temperature overnight. After the reaction was complete (monitored by TLC and LC-MS), the reaction mixture was stirred with basic resin until the solution was basic by pH paper. The mixture was filtered, washed with methanol, and the clear solution was concentrated to give crude 4-(1-methylpyrazol-4-yl)-4,5,6,7-tetrahydroisothiazolo[5,4-c]pyridine (0.1 g, 0.43 mmol) as a brownish-yellow residue. 1 H NMR(400MHz,DMSO-d6)δ ppm 8.17(s,1H),7.48(s,1H),7.29(s,1H),4.08(br d,J=2.9Hz,2H),3.92-4.24(m,1H),3.77(s,3H),3.75(s,1H),3.12(br dd,J=12.9,5.2Hz,1H),2.73(dd,J=12.9,7.2Hz,1H). LC-MS (Method D): Retention time 0.19 min; 221.1 (M+H).

[0422] Step F: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-isothiazolo[5,4-c]pyridin-6-yl]methanone (compound P-26, Table T1) A solution of 5-(2,4-difluorophenyl)isoxazole-3-carboxylic acid (0.09 g, 0.40 mmol) in ethyl acetate (1.7 mL) was treated with N,N-diisopropylethylamine (0.13 mL, 0.73 mmol) under stirring. To this reaction mixture was added 4-(1-methylpyrazol-4-yl)-4,5,6,7-tetrahydroisothiazolo[5,4-c]pyridine (0.085 g, 0.36 mmol) followed by 1-propanephosphonic anhydride (50% by weight) in ethyl acetate (0.65 mL, 1.1 mmol) and the reaction mixture was stirred at room temperature overnight. After the reaction was complete (monitored by TLC and LC-MS), the reaction mixture was diluted with NaHCO 3 The mixture was quenched with ethyl acetate (3 times). The combined organic layers were dried over sodium sulfate and concentrated in vacuo. The crude material was purified by reverse-phase combiflash using an acetonitrile / water eluent system to give [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-(1-methylpyrazol-4-yl)-5,7-dihydro-4H-isothiazolo[5,4-c]pyridin-6-yl]methanone as a white solid. LC-MS (Method D): Retention time 1.07 minutes; 428.2 (M+H).

[0423] Example 12: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-(1-methylpyrazol-4-yl)-6,7-dihydro-4H-isothiazolo[4,5-c]pyridin-5-yl]methanone (compound P-23, Table T1) [ka] (Compound P-23, Table T1)

[0424] Step A: Preparation of 4,5-dibromopyridine-3-carboxylic acid [ka] To a cooled (-70°C) solution of 5-bromopyridine-3-carboxylic acid (12.6 g, 59.3 mmol) in tetrahydrofuran (126 mL) under nitrogen atmosphere was added lithium diisopropylamide (72 mL, 140 mmol, 2.0 mol / L) dropwise over 1 h. The solution was stirred at -55°C for 2.5 h. The mixture was then cooled to -70°C and treated with 1,2-dibromotetrachloroethane (24.9 g, 74.1 mmol) in portions over 30 min. After 1 h, the reaction mixture was allowed to warm to -20°C over 2 h and then water (75 mL) was added slowly. The organic layer was then concentrated in vacuo and the aqueous residue was diluted with water (250 mL) and then washed with ethyl acetate. The aqueous layer was then acidified to pH 3 by the addition of concentrated hydrochloric acid. The precipitated solid was collected by filtration and dried in vacuum at 60° C. to give 4,5-dibromopyridine-3-carboxylic acid as an off-white to light brown solid. 1 H NMR (400MHz, DMSO-d6) δ ppm 8.91 (s, 1H), 8.73 (s, 1H). LC-MS (Method D): Retention time 0.23 min, 280.0 (M+H).

[0425] Step B: Preparation of 4,5-dibromo-N-methoxy-N-methyl-pyridine-3-carboxamide [ka] A solution of 4,5-dibromopyridine-3-carboxylic acid (10 g, 35.6 mmol) in ethyl acetate (200 mL) was treated with N,N-diisopropylethylamine (18.8 mL, 106 mmol) under stirring. To this reaction mixture was added methoxy(methyl)ammonium chloride (5.21 g, 53.4 mmol) followed by 1-propanephosphonic anhydride (50 wt%) in ethyl acetate (200 mL, 106 mmol) and the reaction mixture was stirred at room temperature overnight. After the reaction was complete (monitored by TLC and LC-MS), the reaction mixture was diluted with NaHCO 3and extracted with ethyl acetate (3 times). The combined organic layers were dried over sodium sulfate and concentrated in vacuo. The crude material was purified by combiflash using (ethyl acetate / cyclohexane) as the eluent system to give 4,5-dibromo-N-methoxy-N-methyl-pyridine-3-carboxamide as a gummy mass. 1 H NMR (400 MHz, CDCl 3 )δ ppm 8.73(s,1H),8.38(s,1H)3.50(s,3H)3.40(s,3H). LC-MS (Method D): Retention time 0.97 min, 322.9 (M+H).

[0426] Step C: Preparation of 5-bromo-4-tert-butylsulfanyl-N-methoxy-N-methyl-pyridine-3-carboxamide [ka] In a 50 mL Teflon vessel, 4,5-dibromo-N-methoxy-N-methyl-pyridine-3-carboxamide (10.1 g, 29.6 mmol) dissolved in dry N,N-dimethylformamide (30 mL) was added. To this solution, potassium carbonate (5.0 g, 35.8 mmol) was added under nitrogen atmosphere, followed by 2-methyl-2-propanethiol (3.0 mL, 29.6 mmol) and the reaction mixture was stirred at 130° C. for 20 hours. After the reaction was completed (monitored by TLC and LC-MS), the reaction mixture was cooled to room temperature, quenched with ice, and extracted with ethyl acetate (3 times). The combined organic layers were dried over sodium sulfate and concentrated in vacuo to give a brown residue which was purified by combiflash using (ethyl acetate / cyclohexane) as the eluent system to give 5-bromo-4-tert-butylsulfanyl-N-methoxy-N-methyl-pyridine-3-carboxamide as a brown gummy mass. 1 H NMR (400MHz, CDCl3) δ ppm 8.87 (s, 1H), 8.49 (s, 1H), 3.38 (s, 3H), 3.37 (s, 3H), 1.38 (s, 9H). LC-MS (Method F): Retention time 1.13 minutes, 276.9 (M-tBu).

[0427] Step D: Preparation of 5-bromo-4-tert-butylsulfanyl-pyridine-3-carbaldehyde [ka] To a solution of compound 5-bromo-4-tert-butylsulfanyl-N-methoxy-N-methyl-pyridine-3-carboxamide (3.05 g, 8.70 mmol) in toluene (122 mL) was added diisobutylaluminum hydride (1.0 mol / L) in toluene (9.6 mL, 9.57 mmol) at -50°C and stirred at room temperature for 1 h. After completion of the reaction (monitored by TLC and LC-MS), the mixture was quenched with cold water and extracted with ethyl acetate (3 times). The combined organic phases were washed with brine, dried over sodium sulfate and concentrated in vacuum. The crude aldehyde was purified by column chromatography using (ethyl acetate / cyclohexane) eluent system to give pure 5-bromo-4-tert-butylsulfanyl-pyridine-3-carbaldehyde as an amber oil. 1 H NMR (400MHz, CDCl3) δ ppm 10.72 (s, 1H), 9.06 (s, 1H), 9.01 (s, 1H), 1.37 (s, 9H). LC-MS (Method F): Retention time 1.04 min, 218 (M-tBu).

[0428] Step E: Preparation of 5-bromo-4-tert-butylsulfanyl-pyridine-3-carbaldehyde oxime [ka] A mixture of 5-bromo-4-tert-butylsulfanyl-pyridine-3-carbaldehyde (1.05 g, 3.64 mmol) and hydroxylamine hydrochloride (1.28 g, 18.2 mmol) in isopropanol (160 mL) and water (33 mL) was heated to 90° C. for 16 h. The reaction mixture was cooled and 2-propanol was removed in vacuo. Water was added to the residue followed by saturated aqueous sodium bicarbonate until the pH was about 8. The mixture was extracted with ethyl acetate (3 times) and the combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo to give crude 5-bromo-4-tert-butylsulfanyl-pyridine-3-carbaldehyde oxime as an off-white solid which was used without further purification. 1 H NMR (400MHz, CDCl3) δ ppm 9.07 (s, 1H), 8.83 (s, 2H), 1.36 (s, 9H). LC-MS (Method D): Retention time 1.19 minutes, 233.0 (M-tBu).

[0429] Step F: Preparation of 7-bromoisothiazolo[4,5-c]pyridine [ka] A 100 mL round bottom flask was charged with 5-bromo-4-tert-butylsulfanyl-pyridine-3-carbaldehyde oxime (1.09 g, 3.58 mmol) and p-toluenesulfonic acid (0.31 g, 1.79 mmol) in 1-butanol (17.9 mL) and heated to 90 °C overnight. After monitoring the reaction (by TLC and LC-MS), it was not complete, therefore additional p-toluenesulfonic acid (0.31 g, 1.79 mmol) was added and the mixture was stirred at 117 °C for 2 h. The reaction mixture was cooled to room temperature, diluted with water and extracted with ethyl acetate (3 times). The combined organic fractions were dried over sodium sulfate and concentrated in vacuum. The crude residue was subjected to combiflash purification using (ethyl acetate / cyclohexane) as the eluent system to give pure 7-bromoisothiazolo[4,5-c]pyridine as a white solid. 1H NMR (400MHz, CDCl3) δ ppm 9.35 (s, 1H), 9.18 (s, 1H), 8.67 (s, 1H). LC-MS (Method D): Retention time 1.1 min, 215(M+H).

[0430] Step G: Preparation of 7-(1-methylpyrazol-4-yl)isothiazolo[4,5-c]pyridine [ka] To a solution of 7-bromoisothiazolo[4,5-c]pyridine (0.2 g, 0.88 mmol) in tetrahydrofuran (2 mL) was added 1-methyl-1H-pyrazole-4-boronic acid (0.23 g, 1.76 mmol), followed by cesium fluoride (0.26 g, 1.76 mmol), and the mixture was degassed with argon for 10 min, after which bis(tri-tert-butylphosphine)palladium(0) (0.046 g, 0.09 mmol) was added. The mixture was placed in a microwave oven at 65° C. for 2 h, then cooled to room temperature and diluted with a saturated solution of ammonium chloride. The mixture was extracted with ethyl acetate (3 times) and the combined organic layers were washed with brine, dried over sodium sulfate, and concentrated in vacuo. The crude residue was purified by column chromatography using 10-50% ethyl acetate in cyclohexane to give pure 7-(1-methylpyrazol-4-yl)isothiazolo[4,5-c]pyridine as a white solid. 1 H NMR (400 MHz, CDCl 3 )δ ppm 9.29(s,1H),9.13(s,1H)8.73(s,1H),7.99(s,1H),7.85(s,1H),4.06(s,3H). LC-MS (Method D): Retention time 1.06 min, 217.1 (M+H).

[0431] Step H: Preparation of 7-(1-methylpyrazol-4-yl)-4,5,6,7-tetrahydroisothiazolo[4,5-c]pyridine [ka] A one-necked round bottom flask equipped with a magnetic stir bar was charged with 7-(1-methylpyrazol-4-yl)isothiazolo[4,5-c]pyridine (0.11 g, 0.48 mmol), methanol (7.25 mL) and sodium cyanoborohydride (0.32 g, 4.83 mmol). Hydrogen chloride solution (4.83 mL, 2 mmol, 0.5 mol / L) was then added dropwise at room temperature (gas evolution was observed) and the mixture was stirred at room temperature overnight. After the reaction was complete (monitored by TLC and LC-MS), the reaction mixture was quenched with water, stirred with basic resin, filtered and then concentrated to give a crude residue which was used as is without further purification. LC-MS (Method D): Retention time 0.23 min, 221.2 (M+H).

[0432] Step I: Preparation of [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-(1-methylpyrazol-4-yl)-6,7-dihydro-4H-isothiazolo[4,5-c]pyridin-5-yl]methanone (compound P-23, Table T1) A 100 mL round bottom flask was charged with 5-(2,4-difluorophenyl)isoxazole-3-carboxylic acid (0.12 g, 0.55 mmol) in ethyl acetate (2.2 mL), to which N,N-diisopropylethylamine (0.18 mL, 0.99 mmol) was added under stirring. To this reaction mixture was added 7-(1-methylpyrazol-4-yl)-4,5,6,7-tetrahydroisothiazolo[4,5-c]pyridine (0.11 g, 0.50 mmol) followed by 1-propanephosphonic anhydride (50% by weight) in ethyl acetate (0.88 mL 1.49 mmol, 50% by weight) and the reaction mixture was stirred at room temperature overnight. After the reaction was complete (monitored by TLC and LC-MS), the reaction mixture was diluted with NaHCO 3The crude material was purified by reversed-phase combiflash using an (acetonitrile / water) eluent system to give [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-(1-methylpyrazol-4-yl)-6,7-dihydro-4H-isothiazolo[4,5-c]pyridin-5-yl]methanone as an off-white to light brown solid. LC-MS (Method F): Retention time 1.03 min, 428.6 (M+H). Melting point: 63~65℃.

[0433] Further examples of compounds of formula (I) that have been synthesised are shown in Table T1.

[0434] [Table 8] JPEG2025503432000123.jpg249161 JPEG2025503432000124.jpg250170 JPEG2025503432000125.jpg250162 JPEG2025503432000126.jpg251167 JPEG2025503432000127.jpg251164 JPEG2025503432000128.jpg249164 JPEG2025503432000129.jpg250166 JPEG2025503432000130.jpg244170 JPEG2025503432000131.jpg248170 JPEG2025503432000132.jpg157170

[0435] Biological Examples Example B1: Alternaria solani / tomato / leaf disc (summer blight) Tomato leaf discs (cv. Baby) are placed on agar in multi-well plates (24-well type) and sprayed with the formulated test compounds diluted in water. The leaves are inoculated with a fungal spore suspension 2 days after application. The inoculated leaves are incubated in a climate cabinet under a 12 / 12 h (light / dark) light regime, 23°C / 21°C (day / night) and 80% relative humidity, and the efficacy of the compounds is evaluated as the percentage disease control compared to untreated leaf discs when an appropriate level of disease damage has developed on untreated leaf discs (5-7 days after application).

[0436] The following compounds provided at least 80% control of Alternaria solani at 200 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-2, P-3, P-4, P-6, P-8, P-10, P-12, P-14, P-15, P-18, P-19, P-20, P-23, P-24, P-25, P-26, P-27, P-28, P-29, P-30, P-31, P-32, P-33, P-34, P-35, P-36, P-37.

[0437] Example B2: Botryotinia fuckeliana (Botrytis cinerea) / liquid culture (grey mold) Fungal conidia stored at low temperature are mixed directly into nutrient liquid medium (Vogels liquid medium). A (DMSO) solution of the test compound is placed in a microtiter plate (96-well format) and then the nutrient liquid medium containing the fungal spores is added. The test plate is incubated at 24°C and the inhibition of growth is measured photometrically 3-4 days after application.

[0438] The following compounds provided at least 80% control of Botryotinia fuckeliana at 20 ppm when compared to untreated controls, which showed widespread disease development under identical conditions: P-2, P-3, P-6, P-7, P-8, P-10, P-12, P-14, P-15, P-18, P-19, P-20, P-22, P-24, P-25, P-26, P-29, P-30, P-31, P-32, P-33, P-34, P-35, P-36.

[0439] Example B3: Glomerella lagenarium (Colletotrichum lagenarium) / Liquid Culture (Anthracnose) Fungal conidia stored at low temperature are mixed directly into nutrient liquid medium (potato glucose liquid medium). A DMSO solution of the test compound is placed in a microtiter plate (96-well format) and then the nutrient liquid medium containing the fungal spores is added. The test plate is incubated at 24°C and the inhibition of growth is measured photometrically 3-4 days after application.

[0440] The following compounds provided at least 80% control of Glomerella lagenarium at 20 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-2, P-3, P-4, P-5, P-6, P-7, P-8, P-10, P-12, P-14, P-15, P-18, P-19, P-20, P-22, P -23, P-24, P-25, P-26, P-27, P-28, P-29, P-30, P-31, P-32, P-33, P-34, P-35, P-36.

[0441] Example B4: Blumeria graminis f.sp. tritici (Erysiphe graminis f.sp. tritici) / wheat / leaf disc preventative (powdery mildew in wheat) Wheat leaf segments (cv. Kanzler) are placed on agar in multi-well plates (24-well format) and sprayed with the formulated test compounds diluted in water. One day after application, the leaf segments are inoculated with powdery mildew infected plants by shaking them over the test plates. The inoculated leaf discs are incubated in a climate chamber under a light regime of 24 h darkness followed by 12 h light / 12 h darkness at 20° C. and 60% relative humidity, and compound efficacy is assessed as the percentage disease control compared to untreated when an appropriate level of disease damage appears on the untreated test leaf discs (6-8 days after application).

[0442] The following compounds provided at least 80% control of Blumeria graminis f.sp. tritici at 200 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-2, P-3, P-6, P-7, P-14, P-15, P-18, P-19, P-25, P-27, P-32, P-33, P-35.

[0443] Example B5: Fusarium culmorum / liquid culture (blight disease) Fungal conidia stored at low temperature are mixed directly into nutrient liquid medium (potato glucose liquid medium). A DMSO solution of the test compound is placed in a microtiter plate (96-well format) and then the nutrient liquid medium containing the fungal spores is added. The test plate is incubated at 24°C and the inhibition of growth is measured photometrically 3-4 days after application.

[0444] The following compounds provided at least 80% control of Fusarium culmorum at 20 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-2, P-3, P-6, P-7, P-10, P-14, P-15, P-18, P-24, P-25, P-32, P-33, P-34.

[0445] Example B6: Fusarium culmorum / wheat / spikelet prevention (blight) Wheat spikelets (cv. Monsun) are placed on agar in multi-well plates (24-well format) and sprayed with the formulated test compounds diluted in water. One day after application, the spikelets are inoculated with a fungal spore suspension. The inoculated spikelets are incubated in a climatic chamber under a photoperiod of 72 hours semi-darkness followed by 12 hours light / 12 hours darkness at 20°C and 60% relative humidity, and the activity of the compounds is evaluated as the percentage disease control compared to untreated when an appropriate level of disease damage appears on the untreated test spikelets (6-8 days after application).

[0446] The following compounds provided at least 80% control of Fusarium culmorum at 200 ppm compared to untreated controls exhibiting significant disease development under identical conditions: P-15, P-25.

[0447] Example B7: Gibberella zeae (Fusarium graminearum) / Wheat / Spikelet prevention (Blight) Wheat spikelets (cv. Monsun) are placed on agar in multi-well plates (24-well format) and sprayed with the formulated test compounds diluted in water. One day after application, the spikelets are inoculated with a fungal spore suspension. The inoculated test leaf discs are incubated in a climatic chamber under a light regime of 72 hours semi-darkness followed by 12 hours light / 12 hours darkness at 20°C and 60% relative humidity, and the activity of the compounds is evaluated as the percentage disease control compared to untreated when an appropriate level of disease damage appears on the untreated test spikelets (6-8 days after application).

[0448] The following compounds provided at least 80% control of Gibberella zeae at 200 ppm compared to untreated controls showing significant disease development under identical conditions: P-10, P-25.

[0449] Example B8: Phaeosphaeria nodorum (Septoria nodorum) / Wheat / Leaf disc preventive (Septoria nodorum) Wheat leaf segments (cv. Kanzler) are placed on agar in multi-well plates (24-well format) and sprayed with the formulated test compounds diluted in water. The leaves are inoculated with a fungal spore suspension 2 days after application. The inoculated test leaf segments are incubated in a climate cabinet under a 12-h light / 12-h dark light regime at 20°C and 75% relative humidity, and the efficacy of the compounds is evaluated as the percentage disease control compared to untreated when an appropriate level of disease damage appears on the untreated test leaf segments (5-7 days after application).

[0450] The following compounds provided at least 80% control of Phaeosphaeria nodorum at 200 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-2, P-3, P-4, P-6, P-10, P-12, P-14, P-15, P-18, P-19, P-20, P-22, P-24, P-25, P-26, P-27, P-28, P-29, P-30, P-31, P-32, P-33, P-34, P-35.

[0451] Example B9: Monographella nivalis (Microdochium nivale) / Liquid culture (root rot of cereals) Fungal conidia stored at low temperature are mixed directly into nutrient liquid medium (potato glucose liquid medium). A DMSO solution of the test compound is placed in a microtiter plate (96-well format) and then the nutrient liquid medium containing the fungal spores is added. The test plate is incubated at 24°C and the inhibition of growth is measured photometrically 4-5 days after application.

[0452] The following compounds provided at least 80% control of Monographella nivalis at 20 ppm when compared to untreated controls, which showed widespread disease development under identical conditions: P-1, P-2, P-3, P-4, P-6, P-7, P-8, P-9, P-10, P-12, P-22, P-23, P-24, P-25 , P-26, P-27, P-28, P-29, P-30, P-31, P-32, P-33, P-34, P-35, P-36, P-37.

[0453] Example B10: Mycosphaerella arachidis (Cercospora arachidicola) / liquid culture (early spot disease) Fungal conidia stored at low temperature are mixed directly into nutrient liquid medium (potato glucose liquid medium). A DMSO solution of the test compound is placed in a microtiter plate (96-well format) and then the nutrient liquid medium containing the fungal spores is added. The test plate is incubated at 24°C and the inhibition of growth is measured photometrically 4-5 days after application.

[0454] The following compounds provided at least 80% control of Mycosphaerella arachidis at 20 ppm when compared to untreated controls which showed extensive disease development under identical conditions: P-2, P-5, P-6, P-7, P-8, P-9, P-10, P-12, P-14, P-15, P-18, P-19, P-20, P-22, P-24, P-28, P-29, P-30, P-31, P-32, P-33, P-34, P-35, P-36, P-37.

[0455] Example B11: Magnaporthe grisea (Pyricularia oryzae) / Rice / Leaf-piece preventative (Rice blast) Rice leaf segments (cv. Ballila) are placed on agar in multi-well plates (24-well format) and sprayed with the formulated test compounds diluted in water. The leaf segments are inoculated with a fungal spore suspension 2 days after application. The inoculated leaf segments are incubated in a climate cabinet under a light regime of 24 h darkness followed by 12 h light / 12 h darkness at 22°C and 80% relative humidity, and the efficacy of the compounds is evaluated as the percentage disease control compared to the untreated when an appropriate level of disease damage appears on the untreated test leaf segments (5-7 days after application).

[0456] The following compounds provided at least 80% control of Magnaporthe grisea at 200 ppm when compared to untreated controls, which showed extensive disease development under identical conditions: P-19, P-30.

[0457] Example B12: Pyrenophora teres / barley / leaf disc preventative (net blotch) Barley leaf segments (cv. Hasso) are placed on agar in multi-well plates (24-well format) and sprayed with the formulated test compounds diluted in water. The leaf segments are inoculated with a fungal spore suspension 2 days after application. The inoculated leaf segments are incubated in a climate cabinet under a 12-h light / 12-h dark light regime at 20°C and 65% relative humidity, and the efficacy of the compound is assessed as disease control compared to untreated when an appropriate level of disease damage appears on the untreated test leaf segments (5-7 days after application).

[0458] The following compounds provided at least 80% control of Pyrenophora teres at 200 ppm when compared to untreated controls, which showed widespread disease development under identical conditions: P-2, P-3, P-4, P-6, P-8, P-14, P-15, P-18, P-19, P-22, P-24, P-25, P-27, P-28, P-30, P-31, P-32, P-33, P-34, P-35, P-36.

[0459] Example B13: Thanatephorus cucumeris (Rhizoctonia solani) / Liquid culture (root rot, damping-off) Mycelium fragments from freshly cultured liquid fungi are mixed directly into nutrient broth (potato glucose broth). DMSO solutions of the test compounds are placed in microtiter plates (96-well format) and then the nutrient broth containing the fungal material is added. The test plates are incubated at 24°C and the inhibition of growth is measured photometrically 3-4 days after application.

[0460] The following compounds provided at least 80% control of Thanatephorus cucumeris at 20 ppm when compared to untreated controls which showed widespread disease development under identical conditions: P-9.

[0461] Example B14: Sclerotinia sclerotiorum / liquid culture (sclerotinia rot) Mycelium fragments from freshly grown liquid cultures of the fungus are mixed directly into the nutrient broth (potato glucose broth). A DMSO solution of the test compound is placed in a microtiter plate (96-well format) and then the nutrient broth containing the fungal material is added. The test plates are incubated at 24°C and the inhibition of growth is measured photometrically 3-4 days after application.

[0462] The following compounds provided at least 80% control of Sclerotinia sclerotiorum at 20 ppm when compared to untreated controls, which showed widespread disease development under identical conditions: P-2, P-3, P-6, P-7, P-10, P-12, P-14, P-18, P-19, P-24, P-25, P-30, P-32, P-33, P-34, P-35.

[0463] Example B15: Wheat leaf spot fungus (Mycosphaerella graminicola) (Septoria tritici) / liquid culture (leaf spot) Fungal conidia stored at low temperature are mixed directly into nutrient liquid medium (potato glucose liquid medium). A DMSO solution of the test compound is placed in a microtiter plate (96-well format) and then the nutrient liquid medium containing the fungal spores is added. The test plate is incubated at 24°C and the inhibition of growth is measured photometrically 4-5 days after application.

[0464] The following compounds provided at least 80% control of Mycosphaerella graminicola at 20 ppm when compared to untreated controls that showed widespread disease development under identical conditions: P-1, P-2, P-3, P-4, P-6, P-7, P-8, P-9, P-10, P-12, P-14, P-15, P-16, P-18, P-19, P-20, P-22 , P-23, P-24, P-25, P-26, P-27, P-28, P-29, P-30, P-31, P-32, P-33, P-34, P-35, P-36, P-37.

Claims

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

2. R 1 The compound of formula (I) according to claim 1, wherein is methyl, ethyl or isopropyl.

3. R 2 2. The compound of formula (I) according to claim 1, wherein is selected from the group consisting of hydrogen, fluorine, chlorine and methyl.

4. R 3 2. The compound of formula (I) according to claim 1, wherein is selected from the group consisting of hydrogen, fluorine, chlorine, methyl and ethyl.

5. R 4 2. The compound of formula (I) according to claim 1, wherein is selected from the group consisting of hydrogen, fluorine, chlorine, methyl and ethyl.

6. R 5 and R 6 is independently selected from the group consisting of hydrogen, methyl and ethyl.

7. R 7 is hydrogen, methyl, acetyl, -C(CH 3 ) = NOCH 3 , -C(CH 3 ) = NOCH 2 CH 3 , -C(CH 3 2. The compound of formula (I) according to claim 1, wherein N-(N-methyl-N-methyl)=NOH, methoxycarbonyl, ethoxycarbonyl, N-methoxy-N-methyl-carbonyl, phenyl and cyclopropyl.

8. X 1 is S, and X 2 and X 3 is CR 8 and N, or X 2 is S, and X 1 and X 3 is CR 8 and N, or X 3 is S, and X 1 and X 2 is CR 8 and N, Here, R 8 The compound of formula (I) according to claim 1, wherein is selected from the group consisting of hydrogen, chlorine, bromine, methyl and ethyl.

9. A 1 , A 2 and A 3 is CR 9 , N, O and S, with the proviso that A 1 , A 2 and A 3 is selected from N, O and S, and A 1 , A 2 and A 3 2. The compound of formula (I) according to claim 1, wherein not more than one of is O or S.

10. Z 1 is selected from the group consisting of methyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methylphenyl, 2-fluorophenyl, 4-fluorophenyl, 3-chlorophenyl, 4-fluoro-2-methoxy-phenyl, 2,4-difluorophenyl, 3,4-difluorophenyl, 2,4,6-trifluorophenyl, 3,5-difluoro-2-pyridyl, 2-furyl, 2-thienyl, 3-thienyl and 1-methylpyrazol-4-yl.

11. An intermediate compound of formula (III) or a salt thereof 【Chemistry 2】 (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X 1 , X 2 and X 3 corresponds to the same definition as for the compounds of formula (I) according to any one of claims 1 to 10).

12. An agrochemical composition comprising a fungicidally effective amount of a compound of formula (I) according to any one of claims 1 to 10.

13. 13. The composition of claim 12, further comprising at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

14. A method for controlling or preventing infestation of useful plants by phytopathogenic microorganisms, which comprises applying a fungicidally effective amount of a compound of formula (I) according to any one of claims 1 to 10 or a composition comprising said compound of formula (I) to said plants, parts thereof or their habitats.

15. Use of a compound according to any one of claims 1 to 10 as a bactericide / fungicide.

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