Microbiotoxic heterobicyclic dihydrooxadiazine derivatives

Abstract

A pesticidal agent, particularly useful as a fungicide, of formula (I) JPEG2026515252000131.jpg39150(wherein Q a or Q b is N and the other is C, Q c is N or CH, Q 7 , Q 8 and Q 9 one or two of are N and one or more others are each CR 7 , CR 8 and CR 9 and the other substituents are as defined in claim 1) compounds.

Description

Technical Field

[0001] The present invention relates to unsaturated N-bridged bicyclic heterocyclic derivatives as active ingredients having microbicidal activity, particularly fungicidal activity. The present invention also relates to pesticidal compositions containing at least one of 5,6-dihydro-4H-1,2,4-oxadiazine derivatives, processes for preparing these compounds, and the use of 5,6-dihydro-4H-1,2,4-oxadiazine derivatives or compositions in agriculture or horticulture for controlling or preventing the ectoparasitism of plants, harvested food crops, seeds or abiotic materials by phytopathogenic microorganisms, preferably fungi.

Background Art

[0002] Many plant protection compounds have been developed to prevent or reduce plant diseases caused by microorganisms, such as fungi. For example, WO 2020 / 127780 discloses azabicyclic (thio)amides as fungicidal compounds, and WO 2021 / 249995 discloses azabicyclic-substituted heterocycles as fungicides. The azabicyclic compounds disclosed therein are C-bridged, and the monocyclic compounds are different isomers.

Summary of the Invention

[0003] Thus, in a first aspect, the present invention provides a compound of formula (I)

Chemical formula

[0004] The present invention also provides a method for preparing a compound of formula (I) and an intermediate compound useful for preparing the compound of formula (I).

[0005] Surprisingly, the novel compound of formula (I) was found to possess a highly advantageous level of biological activity for protecting plants from fungal diseases for practical purposes.

[0006] According to a second aspect of the present invention, a pesticide composition is provided comprising a fungicidal amount of a compound of formula (I). Such an agricultural composition may further comprise at least one additional active ingredient and / or an agriculturally acceptable diluent or carrier.

[0007] A third aspect of the present invention provides a method for controlling or preventing ectoparasitism of useful plants by plant pathogenic microorganisms, wherein a fungicidal amount of a compound of formula (I) or a composition containing this compound as an active ingredient is applied to a plant, a part thereof, or its habitat.

[0008] According to a fourth aspect of the present invention, the use of a compound of formula (I) as a fungicide is provided. According to this particular aspect of the present invention, this use does not have to involve methods relating to the treatment of the human or animal body by surgery or therapy.

[0009] According to a fifth aspect, the present invention provides plant propagation material such as seeds that comprises, is treated with, or is attached to a compound of formula (I) or a composition containing such a compound. [Modes for carrying out the invention]

[0010] As used herein, the terms "hydroxyl" or "hydroxy" mean the -OH group.

[0011] As used herein, the term "methylcapto" means the -SH group.

[0012] As used herein, the term "cyano" means the -CN group.

[0013] As used herein, amino means an -NH2 group.

[0014] As used herein, nitro means the -NO2 group.

[0015] As used herein, oxo means an =O group (for example, a carbonyl (C=O) group).

[0016] As used herein, the terms "halogen" or "halo" refer to fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iod), preferably fluorine, chlorine, or bromine. This also applies to halogens when combined with other meanings, such as haloalkyl.

[0017] When used herein, "C 1-4 The term "alkyl" refers to a linear or branched hydrocarbon chain group consisting only of carbon and hydrogen atoms, containing no unsaturation, having 1 to 4 carbon atoms, and bonded to the rest of the molecule by single bonds. 1-3 Alkyl should be interpreted accordingly. C 1-4 Examples of alkyl groups include, but are not limited to, methyl, ethyl, and isopropyl.

[0018] When used herein, "C 2-3 The term "alkenyl" refers to a linear or branched hydrocarbon chain radical group consisting only of carbon and hydrogen atoms, containing at least one double bond which may be in either an (E) or (Z) configuration, and which has two or three carbon atoms bonded to the rest of the molecule by a single bond. 2-3 Examples of alkenyls include vinyl (ethenyl), propa-1-enyl, and allyl (propa-2-enyl), but are not limited to these.

[0019] When used herein, "C 2-3The term "alkynyl" refers to a linear or branched hydrocarbon chain radical group consisting only of carbon and hydrogen atoms, containing at least one triple bond, and having two or three carbon atoms bonded to the rest of the molecule by single bonds. 2-3 Examples of alkynyls include, but are not limited to, propa-1-inyl and propargyl (propa-2-inyl).

[0020] When used herein, "C 1-4 "Haloalkyl", "C 2-3 "Haloalkenil" and "C 2-3 The term "haloalkynyl" refers to a C as defined above, which is substituted by one or more of the same or different halogen atoms. 1-4 Alkyl, C 2-3 Alkenyl and C 2-3 These refer to the alkynyl group. C 1-4 Examples of haloalkyls include, but are not limited to, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, and 2,2,2-trifluoroethyl.

[0021] When used herein, "C 1-3 The term "fluoroalkyl" refers to a C atom that is substituted with one or more fluorine atoms, as generally defined above. 1-3 Refers to an alkyl group. 1-3 Examples of fluoroalkyls include, but are not limited to, difluoromethyl and trifluoromethyl.

[0022] When used herein, "C 1-3 The term "alkoxy" is derived from the formula R a It refers to the O- group, and in the formula, R a This is C as generally defined above. 1-3 It is an alkyl group. C 1-3 Examples of alkoxys include, but are not limited to, methoxy, ethoxy, and isopropoxy.

[0023] When used herein, "C 1-3The term "fluoroalkoxy" refers to a C atom that is substituted with one or more fluorine atoms, as generally defined above. 1-3 Refers to an alkoxy group. 1-3 Examples of fluoroalkoxys include, but are not limited to, trifluoromethoxy.

[0024] When used herein, "C 3-4 The term "cycloalkyl" refers to a stable monocyclic ring group that is saturated and contains three or four carbon atoms.

[0025] When used herein, "C 1-3 The term "alkylsulfanyl" is derived from the formula -SR a It refers to the base of, and in the formula, R a This is C as generally defined above. 1-3 It is an alkyl group.

[0026] When used herein, "C 1-3 The term "alkylsulfonyl," formula -S(O)2R a It refers to the base of, and in the formula, R a This is C as generally defined above. 1-3 It is an alkyl group.

[0027] As used herein, the term “heteroaryl” refers to a five-membered or six-membered aromatic monocyclic ring having one to three heteroatoms independently selected from N, O, and S. Examples of heteroaryls include J-1 to J-41 shown in Table J below. The alternating lines in heteroaryls J-1 to J-43 represent the bonding points with the rest of the compound. Preferred heteroaryls include pyridinyl, pyrimidinyl, pyridadinyl, pyrazinyl, and thiazolyl, preferably pyridinyl and thiazolyl.

[0028] Table J: Heteroaryl J-1~J-43: [ka]

[0029] As used herein, the term “heterocyclyl” refers to three-membered, four-membered, five-membered, and six-membered saturated monocyclic rings having one or two heteroatoms independently selected from nitrogen and oxygen. Examples of heterocyclyls include K-1 to K-26 shown in Table K below. The alternating lines in heterocyclyls K-1 to K-26 represent the bonding points with the rest of the compound. Some of the heterocyclyls shown below contain chiral carbons, meaning that compounds containing them may arise in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. Preferred heterocyclyls include pyrrolidinyl, piperidinyl, piperazinyl, and tetrahydropyranil, preferably pyrrolidinyl, piperazinyl, and tetrahydropyranil.

[0030] Table K: Heterocycline K-1~K-26: [ka]

[0031] As used herein, the term “optionally substituted” means that the group referred to is either unsubstituted or substituted with a specified substituent. For example, “C3-C4 cycloalkyl groups may be optionally substituted with one or two halo atoms” means C3-C4 cycloalkyl groups, C3-C4 cycloalkyl groups substituted with one halo atom, and C3-C4 cycloalkyl groups substituted with two halo atoms.

[0032] For example, in the examples of heteroaryls shown in Table J and heterocyclyls shown in Table K, the staggered lines used herein represent connection points / bonding points to the rest of the compound.

[0033] The presence of one or more possible chiral carbon atoms in a compound of formula (I) means that the compound may arise in chiral isomers, i.e., enantiomers or diastereomers. Atrop isomers may also arise as a result of the constrained rotation of a single bond. Formula (I) is intended to encompass all possible isomeric forms and mixtures thereof. The present invention encompasses all of these possible isomeric forms and mixtures thereof relating to the compound of formula (I). Similarly, formula (I) is intended to encompass all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism) if present. The present invention encompasses all possible tautomer forms relating to the compound of formula (I).

[0034] Compounds of formula (I) having at least one basic center can, for example, form acid addition salts with strong inorganic acids, such as mineral acids, such as perchloric acid, sulfuric acid, nitric acid, nitrite, phosphoric acid, and hydrohalic acid; with strong organic carboxylic acids, such as unsubstituted or halogenated C1-C4 alkane carboxylic acids, such as acetic acid; with saturated or unsaturated dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, and phthalic acid; with hydroxycarboxylic acids, such as ascorbic acid, lactic acid, malic acid, tartaric acid, and citric acid; or with organic sulfonic acids, such as unsubstituted or halogenated C1-C4 alkanes or aryl sulfonic acids, such as methane or p-toluenesulfonic acid. Compounds of formula (I) having at least one acidic group can form salts with a base, for example, mineral salts, for example alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or organic amines, for example morpholine, piperidine, pyrrolidine, mono, di or tri lower alkylamines, for example ethyl, diethyl, triethyl or dimethylpropylamine, or mono, di or trihydroxy lower alkylamines, for example mono, di or triethanolamine.

[0035] Examples of compounds of formula (I) according to the present invention include hydrates that may be formed during salt formation.

[0036] In each case, the compound of formula (I) according to the present invention is in the form of a free form, an oxidized form as an N-oxide, a covalently hydrated form, or a salt form such as an agriculturally usable or agrochemically acceptable form.

[0037] N-oxides are oxidation forms of tertiary amines or nitrogen-containing heteroaromatic compounds. These are described, for example, in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra, CRC Press, Boca Raton 1991.

[0038] In this specification, the compound of formula (I) is defined as follows: [ka] (In the formula, A is, [ka] ## represents -OR 1 This indicates binding to the -5,6-dihydro-4H-1,2,4-oxadiazine-3-yl-G moiety; and R 1 Q a Q b Q c Q 7 Q 8 Q 9 (And G have the same meaning as given above for the compound of formula (I)) It can be represented as follows.

[0039] Q a Q b Q c Q 7 Q 8 and Q 9 The definitions given for this result in the following bases A-1 to A-17, defined in Table 1 and shown in Table 2.

[0040]

Table 1

[0041] Table 2: ## and % have the same meanings as those in the compound of formula (Ia), and R 7 , R 8 , R 9 are groups A having the same meanings as those in the compound of formula (I):

Chemical formula

[0042] The following list provides definitions including preferred definitions for group A and substituents R 1 , G, R 10 , R 10a , R 10b , R 11 , R 12 , R 12a , R 12b , R G1 , R G2 , R G3 and R G4 with reference to the compound of formula (I) according to the present invention. For any one of these groups or substituents, any of the definitions given below can be combined with the definitions of any other substituents given below or elsewhere in this specification.

[0043] In certain embodiments of each aspect of the present invention, A is selected from the following: A. A-1, A-2, A-3, A-4, A-5, A-6, A-7, A-8, A-9, A-10, A-11, A-12, A-13, A-14, A-15, A-16 and A-17; or B. A-1, A-2, A-3, A-4, A-5, A-6, A-7, A-8, A-9, A-10, A-11 and A-12; or C. A-13, A-14, A-15, A-16 and A-17; or D. A-​EA-7, A-8, A-9, A-10, A-11 and A-12; or FA-13, A-14, A-15, A-16 and A-17; or GA-1, A-2, A-3, A-13, A-14 and A-15; or HA-4, A-5, A-6, A-7, A-8, A-9, A-15, A-16 and A-17; or IA-10, A-11 and A-12; or JA-1, A-2, A-3, A-4, A-5, A-7, A-8, A-9, A-10, A-12, A-14, A-15 and A-16; or KA-1, A-2, A-3, A-4, A-5, A-7, A-8, A-9, A-14, A-15 and A-16; or LA-1, A-2, A-3, A-7, A-8, A-9, A-13, A-14 and A-15; or MA-4, A-5, A-6, A-10, A-11, A-12, A-16 and A-17; or NA-1, A-2, A-3, A-5, A-9, A-14 and A-15; or OA-1, A-3, A-5 and A-15; or PA-1, A-3 and A-15; or QA-3, A-5, and A-15.

[0044] In preferred embodiments of each aspect of the present invention, A is selected from A-1, A-2, A-3, A-5, A-9, A-14 and A-15. In other words, Q a Q b Q c Q 7 Q 8 and Q 9 It is defined as follows: AQ a C is Q b is N and Q c CH is also Q 7 Q 8 and Q 9 Only one of them is N; or BQ a C is Qb is N and Q c CH and Q 7 is N or CR 7 Q 8 CR 8 And Q 9 is N; or CQ a is N and Q b C is Q c CH and Q 7 CR 7 And Q 8 and Q 9 Only one of them is N; or DQ a C is Q b is N and Q c CH and Q 7 CR 7 Q 8 CR 8 And Q 9 is N; or EQ a C is Q b is N and Q c CH and Q 7 is N and Q 8 CR 8 And Q 9 is N; or FQ a is N and Q b C is Q c CH is Q 7 CR 7 Q 8 CR 8 And Q 9 It is N.

[0045] In more preferred embodiments of each aspect of the present invention, A is selected from A-3, A-5 and A-15, i.e., Q a C is Q b is N and Q c CH and Q 7 CR 7 Q8 CR 8 And Q 9 Is it N; or Q? a C is Q b is N and Q c CH and Q 7 is N and Q 8 CR 8 And Q 9 Is it N; or Q? a is N and Q b C is Q c CH and Q 7 CR 7 Q 8 CR 8 And Q 9 It is N.

[0046] In some embodiments of each aspect of the present invention, if present, R 7 , R 8 and R 9 They are independent of each other and are as follows: A. Hydrogen, fluoro, chloro, bromo, iodine, methyl, ethyl, propyl, isopropyl, allyl, propargyl, cyclopropylmethyl, cyclopropyl, cyclopentyl, cyclohexyl, -C(=O)OCH3, -C(=O)N(CH3)2, 2-(dimethylamino)-2-oxo-ethyl, 2-(methylamino)-2-oxo-ethyl, difluoromethyl, trifluoromethyl, methylsulfonyl, methylsulfanyl, thiomethoxy, methoxy, ethoxy, cyano, hydroxyl, mercapto, and amino; B. Hydrogen, fluoro, chloro, methyl, ethyl, isopropyl, cyclopropyl, -C(=O)OCH3, -C(=O)N(CH3)2, 2-(dimethylamino)-2-oxoethyl, 2-(methylamino)-2-oxoethyl, difluoromethyl, trifluoromethyl, methylsulfonyl, methoxy or cyano; or C. Hydrogen, fluoro, chloro, methyl, ethyl, cyclopropyl, 2-(methylamino)-2-oxo-ethyl, methylsulfonyl, methoxy or cyano; or D. Hydrogen, chloro, fluoro, methyl, cyclopropyl or cyano; or E. Hydrogen, chloro, fluoro, or methyl; or F. Hydrogen, chloro, or fluoro; or GR 7 R is hydrogen, chloro, or methyl; 8 R is hydrogen, chloro, fluoro, or methyl; 9 is hydrogen or methyl; however, Q 7 Q 8 and Q 9 If only one of them is nitrogen, then R 7 , R 8 and R 9 At least one of them is hydrogen; or HR 7 R is hydrogen, chloro, or methyl; 8 is hydrogen, chloro, or fluoro; R 9 is hydrogen or methyl; however, Q 7 Q 8 and Q 9 If only one of them is nitrogen, then R 7 , R 8 and R 9 At least one of them is hydrogen; or IQ 7 Q 8 and Q 9 If both of these are nitrogen, then R 7 R is hydrogen, chloro, or methyl; 8 R is hydrogen, chloro, fluoro, or methyl; 9 is hydrogen or methyl; JQ 7 Q 8 and Q 9 If both of these are nitrogen, then R 7 and R 9 is hydrogen or methyl, and R 8 It is hydrogen or fluorocarbon.

[0047] In some embodiments of each aspect of the present invention, R 1 The following applies: A. One, two, or three independently selected substituents R11 For example, one or two independently selected substituents R 11 Preferably one substituent R 11 A phenyl which may be optionally substituted with R 11 phenyl selected from hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, propa-2-inoxy, propa-1-inoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl and cyclopropyloxy; or B. One or two substituents R 11 For example, one substituent R 11 A phenyl substituted with R 11 phenyl is hydroxy, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propagyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl and cyclobutyl; or C. Phenyl substituted with one or two substituents, e.g., one substituent independently selected from hydroxy, halogen, cyano, methyl, vinyl, ethynyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl and cyclobutyl; or D. Phenyl which may be optionally substituted with one or two substituents, such as one substituent independently selected from chloro, fluoro, cyano, methyl, methoxy, and cyclopropyl; or E. Phenyl substituted with a single substituent selected from methyl and cyclopropyl; or A five-membered or six-membered monocyclic heteroaryl ring comprising one, two, or three heteroatoms, which may be the same or different, independently selected from FN, O, and S, wherein one or two independently selected substituents R 11 A five-membered or six-membered monocyclic heteroaryl ring which may be optionally substituted with; or G. A six-membered monocyclic heteroaryl ring containing 1, 2, or 3 nitrogen atoms, with one or two independently selected substituents R 11 A six-membered monocyclic heteroaryl ring which may be optionally substituted with; or H. Pyridine, pyrimidine, pyridazine or 1,2,4-triazine, which may be optionally substituted with one or two substituents independently selected from hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, propa-2-inoxy, propa-1-inoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl and cyclopropyloxy; or I. Pyridines substituted with one or two substituents independently selected from hydroxy, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propagyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl and cyclobutyl; or J. Pyridine substituted with a single substituent selected from chloro, fluoro, cyano, methyl, methoxy, difluoromethoxy, and cyclopropyl; or K. Pyridine substituted with a single substituent selected from chloro, cyano, and methyl; or L. One or two substituents independently selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, prop-2-inoxy, prop-1-inoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy 11Phenyl, pyridyl, pyrimidyl, or pyridazinyl, which may be optionally substituted in each; or M. One or two substituents R independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl 11 Phenyl, pyridyl, or pyrimidyl, which may be optionally substituted in each; or N. One or two substituents R independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propagyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl. 11 Phenyl or pyridyl, which may be optionally substituted in each; or O. One or two substituents R independently selected from chloro, fluoro, cyano, methyl, methoxy, difluoromethoxy, and cyclopropyl 11 Phenyl or pyridyl, which may be optionally substituted in each; or P. One or two substituents R independently selected from chloro, cyano, methyl, trifluoromethyl, ethynyl, and cyclopropyl. 11 Phenyl or pyridyl, which may be optionally substituted in each; or Q. One or two substituents R independently selected from chloro, methyl, cyano, and cyclopropyl 11 Phenyl or pyridyl, which may be optionally substituted in each; or R. Phenyl or phenyl substituted with a single substituent selected from methyl, trifluoromethyl, ethinyl, chloro, and cyclopropyl; or 3-cyclopropyl-2-fluorophenyl; or pyridinyl substituted with a single substituent selected from cyano and cyclopropyl; or S.3-Cyclopropyl-2-fluorophenyl, 3-(trifluoromethyl)phenyl, 3-ethynylphenyl, 3-chlorophenyl, 5-cyanopyridine-3-yl, 5-(cyclopropyl)pyridine-3-yl, 3-phenyl, 3-tolyl or 3-cyclopropylphenyl; or T,3-Cyclopropylphenyl.

[0048] In some embodiments of each aspect of the present invention, R 11 The following applies: A. Hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, prop-2-inoxy, prop-1-inoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl and cyclopropyloxy; or B. Hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl and cyclobutyl; or C. Hydroxyl, cyano, methyl, vinyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl and cyclobutyl; or D. Halogen, cyano, methyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, allyloxy, difluoromethoxy, trifluoromethoxy and cyclopropyl; or E. Cyano, methyl, methoxy, allyloxy, trifluoromethoxy, cyclopropyl and cyclobutyl; or F. Chlorochloro, fluorochloro G. Halogen, cyano, methoxy, allyloxy, trifluoromethoxy and cyclopropyl; or H. Chlorochloro, fluoro, cyano, cyclopropyl and cyclobutyl; or I. Chloro, fluoro, cyano, methyl, cyclopropyl, trifluoromethyl, ethinyl; or I. Chlorochlorous acid, cyanochlorous acid, cyclopropyl chlorous acid, and methyl chlorous acid; or J. cyclopropyl.

[0049] In some embodiments of each aspect of the present invention, G is as follows: A. Phenyl which may be optionally substituted with one or two substituents independently selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, prop-2-inoxy, prop-1-inoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, or cyclopropyloxy; or B. Phenyl which may be optionally substituted with one or two substituents independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl and cyclobutyl; or C.1, 2, or 3 substituents, each optionally substituted with two or three substituents independently selected from chloro, fluoro, methyl, and methoxy; or D. Phenyl substituted with one or two substituents, for example, one substituent selected from chloro and methyl; or E. Pyridine, pyrimidine, pyridazine or 1,2,4-triazine, which may be optionally substituted with one or two substituents independently selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, propa-2-inoxy, propa-1-inoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl and cyclopropyloxy; or F. Pyridine, pyrimidine, or pyridazine substituted with one or two substituents independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or G. Pyrimidines or pyridazines substituted with one or two substituents independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl and cyclobutyl; or Pyridine substituted with H1, 2, or 3 substituents, for example, 2 or 3 substituents independently selected from chloro, fluoro, cyano, methyl, and methoxy; or I. Pyridine substituted with one or two substituents, for example, one substituent selected from chloro and methyl; or J.1, chroman-4-yl, isochroman-4-yl, 4H-chromen-4-yl, 2,3-dihydrobenzofuran-2-yl, 2,3-dihydrobenzofuran-3-yl, 1,3-benzodioxol-5-yl, benzothiazole-2-yl, benzothiazole-5-yl, benzothiazole-6-yl, benzoxazole-2-yl, benzoxazole-5-yl, benzoxazole-6-yl, benzofuran-2-yl, benzofuran-3-yl, benzofuran-5-yl, benzofuran-6-yl, benzothiophene-2-yl, benzothiophene-3-yl, benzothiophene-5-yl, benzothiophene-6-yl; or K. Croman-4-yl, isochroman-4-yl, 4H-chromen-4-yl, 2,3-dihydrobenzofuran-2-yl, 2,3-dihydrobenzofuran-3-yl, 1,3-benzodioxol-5-yl, benzothiazole-2-yl, benzothiazole-5-yl, benzothiazole-6-yl, benzoxazole-2-yl, benzofuran-2-yl, benzofuran-3-yl, or benzothiophene-2-yl, benzothiophene-3-yl, substituted with one substituent selected from chloro, fluoro, cyano, methyl, and methoxy. L. Croman-4-yl, isochroman-4-yl, 4H-chromen-4-yl, 2,3-dihydrobenzofuran-2-yl or 2,3-dihydrobenzofuran-3-yl substituted with one substituent selected from chloro, fluoro, cyano, methyl and methoxy; or M.1,3-benzodioxol-5-yl, benzothiazole-2-yl, benzothiazole-5-yl, benzothiazole-6-yl, benzoxazole-2-yl, benzofuran-2-yl, benzofuran-3-yl, benzothiophene-2-yl or benzothiophene-3-yl; or Naphthalene-2-yl, tetralin-1-yl, tetralin-2-yl, tetralin-6-yl, indan-1-yl, indan-2-yl, or indan-5-yl, which may each be optionally substituted with one or two substituents independently selected from N.1, 2, or 3 substituents, e.g., chloro, fluoro, cyano, methyl, and methoxy; or O. Tetralin-1-yl, tetralin-2-yl, indan-1-yl, or indan-2-yl, each optionally substituted with one or two substituents, for example, one substituent independently selected from chloro, fluoro, cyano, methyl, and methoxy; or P. Tetralin-1-yl or indan-1-yl substituted with one substituent selected from chloro, fluoro, cyano, methyl, and methoxy; or Q. 2,4-dimethylphenyl, 2,4-dichlorophenyl, 4-bromo-2-methylphenyl, 4-bromo-2-chlorophenyl, 2,6-dichloro-3-pyridyl, 4,6-dichloro-3-pyridyl, 3,5-dichloro-2-pyridyl, 3,5-dichlorothienyl, 3,5-dimethylthienyl, 3,4-dimethylphenyl, 2-chloro-4-methylphenyl, 2-bromo-4-chlorophenyl, 4-chloro-2-fluorophenyl or 2-chloro-4-fluorophenyl; or R.2,4-dimethylphenyl, 2,4-dichlorophenyl, 4-bromo-2-methylphenyl, 4-bromo-2-chlorophenyl, 3,4-dimethylphenyl, 2-chloro-4-methylphenyl, 2-bromo-4-chlorophenyl, 4-chloro-2-fluorophenyl or 2-chloro-4-fluorophenyl; or S,2,4-dichlorophenyl.

[0050] In some embodiments of each aspect of the present invention, R G1 , R G2 , R G3 and R G4 The following are selected independently: A. Halogens such as hydroxyl, chloro and fluoro, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, prop-2-inoxy, prop-1-inoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl or cyclopropyloxy; or B. Hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethylmethoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl and cyclobutyl; or C. Hydroxyl, chloro, fluoro, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl and cyclobutyl; or D. Chlorochloro, fluorochloro E. Chloro and methyl.

[0051] In one embodiment of the present invention, the compound of formula (I) according to the present invention is selected from the compounds listed in any one of Tables A-1 to A-27.

[0052] Preferably, the compound of formula (I) according to the present invention is selected from the compounds listed in Table T1 (below).

[0053] More preferably, the compound of formula (I) according to the present invention is 3-[6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine, 3-[3-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine, 3-[6-(3-cyclopropylphenoxy)-2-fluoro-pyrazolo[1,5-a]pyrimidine-7-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine, 3-[2-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine, or 3-[7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazin-8-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine Selected from.

[0054] The compound of formula (I) is * (Ia) and (Ia) include the stereocenters indicated by asterisks, where A, G, Q a Q b Q c Q 7 Q 8 Q 9 , R 1 , R 7 , R 8 , R 9 and R 11 This is as defined in the first aspect, and each has the corresponding embodiment as described above. [ka]

[0055] The compounds of the present invention may be enantiomers of compounds of formula (I) or formula (Ia), as represented by formula (IR), or formula (IS), or formula (Ia-R), or formula (Ia-S), where A, G, Q a Q b Q cQ 7 Q 8 Q 9 , R 1 , R 7 , R 8 , R 9 and R 11 This is as defined in the first aspect. [ka]

[0056] The compound of formula (I) can be prepared by those skilled in the art as shown in schemes 1 to 46 below, and unless otherwise stated, G and Q are used in the formula. a Q b Q c Q 7 Q 8 Q 9 , R 1 , R 7 , R 8 , R 9 and R 11 A is defined as for the compound of formula (I), and A is defined as for the compound of formula (Ia). For clarity, in the intermediate compounds shown in schemes 1 to 46, A is, [ka] This represents -OR in the intermediate compound. 1 or indicates binding to the corresponding precursor group, % indicates the -5,6-dihydro-4H-1,2,4-oxadiazine-3-yl-G moiety in the intermediate compound or binding to the corresponding precursor group, Q a Q b Q c Q 7 Q 8 and Q 9 This has the same meaning as given for the compound of formula (I). Specific stereocenters are not explicitly stated for clarity and are not intended to limit the teaching of the scheme.

[0057] As shown in Scheme 1, the compound of formula (I) can be obtained by intramolecular cyclization of the compound of formula (II) using a chlorinating agent, for example POCl3, PCl5, (COCl)2, or SOCl2, in a suitable solvent or mixture of solvents (e.g., dichloromethane, dichloroformamide, 2-methyltetrahydrofuran, tetrahydrofuran, diethyl ether, toluene, ethyl acetate), preferably at a temperature of 0°C to 80°C, more preferably at a temperature of 25°C to 60°C, optionally in the presence of dimethylformamide. See, for example, Heterocycles (2016), 92(12), 2166-2200 or Chinese Patent No. 114437077. [ka] Scheme 1

[0058] As shown in Scheme 2, the compound of formula (II) is of formula (III) (wherein X 1 H is X 2 is a protecting group, or X 1 and X 2 are either the same or different protecting groups, or X 1 and X 2 These can be obtained by amine deprotection of compounds (which, together with the nitrogen to which they are bonded, form a protecting group). Examples of protecting groups include, for example, tert-butyloxycarbonyl, benzylcarbonyl, 9-fluorenylmethylcarbonyl, trifluoroacetyl, benzyl, triphenylmethyl, benzylidenyl, p-trienesulfonyl, phthalimide, or succinimide. The protecting groups can be removed using standard techniques (see Greene's Protective Groups in Organic Synthesis, 4th Ed., Wiley-Interscience). [ka] Scheme 2

[0059] As shown in Scheme 3, the compound of formula (III) (wherein X 1 and X 2 The compound of formula (III) (as defined in Scheme 2) can be obtained by amide coupling conversion of the compound of formula (IV) and the amine compound of formula (V) by activating the carboxylic acid functional group of the compound of formula (IV), that is, in a preferred solvent (e.g., N-methylpyrrolidone, acetonitrile, dimethylacetamide, dichloromethane, or tetrahydrofuran) preferably at a temperature of 25°C to 60°C and optionally in the presence of a base such as triethylamine or N,N-diisopropylethylamine, by converting the -OH of the carboxylic acid to a good leaving group such as a chloride group by using, for example, (COCl)2 or SOCl2 before treatment with the compound of formula (IV).

[0060] Alternatively, the compound of formula (III) can be obtained under conditions described in the literature for amide coupling, using an amidation coupling reagent such as cyclic anhydride 1-propanephosphonic acid (T3P) in a suitable solvent (e.g., acetonitrile) in the presence of an optional base (e.g., triethylamine or N,N-diisopropylethylamine). See, for example, Chem.Soc.Rev.2009,38,606 and Chem.Soc.Rev.2011,40,5084. [ka] Scheme 3

[0061] As shown in Scheme 4, the compound of formula (II) can be obtained by an amide coupling conversion of the compound of formula (IV) and the amine compound of formula (VI) by activating the carboxylic acid functional group of the compound of formula (IV), that is, preferably at a temperature of 25°C to 60°C and optionally in the presence of a base such as triethylamine or N,N-diisopropylethylamine, preferably in a suitable solvent (e.g., N-methylpyrrolidone, acetonitrile, dimethylacetamide, dichloromethane, or tetrahydrofuran), by converting the -OH group of the carboxylic acid to a good leaving group such as a chloride group by using, for example, (COCl)2 or SOCl2 before treatment with the compound of formula (IV), which is a process that usually occurs.

[0062] Alternatively, the compound of formula (II) can be obtained under conditions described in the literature for amide coupling, using an amidation coupling reagent such as cyclic anhydride 1-propanephosphonic acid (T3P) in a suitable solvent (e.g., acetonitrile) in the presence of an optional base (e.g., triethylamine or N,N-diisopropylethylamine). See, for example, Chem.Soc.Rev.2009,38,606 and Chem.Soc.Rev.2011,40,5084. [ka] Scheme 4

[0063] As shown in schemes 5a, 5b, and 5c, respectively, compounds of formula (I), (III), or (II) are converted at a temperature of 10°C to 90°C and preferably using a metal catalyst complex (e.g., Cu or Pd) in a suitable solvent (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, or dimethyl sulfoxide) in the presence of a base (e.g., KO-t-Bu, K3PO4, K2CO3, triethylamine, or Cs2CO3) to convert the nucleophilic compound of formula (VII) into the electrophilic compound of formula (VIII), (IX), or (X) (wherein X is the first term). 1 and X 2This is as defined for the compound of formula (III) in scheme 2, and X 3 It can also be prepared by reacting it with a suitable leaving group such as fluoro, chloro, bromo, iodine, BF3K, B(OH)2, or B(pinacol). For relevant examples, see Eur.J.Org.Chem.2011,18,3353;J.Org.Chem.2009,74,7951;Tetrahedron Lett.,2012,53,5318. Compounds of formula (VII) are known or commercially available. [ka] Scheme 5a [ka] Scheme 5b [ka] Scheme 5c

[0064] As shown in Scheme 6, the compound of formula (VIII) is preferably chlorinated in a suitable solvent or mixture of solvents (e.g., dichloromethane, dimethylformamide, 2-methyltetrahydrofuran, tetrahydrofuran, diethyl ether, toluene, ethyl acetate) at a temperature of 0°C to 80°C, more preferably 25°C to 60°C, using a chlorinating agent, such as POCl3, PCl5, (COCl)2, or SOCl2, optionally in the presence of dimethylformamide, to form the compound of formula (X) (wherein X, 3 This can be obtained by intramolecular cyclization of a suitable leaving group such as fluoro, chloro, bromo, iodo, BF3K, B(OH)2, or B(pinacol). See, for example, Chem.Soc.Rev.2009,38,606 and Chem.Soc.Rev.2011,40,5084. [ka] Scheme 6

[0065] As shown in Scheme 7, the compound of formula (X) is the compound of formula (IX) (wherein X 1 and X 2 This is as defined for the compound of formula (III) in relation to scheme 2, and X 3 This can be obtained by amine deprotection of a suitable leaving group such as fluoro, chloro, bromo, iodine, BF3K, B(OH)2, or B(pinacol). The protecting group can be removed using standard techniques (see Greene's Protective Groups in Organic Synthesis, 4th Ed., Wiley-Interscience). [ka] Scheme 7

[0066] As shown in Scheme 8, the compound of formula (IX) (wherein X 1 and X 2 This is as defined for the compound of formula (III) in relation to scheme 2, and X 3 The compound (where is a suitable leaving group such as fluoro, chloro, bromo, iodine, BF3K, B(OH)2, or B(pinacol)) can be prepared by an amide coupling conversion of the compound of formula (XI) and the amine compound of formula (V) by activating the carboxylic acid functional group of the compound of formula (XI), that is, preferably in a suitable solvent (e.g., N-methylpyrrolidone, dimethylacetamide, dichloromethane, or tetrahydrofuran) at a temperature of 25°C to 60°C and optionally in the presence of a base such as triethylamine or N,N-diisopropylethylamine, by converting the -OH of the carboxylic acid to a good leaving group such as a chloride group by using, for example, (COCl)2 or SOCl2 before treatment with the compound of formula (V). This is a process that usually occurs.

[0067] Alternatively, the compound of formula (IX) can be obtained under conditions described in the literature for amide coupling, using an amidation coupling reagent such as cyclic anhydride 1-propanephosphonic acid (T3P) in a suitable solvent (e.g., acetonitrile) in the presence of an optional base (e.g., triethylamine or N,N-diisopropylethylamine). See, for example, Chem.Soc.Rev.2009,38,606 and Chem.Soc.Rev.2011,40,5084.

[0068] The compound of formula (V) is known, commercially available, or readily available to experts in the field. [ka] Scheme 8

[0069] As shown in Scheme 9, a compound of formula (X) (wherein X) 3 The compound (wherein B(OH)2 or B(pinacol) is a suitable leaving group) can also be obtained by an amide coupling conversion of the compound of formula (XI) and the amine compound of formula (VI) by activating the carboxylic acid functional group of the compound of formula (XI), that is, preferably in a suitable solvent (e.g., N-methylpyrrolidone, dimethylacetamide, dichloromethane or tetrahydrofuran) at a temperature of 25°C to 60°C and optionally in the presence of a base such as triethylamine or N,N-diisopropylethylamine, by converting the -OH of the carboxylic acid to a good leaving group such as a chloride group by using, for example, (COCl)2 or SOCl2 before treatment with the compound of formula (VI).

[0070] Alternatively, the compound of formula (X) can be obtained under conditions described in the literature for amide coupling, using an amidation coupling reagent such as cyclic anhydride 1-propanephosphonic acid (T3P) in a suitable solvent (e.g., acetonitrile) in the presence of an optional base (e.g., triethylamine or N,N-diisopropylethylamine). See, for example, Chem.Soc.Rev.2009,38,606 and Chem.Soc.Rev.2011,40,5084. The compound of formula (VI) is known or commercially available. [ka] Scheme 9

[0071] As shown in schemes 10a and 10b, the compounds of formulas (I) and (III) are converted at a temperature of 10°C to 90°C, preferably using a metal catalyst complex (e.g., Cu or Pd), in a suitable solvent (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane or dimethyl sulfoxide), in the presence of a base (e.g., KO-t-Bu, K3PO4, K2CO3, triethylamine or Cs2CO3), into the electrophilic compounds of formula (XII) (wherein X 1 and X 2 This is as defined for the compound of formula (III) in relation to scheme 2, and X 3 It can also be prepared by reacting it with a suitable leaving group such as fluoro, chloro, bromo, iodine, BF3K, B(OH)2, or B(pinacol). For relevant examples, see Eur.J.Org.Chem.2011,18,3353;J.Org.Chem.2009,74,7951;Tetrahedron Lett.,2012,53,5318. Compounds of formula (XII) are known or commercially available. [ka] Scheme 10a [ka] Scheme 10b

[0072] As shown in Scheme 11, the compound of formula (XIII) can be obtained by intramolecular cyclization of the compound of formula (XV) in a suitable solvent or mixture of solvents (e.g., dichloromethane, dimethylformamide, 2-methyltetrahydrofuran, tetrahydrofuran, diethyl ether, toluene, ethyl acetate), preferably at a temperature of 0°C to 80°C, more preferably at 25°C to 60°C, using a chlorinating agent, such as POCl3, PCl5, (COCl)2, or SOCl2, optionally in the presence of dimethylformamide. See, for example, Chem.Soc.Rev.2009,38,606 and Chem.Soc.Rev.2011,40,5084. [ka] Scheme 11

[0073] As shown in Scheme 12, the compound of formula (XV) is the compound of formula (XIV) (wherein X 1 and X 2 This can be obtained by amine deprotection of the compound (as defined for the compound of formula (III) in Scheme 2). The protecting group can be removed using standard techniques; see Greene's Protective Groups in Organic Synthesis, 4th Ed., Wiley-Interscience. [ka] Scheme 12

[0074] As shown in Scheme 13, the compound of formula (XVII) (wherein X 4 is OH or OR 1 The compounds are the compound of formula (VI) and the compound of formula (XVI) (wherein X 4 This is defined as in the compound of formula (XVII), and X 5This can be obtained by coupling with a C1-C4 alkoxy (e.g., methoxy or ethoxy). Subsequent cyclization can be achieved using an acid, typically acetic acid, at a temperature of 20°C to 120°C, more preferably 80°C to 120°C. For relevant examples, see Heterocycles 2016,92,2166 and International Publication No. 2017 / 031325. Compounds of formula (VI) are known or readily available from experts in the art. [ka] Scheme 13

[0075] As shown in Scheme 14, the compound of formula (XVI) (wherein X 4 is OH or OR 1 X 5 The compounds (where C1-C4 alkoxys are, for example, methoxy or ethoxy) can be obtained in solution at a temperature of -30°C to 20°C in an alkoxide, typically a corresponding alcohol (e.g., sodium methoxide, sodium methoxide, or potassium tert-butoxide), or by reaction of the compound of formula (XVIII) using an excess alcohol, such as methanol or ethanol, and an alkali metal. Alternatively, the compound of formula (XVIII) can be hydrolyzed at a temperature of -30°C to 40°C in a suitable solvent or mixture of solvents, such as methanol, ethanol, dichloromethane, or 1,4-dioxane, in the presence of an acid, such as hydrochloric acid. For relevant examples, see International Publication No. 2012 / 178015, Japanese Patent Publication No. 2014 / 037370, or Angew. Chem. Int. Ed. 2020, 59, 23306. [ka] Scheme 14

[0076] As shown in Scheme 15, a compound of formula (XX) (wherein X 6The compound of formula (XIX) (where OH or C1-C4 alkoxy, such as methoxy or ethoxy) can also be prepared by reacting the compound of formula (XIX) in an aqueous solvent mixture such as isopropanol or ethanol, optionally in an alkaline medium, at a temperature of 90°C to 110°C. For relevant examples, see J.Med.Chem.2012,55,10118. [ka] Scheme 15

[0077] The compound of formula (XIX) is either known or, as shown in Scheme 16, the compound of formula (XXI) (wherein X 7 This compound can be obtained by reacting a chloro, bromo, iodine, or O-trifluoromethanesulfonyl compound (which is chloro, bromo, iodine, or O-trifluoromethanesulfonyl) in a suitable solvent or mixture of solvents (e.g., dioxane, water, toluene, tetrahydrofuran, 2-methyltetrahydrofuran, xylene) at a temperature of 50°C to 120°C, preferably 80°C to 110°C, in the presence of a cyanide source, e.g., potassium ferrocyanide, copper cyanide, zinc cyanide, or potassium cyanide, and a base (e.g., KOAc), using a metal source, e.g., XPhos Pd Generation 1. For relevant examples, see J.Org.Chem.2018,83,4922 and Org.Let.2006,8,1189. Compounds of formula (XXI) are known or can be readily prepared by experts in the art. [ka] Scheme 16

[0078] As shown in Scheme 17, the compound of formula (XVII) (wherein X 4 is OH or OR 1The compound of formula (XXII) can also be obtained by cyclizing the compound of formula (XXII) undiluted or in a suitable solvent such as methanol or ethanol at a temperature of 20°C to 75°C using an acid, such as acetic acid, followed by reduction in a solvent or mixture of solvents, such as tetrahydrofuran, toluene, or methanol, in the presence of a hydride (e.g., sodium cyanoborohydride, sodium borohydride, sodium triacetoxyborohydride, or lithium borohydride). For relevant examples, see International Publication No. 2016 / 201168. [ka] Scheme 17

[0079] As shown in Scheme 18, the compound of formula (XXII) (wherein X 4 is OH or OR 1 The compound of formula (XXIV) (wherein X 8 This can be obtained by reacting a compound of formula (XXIII) with a leaving group (such as chloro, bromo, iodine, mesyl, tosyl, or O-trifluoromethanesulfonyl) at a temperature of 0°C to 110°C, more preferably 20°C to 80°C, in a suitable solvent or mixture of solvents, such as benzene, toluene, tetrahydrofuran, chloroform, acetonitrile, or 2-methyltetrahydrofuran, in the presence of a base (e.g., pyridine, triethylamine, potassium carbonate, sodium carbonate). For relevant examples, see J.Med.Chem.2011,54,8407; International Publication No. 2002 / 051811 or International Publication No. 2010 / 078867. Compounds of formula (XXIV) are known or readily available to experts in the art. [ka] Scheme 18

[0080] Compound of formula (XXIII) (wherein X 4 is OH or OR 1The compound of formula (XVIII) is either publicly known or can be prepared by reacting the compound of formula (XVIII) with a suitable solvent or mixture of solvents, such as methanol, ethanol, 2-methyl-2-butanol, water, or 1-butyl-3-methylimidazolium acetate, in the presence of a base (e.g., potassium carbonate or sodium carbonate), as shown in Scheme 19, using a hydroxyamine or a salt such as a hydroxyamine hydrochloride. For relevant examples, see Org. Biomol. Chem. 2014, 12, 8036; International Publication No. 2016 / 143655 or International Publication No. 201 / 9224743. The compound of formula (XVIII) is either publicly known, commercially available, or readily available from experts in the art. [ka] Scheme 19

[0081] As shown in Scheme 20, a compound of formula (XXVI) or its lithium, sodium, or barium salt (wherein X 5 The nucleophile compound of formula (VII) is converted into the electrophile compound of formula (XXV) (wherein X is C1-C4 alkoxy, e.g., methoxy or ethoxy) at a temperature of 20°C to 110°C and preferably using a metal catalyst complex (e.g., Cu or Pd) in a suitable solvent or mixture of solvents (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, dimethyl sulfoxide) in the presence of a base (e.g., KO-t-Bu, K3PO4, K2CO3, triethylamine, or Cs2CO3). 5 X is a C1-C4 alkoxy, for example, methoxy or ethoxy, and 3This can be prepared by reacting it with a suitable leaving group, such as fluoro, chloro, bromo, iodine, BF3K, B(OH)2, or B(pinacol). For relevant examples, see Eur.J.Org.Chem.2011,18,3353;J.Org.Chem.2009,74,7951;Tetrahedron Lett.2012,53,5318;International Publication Nos. 2008 / 110313 and International Publication Nos. 2012 / 136604. Compounds of formula (VII) are known or commercially available.

[0082] Next, the compound of formula (IV) is the compound of formula (XXVI) (wherein X 5 These can be obtained by ester hydrolysis of a C1-C4 alkoxy (e.g., methoxy or ethoxy) in a suitable solvent or mixture of solvents (e.g., methanol, acetonitrile, ethanol, water, tetrahydrofuran, or 2-methyltetrahydrofuran) at a temperature of 0°C to 80°C using an alkali hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide, or barium hydroxide. Alternatively, the ester can be cleaved under acidic conditions, for example, using hydrochloric acid. For relevant examples, see International Publication 2021 / 086879 or Org. Biomol. Chem. 2015, 13, 7928. [ka] Scheme 20

[0083] As shown in Scheme 21, a compound of formula (XX) (wherein X 6The nucleophile compound of formula (XXVII) (wherein X is OH or C1-C4 alkoxy, e.g., methoxy or ethoxy) is dissolved in a suitable solvent (e.g., dichloromethane, 1,2-dichloromethane, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, N-methylpyrrolidone, dimethylacetamide, dimethyl ether or toluene) at a temperature of 20°C to 80°C using a metal source (e.g., Cu(OAc)2) and preferably in the presence of an oxidizing agent such as O2 or a suitable palladium precatalyst such as third-generation RockPhosPd, in the presence of a suitable solvent (e.g., dichloromethane, 1,2-dichloromethane, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, N-methylpyrrolidone, dimethylacetamide, dimethyl ether or toluene). 6 (As defined for compounds of formula (XX)) is an electrophilic compound of formula (XII) (wherein X 3 It can also be prepared by reacting with a suitable leaving group such as fluoro, chloro, bromo, iodine, BF3K, B(OH)2, or B(pinacol). For relevant examples, see Org. Lett. 2003, 5, 1381; Tetrahedron Lett. 1998, 39, 2933; Tetrahedron Lett. 2003, 44, 3863 and Org. Lett. 2013, 15, 2876. Compounds of formula (XII) are known or commercially available. [ka] Scheme 21

[0084] As shown in Scheme 22, a compound of formula (XXX) or its lithium, sodium, or barium salt (wherein X) 9 (wherein is OH or halogen) can be obtained from the compound of formula (XXIX) by hydrolysis in the same manner as described in Scheme 20 for the conversion of the compound of formula (XXVI) to the compound of formula (IV).

[0085] Compound of formula (XXIX) (wherein X 5 X is a C1-C4 alkoxy, for example, methoxy or ethoxy, and 9The compound of formula (XXVIII) (wherein X is an OH group or halogen) is oxidized at a temperature of 25°C to 200°C in a suitable solvent (e.g., acetic acid) by an oxidation method using a suitable oxidizing agent, such as KMnO4 or a cobalt(II) salt and trihydroxyisocyanuric acid (THICA), to form a compound of formula (XXVIII) (wherein X is an OH group or halogen). 9 It can be obtained from (which is OH or a halogen). For relevant examples, see Can.J.Chem.1978,56,1273 and International Publication No. 2021 / 160470. Compounds of formula (XXVIII) are known or can be prepared as described in Bulletin de la Societe Chimique de France 1972,8,3198. [ka] Scheme 22

[0086] As shown in Scheme 23, the compound of formula (XXXIII) (wherein X 5 The compound of formula (XXXII) (where C1-C4 alkoxy is, for example, methoxy or ethoxy) can be obtained from the compound of formula (XXXII) by an oxidation method using a suitable oxidizing agent, such as KMnO4 or a suitable cobalt(II) salt and trihydroxyisocyanuric acid (THICA), in a suitable solvent (e.g., acetic acid) at a temperature of 25°C to 200°C. For relevant examples, see Can. J. Chem. 1978, 56, 1273 and International Publication No. 2021 / 160470.

[0087] Furthermore, compounds of formula (XXXII) can be prepared by reacting a nucleophilic compound of formula (VII) with an electrophilic compound of formula (XXXI) (wherein X3 is a suitable leaving group such as fluoro, chloro, bromo, iodine, BF3K, B(OH)2, or B(pinacol)) in a suitable solvent (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, dimethyl sulfoxide) in the presence of a base (e.g., KO-t-Bu, K3PO4, K2CO3, triethylamine, or Cs2CO3) at a temperature of 25°C to 120°C, under reflux and optionally with a metal catalyst and ligand complex (e.g., CuI, N,N-dimethylglycine). For related examples, see Eur.J.Org.Chem.2011,18,3353;J.Org.Chem.2009,74,7951;Tetrahedron Lett.2012,53,5318;International Publication Nos. 2008 / 110313 and 2012 / 136604. Compounds of formula (XXXI) are known or commercially available. [ka] Scheme 23

[0088] As shown in Scheme 24, a compound of formula (XX) (wherein X 6 The compound of formula (XXI) (wherein X is OH or C1-C4 alkoxy, e.g., methoxy or methoxy) is heated in the presence of an organic base, e.g., triethylamine or diisopropylethylamine, and a suitable solvent (e.g., methanol or ethanol), typically at a pressure of 1-50 bar, more preferably 5-15 bar, in a pressure vessel filled with carbon monoxide, typically in a stainless steel autoclave, using a metal source such as XPhos Pd G1, at a temperature of 20°C-130°C, preferably 70°C-110°C. 7It can also be obtained from chloro, bromo, iodine, or trifluoromethanesulfonyl-O-. For relevant examples, see J.Med.Chem.2014,57,2692 and Adv.Synth.Catal.2006,348,1255. [ka] Scheme 24

[0089] Instead, as shown in Scheme 25, the compound of formula (IV) is converted to the compound of formula (XXXIV) (wherein X) in a suitable solvent, e.g., hexane, diethyl ether or tetrahydrofuran, at a temperature of -78°C to -30°C. 10 It can also be obtained by reacting a lithium reagent (e.g., n-butyllithium, sec-butyllithium, tert-butyllithium, or lithium diisopropylamine) with a chloro, bromo, or iodine reagent, followed by the addition of carbon dioxide. For relevant examples, see J.Am.Chem.Soc.2018,140,9140 and J.Am.Chem.Soc.2021,143,1539. [ka] Scheme 25

[0090] Compound of formula (XXXIV) (wherein X 10Compounds of formula (XXXV) (wherein is chloro, bromo, or iodine) are known or can be prepared by reacting the compound of formula (XXXV) with an electrophilic halogen reagent such as bromine, dibromohydantoin, N-bromo-, or N-chlorosuccinimide at a temperature of -78°C to 10°C in a suitable solvent (e.g., chloroform, 2-methyltetrahydrofuran, or dimethylformamide), as shown in Scheme 26, and optionally with a base, typically lithium diisopropylamine or n-butyllithium. Compounds of formula (XXXV) are known, commercially available, or readily prepared by experts in the art. For relevant examples, see Tetrahedron Lett. 2003, 44, 823; J.Am. Chem. Soc. 2010, 132, 8858 and Synthesis 2005, 16, 2782. [ka] Scheme 26

[0091] As shown in Scheme 27, the compound of formula (IV) can also be prepared by reacting the compound of formula (XXXV) with a base, typically lithium diisopropylamine or n-butyllithium, in a suitable solvent (e.g., diethyl ether, cyclopentyl methyl ether, methyl tert-butyl ether, or tetrahydrofuran) at a temperature of -78°C to 10°C, optionally in the presence of a catalyst (e.g., potassium tert-butoxide), followed by the addition of carbon dioxide. The compounds of formula (XXXV) are known, commercially available, or readily prepared by experts in the art. For relevant examples, see Bioorg.Med.Chem.2004,12,5579;J.Am.Chem.Soc.2010,132,8858 and Synthesis 2005,16,2782. [ka] Scheme 27

[0092] As shown in Scheme 28, the compound of formula (XXXIV) (wherein X10 (wherein is chloro, bromo, or iodine) are known or can be obtained from tautomers of formulas (XXXVI) and (XXXVII) by treatment with a phosphorus compound, such as phosphorus oxychloride, phosphorus pentachloride, or phosphorus tribromide, in a suitable catalyst (e.g., toluene, acetonitrile, dichloromethane, or chloroform) in the presence of a quasi-stoichiometric amount of a catalyst (e.g., triphenylphosphine or 4-(dimethylamino)pyridine). For relevant examples, see Tetrahedron Lett. 2012, 53, 674; Synth.Commun. 2016, 46, 1619 and J.Org.Chem. 2011, 76, 4149. All such tautomers of formulas (XXXVI) and (XXXVII), as well as mixtures thereof in all proportions, are considered herein. [ka] Scheme 29

[0093] As shown in Scheme 30, tautomers of formulas (XXXVI) and (XXXVII) are known or obtained by a one-pot nucleophilic addition reaction, followed by the compound of formula (XXXVIII) (wherein X) in a preferred solvent, preferably in the presence of a base (e.g., potassium carbonate, triethylamine) at a temperature of 50°C to 110°C, preferably in the presence of a base (e.g., potassium carbonate, triethylamine), such as ethanol, isopropanol, dimethylformamide, acetic acid, or acetonitrile. 11 It is either a C1-C4 alkyl or C5-C6 cycloalkyl, or forms a saturated heterocycle with the nitrogen to which it is bonded, X 6 (wherein Q is an OH or C1-C4 alkoxy, such as methoxy or ethoxy) and a compound of formula (XXXIX) or its hydrochloride (wherein Q is a C1-C4 alk 7 Q 8 and Q 9 This is as defined for the compound of formula (I), and X 13This can be prepared by cyclization using H or a protecting group (e.g., tetrahydrofuran, 2-(trimethylsilyl)ethoxymethyl, or benzyl). For relevant examples, see U.S. Patent Application Publication 2018 / 0230157; Synthesis 2006, 1, 59 and International Publication 2010 / 016005. Compounds of formula (XXXIX) or salts thereof are known or commercially available. All such tautomers of formulas (XXXV) and (XXXVI), as well as mixtures thereof in all proportions, are considered herein. [ka] Scheme 30

[0094] Compounds of formulas (XXXVI) and (XXXVII) (wherein Q a Q b Q 7 Q 8 Q 9 and R 1 The following is the definition for the compound of formula (I): [ka]

[0095] As shown in Scheme 31, the tautomers of formulas (XXXVI) and (XXXVII) are volatile compounds of formula (XL) or their hydrochloride salts (wherein Q) in a suitable solvent, such as water or ethanol, at a temperature of 20°C to 100°C. 7 Q 8 and Q 9 This is as defined for the compound of formula (I), and X 11 These can be prepared by intramolecular cyclization of C1-C4 alkyl or C5-C6 cycloalkyl compounds (or compounds that form a saturated heterocycle with the nitrogen to which they are bonded). For relevant examples, see International Publication No. 2005 / 012262. All such tautomers of formulas (XXXV) and (XXXVI), as well as mixtures thereof in all proportions, are considered herein. [ka] Scheme 31

[0096] As shown in Scheme 32, the tautomers of formulas (XXXVI) and (XXXVII) are compounds of formula (XLI) (wherein Q 7 Q 8 and Q 9 This is as defined for the compound of formula (I), and X 11 It is either a C1-C4 alkyl or C5-C6 cycloalkyl, or forms a saturated heterocycle with the nitrogen to which it is bonded, X 13 These can be prepared by amination and direct cyclization from H or a protecting group (e.g., tetrahydropyran, 2-(trimethylsilyl)ethoxymethyl, or benzyl), i.e., at a temperature of 0°C to 110°C, more preferably 20°C to 50°C, in the optional presence of a base (e.g., KOH, NaOH), in a suitable solvent, e.g., dimethyl sulfoxide, dimethylformamide, dichloromethane, N-methyl-2-pyrrolidone, or ethanol, with an amination reagent (e.g., amino-4-nitrobenzoate, N-(tert-butoxycarbonyl)-2-nitrobenzenesulfonamide, hydroxylamine-O-sulfonic acid, or sodium diformylamide). For relevant examples, see J.Med.Chem.1996,39,582; Organometallics 2014,33,4035 and Chem.Eur.J.2019,25,1963. All such tautomers of formulas (XXXV) and (XXXVI), as well as mixtures thereof in all proportions, are considered herein. [ka] Scheme 32

[0097] As shown in Scheme 33, a compound of formula (XL) or its hydrochloride (wherein Q) 7 Q 8 and Q 9 This is as defined for the compound of formula (I), and X 11A compound of formula (XLIII) (wherein Q is a C1-C4 alkyl or C5-C6 cycloalkyl, or forms a saturated heterocycle with the nitrogen to which it is bonded) is found in a suitable solvent, such as dimethyl sulfoxide, N-methyl-2-pyrrolidone, or dimethylacetamide, at a temperature of 20°C to 120°C. 7 Q 8 and Q 9 This is as defined for the compound of formula (I), and X 11 It can be obtained by amination of the compound of formula (XL) (as defined). For relevant examples, see Dalton Trans. 2016, 45, 15644, J. Med. Chem. 1996, 39, 582 or Chem. Eur. J. 2019, 25, 1963. [ka] Scheme 33

[0098] As shown in Scheme 34, the compound of formula (XLI) (wherein Q) 7 Q 8 and Q 9 This is as defined for the compound of formula (I), and X 11 It is either a C1-C4 alkyl or C5-C6 cycloalkyl, or forms a saturated heterocycle with the nitrogen to which it is bonded, X 13 The compound of formula (XLIII) (wherein Q is H or a protecting group (e.g., tetrahydropyran, 2-(trimethylsilyl)ethoxymethyl, or benzyl)) is reacted with a formamide synthetic equivalent, such as dimethylformamide, dimethylacetal, or 1-(dimethoxymethyl)pyrrolidine, at a temperature of 50°C to 120°C, either undiluted or in a suitable solvent (e.g., toluene, dimethylformamide), to form a compound of formula (XLIII) (wherein Q is H or a protecting group (e.g., tetrahydropyran, 2-(trimethylsilyl)ethoxymethyl, or benzyl)). 7 Q 8 and Q 9 This is as defined for the compound of formula (I), and X 13It can be obtained as defined for compounds of formula (XLI). For relevant examples, see International Publication 2021 / 2296621; International Publication 2008 / 149379 and Bioorg.Med.Chem.Lett.2022,61,128552. [ka] Scheme 34

[0099] As shown in Scheme 35, compound (Q of formula (XLIII) 7 Q 8 and Q 9 This is as defined for the compound of formula (I), and X 13 (wherein H is H or a protecting group (e.g., tetrahydropyran, 2-(trimethylsilyl)ethoxymethyl or benzyl)) is mixed with an organometallic reagent (e.g., methylmagnesium bromide, isopropylmagnesium chloride-lithium chloride, butyllithium, tert-butyllithium or phenylmagnesium chloride) in a suitable solvent (e.g., tetrahydrofuran, diethyl ether, cyclopentyl methyl ether or 2-methyltetrahydrofuran) at a temperature of -78°C to 15°C, preferably -20°C to 10°C, to produce the compound of formula (XLIV) and the compound of formula (XLV) (Q 7 Q 8 and Q 9 This is as defined for the compound of formula (I), and X 10 is chloro, bromo, or iodine, and X 13 It can be prepared from (as defined for the compound of formula (XLIII)). For relevant examples, see International Publication 2009 / 130193 and International Publication 2015 / 057205. [ka] Scheme 35

[0100] Compounds of formula (XLIV) are known or can be obtained by reacting a compound of formula (XLVI) or its lithium, sodium, or barium salt with N,O-dimethylhydroxylamine hydrochloride in a suitable solvent or mixture of solvents (e.g., dimethylformamide, dichloromethane, or 2-methyltetrahydrofuran) at a temperature of optionally -10°C to 80°C, more preferably 0°C to 30°C, in the presence of a mixture of oxalyl chloride or thionyl chloride and dimethylformamide, or in a suitable solvent or mixture of solvents (e.g., dimethylformamide, dichloromethane, trichloromethane, tetrahydrofuran, or 2-methyltetrahydrofuran) at a temperature of 0°C to 80°C, in the presence of a coupling agent (e.g., T3P, HATU, COMU). For relevant examples, see International Publication No. 2011 / 023706 and J.Med.Chem.2004, 47, 2405. Compounds of formula (XLVI) are known, commercially available, or readily prepared by experts in the art. [ka] Scheme 36

[0101] As shown in Scheme 37, the compound of formula (XLVIII) (wherein X 5 is OH or C1-C4 alkoxy, and X 11 (wherein X is a C1-C4 alkyl or C5-C6 cycloalkyl, or forms a saturated heterocycle with the nitrogen to which they are bonded) is prepared in an undiluted state or in a suitable solvent or mixture of solvents (e.g., dimethylformamide, 2-methyltetrahydrofuran) at a temperature of 25°C to 120°C in the presence of C1-C6-alkoxy- or C1-C6-cycloalkoxy-N,N,N',N'-tetra(C1-C6-alkyl or C1-C6-cycloalkyl) methanediamine (e.g., methoxy- or tert-butoxy-N,N,N',N',-tetramethylmethanediamine), formula (XLVII) (wherein X 5The compounds of formula (XLVIII) can be prepared by reacting them as defined for the compounds of formula (XLVIII). For relevant examples, see Tetrahedron 1998, 54, 9799; J.Het.Chem. 2014, 51, 954 and Synth.Commun. 2021, 51, 2160). The compounds of formula (XLVII) are known, commercially available, or readily prepared by experts in the art from, for example, the compounds of formula (XLV) in scheme 36. [ka] Scheme 37

[0102] As shown in Scheme 38, tautomers of formulas (XXXVI) and (XXXVII) are converted at a temperature of 40°C to 80°C and using a catalyst (e.g., Cu(OAc)2), preferably in the presence of an oxidizing agent such as O2, in a suitable solvent (e.g., dichloromethane, 1,2-dichloromethane, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, N-methylpyrrolidone, dimethylacetamide), or at a temperature of 20°C to 80°C, in the presence of a base (e.g., K3PO4) and a suitable solvent (e.g., 1,2-dimethoxyethane or toluene), using a suitable palladium precatalyst such as RockPhos Pd G3, to convert the nucleophilic tautomer compounds of formulas (XLIX) and (L) into the electrophilic compound of formula (XII) (wherein X 3 It can be prepared by reacting with a suitable leaving group such as fluoro, chloro, bromo, iodine, BF3K, B(OH)2, or B(pinacol). For relevant examples, see Org. Lett. 2003, 5, 1381; Tetrahedron Lett. 1998, 39, 2933; Tetrahedron Lett. 2003, 44, 3863 and Org. Lett. 2013, 15, 2876. Compounds of formula (XII) are known or commercially available. All such tautomers of formulas (XXXV), (XXXVI), (XLIX), and (L), as well as mixtures thereof in any proportion, are considered herein. [ka] Scheme 38

[0103] Instead, as shown in Scheme 39, the tautomers of formulas (XXXVI) and (XXXVII) are catalyzed at a temperature of 50°C to 110°C and preferably using a metal catalyst complex (e.g., Cu or Pd) in a suitable solvent or mixture of solvents (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, dimethyl sulfoxide), optionally in the presence of a base (e.g., KO-t-Bu, K3PO4, K2CO3, triethylamine, or Cs2CO3) to form the compound of formula (VII) (wherein X, X 3 By reacting with a suitable leaving group such as fluoro, chloro, bromo, iodine, BF3K, B(OH)2, or B(pinacol), tautomers of formulas (LI) and (LII) (wherein X, X) are obtained. 10 It can be prepared from (which is chloro, bromo, or iodine). For relevant examples, see Eur.J.Org.Chem.2011,18,3353;J.Org.Chem.2009,74,7951;Tetrahedron Lett.2012,53,5318;International Publication No. 2008 / 110313 and International Publication No. 2012 / 136604. Compounds of formula (VII) are known or commercially available. All such tautomers of formulas (XXXV), (XXXVI), (LI), and (LII), as well as mixtures thereof in any proportion, are considered herein. [ka] Scheme 39

[0104] As shown in Scheme 40, tautomers of formulas (LI) and (LII) (wherein X 10(wherein the salt is chloro, bromo, or iodine) can be obtained from tautomers of formulas (LIII) and (LIV) by treating with hydrochloric acid or hydrogen bromide, or with sodium nitrite, in a suitable solvent or mixture of solvents (e.g., water, acetonitrile, ethanol) at a temperature of 0°C to 50°C, optionally in the presence of a transition metal (e.g., zinc, palladium), followed by the addition of a copper salt, such as bromide or chloride. For relevant examples, see Mendeleev Commun. 2017, 27, 285. [ka] Scheme 40

[0105] As shown in Scheme 41, tautomers of formulas (LIII) and (LIV) are obtained by treatment with sodium nitrite or potassium nitrite, sodium hypochlorite or sodium azide in a suitable solvent, typically water or acetonitrile, at a temperature of -10°C to 30°C, in the presence of a strong acid (e.g., hydrochloric acid, trifluoroacetic acid, sulfuric acid, nitric acid), to obtain compounds of formula (XXXIX) or their hydrochloride salts (wherein Q is the first character in the formula). 7 Q 8 and Q 9 This is as defined for the compound of formula (I), and X 13The diazonium salt can be obtained from H or a protecting group (e.g., tetrahydropyran, 2-(trimethylsilyl)ethoxymethyl, or benzyl). For relevant examples, see J.Org.Chem.2010,75,8487;Bioorg.Med.Chem.Lett.2020,30,127216 and J.Org.Chem.1987,52,5538. The resulting diazonium salt can optionally be reacted with a nitro compound (e.g., 4-(2-nitroethenyl)morpholine, 2-nitroacetaldehyde, 2-nitropropanedial, 1,3-diethyl2-nitropropanediate) in a suitable solvent or mixture of solvents, such as water or ethanol, at a temperature of 0°C to 60°C in the presence of a base (e.g., Na2CO3, K2CO3, KOH) or a strong acid (e.g., nitric acid, hydrochloric acid). For related examples, see Mendeleev Commun. 2017, 27, 285; International Publication No. 2017 / 144708 or Khimiya Geterotsiklicheskikh Soedinenii 1986, 5, 662. Compounds of formula (XXXIX) or their hydrochlorides are known, commercially available, or readily available to experts in the art. [ka] Scheme 41

[0106] As shown in Scheme 42, a compound of formula (XX) (wherein X 6 (wherein X is an OH or C1-C4 alkoxy, e.g., methoxy or ethoxy) is optionally heated in a microwave reactor at a temperature of 30°C to 125°C in a suitable solvent or mixture of solvents (e.g., dimethylformamide, dimethyl sulfoxide, toluene, ethanol, isopropanol, water), optionally in the presence of a catalyst, e.g., hydrogen bromide or sodium carbonate, to form a compound of formula (LVI) or its hydrochloride (wherein X is an OH or C1-C4 alkoxy, e.g., methoxy or ethoxy). 6 (As defined for compounds of formula (XX)) is a compound of formula (LVII) (wherein X 14 and X 15These compounds may be the same or different and can be obtained by reacting them with chloro, bromo, iodine, O-mesyl, O-tosyl, O-trifluoromethanesulfonyl, or carbonyl or carbonyl synthetic equivalents (e.g., independently selected from aldehydes, acetals, acyl chloride or acyl bromide, esters or orthoesters). For relevant examples, see J.Med.Chem.2021,64,1197;Tetrahedron Lett.2017,58,4816 and Chem.Pharm.Bull.1992,40,1170. Compounds of formula (LVII) are known or commercially available. [ka] Scheme 42

[0107] As shown in Scheme 43, a compound of formula (LVI) or its hydrochloride (wherein R 1 This is as defined for the compound of formula (I), and X 6 The compound of formula (LVIII) (wherein R is OH or C1-C4 alkoxy, e.g., methoxy or ethoxy) is a compound of formula (LVIII) (wherein R is OH or C1-C4 alkoxy, e.g., methoxy or ethoxy) in a suitable solvent or mixture of solvents (e.g., dimethyl sulfoxide, water, tetrahydropyran, 1,4-dioxane, isopropanol, ethanol, methanol, dichloromethane) in the presence of an amination reagent (e.g., NH4OH, NH3, NH4OAc) and optionally in the presence of a base, e.g., triethylamine. 1 and X 6 This is as defined for compounds of formula (LVI), and X 16 These can be obtained by nucleophilic substitution of an alkyl or cycloalkyl group (e.g., methyl, ethyl, or cyclohexyl) sulfone. For relevant examples, see Tetrahedron 2009, 65, 1697; Heterocycles 1977, 8, 299 and Org. Biomol. Chem. 2015, 13, 10620. [ka] Scheme 43

[0108] As shown in Scheme 44, the compound of formula (LVIII) (wherein R 1 This is as defined for the compound of formula (I), and X 6 X is an OH or C1-C4 alkoxy, such as methoxy or ethoxy, and 16 A compound of formula (LIX) (wherein R is an alkyl or cycloalkyl group, e.g., methyl, ethyl, or cyclohexyl) is oxidized in a suitable solvent or mixture of solvents, e.g., dichloromethane, acetonitrile, chloroform, water, toluene, or 2-methyltetrahydrofuran, at a temperature of -10°C to 50°C, in the presence of an oxidizing agent (e.g., 3-chloroperbenzoic acid, hydrogen peroxide, oxone, or chlorine). 1 , X 6 and X 16 It can be obtained by oxidation of (as defined for the compound of formula (LVIII)). For relevant examples, see Chem.Eur.J.2021,27,14826;J.Org.Chem.2017,82,2664 and J.Chem.Soc.(C)Organic 1967,7,568. [ka] Scheme 44

[0109] As shown in Scheme 45, the compound of formula (LIX) (wherein R 1 This is as defined for the compound of formula (I), and X 6 is OH or C1~ C4 -alkoxy, for example, methoxy or ethoxy, X 16The compound of formula (LX) (wherein X is an alkyl or cycloalkyl group, e.g., methyl, ethyl, or cyclohexyl) is mixed in a suitable solvent (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, dimethyl sulfoxide) in the presence of a base (e.g., KO-t-Bu, K3PO4, K2CO3, triethylamine, or Cs2CO3) at a temperature of 25°C to 110°C under reflux and optionally with a metal catalyst and ligand complex (e.g., CuI, N,N-dimethylglycine) 6 and X 16 This is defined for compounds of formula (LVIII), and X 3 This can be obtained by reacting with a suitable leaving group such as fluoro, chloro, bromo, iodine, BF3K, B(OH)2, or B(pinacol). For relevant examples, see Eur.J.Org.Chem.2011,18,3353;J.Org.Chem.2009,74,7951;Tetrahedron Lett.2012,53,5318;International Publication Nos. 2008 / 110313 and International Publication Nos. 2012 / 136604. Compounds of formula (LX) are known or readily available to experts in the art. [ka] Scheme 45

[0110] As shown in Scheme 46, the compound of formula (V) is the compound of formula (LXI) (wherein X 1 H is X 2 is a protecting group, or X 1 and X 2 are either the same or different protecting groups, or X 1 and X 2 They form a protecting group together with the nitrogen to which they are bonded, X 1a H is X 2a is a protecting group, or X 1a and X 2a are either the same or different protecting groups, or X 1aand X 2a They form a protecting group together with the nitrogen to which they are bonded, X 2 X 2a It is different from X. 1 and X 1a Both can be hydrogen. Also, one of X 1 and X 2 And the other X 1a and X 2a However, if they form a protecting group together with the nitrogen to which they are bonded, the protecting group shall be different. Examples of protecting groups include, for example, tert-butyloxycarbonyl, benzylcarbonyl, 9-fluorenylmethylcarbonyl, trifluoroacetyl, benzyl, triphenylmethyl, benzylidenyl, p-trienesulfonyl, phthalimide, or succinimide. Here, protecting group X 1 and X 2 These compounds (which are identical or different, and optionally form a ring with the nitrogen to which they are bonded, e.g., tert-butyloxycarbonyl, benzylcarbonyl, 9-fluorenylmethylcarbonyl, trifluoroacetyl, benzyl, phthalyl, triphenylmethyl, benzylidenyl, or p-toluenesulfonyl) can be obtained by treating them with an acid (e.g., hydrochloric acid, trifluoroacetic acid) at a temperature of 0°C to 50°C in an optionally suitable solvent or mixture of solvents, e.g., dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, or diethyl ether. For relevant examples, see ChemBioChem. 2009, 10, 323 and Org. Process Res. Dev. 2002, 6, 520. Compounds of formula (LXI) are known or readily available to experts in the art. [ka] Scheme 46

[0111] As previously stated, it has been found that, surprisingly, the compound of formula (I) of the present invention possesses a very advantageous level of biological activity for practical use in protecting plants from fungal diseases.

[0112] Compounds of formula (I) can be used, for example, as active ingredients for controlling plant pests, or as non-living substances for controlling potentially harmful microorganisms or organisms to humans in the agricultural sector and related fields of use. Novel compounds are distinguished by their excellent activity at low application rates, their tolerance to plants, and their environmental safety. They possess highly useful curative, preventative, and systemic properties and can be used to protect a large number of cultivated plants. Compounds of formula (I) can also be used to suppress or eliminate pests appearing on plants or parts of plants (fruits, flowers, leaves, stems, tubers, roots) of different crops of useful plants, while simultaneously protecting those parts of the plant that will grow later from, for example, plant pathogenic microorganisms.

[0113] The present invention further relates to a method for controlling or preventing extrinsic infestation of plants or plant reproductive materials and / or harvested food crops that are susceptible to microbial attack by treating the plants or plant reproductive materials and / or harvested food crops, wherein an effective amount of the compound of formula (I) is applied to the plant, a part thereof, or its habitat.

[0114] The compound of formula (I) can also be used as a fungicide. As used herein, the term “fungicide” means a compound that controls, modifies, or prevents the growth of fungi. The term “fungicidal amount” means the amount of such compound or combination of such compounds that, when used, can produce an effect against the growth of fungi. Controlling or modifying effects include all deviations from natural occurrence, such as fungicidal or delayed growth, and prevention includes the formation of barriers or other defenses in plants to prevent fungal infections.

[0115] For protection against fungal infections and plant pathogenic fungi in the soil, the compound of formula (I) may also be used as a coating agent for treating plant propagation materials such as seeds, fruits, tubers, or seeds, or plant cuttings. The propagation material may be treated with a composition containing the compound of formula (I) before planting. For example, seeds may be treated with the coating agent before sowing. The active compound of formula (I) may also be applied (coated) to seeds by impregnating them in a liquid formulation or by coating them with a solid formulation. When the propagation material is planted, the composition may also be applied to the planting site, for example, to the sowing furrow during sowing. The present invention also relates to a method for treating such plant propagation materials and to plant propagation materials treated in this manner.

[0116] Furthermore, compounds of formula (I) can be used in relevant fields to control fungi, for example, in the protection of industrial materials including wood and wood-related industrial products, food storage, and hygiene management.

[0117] In addition, the present invention can be used, for example, to protect non-biological materials such as timber, wall panels, and paints from fungal attacks.

[0118] Compounds of formula (I) are effective against, for example, disease-causing fungi and fungal vectors, as well as plant pathogenic bacteria and viruses. Examples of these disease-causing fungi and fungal vectors, as well as plant pathogenic bacteria and viruses, are as follows: Absidia corymbifera, Alternaria spp., Aphanomyces spp., Ascochyta spp., Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A. niger, A. terrus, Aureobasidium spp. including A. pullulans, Blastomyces dermatitidis, Blumeria graminis, Bremia lactucaea This includes species of the genus Botryosphaeria (including B. lactucae, B. dothidea, and B. obtusa), species of the genus Botrytis (including B. cinerea), species of Candida (including C. albicans, C. glabrata, C. krusei, C. lusitaniae, C. parapsilosis, and C. tropicalis), species of Cephaloascus fragrans, and species of Ceratocystis. Cercospora spp. (including C. arachidicola), Cercosporidium personatum, Cladosporium spp., Claviceps purpurea, Coccidioides immitis, Cochliobolus spp., C. musae (C.This includes species of the genus Colletotrichum (including E. musae), Cryptococcus neoformans, Diaporthe, Didymella, Drecxlera, Elsinoe, Epidermophyton, Erwinia amylovora, Erysiphe (including E. cichoracearum), and Eutypa Fusarium spp., including Fusarium lata, F. culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, F. solani, Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, and Glomerella singrate. Species of the genus Histoplasma, including H. capsulatum, Guignardia bidwellii, Gymnosporangium juniperi-virginianae, Helminthosporium spp., Hemileia spp., and Histoplasma spp., including H. capsulatum.), Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, species of the genera Microsporum, Monilinia, Mucor, M. graminicola, M. pomi, Mycosphaerella spp., Oncobasidium theobromaeon, Ophiostoma picee This includes species of the genus *P. piceae*, *Paracoccidioides* spp., *P. digitatum*, *P. italicum*, *Penicillium* spp., *Petriellidium* spp., *P. maydis*, *P. philippinensis*, and *P. sorghi*, *Peronosclerospora* spp., *Peronospora* spp., *Phaeosphaeria nodorum*, *Phakopsora pachyrhizi*, and *Phellinus* ignialas. This includes species of the genera Phialophora (Phialophora spp.), Phoma (Phoma spp.), Phomopsis viticola, Phytophthora (Phytophthora spp.) including P. infestans, and Plasmopara (P. halstedii, P. viticola) including P. viticola.), species of the genus Pleospora (including P. leucotricha), species of the genus Podosphaera (including Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides), species of the genus Pseudomonas (including P. cubensis, P. humuli), species of the genus Pseudoperonospora (including P. humuli), and Pseudopeziza tracheiphylla Puccinia spp. (including P. tracheiphila, P. hordei, P. recondita, P. striiformis, P. triticina), Pyrenopeziza spp., Pyrenophora spp., Pyricularia spp. (including P. oryzae), Pythium spp. (including P. ultimum), Ramularia spp., Rhizoctonia spp., Rhizomucor pusillus, Rhizopus allitus This includes species of the genus Rhynchosporium (including S. arrhizus), species of the genus Scedosporium (including S. apiospermum and S. prolificans), species of Schizothyrium pomi, species of Sclerotinia, species of Sclerotium, species of Septoria (including S. nodorum and S. tritici), and species of Septoria.), Sphaerotheca macularis, Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix spp., Stagonospora nodorum, Stemphylium spp., Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola, Tilletia genus This includes species of the genus Trichoderma (Trichoderma spp.), including T. hazianum, T. pseudokoningii, and T. viride; species of the genus Trichophyton; species of Typhula; species of Uncinula necator; species of Urocystis; species of Ustilago; species of Venturia (Venturia spp.), including V. inaequalis; species of Verticillium; and species of Xanthomonas.

[0119] The compound of formula (I) can be used, for example, for ornamental plants such as lawns and flowers, shrubs, broad-leaved trees, or evergreen trees such as conifers, as well as for trunk injection and pest control.

[0120] Within the scope of the present invention, target crops and / or useful plants to be protected are typically berry plants, e.g., blackberries, blueberries, cranberries, raspberries and strawberries; cereals, e.g., barley, corn, millet, oats, rice, rye, sorghum, rye and wheat; fiber plants, e.g., cotton, flax, hemp, jute and sisal; crops, e.g., sugar and fodder beets, coffee, hops, mustard, rapeseed (canola), poppies, sugarcane, sunflowers, tea and tobacco; fruit trees, e.g., apples, apricots, avocados, bananas, cherries, citrus fruits, nectarines, peaches, pears and plums; grasses, e.g., Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, ryegrass, St. Augustine grass and zoysia grass Herbs, such as basil, borage, chives, coriander, lavender, lavender, mint, oregano, parsley, rosemary, sage, and thyme; legumes, such as kidney beans, lentils, peas, and soybeans; nuts, such as almonds, cashews, peanuts, hazelnuts, peanuts, pecans, pistachios, and walnuts; palms, such as oil palms; ornamental plants, such as flowers, shrubs, and trees; other trees, such as cocoa, coconuts, olives, and rubber; vegetables, such as asparagus, eggplant, broccoli, cabbage, carrots, cucumbers, garlic, lettuce, mallow, melon, okra, onions, peppers, potatoes, pumpkins, rhubarb, spinach, and tomatoes; and climbing plants, including perennial and annual crops such as grapes.

[0121] The term "useful plants" should be understood to include useful plants that have been given resistance to herbicides such as bromoxynil or certain classifications of herbicides (e.g., HPPD inhibitors, ALS inhibitors, e.g., primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovir-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors, or PPO (protoporphyrinogen-oxidase) inhibitors) through conventional breeding or genetic engineering methods. Examples of crops that have been given resistance to imidazolinones, e.g., imazamox, through conventional breeding (mutation) methods include Clearfield® Rapeseed (Canola). Examples of crops in which resistance to herbicides or a certain class of herbicides has been induced through genetic engineering include glyphosate and glufosinate-resistant maize varieties marketed under trade names RoundupReady®, Herculex I®, and LibertyLink®.

[0122] It should be understood that the term "useful plants" also includes useful plants that have been transformed using recombinant DNA techniques to synthesize one or more selectively acting toxins, such as those known from toxin-producing bacteria, particularly those of the genus Bacillus.

[0123] Examples of such plants include: YieldGard® (maize variety expressing CryIA(b) toxin); YieldGard Root-Eater Nematode® (maize variety expressing CryIIIB(b1) toxin); YieldGard Plus® (maize variety expressing CryIA(b) and CryIIIB(b1) toxins); Starlink® (maize variety expressing Cry9(c) toxin); Herculex I® (maize variety expressing CryIF(a2) toxin and the enzyme phosphinothrysin N-acetyltransferase (PAT) to achieve resistance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety expressing CryIA(c) toxin); Bollgard I® (cotton variety expressing CryIA(c) toxin); Bollgard II (registered trademark) (cotton varieties expressing CryIA(c) and CryIIA(b) toxins); VIPCOT (registered trademark) (cotton varieties expressing VIP toxin); NewLeaf (registered trademark) (potato varieties expressing CryIIIA toxin); NatureGard (registered trademark); Agrisure (registered trademark) GT advantages (GA21 glyphosate resistance trait); Agrisure (registered trademark) CB advantages (Bt11 corn-boring insect (CB) trait); Agrisure (registered trademark) RW (corn root-boring nematode trait); and Protecta (registered trademark).

[0124] The term "crop" should be understood to include crop plants transformed using recombinant DNA technology to synthesize one or more selectively acting toxins, such as those known to be derived from toxin-producing bacteria belonging to the genus Bacillus.

[0125] Toxins that can be expressed by transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis such as δ-endotoxins like Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C; or vegetative insecticidal proteins (Vip) such as Vip1, Vip2, Vip3 or Vip3A; or species of the genus Photorhabdus, such as Photorhabdus luminescens or Xenorhabdus nematophilus, for example Photorhabdus spp. or Xenorhabdus Insecticidal proteins of nematode-symbiotic bacteria such as spp.; toxins produced by animals such as scorpion toxin, spider toxin, large wasp (wasp) toxin and other insect-specific neurotoxins; toxins produced by fungi such as Streptomycete toxin, plant lectins such as pea lectin, barley lectin or snowdrop lectin; aglutinin; proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patain, cystatin, and papain inhibitors; lysine, Examples include ribosome-inactivating proteins (RIPs) such as corn-RIP, abrin, rufin, saporin, or briodin; steroid metabolic enzymes such as 3-hydroxysteroid xidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, and 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.

[0126] Furthermore, it should be understood that in connection with the present invention, there exist δ-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or plant insecticidal proteins (Vip), such as Vip1, Vip2, Vip3, or Vip3A, as well as explicitly hybrid toxins, cleavage toxins, and modified toxins. Hybrid toxins are produced by recombination through novel combinations of different domains of these proteins (see, for example, International Publication No. 02 / 15701). For example, cleavage toxins such as cleavage Cry1Ab are known. In the case of modified toxins, one or more amino acids of the natural toxin are substituted. In such amino acid substitutions, a naturally occurring protease recognition sequence is preferably inserted into the toxin; for example, in the case of Cry3A055, a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see International Publication No. 03 / 018810).

[0127] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in European Patent Publication No. 0374753, International Publication No. 93 / 07278, International Publication No. 95 / 34656, European Patent Publication No. 0427529, European Patent Publication No. 451878, and International Publication No. 03 / 052073.

[0128] The processes for preparing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acid and its preparations are known, for example, from International Publication No. 95 / 34656, European Patent Application Publication No. 0367474, European Patent Application Publication No. 0401979, and International Publication No. 90 / 13651.

[0129] The toxins contained in transgenic plants confer resistance to harmful insects. Such insects may belong to any of the insect taxa, but are typically found among beetles (Coleoptera), diptera (Diptera), and butterflies (Lepidoptera).

[0130] 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® (maize variety expressing Cry1Ab toxin); YieldGard Rootworm® (maize variety expressing Cry3Bb1 toxin); YieldGard Plus® (maize variety expressing Cry1Ab and Cry3Bb1 toxins); Starlink® (maize variety expressing Cry9C toxin); Herculex I® (maize variety expressing Cry1Fa2 toxin and the enzyme phosphinothrysin N-acetyltransferase (PAT) to achieve resistance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety expressing Cry1Ac toxin); Bollgard I® (cotton variety expressing Cry1Ac toxin); Bollgard These include II (registered trademark) (cotton varieties expressing Cry1Ac and Cry2Ab toxins); VipCot (registered trademark) (cotton varieties expressing Vip3A and Cry1Ab toxins); NewLeaf (registered trademark) (potato varieties expressing Cry3A toxin); NatureGard (registered trademark), Agrisure (registered trademark) GT Advantage (GA21 glyphosate-tolerant trait), Agrisure (registered trademark) CB Advantage (Bt11 corn-boring insect (CB) trait), and Protecta (registered trademark).

[0131] Further examples of such transgenic crops are as follows: 1. Bt11 maize, manufactured by Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31, 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified maize (Zea mays) conferred resistance to attacks by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) through transgenic expression of the cleavage-type Cry1Ab toxin. Bt11 maize also achieves resistance to the herbicide glufosinate ammonium by transgenic expression of the enzyme PAT. 2. Bt176 maize, manufactured by Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified maize (Zea mays) conferred resistance to attacks by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) through transgenic expression of Cry1Ab toxin. Bt176 maize also achieves resistance to the herbicide glufosinate ammonium through transgenic expression of the enzyme PAT. 3. MIR604 maize, manufactured by Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Maize conferred insect resistance by transgenic expression of modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G protease recognition sequence. The preparation of such transgenic maize plants is described in International Publication No. 03 / 018810. 4. MON863 maize from Monsanto Europe, SA270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON863 expresses the Cry3Bb1 toxin and has resistance to certain Coleoptera insects. 5. Monsanto Europe SA270-272 Avenue de Tervuren, B-1150 Brussels, Belgium. IPC531 cotton, registration number C / ES / 96 / 02. 6. 1507 maize, manufactured by Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Genetically modified maize to express the protein Cry1F to achieve resistance to certain Lepidoptera insects and the PAT protein to achieve resistance to the herbicide glufosinate ammonium. 7. NK603×MON810 corn, registered in Monsanto Europe, SA270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. This is a conventional hybrid corn variety created by crossing genetically modified varieties NK603 and MON810. NK603×MON810 corn transgenically expresses the protein CP4 EPSPS obtained from the Agrobacterium sp. strain CP4, thereby conferring resistance to the herbicide Roundup® (containing glyphosate). It also transgenicly expresses the Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstaki, thereby providing resistance to certain Lepidoptera, including the European corn borer.

[0132] Compounds of formula (I) are particularly effective against Botrytis cinerea in the Rosaceae, Vitaceae, Solanaceae, Cucurbitaceae, and Fabaceae families; Glomerella lagenarium in the Cucurbitaceae family; Sclerotinia sclerotiorum in the Fabaceae, Brassicaceae, and Asteraceae families, such as soybeans, rapeseed, and sunflowers, respectively; Alternaria solani in the Solanaceae family, such as tomatoes and potatoes; and Monographella nivalis in the Poaceae family. It can be used to control or prevent plant pathogenic diseases caused by plant pathogenic fungi such as Pyrenophora teres against grasses such as barley, and Mycosphaerella graminicola against grasses such as wheat.

[0133] As used herein, the term “habitat” means a field where plants are growing, or where the seeds of a cultivated plant have been sown, or where the seeds will be sown in the soil. This includes the soil, seeds and seedlings, and established vegetation.

[0134] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves, and fruits.

[0135] The term “plant propagation material” is understood to refer to the reproductive parts of a plant, such as seeds, and its vegetative parts, such as cuttings or tubers, which can be used for propagation, such as potatoes. Examples include seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes, and parts of the plant body. Sprouted plants and young plants that are transplanted after germination or after emerging from the soil may also be included. These young plants can be protected by complete or partial immersion treatment before transplanting. Preferably, “plant propagation material” is understood to refer to seeds.

[0136] Compounds of formula (I) may be used in their original form or, preferably, in combination with formulations conventionally used in the art of formulation. For this purpose, they may be appropriately incorporated in known forms into emulsifiable concentrates, coating pastes, ready-to-spray or dilutable solutions or suspensions, diluted emulsions, wettable powders, soluble powders, powdering powders, granules, as well as encapsulations in polymeric substances. As with the types of compositions, methods of application such as spraying, misting, powdering, granulation, coating, or pouring are selected according to the intended purpose and general circumstances. The compositions may also include further auxiliary agents such as stabilizers, defoamers, viscosity modifiers, binders, or tackifiers, as well as fertilizers, sources of trace elements, or other formulations for obtaining special effects.

[0137] Suitable carriers and auxiliaries, for example, carriers and auxiliaries for agricultural use, may be solids or liquids and are substances useful in compounding techniques, such as natural or recycled inorganic substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders, or fertilizers. Such carriers are described, for example, in International Publication No. 97 / 33890.

[0138] A suspension concentrate is an aqueous formulation in which finely ground solid particles of an active compound are suspended. Such formulations contain anti-settling agents and dispersants, and may further contain wetting agents, as well as defoaming agents and crystal growth inhibitors to enhance activity. When used, these concentrates are diluted in water and typically applied as a spray to the area to be treated. The amount of the active ingredient may range from 0.5% to 95% of the concentrate.

[0139] Wettable powders are in the form of finely ground particles that disperse easily in water or other liquid carriers. The particles contain the active ingredient held within a solid matrix. Typical solid matrices include Fuller's earth, kaolin clay, silica, and other easily hygroscopic organic or inorganic solids. Wettable powders typically contain 5% to 95% of the active ingredient and small amounts of wetting agents, dispersants, or emulsifiers.

[0140] Emulsifying concentrates are homogeneous liquid compositions that are dispersible in water or other liquids and may consist solely of an active compound and a liquid or solid emulsifier, or they may also contain liquid carriers such as xylene, high-boiling aromatic naphtha, isophorone, and other non-volatile organic solvents. When used, these concentrates are dispersed in water or other liquids and typically 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.

[0141] Granular formulations include both extruded materials and relatively coarse particles and are typically applied undiluted to the area requiring treatment. Typical carriers for granular formulations include sand, fuller's soil, attapulgite clay, bentonite clay, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, gypsum, wood flour, crushed corn cobs, crushed peanut shells, sugars, 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 typically contain 5% to 25% active ingredients, which may include surfactants such as high-boiling aromatic naphtha, kerosene, and other petroleum fractions or vegetable oils; and / or adhesives such as dextrin, glue, or synthetic resins.

[0142] Powder for dispersal is a fluid mixture of an active ingredient and finely ground solids such as talc, clay, powder, and other organic and inorganic solids that act as a dispersant and carrier.

[0143] Microcapsules are typically droplets or granules of an active ingredient encapsulated in an inert, porous shell that allows the encapsulated material to be released into the surroundings at a controlled rate. Encapsulated droplets are typically 1 to 50 microns in diameter. The encapsulated liquid typically constitutes 50 to 95% of the capsule's weight and may include a solvent in addition to the active compound. Encapsulated granules are generally porous granules having a porous membrane that seals the pore openings of the granule, retaining the active species in liquid form within the pores of the granule. Granules are typically in the range of 1 millimeter to 1 centimeter in diameter, preferably 1 to 2 millimeters. Granules are formed by extrusion, agglomeration, or prilling, or are naturally occurring. Examples of such materials include vermiculite, calcined clay, kaolin, attapulgite clay, sawdust, and granular carbon. The shell or membrane material includes natural and synthetic rubber, cellulosic materials, styrene-butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes, and starch xanthetes.

[0144] Other useful formulations for agricultural chemical applications include simple solutions of the active ingredient in a solvent that completely dissolves it at the desired concentration, such as acetone, alkylated naphthalene, xylene, and other organic solvents. Pressurized sprayers may also be used, in which the active ingredient is dispersed in a finely powdered form as a result of evaporation of a low-boiling point dispersant solvent carrier.

[0145] Suitable agricultural additives and carriers useful for formulating the above-described composition of the present invention are well known to those skilled in the art.

[0146] Examples of liquid carriers that can be used include water, toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetate, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidinone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-Trichloroethane, 2-Heptanone, 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, Methoxypropanol, Methyl isoamyl ketone, Methyl isobutyl ketone, Methyl laurate, Methyl octanoate, Methyl oleate, Methylene chloride, m-Xylene, n-Hexane, n-Oc Examples include tylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol and amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol and other high molecular weight alcohols, ethylene glycol, propylene glycol, glycerin and N-methyl-2-pyrrolidinone. Water is generally the optimal carrier for diluting concentrates.

[0147] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselgool, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, fuller's earth, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, walnut husk powder, and lignin.

[0148] A wide range of surfactants are advantageously used in both liquid and solid compositions, particularly those designed to be diluted with a carrier before application. These agents, when used, typically constitute 0.1% to 15% by weight of the formulation. They can be anionic, cationic, nonionic, or polymeric and can be used as emulsifiers, wetting agents, suspending agents, or for other purposes. Typical surfactants include alkyl sulfates such as diethanolammonium lauryl sulfate; alkylaryl sulfonates, e.g., calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, e.g., nonylphenol-C.sub.18 ethoxylate; alcohol-alkylene oxide addition products, e.g., tridecyl alcohol-C.sub.16 ethoxylate; soaps such as sodium stearate; alkylnaphthalene sulfonate salts, e.g., sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, e.g., sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, e.g., sorbitol oleate; quaternary amines such as lauryltrimethylammonium chloride; polyethylene glycol esters of fatty acids, e.g., polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters.

[0149] Other additives commonly used in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet regulators, pigments, antioxidants, foaming agents, defoaming agents, light-shielding agents, compatibilizers, defoaming agents, metal ion chelating agents, neutralizing agents and buffering agents, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, micronutrients, mitigating agents, lubricants and fixing agents.

[0150] In addition, other biocides or compositions may be combined with the composition of the present invention and used in the method of the present invention, either simultaneously with or sequentially with the composition of the present invention. When applied simultaneously, these further active ingredients may be compounded together with the composition of the present invention or mixed, for example, in a spray tank. These further biocides may be fungicides, herbicides, insecticides, fungicides, acaricides, nematicides, and / or plant growth regulators.

[0151] Pesticides are referred to herein by their common names and are publicly known, for example, from “The Pesticide Manual”, 15th Ed., British Crop Protection Council 2009.

[0152] In addition, the compositions of the present invention may also be applied in combination with one or more systemic acquired resistance inducers ("SAR" inducers). SAR inducers are known and 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.

[0153] The compound of formula (I) is typically used in the form of a pesticide composition and may be applied simultaneously with or consecutively to a crop or plant to be treated with further compounds. These further compounds may be, for example, fertilizers or sources of trace elements or other preparations that affect plant growth. These may also be selective or non-selective herbicides, as well as insecticides, fungicides, bactericidal agents, nematicides, molluskicides, or mixtures thereof, and may include, as necessary, further carriers, surfactants, or application enhancers commonly used in the art of the formulations.

[0154] The compounds of formula (I) may be used in the form of compositions for the control or protection against plant pathogenic microorganisms, comprising at least one compound of formula (I) or at least one preferred individual compound as defined herein as an active ingredient, in free form or in the form of an agrochemically usable salt, and at least one of the adjuvants described above.

[0155] Accordingly, the present invention provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I), an agriculturally acceptable carrier, and optionally an auxiliary agent. The agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural carriers are well known in the art. Preferably, in addition to the compound of formula (I), the composition may include at least one or more toxicogenic compounds, such as additional fungicidal active ingredients.

[0156] The compound of formula (I) may be the sole active ingredient in the composition, or, where appropriate, may be mixed with one or more additional active ingredients such as pest control agents, fungicides, synergists, herbicides, or plant growth regulators. The additional active ingredients may, in some cases, result in unexpected synergistic effects.

[0157] Suitable additional active ingredients include: acyl amino acid fungicides, aliphatic nitrogen fungicides, amide fungicides, anilide fungicides, antibiotic fungicides, aromatic fungicides, arsenic fungicides, arylphenyl ketone fungicides, benzamide fungicides, benzanilide fungicides, benzimidazole fungicides, benzothiazole fungicides, botanical fungicides, cross-linked diphenyl fungicides, carbamate fungicides, carbanilate fungicides, conazole fungicides, copper fungicides, dicarboximide fungicides, dinitrophenol fungicides, dithiocarbamate fungicides, dithiolane fungicides, flamido fungicides, flanilide fungicides, hydrazide fungicides, and imidazole fungicides. Fungicides, mercury fungicides, morpholine fungicides, organophosphate fungicides, organotin fungicides, oxathiin fungicides, oxazole fungicides, phenylsulfamide fungicides, polysulfide fungicides, pyrazole fungicides, pyridine fungicides, pyrimidine fungicides, pyrrole fungicides, quaternary ammonium fungicides, quinoline fungicides, quinone fungicides, quinoxaline fungicides, strobilurin fungicides, sulfonanilide fungicides, thiadiazole fungicides, thiazole fungicides, thiazolidinedione fungicides, thiocarbamate fungicides, thiophene fungicides, triazine fungicides, triazole fungicides, triazolopyrimidine fungicides, urea fungicides, valinamide fungicides, and zinc fungicides.

[0158] Specific examples of suitable additional active ingredients include petroleum, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol, 2,4-dichlorophenylbenzenesulfonate, 2-fluoro-N-methyl-N-1-naphthylacetamide, 4-chlorophenylphenylsulfone, acetoprole, aldoxycarb, amidithione, amidethioate, amiton, amiton hydrogen oxalate, amitraz, aramite, arsenic trioxide, azobenzene, azothoate, benomyl, benoxaphos, benzyl benzoate, bixafen, brofenvalerate, and bromocicle. Bromophos, bromopropylate, buprofezin, butocarboxime, butoxycarboxime, butylpyridaben, calcium polysulfide, campechlor, carbanolate, carbophenothione, simiazole, chymitianato, chlorbenside, chlordimeform, chlordimeform hydrochloride, chlorphenetol, chlorfensone, chlorfensulfide, chlorobenzilate, chloromebform, chloromethiurone, chloropropylate, chlorthiophos, synerin I, synerin II, synerin, closantel, coumaphos, crotamiton, cloto Xyphos, Cufraneb, Cyanthoate, DCPM, DDT, Demefion, Demefion-O, Demefion-S, Demeton-Methyl, Demeton-O, Demeton-O-Methyl, Demeton-S, Demeton-S-Methyl, Demeton-S-Methylsulfone, Diclofluanide, Dichlorvos, Dicriphos, Dienochlor, Dimehox, Dynex, Dynex-Dikrexin, Dinocap-4, Dinocap-6, Dinoctone, Dinopenton, Dinosulfone, Dinotervone, Dioxathione, Diphenylsulfone, Disulfiram, DNOC, Dofenapine, Dora Mectin, Endothion, Eprinomectin, Ethoate-methyl, Etrimphos, Phenazaflor, Fenbutasin oxide, Phenothiocarb, Fenpyrad, Fenpyroximate, Fenpyrazamine, Fenson, Fentriphanil, Flubendimine, Flucycloxurone, Fluenetil, Fluolbenside, FMC1137, Formetanate, Formetanate hydrochloride, Formparanate, Gamma-HCH, Gliodin, Halfenprox, Hexadecylcyclopropane carboxylate, Isocarbophos, Jasmolin I, Jasmolin II,Iodophenphos, Lindan, Malonoben, Mecarbam, Mephosphoran, Mesulfen, Methacryphos, Methyl bromide, Metolcarb, Mexacarbate, Milbemycin oxime, Mipahox, Monoclotophos, Morphothion, Moxidectin, Nared, 4-Chloro-2-(2-Chloro-2-methylpropyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one, Niflulidide, Nikcomycin, Nitrilacarb, Nitrilacarb 1:1 zinc chloride complex, Omethoate, Oxydeprophos, Oxydisulfone, pp'-DDT Parathion, permethrin, fencapton, phosalon, phosphoran, phosphamidone, polychloroterpenes, polynactin, proclonol, promacil, propoxer, protidathion, protoate, pyrethrin I, pyrethrin II, pyrethrin, pyridafenthion, pyrimitate, quinalphos, quinthiophos, R-1492, phosglycine, rotenone, shlardan, sebuphos, selamectin, sofamide, SSI-121, sulfiram, sulfuramide, sulfotep, sulfur, diflovidazine, tau-fluvalinate, TEPP, terba Tetradiphon, Tetrasul, Thiaphanox, Thiocarboxim, Thiophanox, Thiometon, Thioquinox, Thuringensis, Triamiphos, Triatene, Triazophos, Triazurone, Triphenophos, Trinactin, Bamidthione, Vaniliprole, Bethoxazine, Copper Dioctanoate, Copper Sulfate, Sibutrin, Diclofen, Dichlorophene, Endotar, Fetin, Slaked Lime, Narbam, Quinoclamine, Quinonamide, Simazine, Triphenyltin Acetate, Triphenyltin Hydroxide, Culfomate, Piperazine, Thiophanate, Chloride Larose, fenthion, pyridine-4-amine, strychnine, 1-hydroxy-1H-pyridine-2-thion, 4-(quinoxaline-2-ylamino)benzenesulfonamide, 8-hydroxyquinoline sulfate, bronopol, copper hydroxide, cresol, dipyrithione, dodicine, phenaminosulf, formaldehyde, hydrargafen, kasugamycin, kasugamycin hydrochloride hydrate, nickel bis(dimethyldithiocarbamate), nitrapyrine, octylinone, oxolinic acid, oxytetracycline, potassium hydroxyquinoline sulfate,Probenazole, streptomycin, streptomycin sesquisulfate, tecrophthalam, thiomersal, Adoxophyes orana GV, Agrobacterium radiobacter, Amblyseius spp., Anagrapha falcifera NPV, Anagrus atomus, Aphelinus abdominalis, Aphidius colemani, Aphidoletes aphidimyza, Autographa californica NPV, Bacillus sphaericus Neide, Beauveria blongniartii brongniartii), Chrysoperla carnea, Cryptolaemus montrouzieri, Cydia pomonella GV, Dacnusa sibirica, Diglyphus isaea, Encarsia formosa, Eretmocerus eremicus, Heterorhabditis bacteriophora and H. megidis (H.megidis), ladybug (Hippodamia convergens), leptomastix dactylopii, Macrolophus caliginosus, cutworm (Mamestra brassicae) NPV, Metaphycus helvolus, Metarhizium anisopliae var. acridum, Metarhizium anisopliae var. anisopliae, pine sawfly (Neodiprion sertifer NPV and N. lecontei NPV), Orius (spp.), Paecilomyces fumosoroseus, Chilean predatory mite (Phytoseiulus persimilis), Steinernema bibionis, Steinernema carpocapsae, Steinernema feltiae, Steinernema glaseri, Steinernema riobrave, Steinernema riobravis, Steinernema scapterisci, Steinernema spp., Trichogramma (spp.), Typhlodromus occidentalis, Verticillium lecanii, etc. Aphorate, Bisadyl, Busulfan, Dimatif, Hemel, Hempa, Metepa, Methiotepa, Methyl aphorate, Moldido, Penflurone, Tepa, Thiohempa, Thiotepa, Tretamine, Uredepa, (E)-Deca-5-en-1-yl acetate and (E)-Deca-5-en-1-ol, (E)-Trideca-4-en-1-yl acetate, (E)-6-methylhepta-2-en-4-ol, (E,Z)-Tetradeca-4,10-dien-1-yl acetate, (Z)-Dodeca-7-en-1-yl acetate, (Z)-Hexadeca-11-enal, (Z)-Hexadeca-11-en-1-ylacetate, (Z)-Hexadeca-13-en-11-in-1-ylacetate, (Z)-Icosa-13-en-10-one, (Z)-Tetradeca-7-en-1-ar, (7E,9Z)-Dodeca-7,9-diene-1-ylacetate, (9Z,11E)-Tetradeca-9,11-diene-1-ylacetate, (9Z,12E)-Tetradeca-9,12-diene-1-ylacetate, 14-Methyloctadeca-1-en, 4-Methylnonan-5-ol and 4-Methylnonan-5-one, Alpha-Ma Lucistriatin, Brevicomin, Codrelua, Codlememon, Kyurua, Disparua, Dodeca-8-en-1-ylacetate, Dodeca-9-en-1-ylacetate, Dodeca-8,10-dien-1-ylacetate, Dominicalua, Ethyl 4-methyloctanoate, Eugenol, Frontalin, Grandlua, Grandlua I, Grandlua II, Grandlua III, Grandlua IV, Hexalua, Ipsdienol, Ipsenol, Japonilua, Lineatin, Littleua, Luluua, Medlua, Megatomoic acid, Methyl eugenol Muscarua, Octadeca-2,13-diene-1-ylacetate, Octadeca-3,13-diene-1-ylacetate, Orfura, Orictalua, Ostramon, Sigurua, Solzidine, Sulcatol, Tetradeca-11-en-1-ylacetate, Trimedolua, Trimedolua A, Trimedolua B1, Trimedolua B2, Trimedolua C, Trunk-Col, 2-(octylthio)ethanol, Butopyronoxyl, Butoxy(polypropylene glycol), Dibutyl adipate, Dibutyl phthalate, Dibutyl succinate, Diethyltoluamide,Dimethyl carbate, dimethyl phthalate, ethyl hexanediol, hexaamide, methquin-butyl, methyl neodecanamide, oxamate, picaridin, 1-dichloro-1-nitroethane, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane, 1,2-dichloropropane and 1,3-dichloropropene, 1-bromo-2-chloroethane, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate, 2-(1,3-dithiolan-2-yl)phenyldimethylcarbamate, 2-(2-butoxyethoxy)ethylthiocyanate, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenylmethylcarbamate, 2-(4-chloro-3,5-xy (Lyloxy)ethanol, 2-chlorovinyldiethyl phosphate, 2-imidazolidone, 2-isovalerylindan-1,3-dione, 2-methyl(propa-2-inyl)aminophenylmethylcarbamate, 2-thiocyanatoethyl laurate, 3-bromo-1-chloropropa-1-ene, 3-methyl-1-phenylpyrazole-5-yldimethylcarbamate, 4-methyl(propa-2-inyl)amino-3,5-xylylmethylcarbamate, 5,5-dimethyl-3-oxocyclohexa-1-enyldimethylcarbamate, acetylone, acrylonitrile, aldrin, allosamidin, allylxycarb, alpha-ecdysone, aluminum phosphide, aminocarb, anabasine, atedathion, azamethiphos, Bacillus thuringiensis (thuringiensis) Delta endotoxin, barium hexafluorosilicate, barium polysulfide, bartholin, Bayer 22 / 190, Bayer 22408, beta-cyfluthrin, beta-cypermethrin, bioetanomethrin, biopermethrin, bis(2-chloroethyl) ether, borax, bromfenbinphos, bromo-DDT, bufencarb, butacarb, butathiophos, butonate, calcium arsenate, calcium cyanide, carbon disulfide, carbon tetrachloride, cartap hydrochloride, sebadin, chlorbicycline, chlordan, chlordecone, chloroform, chloropicrin, chlorphoxime, chlorprazophos, cis-resmethrin, cismethrin,Crocitrin, copper acetoarsenite, copper arsenate, copper oleate, cumithoate, cryolite, CS708, cyanophenphos, cyanophos, ciclethrin, cythioate, d-tetramethrin, DAEP, dazomet, decarbofuran, diamidaphos, dicapton, diclofenthion, diclesyl, dicyclanil, dierudrin, diethyl 5-methylpyrazole-3-yl phosphate, dirol, dimefluthrin, dimethane, dimethrin, dimethylvinphos, dimethilane, dinoprop, dinosam, dinoseb, diophenolane, dioxabenzophos, diticlophos DSP, Ecdysterone, EI1642, EMPC, EPBP, Etaphos, Ethiofencarb, Ethyl Formate, Ethylene Dibromide, Ethylene Dichloride, Ethylene Oxide, EXD, Fenchlorphos, Phenetacarb, Fenitrothion, Phenoxacrim, Fenpyritrin, Fensulfothion, Fenthion-Ethyl, Flucoflon, Fosmethilane, Fospilate, Phosthiethane, Frathiocarb, Frethrin, Guazatin, Guazatin Acetate, Sodium Tetrathiocarbonate, Halfenprox, HCH, HEOD, Heptachlor, Heterophos, HHDN Hydrogen cyanide, Hikincarb, IPSP, Isazofos, Isobenzan, Isodrine, Isofenphos, Isolane, Isoprothiolane, Isoxathion, Juvenile hormone I, Juvenile hormone II, Juvenile hormone III, Kereban, Quinoprene, Lead arsenic, Leptophos, Lilimphos, Litidathion, m-Cumenylmethylcarbamate, Magnesium phosphide, Magidox, Mecarfone, Menazone, Mercurous chloride, Mesulfenphos, Metam, Metam-potassium, Metam-sodium, Methanesulfonyl fluoride, Metoclophos, Methoprene, Methotrine, Methoxychloride Lol, methyl isothiocyanate, methyl chloroform, methylene chloride, methoxadiazone, Milex, naphthalophos, naphthalene, NC-170, nicotine, nicotine sulfate, nithiazine, nornicotine, O-5-dichloro-4-iodophenyl O-ethylethyl phosphonothioate, O,O-diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate, O,O-diethyl O-6-methyl-2-propylpyrimidine-4-yl phosphorothioate, O,O,O',O'-tetrapropyl dithiopyrophosphate, oleic acid,Para-dichlorobenzene, parathion-methyl, pentachlorophenol, pentachlorophenyl laurate, PH60-38, fencapton, fosnikrol, phosphine, phoxime-methyl, pyrimetaphos, polychlorodicyclopentadiene isomer, potassium arsenite, potassium thiocyanate, precosen I, precosen II, precosen III, primidophos, profluthrin, promecarb, prothiophos, pyrazofos, pyresmethrin, quassia, quinalphos-methyl, quinothion, lafoxanide, resmethrin, rotenone, cadetrin, liania, ryanodine, sabajira), shlardan, sebuphos, SI-0009, Thiapronil, sodium arsenite, sodium cyanide, sodium fluoride, sodium hexafluorosilicate, sodium pentachlorophenoxide, sodium selenite, sodium thiocyanate, sulcoflon, sulcoflon-sodium, sulfuryl fluoride, sulprophos, tar oil, tadimucarb, TDE, tebupyrimphos, temephos, terarethrin, tetrachloroethane, cyclaphos, thiocyclam, thiocyclam hydrogen oxalate, thionazine, thiosultap, thiosultap-sodium, tralomethrin, transpermethrin, triazamate, trichlormetaphos-3, trichloronato, trimetacarb, tolprocarb, triclopyricarb, triplen, veratridine, veratrin, XMC, Zetameth Thrin, zinc phosphide, zolaprophos and meperfluthrin, tetramethylfluthrin, bis(tributyltin) oxide, bromoacetamide, ferric phosphate, niclosamide-olamine, tributyltin oxide, pyrimorph, triphenmorph, 1,2-dibromo-3-chloropropane, 1,3-dichloropropane, 3,4-dichlorotetrahydrothiophene 1,1-dioxide, 3-(4-chlorophenyl)-5-methylrhodanine, 5-methyl-6-thioxo-1,3,5-thiadiadinan-3-ylacetic acid, 6-isopentanylaminopurine, anisifurupurine, benkrothiaz, cytokinin, DCIP, furfural, isamidophos, kinetin, mulberry dark spot fungus (Myrothecium vercaria) Composition of verrucaria, tetrachlorothiophene, xylenol, zeatin, potassium ethylxanthogenicate, acibenzolar, acibenzolar-S-methyl, Japanese knotweed (Reynoutria sachalinensis) extract, alpha-chlorohydrin, anthucina, barium carbonate, bisthiosemi, brodiphacomum, bromadiolon, bromethaline, chlorophacinone, cholecalciferol, coumacrol, coumafuryl, coumatetralyl, crimidine, diphenacum, difethiaron, diphacinone, ergocalciferol, fulocumafen, fluoroacetamide, flupropadine, flupropadine hydrochloride, norbolmid, fosacetim, phosphorus, pidomone, pyrinulone, siriloside,Sodium fluoroacetate, thallium sulfate, warfarin, 2-(2-butoxyethoxy)ethyl piperonylate, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohexa-2-enone, farnesol and nerolidol, berbutin, MGK264, piperonyl butoxide, piperotal, propyl isomer, S421, sesamex, sesamolin, sulfoxide, anthraquinone, copper naphthenate, copper oxychloride, dicyclopentadiene, thyram, zinc naphthenate, thyram, imanin, ribavirin, chloroinconazide, mercuric oxide, thi Ophanate-methyl, azaconazole, vitertanol, bromconazole, cyproconazole, difenoconazole, diniconazole, epoxyconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafole, flametopyr, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, mycrobutanil, paclobutrazol, pefurazoate, penconazole, prothioconazole, pyrifenox, prochloraz, propiconazole, pyrizoxazole, simeconazole, tebuconazole Tetraconazole, triadimephon, triadimenol, triflumizole, triticonazole, ancimidor, phenalimol, nualimol, bupirimate, dimethirimol, etirimol, dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph, cyprodinil, mepanipyrim, pyrimethanil, fenpiclonil, fludioxonil, venalaxyl, flaraxyl, metalaxyl, R-metalaxyl, ofurase, oxadixyl, carbendazim, debacarb, fuberidazole, thiabendazole, clozoline Diclozolin, microzolin, procymidone, vinclozolin, boscalid, carboxyne, fenflam, flutolanil, mepronil, oxycarboxyne, penthiopyrad, tifluzamide, dozin, iminooctadine, azoxystrobin, dimoxystrobin, enestrobrin, phenaminestrobin, fluphenoxystrobin, fluoxastrobin, kresoxim-methyl, metminostrobin, trifloxystrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin,Farbum, Mancozeb, Maneb, Methylam, Propineb, Zineb, Captahol, Captan, Fluorimide, Forpet, Tolfluanide, Bordeaux mixture, Copper oxide, Mancopper, Oxine-copper, Nitrotar-isopropyl, Edifenphos, Iprobenphos, Phosdiphen, Torukurophos-methyl, Anirazine, Benthiavaricarb, Blastocydin-S, Chloroneb, Chlorothalonil, Cyflufenamid, Simoxani Ru, cyclobutrifluram, diclocimet, diclomazine, dichloran, diethofencarb, dimethomorph, flumorph, dithianone, etaboxam, etridiazole, famoxadone, phenamidon, phenoxanil, ferimzon, fluazinam, flumethylsulfolim, fluopicolide, fluoxythioconazole, flusulfamide, fluxapyroxad, fenhexamide, fosetyl-aluminum, himexazole, Iprovalicarb, cyazofamide, metasulfocarb, metraphenone, pencyclon, phthalide, polyoxin, propamocarb, pyribencarb, proquinazide, pyroquilon, pyriophenone, quinoxyfen, quintozen, thiadinyl, triazoxide, tricyclazole, triforine, validamycin, valifenarate, zoxamide, mandipropamide, flubeneteram, isopyrazam, sedaxane, benzovindiflupir, pidflumetofen, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4 ',5'-trifluorobiphenyl-2-yl)amide, isoflucipram, isothianil, dipimethitron, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carboniriltrine, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethylindan-4-yl]pyridine-3-carboxamide, 4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine-3-carboniriltrine, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3- [Rimethylindan-4-yl]pyrazole-4-carboxamide, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-2,5-dimethylpyrazole-3-amine, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, Fluindapyr, Cumethoxystrobin (Diaxiangjun), Rubenmixianane, Diclobentiazox, Mandestrobin, 3-(4,4-difluoro-3,4-dihydro- 3,3-dimethylisoquinoline-1-yl)quinolone, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol, oxathiapiproline, tert-butyl N-[6-[[[(1-methyltetrazole-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate, pyraziflumid, impulfluxam, trollprocarb, mefentrifluconazole, ibufentrifluconazole, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethylindan-4-yl]pyridine-3-carboxamide, N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methyl-formamidine, N'-[4-(4,5-dichlorothiazole-2-yl)oxy-2,5-dimethylphenyl]-N-ethyl-N-methyl-formamidine, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazole-1-yl]acetyl]-4-piperidyl]thiazole-4-yl]-4,5-dihydroisoxazole-5-yl]-3- [Lolophenyl]methanesulfonate, buta-3-inyl N-[6-[[(Z)-[(1-methyltetrazole-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate, methyl N-[[5-[4-(2,4-dimethylphenyl)triazole-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-tri Methylindan-4-yl]pyrazole-4-carboxamide, 1-[2-[[1-(4-chlorophenyl)pyrazole-3-yl]oxymethyl]-3-methylphenyl]-4-methyltetrazole-5-one, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazole-1-yl)phenoxy]methyl]phenyl]tetrazole-5-one, aminopyriphen, ametoctrazine, amisulbrom, penfluphen, (Z,2E)-5-[1-(4-chlorophenyl)pyrazole- 3-yl]oxy-2-methoxyimino-N,3-dimethyl-penta-3-enamide, floryl picoxamide, fenpicoxamide, tebufloxin, isofetamide, N-[2-[2,4-dichlorophenoxy]phenyl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide, benzothiostrobin, phenamacryl, 5-amino-1,3,4-Thiadianazole-2-thiol zinc salt (2:1), fluopyram, fluthianil, fluopimomide, pyrapropoin, picarbtrazox, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethylindan-4-yl)pyridine-3-carboxamide, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazole-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-pyrimidine methanol, fluoxapiproline, enoxastrobin, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazole-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazole-1-yl)propyl]-3-pyridyl]oxy]benzonitrile, trinexapac, chemoxystrobin, johnshenmycin, thiodiazole copper, zinc thiazole, amectotractin, iprodione, sevoctylamine, , N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxyethoxy]-3-pyridyl]-N-ethyl-N-methylformamidine, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxyethoxy]-3-pyridyl]-N-ethyl-N-methylformamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-ethyl-N-methylformamidine, N'-[5-chloro N'-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-ethyl-N-methylformamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-isopropyl-N-methylformamidine (These compounds can be prepared by the method described in International Publication No. 2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl N-formamidine (this compound can be prepared by the method described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methylformamidine, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methylphenyl]-N-isopropyl-N-methylformamidine (these compounds These compounds can be prepared by the method described in International Publication No. 2018 / 228896; N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetane-2-yl]phenyl]-N-methyl-formamidine, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine (these compounds can be prepared by the method described in International Publication No. 2019 / 110427);N-[(1R)-1-benzyl-3-chloro-1-methylbuta-3-enyl]-8-fluoroquinoline-3-carboxamide, N-[(1S)-1-benzyl-3-chloro-1-methylbuta-3-enyl]-8-fluoroquinoline-3-carboxamide, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methylpropyl]-8-fluoroquinoline-3-carboxamide, N-[( 1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoroquinoline-3-carboxamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoroquinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoroquinoline-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-fluoroquinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl N-((1R)-1-benzyl-3-chloro-1-methylbuta-3-enyl)-8-fluoroquinoline-3-carboxamide, N-((1S)-1-benzyl-3-chloro-1-methylbuta-3-enyl)-8-fluoroquinoline-3-carboxamide (These compounds can be prepared by the method described in International Publication No. 2017 / 153380);1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethylisoquinoline, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 1-(6-chloro-7-methylpyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethylisoquinoline (These compounds are obtained by the method described in International Publication No. 2017 / 025510) Prepareable); 1-(4,5-dimethylbenzimidazole-1-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline, 1-(4,5-dimethylbenzimidazole-1-yl)-4,4-difluoro-3,3-dimethylisoquinoline, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazole-1-yl)isoquinoline, 4,4-difluoro-1-(5-fluoro-4-methylbenzimidazole-1-yl)-3,3-dimethylisoquinoline, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole (These compounds can be prepared by the method described in International Publication No. 2016 / 156085);N-Methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]propanamide, 1-Me Toxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]urea, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]urea, N-[[4-[5-(trifluoromethyl)-1 ,2,4-Oxadiazole-3-yl]phenyl]methyl]propanamide, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]isoxazolidine-3-one, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]isoxazolidine-3-one, ethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-Ox Sadiazole-3-yl]phenyl]methyl]pyrazole-4-carboxylate, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]-1,2,4-triazole-3-amine (These compounds can be prepared by the methods described in International Publications 2017 / 055473, 2017 / 055469, 2017 / 093348 and 2017 / 118689); 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazole-1-yl)propan-2-ol (This compound can be prepared by the method described in International Publication No. 2017 / 029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazole-1-yl)propan-2-ol (This compound can be prepared by the method described in International Publication No. Prepared by the method described in publication 2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (This compound can be prepared by the method described in International Publication 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxy-propyl]imidazole-4- Carbonitride (this compound can be prepared by the method described in International Publication No. 2016 / 156290); (4-phenoxyphenyl)methyl 2-amino-6-methylpyridine-3-carboxylate (this compound can be prepared by the method described in International Publication No. 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetron (this The compounds can be prepared by the method described in International Publication No. 2011 / 138281) N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzenecarbothioamide; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazole-3-yl]oxy-2-methoxyimino-N,3-Dimethyl-penta-3-enamide (this compound can be prepared by the method described in International Publication No. 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 by the method described in International Publication No. 2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1, 1-Dimethyl-indan-4-yl]pyridine-3-carboxamide (This compound can be prepared by the method described in International Publication No. 2014 / 095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methanone, (3-methylisoxazole-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methanone (These compounds are described in International Publication No. 2017 / 220485) Prepared by the method described in International Publication No. 2018 / 065414); 2-Oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]acetamide (this compound can be prepared by the method described in International Publication No. 2018 / 065414); ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate (this compound can be prepared by the method described in International Publication No. 2018 / 158365); 2,2-Diflu Oro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]acetamide, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide, N-[N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-Oxadiazole-3-yl]benzamide (these compounds can be prepared by the method described in International Publication No. 2018 / 202428), fluoxapiproline, enoxastrobin, trinexapac, chemoxystrobin, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]cyclopropane-carboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-Oxadiazole-3-yl]phenyl]methyl]cyclopropane-carboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-Oxadiazole-3-yl]phenyl]methyl] Sadiazole-3-yl]phenyl]methyl]propanamide, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]propanamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl [nyl]methyl]urea, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]urea, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]propanamide, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]isoxazolidine-3-one, 5,5-dimethyl-2 Other examples include -[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]isoxazolidine-3-one, ethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]pyrazole-4-carboxylate, and N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]-1,2,4-triazole-3-amine. The compounds in this paragraph can be prepared by the methods described in International Publications 2017 / 055473, 2017 / 055469, 2017 / 093348, and 2017 / 118689, including 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazole-1-yl)propan-2-ol (this compound can be prepared by the method described in International Publication 2017 / 029179), 2-[6-(4- Romophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazole-1-yl)propan-2-ol (this compound can be prepared by the method described in International Publication No. 2017 / 029179), 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile (this compound can be prepared by the method described in International Publication No. 2016 / 156290), 3-[2-(1-chlorocyclo [Propyl]-3-(3-chloro-2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitride (this compound can be prepared by the method described in International Publication No. 2016 / 156290), (4-phenoxyphenyl)methyl 2-amino-6-methylpyridine-3-carboxylate (this compound can be prepared by the method described in International Publication No. 2014 / 006945), 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipy Roll-1,3,5,7(2H,6H)-tetron (this compound can be prepared by the method described in International Publication No. 2011 / 138281), N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzenecarbothioamide, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide, (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazole-3-yl]oxy-2-methoxyimino-N,3-dimethyl-penta-3-enamide (this compound can be prepared by the method described in International Publication No. 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 by the method described in International Publication No. 2016 / 202742), 2-(difluoromethyl)-N-[(3S)-3-ethyl [Lu-1,1-dimethylindan-4-yl]pyridine-3-carboxamide (this compound can be prepared by the method described in International Publication No. 2014 / 095675), johnshenmycin, thiodiazole copper, zinc thiazole, amectotlactin, iprodione, cyclobutriflurum, flubeneterum, anisifurupurine, N-[(1R)-1-benzyl-3-chloro-1-methylbuta-3-enyl]-8-fluoroquinoline-3-carboxamide, N-[(1S)-1-benzyl-3-chloro-1- Methyl-buta-3-enyl]-8-fluoroquinoline-3-carboxamide, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoroquinoline-3-carboxamide, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoroquinoline-3-carboxamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoroquinoline-3-carboxamide, N-[(1S)-1-benzyl-1, 3-dimethyl-butyl]-7,8-difluoroquinoline-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-fluoroquinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethylbutyl]-8-fluoroquinoline-3-carboxamide, N-((1R)-1-benzyl-3-chloro-1-methylbuta-3-enyl)-8-fluoroquinoline-3-carboxamide, N-((1S)-1-benzyl-3-chloro-1-methylbuta-3-enyl)-8-fluoroquinoline-3-carboxamide (These compounds can be prepared by the method described in International Publication No. 2017 / 153380), 1-( 6,7-dimethylpyrazolo[1,5-a]pyridine-3-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline, 1-(6,7-dimethylpyrazolo[1,5-a]pyridine-3-yl)-4,4,6-trifluoro-3,3-dimethylisoquinoline, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridine-3-yl)isoquinoline, 4,4-difluoro-3,3-dimethyl-1- (7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline, 1-(6-chloro-7-methylpyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethylisoquinoline (these compounds can be prepared by the method described in International Publication No. 2017 / 025510), 1-(4,5-dimethylbenzimidazole-1-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline, 1- (4,5-dimethylbenzimidazole-1-yl)-4,4-difluoro-3,3-dimethylisoquinoline, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazole-1-yl)isoquinoline, 4,4-difluoro-1-(5-fluoro-4-methylbenzimidazole-1-yl)-3,3-dimethylisoquinoline, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole (these compounds can be prepared by the method described in International Publication No. 2016 / 156085), N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxyethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxyethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy N'-[5-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 by the method described in International Publication No. 2015 / 155075), N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3 -Pyridyl]-N-ethyl-N-methyl-formamidine (this compound can be prepared by the method described in IPCOM000249876D), N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine (these compounds are described in International Publication No. 201 (Preparable by the method described in publication 8 / 228896), N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetane-2-yl]phenyl]-N-methyl-formamidine, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine (These compounds can be prepared by the method described in International Publication 2019 / 110427), (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-Oxadiazole-3-yl]phenyl]methanone, (3-methylisoxazole-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methanone (These compounds can be prepared by the method described in International Publication No. 2017 / 220485); 2-Oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]acetamide (This compound can be prepared by the method described in International Publication No. 2018 Prepared by the method described in / 065414); Ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate (this compound can be prepared by the method described in International Publication No. 2018 / 158365); 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]acetamide, N-[(E)-methoxyyl [minomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide, N-[N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide (These compounds are described in International Publication No. 2018 / 202428) The following compounds can be prepared by method; these also include compounds selected from the group of substances consisting of N-(2-fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide, [(1S,2S)-1-methyl-2-(o-tolyl)propyl](2S)-2-[(4-methoxy-3-propanoyloxypyridine-2-carbonyl)amino]propanoate, sevoctylamine, chloroinconazide, flumethylsulfolime, and fluoxythioconazole.

[0159] The following mixtures of the compound of formula (I) and the active ingredient are preferred (where the abbreviation "TX" means "a compound selected from the compounds defined in Tables A-1 to A-17 and their subtables, and compounds 1.1 to 1.5 of Table T1"): petroleum + TX, 1,1-bis(4-chlorophenyl)-2-ethoxyethanol + TX, 2,4-dichlorophenylbenzenesulfonate + TX, 2-fluoro-N-methyl-N-1-naphthylacetamide + TX, 4-chlorophenylphenylsulfone + TX, acetoprole + TX, aldoxycarb + TX, amiditiol N+TX, Amidothioate+TX, Amitone+TX, Amitone Hydroxalate+TX, Amitraz+TX, Aramite+TX, Arsenic Trioxide+TX, Azobenzene+TX, Azothoate+TX, Benomyl+TX, Benoxaphos+TX, Benzyl Benzoate+TX, Bixafen+TX, Brofenvalerate+TX, Bromocyclene+TX, Bromophos+TX, Bromopropylate+TX, Buprofezin+TX, Butocarboxyme+TX, Butoxycarboxyme+TX, Butylpyridabene+TX, Calcium Polysulfide+TX, Campechlor+TX, Carba Nolate + TX, Carbophenothione + TX, Simiazole + TX, Kimitianat + TX, Chlorbenside + TX, Chlorphenthone + TX, Chlordimeform hydrochloride + TX, Chlorphenetol + TX, Chlorphenthone + TX, Chlorfensulfide + TX, Chlorobenzylate + TX, Chloromebform + TX, Chloromethion + TX, Chloropropylate + TX, Chlorthiofos + TX, Synerin I + TX, Synerin II + TX, Synerin + TX, Closantel + TX, Coumaphos + TX, Crotamiton + TX, Clotoxyfos + TX, Cufra Neb+TX, Cyanthoate+TX, DCPM+TX, DDT+TX, Demefion+TX, Demefion-O+TX, Demefion-S+TX, Demeton-Methyl+TX, Demeton-O+TX, Demeton-O-Methyl+TX, Demeton-S+TX, Demeton-S-Methyl+TX, Demeton-S-Methylsulfone+TX, Diclofluanide+TX, Dichlorvos+TX, Dicliphos+TX, Dienochlor+TX, Dimehox+TX, Dynex+TX, Dynex-Dicrexin+TX, Dinocap-4+TX, Dinocap-6+TX, Dinoctone+TX,Dinopenton+TX, Dinosulfone+TX, Dinotervon+TX, Dioxathion+TX, Diphenylsulfone+TX, Disulfiram+TX, DNOC+TX, Dofenapine+TX, Doramectin+TX, Endothion+TX, Eprinomectin+TX, Ethoate-methyl+TX, Etrimophos+TX, Fenazaflor+TX, Fenbutatin oxide+TX, Phenothiocarb+TX, Fenpyrad+TX, Fenpyroximate+TX, Fenpyrazamine+TX, Fenson+TX, Fentriphanil+TX, Flubendimine+TX, Flucyclo Xuron+TX, Fluenetil+TX, Fluolbenside+TX, FMC1137+TX, Formetanate+TX, Formetanate hydrochloride+TX, Formparanate+TX, Gamma-HCH+TX, Gliodin+TX, Halfenprox+TX, Hexadecylcyclopropane carboxylate+TX, Isocarbofos+TX, Jasmolin I+TX, Jasmolin II+TX, Iodofenphos+TX, Lindan+TX, Malonoben+TX, Mecarbam+TX, Mephosphoran+TX, Mesulfen+TX, Methacryphos+TX, Methyl bromide+TX, Metolcarb + TX, Mexacalbate + TX, Milbemycin oxime + TX, Mipahox + TX, Monoclotophos + TX, Morphothion + TX, Moxidectin + TX, Nared + TX, 4-Chloro-2-(2-Chloro-2-methylpropyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazine-3-one + TX, Niflulidide + TX, Nikcomycin + TX, Nitrilacarb + TX, Nitrilacarb 1:1 zinc chloride complex + TX, Omethoate + TX, Oxydeprophos + TX, Oxydisulfonate + TX, pp'-DDT + TX, Pa Lathion + TX, Permethrin + TX, Fencapton + TX, Phosalon + TX, Phosphane + TX, Phosphamidone + TX, Polychloroterpene + TX, Polynactin + TX, Proclonol + TX, Promacil + TX, Propoxar + TX, Protidathion + TX, Protoate + TX, Pyrethrin I + TX, Pyrethrin II + TX, Pyrethrin + TX, Pyridafenthion + TX, Pyrimitate + TX, Quinalfos + TX, Quinthiofos + TX, R-1492 + TX, Phosglycine + TX, Rotenone + TX, Shuladan + TX, Cebufos + TX,Selamectin + TX, Sofamide + TX, SSI-121 + TX, Sulfiram + TX, Sulfuramide + TX, Sulfotep + TX, Sulfur + TX, Diflovidazine + TX, Tau-fluvalinate + TX, TEPP + TX, Terbam + TX, Tetradiphon + TX, Tetrasul + TX, Thiaphanox + TX, Thiocarboxim + TX, Thiofanox + TX, Thiometon + TX, Thioquinox + TX, Thuringiensis + TX, Triamiphos + TX, Tria Latino+TX, Triazophos+TX, Triazurone+TX, Triphenophos+TX, Trinactin+TX, Bamidthione+TX, Vaniliprole+TX, Bethoxazine+TX, Copper Dioctanoate+TX, Copper Sulfate+TX, Sibutrin+TX, Diclon+TX, Dichlorophene+TX, Endotal+TX, Fetin+TX, Slaked Lime+TX, Narbam+TX, Quinoclamine+TX, Quinonamide+TX, Simazine+TX, Triphenyltin Acetate+TX, Triphenyl Hydroxide Zu+TX, Culfomate+TX, Piperazine+TX, Thiophanate+TX, Chloralose+TX, Fenthion+TX, Pyridine-4-amine+TX, Strychnine+TX, 1-H-Pyridine-2-thion+TX, 4-(Quinoxaline-2-Ilyamino)Benzenolsulfonamide+TX, 8-Hydroxyquinoline Sulfate+TX, Bronopol+TX, Copper Hydroxide+TX, Cresol+TX, Dipyrithione+TX, Dodicine+TX, Phenaminosulf+ TX, Formaldehyde + TX, Hydralgafen + TX, Kasugamycin + TX, Kasugamycin hydrochloride hydrate + TX, Nickel bis(dimethyldithiocarbamate) + TX, Nitrapyrine + TX, Octylinone + TX, Oxolinic acid + TX, Oxytetracycline + TX, Potassium hydroxyquinoline sulfate + TX, Probenazole + TX, Streptomycin + TX, Streptomycin sesquisulfate + TX, Tecrophthalam + 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 (ladybug)+TX, Leptomastix dactylopii+TX, Macrolophus caliginosus+TX,Cutworm (Mamestra brassicae) NPV+TX, Metaphycus helvolus+TX, Metarhizium anisopliae var. acridum+TX, Metarhizium anisopliae var. anisopliae+TX, Pine sawfly (Neodiprions ertifer NPV and N. lecontei NPV+TX), Orius spp.+TX, Paecilomyces fumosoroseus+TX, Chilean predatory mite (Phytoseiulus persimilis) 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 osidentalis occidentalis)+TX, Verticillium lecanii+TX, aphorate+TX, bisadyl+TX, busulfan+TX, dimatif+TX, hemel+TX, hempa+TX, metepa+TX, methiotepa+TX, methyl aphorate+TX, molzide+TX, penfluron+TX, tepa+TX, thiohempa+TX, thiotepa+TX, tretamine+TX, uredepa+TX,(E)-Deca-5-en-1-ylacetate and (E)-Deca-5-en-1-ol + TX, (E)-Trideca-4-en-1-ylacetate + TX, (E)-6-methylhepta-2-en-4-ol + TX, (E,Z)-Tetradeca-4,10-diene-1-ylacetate + TX, (Z)-Dodeca-7-en-1-ylacetate + TX, (Z)-Hexadeca-11-enal + TX, (Z)-Hexadeca-11-en-1-ylacetate + TX, (Z)-Hexadeca-13-en-11-in-1-ylacetate + TX, (Z)-Icos -13-en-10-one + TX, (Z)-tetradeca-7-en-1-ar + TX, (Z)-tetradeca-9-en-1-ol + TX, (Z)-tetradeca-9-en-1-ylacetate + TX, (7E,9Z)-dodeca-7,9-diene-1-ylacetate + TX, (9Z,11E)-tetradeca-9,11-diene-1-ylacetate + TX, (9Z,12E)-tetradeca-9,12-diene-1-ylacetate + TX, 14-methyloctadeca-1-ene + TX, 4-methylnonan-5-ol and 4-methylnonan-5-one + T X, Alpha-Multistriatin+TX, Brevicomin+TX, Chodrelua+TX, Chodremon+TX, Kyurua+TX, Disparua+TX, Dodeca-8-en-1-ylacetate+TX, Dodeca-9-en-1-ylacetate+TX, Dodeca-8,10-dien-1-ylacetate+TX, Dominicalua+TX, Ethyl 4-methyloctanoate+TX, Eugenol+TX, Frontalin+TX, Grandlua+TX, Grandlua I+TX, Grandlua II+TX, Grandlua III+TX, Grandlua IV+TX, Hexal A+TX, Ipsdienol+TX, Ipsenol+TX, Japonilua+TX, Lineatin+TX, Littleua+TX, Lupulua+TX, Medruua+TX, Megatomoic acid+TX, Methyl eugenol+TX, Muscarua+TX, Octadeca-2,13-diene-1-ylacetate+TX, Octadeca-3,13-diene-1-ylacetate+TX, Orfuralua+TX, Orictalua+TX, Ostramon+TX, Siglua+TX, Solzidine+TX, Sulcatol+TX, Tetradeca-11-ene-1-ylacetate+TX, Trimedrua+TX,Trimedolua A+TX, Trimedolua B1+TX, Trimedolua B2+TX, Trimedolua C+TX, Trunk-Col+TX, 2-(octylthio)ethanol+TX, Butopyronoxyl+TX, Butoxy(polypropylene glycol)+TX, Dibutyl adipate + TX, Dibutyl phthalate + TX, Dibutyl succinate + TX, Diethyltoluamide + TX, Dimethyl carbate + TX, Dimethyl phthalate + TX, Ethyl hexanediol + TX, Hexaamide + TX, Methquine-butyl + TX, Methylneodecanamide + TX, Oxamate + TX, Picalidine + 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)ethyl acetate + TX, 2,2-Dichlorovinyl 2-ethyl sulfinylethyl methyl phosphate + TX, 2-(1,3-Dithiolan-2-yl)phenyldimethylcarbamate + TX, 2-(2-Butoxyethoxy)ethylthiocyanate + TX, 2-(4,5-Dimethyl-1,3-Dioxolan-2-yl)phenylmethyl Chilcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyldiethyl phosphate + TX, 2-imidazolidone + TX, 2-isovalerylindan-1,3-dione + TX, 2-methyl(propa-2-inyl)aminophenylmethylcarbamate + TX, 2-thiocyanatoethyl laurate + TX, 3-bromo-1-chloropropa-1-ene + TX, 3-methyl-1-phenylpyrazole-5-yldimethylcarbamate T+TX, 4-methyl(propa-2-inyl)amino-3,5-xylmethylcarbamate+TX, 5,5-dimethyl-3-oxocyclohexa-1-enyldimethylcarbamate+TX, acetylone+TX, acrylonitrile+TX, aldrin+TX, allosamidin+TX, alixicarb+TX, aluminum phosphide+TX, aminocarb+TX, anabasin+TX, atidathion+TX, azamethiphos+TX, Bacillus thuringiensis delta-endotoxin+TX, barium hexafluorosilicate+TX, barium polysulfide+TX, bartholin+TX, Bayer 22 / 190+TX, Bayer 22408+TX, beta-cyfluthrin+TX, beta-cypermethrin+TX, bioetanomethrin+TX, biopermethrin+TX,Bis(2-chloroethyl) ether + TX, Borax + TX, Bromfenbinphos + 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, Sebadin + TX, Chlorbicycline + TX, Chlordan + TX, Chlordecone + TX, Chloroform + TX, Chloropicrin + TX, Chlorphoxime + TX, Chlorprazophos + TX, Cis-resmethrin + TX, Cismethrin + TX, Crocitrin+TX, Copper acetoarsenite+TX, Copper arsenate+TX, Copper oleate+TX, Cumithoate+TX, Cryolite+TX, CS708+TX, Cyanophenphos+TX, Cyanophos+TX, Ciclethrin+TX, Cythioate+TX, d-Tetramethrin+TX, DAEP+TX, Dazomet+TX, Decarbofuran+TX, Diamidaphos+TX, Dicapton+TX, Diclofenthion+TX, Diclesyl+TX, Dicyclanil+TX, Dierdrin+TX, Diethyl 5-methylpyrazole-3-yl phosphate+TX, Dirol+TX, Dimefluthrin + TX, Dimethane + TX, Dimethrin + TX, Dimethylvinphos + TX, Dimethilane + TX, Dinoprop + TX, Dinosam + TX, Dinoseb + TX, Diophenolane + TX, Dioxabenzophos + TX, Diticlophos + TX, DSP + TX, Ecdysterone + TX, EI1642 + TX, EMPC + TX, EPBP + TX, Etaphos + TX, Ethiofencarb + TX, Ethyl formate + TX, Dibromide ethylene + TX, Dichloride ethylene + TX, Ethylene oxide + TX, EXD + TX, Fenchlorphos + TX, Phenetacarb + TX, Fe Nitrothion + TX, Phenoxacrim + TX, Fenpyritrin + TX, Fensulfothion + TX, Fenthion-ethyl + TX, Flucoflon + TX, Fosmethilan + TX, Fosspire + TX, Fosthethane + TX, Frathiocarb + TX, Frethrin + TX, Guazatin + TX, Guazatin acetate + TX, Sodium tetrathiocarbonate + TX, Halfenprox + TX, HCH + TX, HEOD + TX, Heptachlor + TX, Heterophos + TX, HHDN + TX, Hydrogen cyanide + TX, Hikincarb + TX, IPSP + TX, Isazofos + TX,Isobenzane + TX, Isodrine + TX, Isofenphos + TX, Isolane + TX, Isoprothiolane + TX, Isoxathion + TX, Juvenile Hormone I + TX, Juvenile Hormone II + TX, Juvenile Hormone III + TX, Kereban + TX, Quinoprene + TX, Lead Arsenic + TX, Leptophos + TX, Lilimphos + TX, Litidathion + TX, m-Cumenyl Methylcarbamate + TX, Magnesium Phosphate + TX, Magidox + TX, Mecarfone + TX, Menazone + TX, Mercurous Chloride + TX, Mesulfenphos + TX, Metam + TX, Metam-Potassium + TX Metam-sodium + TX, methanesulfonyl fluoride + TX, metoclophos + TX, methoprene + TX, methotrin + TX, methoxychloride + TX, methyl isothiocyanate + TX, methylchloroform + TX, methylene chloride + TX, methoxadiazone + TX, milex + TX, naphthalophos + TX, naphthalene + TX, NC-170 + TX, nicotine + TX, nicotine sulfate + TX, nithiazine + TX, nornicotine + TX, O-5-dichloro-4-iodophenyl O-ethylethyl phosphonothioate + TX, O,O-diethyl O-4-methyl- 2-Oxo-2H-Cromen-7-ylphosphorothioate + TX, O,O-Diethyl O-6-methyl-2-propylpyrimidine-4-ylphosphorothioate + TX, O,O,O',O'-Tetrapropyldithiopyrophosphate + TX, Oleic acid + TX, Para-dichlorobenzene + TX, Parathion-methyl + TX, Pentachlorophenol + TX, Pentachlorophenyl laurate + TX, PH60-38 + TX, Fenkapton + TX, Fosnikrol + TX, Phosphine + TX, Phoxime-methyl + TX, Pyrimethaphos + TX, Polychlorodi Cyclopentadiene isomer + TX, potassium arsenite + TX, potassium thiocyanate + TX, plecosen I + TX, plecosen II + TX, plecosen III + TX, primidophos + TX, profluthrin + TX, promecarb + TX, prothiophos + TX, pyrazofos + TX, pyresmethrin + TX, quassia + TX, quinalphos-methyl + TX, quinothion + TX, lafoxanide + TX, resmethrin + TX, rotenone + TX, cadetrin + TX, liania + TX, ryanodine + TX, sabajira + TX, schladan + TX, cebuphos + TX,SI-0009+TX, thiapronil+TX, sodium arsenite+TX, sodium cyanide+TX, sodium fluoride+TX, sodium hexafluorosilicate+TX, sodium pentachlorophenoxide+TX, sodium selenite+TX, sodium thiocyanate+TX, sulcoflon+TX, sulcoflon-sodium+TX, sulfuryl fluoride+TX, sulprophos+TX, tar oil+TX, tadimucarb+TX, TDE+TX, tebupyrimphos+TX, temephos+TX, terarethrin+TX, tetrachloroethane+TX, cyclamphos+TX, thiocyclam+TX, thiocyclam hydrogen oxalate+TX, thionazine+TX, Thiosultap+TX, Thiosultap-sodium+TX, Tralomethrin+TX, Transpermethrin+TX, Triazamate+TX, Trichlormetaphos-3+TX, Trichloronat+TX, Trimetacarb+TX, Tolprocarb+TX, Triclopyricarb+TX, Triprene+TX, Veratridine+TX, Veratrin+TX, XMC+TX, Zetametrin+TX, Zinc phosphide+TX, Zolaprophos+TX, Meperfluthrin+TX, Tetramethylfluthrin+TX, Bis(tributyltin) oxide+TX, Bromoacetamide+TX, Ferric phosphate+TX, Niclosamide-olamine+TX, Tributyltin oxide+TX, Pyrimorph + TX, Triphenmorph + TX, 1,2-Dibromo-3-chloropropane + TX, 1,3-Dichloropropane + TX, 3,4-Dichlorotetrahydrothiophene 1,1-Dioxide + TX, 3-(4-Chlorophenyl)-5-Methylrhodanine + TX, 5-Methyl-6-Thioxo-1,3,5-Thiasiadinane-3-Ylacetic Acid + TX, 6-Isopentanylaminopurine + TX, Anisifurupurine + TX, Bencrotiaz + TX, Cytokinin + TX, DCIP + TX, Furfural + TX, Isamidophos + TX, Kinetin + TX, Mulberry dark spot fungus (Myrothecium vercaria) Reynoutria saccharinensis (Reynoutria verrucaria) composition + TX, tetrachlorothiophene + TX, xylenol + TX, zeatin + TX, potassium ethylxanthogenicate + TX, acibenzolar + TX, acibenzolar-S-methyl + TX, Japanese knotweed (Reynoutria saccharinensis) Sachalinensis extract + TX, alpha-chlorohydrin + TX, anchu + TX, barium carbonate + TX, bisthiosemi + TX, brodiphacomum + TX, bromadiolon + TX, bromethalin + TX, chlorophacinone + TX, cholecalciferol + TX, coumacrol + TX, coumafuryl + TX, coumatetralyl + TX, crimidine + TX, diphenacum + TX, difethiaron + TX, diphacinone + TX, ergocalciferol + TX, fulocumafen + TX, fluoroacetamide + TX, flupropadine + TX, flupropadine hydrochloride + TX, norbolmid + TX, fosacetim + TX, phosphorus + TX, pin Don+TX, Pyrinulone+TX, Siliroside+TX, Sodium Fluoroacetate+TX, Thallium Sulfate+TX, Warfarin+TX, 2-(2-Butoxyethoxy)ethyl Piperonylate+TX, 5-(1,3-Benzodioxol-5-yl)-3-Hexylcyclohexa-2-enone+TX, Farnesol and Nerolidol+TX, Berbutin+TX, MGK264+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, Thyram+TX,Zinc naphthenate + TX, Ziram + TX, Imanin + TX, Ribavirin + TX, Chloroinconazide + TX, Mercuric oxide + TX, Thiophanate-methyl + TX, Azaconazole + TX, Vitertanol + TX, Bromuconazole + TX, Cyproconazole + TX, Difenoconazole + TX, Diniconazole + TX, Epoxyconazole + TX, Fenbuconazole + TX, Fluquinconazole + TX, Flusilazole + TX, Flutriafole Flusilazole + TX, Flamethopyr + TX, Hexaconazole + TX, Imazalil + TX, Imibenconazole Ibuconazole + TX, Ibuconazole + TX, Metoconazole + TX, Mycrobutanil + TX, Paclobutrazol + TX, Peflazoate + TX, Penconazole + TX, Prothioconazole + TX, Pyriphenox + TX, Prochloraz + TX, Propiconazole + TX, Pyrizoxazole + TX, Simeconazole + TX, Tebuconazole + TX, Tebuconazole + TX, Tetraconazole + TX, Triadimephon + TX, Triadimenol + TX, Triflumizole + TX, Triticonazole + TX, Ancimidol + TX, Fenarimol + TX, Nualimol + TX, Bupirime T+TX, Dimethyrimol+TX, Ethyrimol+TX, Dodemorph+TX, Fenpropidine+TX, Fenpropimorph+TX, Spiroxamine+TX, Tridemorph+TX, Cyprodinil+TX, Mepanipyrim+TX, Pyrimethanil+TX, Fenpiclonil+TX, Fludioxonil+TX, Benalaxil+TX, Flalaxil+TX, Metalaxil+TX, R-Metalaxil+TX, Ofrace+TX, Oxadixyl+TX, Carbendazim+TX, Debacarb+TX, Fuberidazole+TX, Thiabendazole+TX, Clozolinate+TX, Diclozoline + TX, Microzoline + TX, Procymidone + TX, Vinclozoline + TX, Boscalid + TX, Carboxyne + TX, Fenflame + TX, Flutolanil + TX, Mepronil + TX, Oxycarboxyne + TX, Penthiopyrad + TX, Tifluzamide + TX, Dozin + TX, Iminooctadine + TX, Azoxystrobin + TX, Dimoxystrobin + TX, Enestrobrin + TX, Phenaminestrobin + TX, Fluphenoxystrobin + TX, Fluoxastrobin + TX, Cresoxim-methyl + TX, Metominostrobin + TX,Trifloxystrobin+TX, Orysastrobin+TX, Picoxystrobin+TX, Pyraclostrobin+TX, Pyramethostrobin+TX, Pyraoxystrobin+TX, Farbam+TX, Mancozeb+TX, Maneb+TX, Methylam+TX, Propineb+TX, Zineb+TX, Captahol+TX, Captan+TX, Fluorimide+TX, Forpet+TX, Trilfluanide+TX, Bordeaux mixture+TX, Copper oxide+TX, Mancopper+TX, Oxine-copper+TX, Nitrotar-iso Propyl+TX, Edifenphos+TX, Iprobenphos+TX, Phosdiphen+TX, Torukurophos-methyl+TX, Anirazine+TX, Bentiavaricarb+TX, Blastocydin-S+TX, Chloroneb+TX, Chlorothalonil+TX, Cyflufenamid+TX, Cymoxanil+TX, Cyclobtrifluram+TX, Diclosimet+TX, Diclomazine+TX, Dichloran+TX, Dietofencarb+TX, Dimethomorph+TX, Flumorph+TX, Dithianone+TX, Etaboxam+TX, E Tridiazole + TX, Famoxadone + TX, Phenamidone + TX, Phenoxanil + TX, Ferimzon + TX, Fluazinam + TX, Flumethylsulfolim + TX, Fluopicolide + TX, Fluoxythioconazole + TX, Flusulfamide + TX, Fluxapiroxad + TX, Fenhexamide + TX, Fosetyl-aluminum + TX, Himexazole + TX, Iprovalicarb + TX, Cyazofamide + TX, Metasulfocarb + TX, Metraphenone + TX, Pencyclon + TX, Phthalide +TX, Polyoxin +TX, Propamocarb +TX, Piribencarb +TX, Proquinazide +TX, Pyroxine +TX, Pyriophenone +TX, Quinoxifen +TX, Quintozene +TX, Thiazinil +TX, Triazoxide +TX, Tricyclazole +TX, Triforine +TX, Validamycin +TX, Valifenarate +TX, Zoxamide +TX, Mandipropamide +TX, Flubeneteram +TX, Isopyrazam +TX, Sedaxane +TX, Benzovindiflupir +TX, Pidiflumetofen +TX, 3-Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluorobiphenyl-2-yl)amide + TX, Isoflucipram + TX, Isothianil + TX, Dipimethitron + TX, 6-Ethyl-5,7-Dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazol-3-carbonitride + TX, 2-(Difluoromethyl)-N-[3-ethyl-1,1-dimethylindan-4-yl]pyridine-3-carboxamide + TX, 4-(2,6-difluorophenyl)-6 -Methyl-5-phenylpyridazine-3-carbonitrile + TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-2,5-dimethylpyrazole-3-amine + TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine + TX, Fluindapyr +TX, Cumethoxystrobin (Diaxylangeus) +TX, Rubenmixianan +TX, Diclobentiazox +TX, Mandestrobin +TX, 3-(4,4-Difluoro-3,4-Dihydro-3,3-Dimethylisoquinoline-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-Methyltetrazole-5-yl)-phenyl-methylene]amino]ol [Xyxymethyl]-2-pyridyl]carbamate + TX, pyraziflumid + TX, impulfluxam + TX, trollprocarb + TX, mefentrifluconazole + TX, ibuphentrifluconazole + TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethylindan-4-yl]pyridine-3-carboxamide + TX, N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methyl-formamidine + TX, N'-[4-(4,5-dichlorothiazole-2-yl)oxy-2,5-dimethylphenyl]-N-ethyl-N-methyl-formamidine + TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazole-1-yl]acetyl]-4-piperidyl]thiazole-4-yl]-4,5-dihydroisoxazole-5-yl]-3-chlorophenyl]methanesulfonate + TX, buta-3-inyl N-[6-[[(Z)-[(1-methyltetrazole-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX , Methyl N-[[5-[4-(2,4-dimethylphenyl)triazole-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)pyrazole-3-yl]oxymethyl]-3- Methyl-phenyl]-4-methyl-tetrazole-5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazole-1-yl)phenoxy]methyl]phenyl]tetrazole-5-one + TX, aminopyriphen + TX, ametoctrazine + TX, amisulbrom + TX, penflufen + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazole-3-yl]oxy-2-methoxyimino-N,3-dimethyl-penta-3-enamide + TX , Floryl picoxamide + TX, Fenpicoxamide + TX, Metallyl picoxamide + TX, Tebufloxin + TX, Ipfluphenoquine + TX, Quinofumeline + TX, Isofetamide + TX, Ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate + TX (These compounds can be prepared by the method described in International Publication No. 2020 / 056090), Ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoropropaneoxy]phenyl]methyl]pyrazole-3-carboxylate + TX (preparable from the method described in International Publication No. 2020 / 056090), methyl N-[[4-[1-(4-cyclopropyl-2,6-difluorophenyl)pyrazole-4-yl]-2-methylphenyl]methyl]carbamate + TX (preparable from the method described in International Publication No. 2020 / 097012), methyl N-[[4-[1-(2,6-difluoro-4-isopropylphenyl)pyrazole-4-yl]-2-methylphenyl]methyl]carbamate + TX (preparable from the method described in International Publication No. 2020 / 097012), 6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)-N-[2-(2,4 -dimethylphenyl)-2,2-difluoro-ethyl]-5-methylpyridazine-4-carboxamide + TX (preparable from the method described in International Publication No. 2020 / 109391), 6-chloro-N-[2-(2-chloro-4-methylphenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluorophenoxy)-5-methylpyridazine-4-carboxamide + TX (preparable from the method described in International Publication No. 2020 / 109391), 6-chloro-3-(3-cyclopropyl-2-fluorophenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methylpyridazine-4-carboxamide + TX (preparable from the method described in International Publication No. 2020 / 109391), N-[2-[2,4-dichlorophenoxy]phenyl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide + TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide + TX, Benzothiostrobin + TX, Phenamacryl + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, Fluopyram + TX, Fluphenoxadiazam + T X, Fluthianil + TX, Fluopimomide + TX, Pirapropoin + TX, Picarbutrazox + TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethylindan-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-triazole-1- [Iyl)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-pyrimidine methanol + TX, fluoxapiproline + TX, enoxastrobin + TX, 4-[[6-[2-(2,4-difluorophenyl)-1 ,1-difluoro-2-hydroxy-3-(1,2,4-triazole-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-triazole-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-Triazole-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, Trinexapac + TX, Acumoxystrobin + TX, John Shenmycin + TX, Thiodiazole copper + TX, Zinc thiazole + TX, Amectotractin + TX, Iprodione + TX, Seboctylamine + TX; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxyethoxy]-3-pyridyl N'-[5-Brom-2-methyl-6-[(1R)-1-methyl-2-propoxyethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine+TX, N'-[5-Brom-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine+TX, N'-[5-Chloro-2-methyl-6 -(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-ethyl-N-methylformamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxyethoxy)-3-pyridyl]-N-isopropyl-N-methylformamidine + TX (These compounds can be prepared by the method described in International Publication No. 2015 / 155075); N'-[5-bromo-2-methyl-6-(2 -propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared by the method described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine + 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 method described in International Publication No. 2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetane-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 method described in International Publication No. 2019 / 110427); N-[(1R)-1-benzyl-3-chloro-1-methylbuta-3-enyl]-8-fluoroquinoline-3-carboxamide+TX, N-[(1S)-1-benzyl-3-chloro-1-methylbuta-3-enyl]-8-fluoroquinoline-3-carboxamide+TX, N-[(1R)-1-benzyl-3,3,3-ttrifluoro-1-methylppropyl]-8-fluoroquinoline-3-carboxamide+TX, N-[ (1S)-1-benzyl-3,3,3-trifluoro-1-methylpropyl]-8-fluoroquinoline-3-carboxamide+TX,N-[(1R)-1-benzyl-1,3-dimethylbutyl]-7,8-difluoroquinoline-3-carboxamide+TX,N-[(1S)-1-benzyl-1,3-dimethylbutyl]-7,8-difluoroquinoline-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-methylbuta-3-enyl)-8-fluoroquinoline-3-carboxamide+TX, N-((1S)-1-benzyl-3-chloro-1-methylbuta-3-enyl)-8-fluoroquinoline-3-carboxamide+TX (These compounds can be prepared by the method described in International Publication No. 2017 / 153380);1-(6,7-dimethylpyrazolo[1,5-a]pyridine-3-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridine-3-yl)-4,4,6-trifluoro-3,3-dimethylisoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridine- 3-yl)isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridine-3-yl)isoquinoline + TX, 1-(6-chloro-7-methylpyrazolo[1,5-a]pyridine-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX (These compounds are obtained by the method described in International Publication No. 2017 / 025510 or These compounds can be prepared from the methods described in International Publication 2016 / 156085: 1-(4,5-dimethylbenzimidazole-1-yl)-4,4,5-trifluoro-3,3-dimethylisoquinoline + TX, 1-(4,5-dimethylbenzimidazole-1-yl)-4,4-difluoro-3,3-dimethylisoquinoline + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazole-1-yl)isoquinoline + TX, 4,4-difluoro-1-(5-fluoro-4-methylbenzimidazole-1-yl)-3,3-dimethylisoquinoline + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole + TX (these compounds can be prepared from the methods described in International Publication 2016 / 156085);N-Methoxy N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N,2-Dimethoxy N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]propanamide + TX, N-Ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl ]phenyl]methyl]propanamide + TX, 1-methoxy3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]urea + TX, 1,3-dimethoxy1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]urea + TX, 3-ethyl-1-methoxy1-[[4-[5-(trifluoromethyl)-1,2,4-oxadi Azole-3-yl]phenyl]methyl]urea + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]propanamide + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]isoxazolidine-3-one + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2, 4-Oxadiazole-3-yl]phenyl]methyl]isoxazolidine-3-one + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]pyrazole-4-carboxylate + TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methyl]-1,2,4-triazole-3-amine + TX. The compounds in this paragraph can be prepared by the methods described in International Publication Nos. 2017 / 055473, 2017 / 055469, 2017 / 093348 and 2017 / 118689; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazole-1-yl)propan-2-ol + TX (this compound can be prepared by the method described in International Publication No. 2017 / 029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl [3-(1,2,4-triazole-1-yl)propan-2-ol + TX (This compound can be prepared by the method described in International Publication No. 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 International Publication No. 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxy -Propyl]imidazole-4-carbonitride + TX (This compound can be prepared by the method described in International Publication No. 2016 / 156290); (4-phenoxyphenyl)methyl 2-amino-6-methylpyridine-3-carboxylate + TX (This compound can be prepared by the method described in International Publication No. 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrolo-1,3,5,7(2H,6H)-tetron + TX (This compound can be prepared by the method described in International Publication No. 2011 / 138281 It can be prepared by the method described in publication number 2018 / 153707); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzenecarbothioamide + TX; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide + TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazole-3-yl]oxy-2-methoxyimino-N,3-dimethyl-penta-3-enamide + TX (This compound can be prepared by the method described in International Publication No. 2018 / 153707);N'-(2-chloro-5-methyl-4-phenoxyphenyl)-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 International Publication No. 2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethylindan-4-yl]pyridine-3-carboxamide + TX (This compound can be prepared by the method described in International Publication No. 2014 / 095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methanone + TX, (3-methyliso Xazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]methanone + TX (These compounds can be prepared by the method described in International Publication No. 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]acetamide + TX (This compound can be prepared by the method described in International Publication No. 2018 / 065414); Ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate + TX (This compound can be prepared by the method described in International Publication No. 2018 / 158365);Compounds selected from the group of substances comprising: 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]phenyl]acetamide + TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide + TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide + TX, and N-[N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzamide + TX (these compounds can be prepared by the method described in International Publication No. 2018 / 202428).

[0160] For example, a reference in parentheses following an active ingredient, such as [3878-19-1], refers to a Chemical Abstracts Registry number. The aforementioned mixing partners are publicly known. If an active ingredient is included in “The Pesticide Manual” [The Pesticide Manual-A World Compendium; Thirteenth Edition; Editor: CDSTomLin; The British Crop Protection Council], it is listed therein under the entry number indicated in parentheses above for the specific compound; for example, the compound “abamectin” is listed under entry number (1). If a specific compound is appended with "[CCN]", the compound in question is included in the “Compendium of Pesticide Common Names” accessible via the internet under [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.

[0161] Most of the active ingredients listed above are referred to by so-called "generic names," where the relevant "ISO generic name" or another "generic name" is used in each case. If a name is not a "generic name," the nature of that name used instead is given in parentheses for the specific compound. In such cases, the IUPAC name, IUPAC / chemical abstract name, "chemical name," "common name," "compound name," or "development code" is used, or if none of these names are used and neither is the "generic name," an "alternative name" is used. "CAS registry number" means chemical abstract registry number.

[0162] The active ingredient mixture of one compound represented in Tables A-1 to A-17 and their subtables (below) or a compound of formula (I) selected from compounds 1.1 to 1.5 listed in Table T1 (below) is a mixture ratio of 100:1 to 1:6000, particularly 50:1 to 1:50, more particularly 20:1 to 1:20, even more particularly 10:1 to 1:10, very particularly 5:1 to 1:5, a ratio of 2:1 to 1:2 is particularly preferred, a ratio of 4:1 to 2:1 is equally preferred, and especially 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or A ratio of 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750 is preferred. These mixing ratios are determined by weight.

[0163] The above mixture may be used in a method for controlling pests and diseases, which includes applying a composition containing the above mixture to pests or diseases or their environment, but excluding methods of treating the human or animal body by surgery or therapeutic means, or diagnostic methods performed on the human or animal body.

[0164] A mixture comprising the compounds shown in Tables A-1 to A-17 and their subtables (below), or compounds 1.1 to 1.5 listed in Table T1 (below), and one or more of the above-mentioned active ingredients, can be used in combination with a single active ingredient, for example, in a single "component-formulated" form, in a combination spray mixture consisting of separate formulations of a single active ingredient, such as a "tank mix," and applied sequentially, i.e., over a moderately short period of time, such as a few hours or a few days. The order in which the compounds shown in Tables A-1 to A-17 and their subtables (below), or compounds 1.1 to 1.5 listed in Table T1 (below), and the active ingredients are applied is not essential for carrying out the present invention.

[0165] The compounds of the present invention may also be used in combination with anthelmintics. Such anthelmintics include compounds selected from the macrocyclic lactone class, such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemadectin, and milbemycin derivatives, as described in European Patent No. 357460, European Patent No. 444964, and European Patent No. 594291. Additional anthelmintics include semi-synthetic and biosynthetic avermectin / milbemycin derivatives, as described in U.S. Patent No. 5015630, International Publication No. 9415944, and International Publication No. 9522552. Further anthelmintics include benzimidazoles such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxybendazole, and parbendazole, and other members of this class. Further anthelmintics include imidazothiazoles and tetrahydropyrimidines such as tetramizole, rebamizole, pyrantel pamoate, oxantel, or morantel. Further anthelmintics include trematodeicides such as triclabendazole and chlorthrone, and tapeworm killers such as praziquantel and epsiplantel.

[0166] The compounds of the present invention may be used in combination with derivatives and analogues of paraherquamid / markfortin class anthelmintics, as well as anthelmintic oxazolines such as those disclosed in U.S. Patent No. 5,478,855, U.S. Patent No. 4,639,771, and German Patent No. 1,952,0936.

[0167] The compounds of the present invention may be used in combination with anthelmintic cyclic depsipeptides, such as derivatives and analogues of the general class of dioxomorphone anthelmintics described in International Publication No. 96 / 15121, as well as those described in International Publication No. 96 / 11945, International Publication No. 93 / 19053, International Publication No. 93 / 25543, European Patent No. 0626375, European Patent No. 0382173, European Patent No. 94 / 19334, European Patent No. 0382173, and European Patent No. 0503538.

[0168] The compounds of the present invention can be used in combination with other ectoparasite control agents, such as fipronil; pyrethroids; organophosphates; insect growth regulators such as lufenuron; ecdysone agonists such as tebufenozide; and neonicotinoids such as imidacloprid.

[0169] The compounds of the present invention may be used in combination with terpene alkaloids, for example those described in International Publication 95 / 19363 or International Publication 04 / 72086, particularly the compounds disclosed in these specifications.

[0170] Other examples of such biologically effective compounds that can be used in combination with the compounds of the present invention include, but are not limited to, the following: Organophosphates: Acephate, Azamethiphos, Adinphos-ethyl, Adinphos-methyl, Bromophos, Bromophos-ethyl, Kazusaphos, Chlorethoxyphos, Chlorpyrifos, Chlorfenbinphos, Chlormephos, Demeton, Demeton-S-methyl, Demeton-S-methylsulfone, Dialiphos, Diazinon, Dichlorvos, Diclotophos, Dimethoate, Disulfoton, Ethion, Etoprophos, Etrimophos, Famfur, Phenamiphos, Fenitrothion, Fensulfothion, Fenthion, Flupyrazophos, Honophos, Formothion, Fostiazate, Heptenophos, Isazofos, Isothioate, Isoxa Thione, malathion, methacryphos, methamidophos, methidathion, methylparathion, mevinphos, monoclotophos, naled, omethoate, oxydemethone methyl, paraoxone, parathion, parathion methyl, fenthoate, phosalon, phospholan, phosphocarb, phosmet, phosphamidone, phorate, foxim, pirimiphos, pirimiphos methyl, profenophos, propaphos, proethanphos, prothiophos, pyraclophos, pyridapention, quinalphos, sulprophos, temephos, terbuphos, tebupyrimphos, tetrachlorvinphos, thymetone, triazophos, trichlorfon, bamidothion. Carbamates: Alanicarb, Aldicarb, 2-sec-butylphenyl methylcarbamate, Benfuracarb, Carbaryl, Carbofuran, Carbosulfan, Chloetocarb, Ethiophenecarb, Phenoxycarb, Fenthiocarb, Frathiocarb, HCN-801, Isoprocarb, Indoxacarb, Methiocarb, Methomyl, 5-Methyl-m-cumenylbutyryl(methyl)carbamate, Oxamyl, Pyrimicarb, Propoxul, Thiodicarb, Thiofanox, Triazamate, UC-51717. Pyrethroids: Acrinatin, Allethrin, Alphamethrin, 5-benzyl-3-furylmethyl(E)-(1R)-cis-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, Bifenthrin, Beta-cyfluthrin, Cyfluthrin, α-cypermethrin, Beta-cypermethrin, Bioallethrin, Bioallethrin ((S)-cyclopentyl isomer), Bioallethrin, Bifenthrin, NCI-85193, Cycloprotrin, Cyhalothrin, Citrin, Cypheno Thrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenfluthrin, fenpropathrin, fenvalerate, flucitrin, flumethrin, fluvaric acid (D isomer), imiprothrin, cyhalothrin, lambda-cyhalothrin, permethrin, phenothrin, prallethrin, pyrethrin (natural product), resmethrin, tetramethrin, transfluthrin, theta-cypermethrin, silafluofen, t-fluvaric acid, tefluthrin, tralomethrin, zeta-cypermethrin. Arthropod growth regulators: a) Chitin synthesis inhibitors: Benzoylureas: Chlorfluazurone, diflubenzuron, fluazurone, flucycloxurone, flufenoxurone, hexaflumurone, lufenuron, novaron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythiazox, etoxazole, chlorfentadine; b) Ecdysone antagonists: Halofenozide, methoxyfenozide, tebufenozide; c) Juvenoids: Pyriproxyfen, methoprene (including S-methoprene), phenoxycarb; d) Lipid biosynthesis inhibitors: Spirodiclofen. Other antiparasitic agents: Asequinosyl, Amitraz, AKD-1022, ANS-118, Azadirachtin, Bacillus thuringiensis, Bensultap, Bifenazate, Binapcryl, Bromopropylate, BTG-504, BTG-505, Camfechlor, Cartap, Chlorobenzylate, Chlordimeform, Chlorfenapyr, Chromafenozide, Clothianidin, Cyromazine, Diaclodene, Diafenthiuron, DBI-3204, Dinactin, Dihydroxymethyldihydroxypyrrolidine, Dinobutone, Dinocap, Endosulfan, Ethiprole, Etofenprox, Phenazaquin, Flumite, MTI-800, Fenpyroximate, Fluacrypyrim, Flubendimine, Flubrocitrinate, Flufenzin, Flufenprox, Fluproxyfen, Ha Lofenprox, hydramethylnon, IKI-220, Kanemite, NC-196, Neem Guard, Nidinorterfuran, Nitenpyram, SD-35651, WL-108477, Pyridaryl, Propargit, Protrifenbut, Pymetrozine, Pyridaben, Pyrimidifen, NC-1111, R-195, RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601, Silafluofen, Cyromazine, Spinosad, Tebufenpyrad, Tetradiphon, Tetranactin, Thiacloprid, Thiocyclam, Thiamethoxam, Tolfenpyrad, Triazamate, Triethoxyspinosin, Trinactin, Berbutin, Bertarec, YI-5301. Biological agents: Bacillus thuringiensis subspecies aizawai, kurstaki, Bacillus thuringiensis delta-endotoxin, baculoviruses, entomopathogenic bacteria, viruses, and fungi. Fungicides: Chlortetracycline, oxytetracycline, streptomycin. Other biological drugs: Enrofloxacin, Febantel, Penetamate, Meloxicam, Cephalexin, Kanamycin, Pimobendan, Clenbuterol, Omeprazole, Thiamrin, Benazepril, Pyriprole, Cefquinom, Florfenicol, Buserelin, Cefovecine, Tulathromycin, Cefthiol, Carprofen, Metaflumizone, Prazicalantel, Triclabendazole.

[0171] The compositions according to the present invention may also include further solid or liquid additives such as stabilizers, e.g., non-epoxidized or epoxidized vegetable oils (e.g., epoxidized coconut oil, rapeseed oil, or soybean oil), defoamers, e.g., silicone oils, preservatives, viscosity modifiers, binders and / or tackifiers, fertilizers, or other active ingredients for obtaining specific effects, e.g., fungicides, fungicides, nematicides, plant activators, molluscicides, or herbicides.

[0172] The compositions according to the present invention are prepared by methods known to the present invention, for example, by grinding, sieving, and / or compressing a solid active ingredient in the absence of auxiliary agents, and by homogeneously mixing the active ingredient with one or more auxiliary agents and / or grinding, for example, in the presence of at least one auxiliary agent. These methods for preparing these compositions and the use of compound (I) for the preparation of these compositions are also the subject of the present invention.

[0173] Another aspect of the present invention relates to the use of a fungicidal or insecticidal mixture comprising at least one compound of formula (I) or at least one 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 above, or mixed with the other fungicidal or insecticidal agents described above, for use to control or prevent extrinsing of non-biological materials by plants such as useful plants, such as crop plants, such as their reproductive materials such as seeds, or harvested crops such as harvested food crops, or by plant pathogenic microorganisms such as insects or preferably fungal organisms.

[0174] Further aspects of the present invention relate to a method for controlling or preventing ectoparasitism of plants, such as useful plants, such as crop plants, their reproductive materials, such as seeds, harvested crops, such as harvested food crops, or non-biological materials, by insects or plant pathogenic or putrefactive microorganisms or organisms, particularly fungi, that include applying a compound of formula (I) or any of the preferred individual compounds defined above as an active ingredient to any part of a plant, a part of a plant or its habitat, its reproductive material, or non-biological material.

[0175] Control or prevention means reducing ectoparasitism or decay by plant pathogenic microorganisms or organisms potentially harmful to humans, particularly fungi, to the extent that improvement is demonstrated.

[0176] Preferred methods for controlling or preventing ectoparasitism of crop plants by plant pathogenic microorganisms, particularly fungi or insects, include foliar application of a pesticide composition containing the compound of formula (I) or at least one of the said compounds. The frequency and amount of application depend on the risk of damage caused by the corresponding pathogen or insect. However, the compound of formula (I) can also be infiltrated into the plant from the roots through the soil (osmotic translocation) by drenching the plant with a liquid formulation or by applying the compound to the soil in solid form, such as granular form (soil application). In rice crops, such granular material can be applied to flooded paddy fields. The compound of formula (I) can also be applied to seeds (coated) by impregnating the seeds or tubers with a liquid formulation of the fungicide or by coating them with a solid formulation.

[0177] Formulations such as compositions containing the compound of formula (I) and, optionally, a solid or liquid additive or a monomer that encapsulates the compound of formula (I) can typically be prepared by known methods by closely mixing and / or grinding the compound together with an expander, such as a solvent, a solid carrier, and optionally a surface-active compound (surfactant).

[0178] The advantageous dosage is typically 5 g to 2 kg of the active ingredient (ai) per hectare (ha), preferably 10 g to 1 kg ai / ha, and most preferably 20 g to 600 g ai / ha. When used as a seed drenching agent, a favorable dosage is 10 mg to 1 g of the active substance per 1 kg of seeds.

[0179] When the combination of the present invention is used for seed treatment, an amount of 0.001 to 50 g of the compound of formula (I) per 1 kg of seed, preferably 0.01 to 10 g per 1 kg of seed, is generally considered sufficient.

[0180] Preferably, a composition comprising the compound of formula (I) according to the present invention is applied either preventively (meaning before the onset of disease) or therapeutically (meaning after the onset of disease).

[0181] The compositions of the present invention may be any of the conventional forms, for example, a two-component system, a dry seed treatment powder (DS), a seed treatment emulsion (ES), a seed treatment fluid concentrate (FS), a seed treatment solution (LS), a seed treatment water-dispersible powder (WS), a seed treatment capsule suspension (CF), a seed treatment gel (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspension emulsion (SE), a capsule suspension (CS), water-dispersible granules (WG), or emulsifying granules. It may be employed in the form of any technically feasible formulation, such as 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), industrial concentrates (TK), dispersible concentrates (DC), wettable powders (WP), or in combination with agriculturally acceptable auxiliaries.

[0182] Such compositions may be produced by conventional methods, for example, by mixing an active ingredient with a suitable formulation deactivator (diluent, solvent, filler, and optionally other formulation components such as surfactants, biocides, antifreezes, spreading agents, thickeners, and compounds that provide auxiliary effects). Conventional sustained-release formulations may also be used when sustained effectiveness over a long period is desired. 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 agents and dispersants, and other compounds that provide auxiliary effects, such as formaldehyde, and condensation products of naphthalene sulfonates, alkylaryl sulfonates, lignin sulfonates, fatty alkyl sulfates, and ethoxylated alkylphenols and ethoxylated fatty alcohols.

[0183] The seed coating formulation is applied to seeds in a manner known to the present invention, utilizing the combination and diluent of the present invention in a preferred seed coating formulation form, such as an aqueous suspension or a dry powder form having good adhesion to seeds. Such seed coating formulations are known in the art. The seed coating formulation may contain a single active ingredient or a combination of active ingredients in encapsulated form, such as slow-release capsules or microcapsules.

[0184] Generally, a formulation comprises 0.01 to 90% by weight of an active agent, 0 to 20% of an agriculturally acceptable surfactant, and 10 to 99.99% of a solid or liquid inert formulation and an auxiliary agent, wherein the active agent optionally consists of at least compounds of formula (I) together with other active agents such as microbiotacitists, preservatives, etc. The concentrated form of the composition generally contains about 2 to 80%, preferably about 5 to 70% by weight of the activator. The application form of the formulation may contain, for example, 0.01 to 20% by weight, preferably 0.01 to 5% by weight of the activator. Commercial products are preferably formulated as concentrates, but end users typically use diluted formulations.

[0185] Commercial products are preferably formulated as a concentrate, but end users typically use diluted formulations.

[0186] The compounds shown in Tables A-1 to A-17 and their subtables below can be prepared according to the methods described above. The following examples are intended to illustrate the present invention and to show preferred compounds of formula (Ia). [ka]

[0187] Table A: Compounds of formula (Ia) (wherein R 1 , R 7 , R 8 and R 9 (These are defined in Tables A-1 to A-17, and G is defined in Table Z below).

[0188] [Table 2]

[0189] Table A-1: ​​Compounds of formula (Ia-A-1) (wherein R 1 , R 7 , R 8 and R 9 (These are defined in Tables A-1a to A-1k, and G is defined in Table Z above.) [ka]

[0190] Table A-1a: This subtable lists nine compounds of formula (Ia-A-1) A-1a.01 to A-1a.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 8 and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0191] Table A-1b: This subtable lists nine compounds of formula (Ia-A-1) A-1b.01 to A-1b.12 (where R is used in the formula). 1 It is 3-(trifluoromethyl)phenyl, and R 8 and R 9 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0192] Table A-1c: This subtable lists nine compounds of formula (Ia-A-1) A-1c.01 to A-1c.12 (where R is used in the formula). 1 is 3-ethynylphenyl, and R 8 and R 9 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0193] Table A-1d: This subtable lists nine compounds of formula (Ia-A-1) A-1d.01 to A-1d.12 (where R is used in the formula). 1 It is 3-chlorophenyl, and R 8 and R 9 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0194] Table A-1e: This subtable lists the nine compounds of formula (Ia-A-1) A-1e.01 to A-1e.12 (where R is used in the formula). 1 It is 5-cyanopyridine-3-yl, and R 8 and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0195] Table A-1f: This subtable lists nine compounds of formula (Ia-A-1) A-1f.01 to A-1f.12 (where R is used in the formula). 1 It is 3-cyclopropylphenyl, and R 8 and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0196] Table A-1g: This subtable lists the nine compounds of formula (Ia-A-1) A-1g.01 to A-1g.12 (where R is used in the formula). 1It is 3-phenyl, and R 8 and R 9 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0197] Table A-1h: This subtable lists nine compounds of formula (Ia-A-1) A-1h.01 to A-1h.12 (where R is used in the formula). 1 This is a 3-trill, and R 8 and R 9 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0198] Table A-1i: This subtable lists the nine compounds of formula (Ia-A-1) A-1i.01 to A-1i.12 (where R is used in the formula). 1 It is 3-cyclopropylphenyl, and R 8 is methyl, and R 9 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0199] For example, compound A-1i.01 is as follows: [ka]

[0200] Table A-1j: This subtable lists nine compounds of formula (Ia-A-1) A-1j.01 to A-1j.12 (where R is used in the formula). 1 It is 3-(trifluoromethyl)phenyl, and R 8 is chloroform, R 9 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0201] Table A-1k: This subtable lists nine compounds of formula (Ia-A-1) A-1k.01 to A-1k.12 (where R is used in the formula). 1 It is 5-cyclopyridine-3-yl, and R 8 is hydrogen, R 9 (where is chloro and substituent G is substituent G as defined in Table Z above).

[0202] Table A-2: Compounds of formula (Ia-A-2) (wherein R 1 , R 7 , R 8 and R 9 (These are defined in Tables A-2a to A-2i, and G is defined in Table Z above.) [ka]

[0203] Table A-2a: This subtable lists nine compounds of formula (Ia-A-2) A-2a.01 to A-2a.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 7 and R 9 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0204] Table A-2b: This subtable lists nine compounds of formula (Ia-A-2) A-2b.01 to A-2b.12 (where R is used in the formula). 1 It is 3-(trifluoromethyl)phenyl, and R 7 and R 9 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0205] Table A-2c: This subtable lists 23 compounds of formula (Ia-A-2) A-2c.01 to A-2c.12 (where R is used in the formula). 1 is 3-ethynylphenyl, and R 7 and R 9 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0206] Table A-2d: This subtable lists nine compounds of formula (Ia-A-2) A-2d.01 to A-2d.12 (where R is used in the formula). 1 It is 3-chlorophenyl, and R 7 and R 9 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0207] Table A-2e: This subtable lists nine compounds of formula (Ia-A-2) A-2e.01 to A-2e.12 (where R is used in the formula). 1 It is 5-cyanopyridine-3-yl, and R 7 and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0208] For example, compound A-2e.09 is as follows: [ka]

[0209] Table A-2f: This subtable lists the nine compounds of formula (Ia-A-2) A-2g.01 to A-2g.9 (where R is used in the formula). 1 It is 3-cyclopropylphenyl, and R 7 and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0210] Table A-2g: This subtable lists nine compounds of formula (Ia-A-2) A-2h.01 to A-2h.9 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 7 is hydrogen, R 9 (where is methyl, and substituent G is substituent G as defined in Table Z above).

[0211] Table A-2h: This subtable lists the nine compounds of formula (Ia-A-2) A-2i.01 to A-2i.9 (where R is used in the formula). 1 It is 3-(trifluoromethyl)phenyl, and R 7 is hydrogen, R 9 (where is methyl, and substituent G is substituent G as defined in Table Z above).

[0212] Table A-2i: This subtable lists nine compounds of formula (Ia-A-2) A-2j.01 to A-2j.9 (where R is used in the formula). 1It is 5-cyanopyridine-3-yl, and R 7 is methyl, and R 9 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0213] Table A-3: Compounds of formula (Ia-A-3) (wherein R 1 , R 7 , R 8 and R 9 (These are defined in Tables A-3a to A-3m, and G is defined in Table Z above.) [ka]

[0214] Table A-3a: This subtable lists nine compounds of formula (Ia-A-3) A-3a.01 to A-3a.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 7 and R 8 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0215] Table A-3b: This subtable lists nine compounds of formula (Ia-A-3) A-3b.01 to A-3b.12 (where R is used in the formula). 1 It is 3-(trifluoromethyl)phenyl, and R 7 and R 8 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0216] Table A-3c: This subtable lists nine compounds of formula (Ia-A-3) A-3c.01 to A-3c.12 (where R is used in the formula). 1 is 3-ethynylphenyl, and R 7 and R 8 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0217] Table A-3d: This subtable lists nine compounds of formula (Ia-A-3) A-3d.01 to A-3d.12 (where R is used in the formula).1 It is 3-chlorophenyl, and R 7 and R 8 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0218] Table A-3e: This subtable lists nine compounds of formula (Ia-A-3) A-3e.01 to A-3e.12 (where R is used in the formula). 1 It is 5-cyanopyridine-3-yl, and R 7 and R 8 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0219] Table A-3f: This subtable lists nine compounds of formula (Ia-A-3) A-3f.01 to A-3f.12 (where R is used in the formula). 1 This is a 3-trill, and R 7 and R 8 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0220] Table A-3g: This subtable lists the nine compounds of formula (Ia-A-3) A-3g.01 to A-3g.12 (where R is used in the formula). 1 It is 3-phenyl, and R 7 and R 8 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0221] Table A-3h: This subtable lists nine compounds of formula (Ia-A-3) A-3h.01 to A-3h.12 (where R is used in the formula). 1 It is 3-cyclopropylphenyl, and R 7 and R 8 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0222] Table A-3i: This subtable lists nine compounds of formula (Ia-A-3) A-3i.01 to A-3i.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 7 is methyl, and R8 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0223] Table A-3j: This subtable lists nine compounds of formula (Ia-A-3) A-3j.01 to A-3j.12 (where R is used in the formula). 1 It is 3-(trifluoromethyl)phenyl, and R 7 is chloroform, R 8 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0224] Table A-3k: This subtable lists nine compounds of formula (Ia-A-3) A-3k.01 to A-3k.12 (where R is used in the formula). 1 It is 3-(trifluoromethyl)phenyl, and R 7 is hydrogen, R 8 (where is fluoro and substituent G is substituent G as defined in Table Z above).

[0225] For example, compound A-3k.02 is as follows: [ka]

[0226] Table A-3l: This subtable lists nine compounds of formula (Ia-A-3) A-3l.01 to A-3l.12 (where R is used in the formula). 1 It is 5-cyanopyridine-3-yl, and R 7 is hydrogen, R 8 (where is chloro and substituent G is substituent G as defined in Table Z above).

[0227] Table A-3m: This subtable lists nine compounds of formula (Ia-A-3) A-3m.01 to A-3m.12 (where R is used in the formula). 1 It is 3-cyclopropylphenyl, and R 7 is hydrogen, R 8 (where is fluoro and substituent G is substituent G as defined in Table Z above).

[0228] Table A-4: Compounds of formula (Ia-A-4) (wherein R 1 , R 7 , R 8 and R 9 (These are defined in Tables A-4a to A-4e, and G is defined in Table Z above.) [ka]

[0229] Table A-4a: This subtable lists nine compounds of formula (Ia-A-4) A-4a.01 to A-4a.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 9 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0230] Table A-4b: This subtable lists nine compounds of formula (Ia-A-4) A-4b.01 to A-4b.12 (where R is used in the formula). 1 It is 3-(trifluoromethyl)phenyl, and R 9 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0231] Table A-4c: This subtable lists nine compounds of formula (Ia-A-4) A-4c.01 to A-4c.12 (where R is used in the formula). 1 It is 5-cyanopyridine-3-yl, and R 9 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0232] Table A-4d: This subtable lists nine compounds of formula (Ia-A-4) A-4d.01 to A-4d.12 (where R is used in the formula). 1 It is 3-cyclopropylphenyl, and R 9 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0233] Table A-4e: This subtable lists nine compounds of formula (Ia-A-4) A-4e.01 to A-4e.12 (where R is used in the formula). 1 It is 3-phenyl, and R 9 (where is methyl, and substituent G is substituent G as defined in Table Z above).

[0234] Table A-5: Compounds of formula (Ia-A-5) (wherein R 1 , R 7 , R 8 and R 9 (These are defined in Tables A-5a to A-5g, and G is as defined in Table Z above.) [ka]

[0235] Table A-5a: This subtable lists nine compounds of formula (Ia-A-5) A-5a.01 to A-5a.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 8 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0236] Table A-5b: This subtable lists nine compounds of formula (Ia-A-5) A-5b.01 to A-5b.12 (where R is used in the formula). 1 It is 3-(trifluoromethyl)phenyl, and R 8 (where is hydrogen, and substituent G is substituent G as defined in Table Z above).

[0237] Table A-5c: This subtable lists nine compounds of formula (Ia-A-5) A-5c.01 to A-5c.12 (where R is used in the formula). 1 It is 5-(cyclopropyl)pyridine-3-yl, and R 8 (where is hydrogen, and substituent G is as defined in Table Z above).

[0238] Table A-5d: This subtable lists nine compounds of formula (Ia-A-5) A-5d.01 to A-5d.12 (where R is used in the formula). 1It is 3-cyclopropylphenyl, and R 8 (where is hydrogen, and substituent G is as defined in Table Z above).

[0239] Table A-5e: This subtable lists nine compounds of formula (Ia-A-5) A-5e.01 to A-5e.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 8 (where is methyl, and substituent G is as defined in Table Z above).

[0240] Table A-5f: This subtable lists nine compounds of formula (Ia-A-5) A-5f.01 to A-5f.12 (where R is used in the formula). 1 It is 3-phenyl, and R 8 (where is chloro and substituent G is as defined in Table Z above).

[0241] Table A-5g: This subtable lists the nine compounds of formula (Ia-A-5) A-5g.01 to A-5g.12 (wherein R 1 It is 3-cyclopropylphenyl, and R 8 (where is fluoro, and substituent G is as defined in Table Z above).

[0242] Table A-6: Compounds of formula (Ia-A-6) (wherein R 1 , R 7 , R 8 and R 9 (These are defined in Tables A-6a to A-6c, and G is defined in Table Z above.) [ka]

[0243] Table A-6a: This subtable lists nine compounds of formula (Ia-A-6) A-6a.01 to A-6a.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 7 (where is hydrogen, and substituent G is as defined in Table Z above).

[0244] Table A-6b: This subtable lists nine compounds of formula (Ia-A-6) A-6b.01 to A-6b.12 (where R is used in the formula). 1 It is 3-(trifluoromethyl)phenyl, and R 7 (where is hydrogen, and substituent G is as defined in Table Z above).

[0245] Table A-6c: This subtable lists nine compounds of formula (Ia-A-6) A-6c.01 to A-6c.12 (where R is used in the formula). 1 It is 3-cyclopropylphenyl, and R 7 (where is hydrogen, and substituent G is as defined in Table Z above).

[0246] For example, compound A-6c.06 is as follows: [ka]

[0247] Table A-7: Compounds of formula (Ia-A-7) (wherein R 1 , R 7 , R 8 and R 9 (These are defined in Tables A-7a to A-7d, and G is defined in Table Z above.) [ka]

[0248] Table A-7a: This subtable lists nine compounds of formula (Ia-A-7) A-7a.01 to A-7a.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 8 and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0249] Table A-7b: This subtable lists nine compounds of formula (Ia-A-7) A-7b.01 to A-7b.12 (where R is used in the formula). 1It is 3-(trifluoromethyl)phenyl, and R 8 and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0250] Table A-7c: This subtable lists nine compounds of formula (Ia-A-7) A-7c.01 to A-7c.12 (where R is used in the formula). 1 It is 3-cyclopropylphenyl, and R 8 and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0251] Table A-7d: This subtable lists nine compounds of formula (Ia-A-7) A-7d.01 to A-7d.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 8 is chloroform, R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0252] For example, compound A-7d.04 is as follows: [ka]

[0253] Table A-7e: This subtable lists nine compounds of formula (Ia-A-7) A-7e.01 to A-7e.12 (where R is used in the formula). 1 It is 3-cyclopropylphenyl, and R 8 is fluoro, and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0254] Table A-8: Compounds of formula (Ia-A-8) (wherein R 1 , R 7 , R 8 and R 9 (These are defined in Tables A-8a to A-8f, and G is defined in Table Z above.) [ka]

[0255] Table A-8a: This subtable lists nine compounds of formula (Ia-A-8) A-8a.01 to A-8a.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 7 and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0256] Table A-8b: This subtable lists nine compounds of formula (Ia-A-8) A-8b.01 to A-8b.12 (where R is used in the formula). 1 It is 3-(trifluoromethyl)phenyl, and R 7 and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0257] Table A-8c: This subtable lists nine compounds of formula (Ia-A-8) A-8c.01 to A-8c.12 (where R is used in the formula). 1 It is 5-cyanopyridine-3-yl, and R 7 and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0258] Table A-8d: This subtable lists nine compounds of formula (Ia-A-8) A-8d.01 to A-8d.12 (where R is used in the formula). 1 This is a 3-trill, and R 7 and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0259] Table A-8e: This subtable lists nine compounds of formula (Ia-A-8) A-8e.01 to A-8e.12 (where R is used in the formula). 1 It is 3-cyclopropylphenyl, and R 7 and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0260] Table A-8f: This subtable lists nine compounds of formula (Ia-A-8) A-8f.01 to A-8f.12 (where R is used in the formula). 1 It is 3-cyclopropylphenyl, and R 7 is hydrogen, R 9 (where is methyl, and substituent G is as defined in Table Z above).

[0261] For example, compound A-8f.5 is as follows: [ka]

[0262] Table A-9: Compounds of formula (Ia-A-9) (wherein R 1 , R 7 , R 8 and R 9 (These are defined in Tables A-9a to A-9d, and G is as defined in Table Z above.) [ka]

[0263] Table A-9a: This subtable lists the nine compounds of formula (Ia-A-9) A-9a.01 to A-9a.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 7 and R 8 (where is hydrogen, and substituent G is as defined in Table Z above).

[0264] Table A-9b: This subtable lists the nine compounds of formula (Ia-A-9) A-9b.01 to A-9b.12 (where R is used in the formula). 1 It is 3-(trifluoromethyl)phenyl, and R 7 and R 8 (where is hydrogen, and substituent G is as defined in Table Z above).

[0265] Table A-9c: This subtable lists the nine compounds of formula (Ia-A-9) A-9c.01 to A-9c.12 (where R is used in the formula). 1It is 3-phenyl, and R 7 and R 8 (where is hydrogen, and substituent G is as defined in Table Z above).

[0266] For example, compound A-9c.7 is as follows: [ka]

[0267] Table A-9d: This subtable lists the nine compounds of formula (Ia-A-9) A-9d.01 to A-9d.12 (where R is used in the formula). 1 It is 3-cyclopropylphenyl, and R 7 and R 8 (where is hydrogen, and substituent G is as defined in Table Z above).

[0268] Table A-10: Compounds of formula (Ia-A-10) (wherein R 1 , R 7 , R 8 and R 9 (These are defined in Tables A-10a to A-10c, and G is defined in Table Z above.) [ka]

[0269] Table A-10a: This subtable lists nine compounds of formula (Ia-A-10) A-10a.01 to A-10a.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0270] Table A-10b: This subtable lists nine compounds of formula (Ia-A-10) A-10b.01 to A-10b.12 (where R is used in the formula). 1 It is 3-trifluoromethyl)phenyl, and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0271] For example, compound A-10b.4 is as follows: [ka]

[0272] Table A-10c: This subtable lists nine compounds of formula (Ia-A-10) A-10c.01 to A-10c.12 (where R is used in the formula). 1 It is 3-cyclopropylphenyl, and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0273] Table A-11: Compounds of formula (Ia-A-11) (wherein R 1 , R 7 , R 8 and R 9 (These are defined in Tables A-11a to A-11c, and G is defined in Table Z above.) [ka]

[0274] Table A-11a: This subtable lists nine compounds of formula (Ia-A-11) A-11a.01 to A-11a.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 7 (where is hydrogen, and substituent G is as defined in Table Z above).

[0275] Table A-11b: This subtable lists nine compounds of formula (Ia-A-11) A-11b.01 to A-11b.12 (where R is used in the formula). 1 It is 3-(trifluoromethoxy)phenyl, and R 7 (where is hydrogen, and substituent G is as defined in Table Z above).

[0276] Table A-11c: This subtable lists 293 compounds of formula (Ia-A-11) A-11c.01 to A-11c.12 (where R is used in the formula). 1It is 3-cyclopropylphenyl, and R 7 (where is hydrogen, and substituent G is as defined in Table Z above).

[0277] Table A-12: Compounds of formula (Ia-A-12) (wherein R is used in the formula) 1 , R 7 , R 8 and R 9 (These are defined in Tables A-12a to A-12c, and G is defined in Table Z above.) [ka]

[0278] Table A-12a: This subtable lists nine compounds of formula (Ia-A-12) A-12a.01 to A-12a.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 8 (where is hydrogen, and substituent G is as defined in Table Z above).

[0279] Table A-12b: This subtable lists nine compounds of formula (Ia-A-12) A-12b.01 to A-12b.12 (where R is used in the formula). 1 This is a 3-trill, and R 8 (where is hydrogen, and substituent G is as defined in Table Z above).

[0280] Table A-12c: This subtable lists nine compounds of formula (Ia-A-12) A-12c.01 to A-12c.12 (where R is used in the formula). 1 It is 3-cyclopropylphenyl, and R 8 (where is chloro and substituent G is as defined in Table Z above).

[0281] Table A-13: Compounds of formula (Ia-A-13) (wherein R 1 , R 7 , R 8 and R 9 (These are defined in Tables A-13a to A-13b, and G is defined in Table Z above.) [ka]

[0282] Table A-13a: This subtable lists nine compounds of formula (Ia-A-13) A-13a.01 to A-13a.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 8 and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0283] Table A-13b: This subtable lists nine compounds of formula (Ia-A-13) A-13b.01 to A-13b.12 (where R is used in the formula). 1 It is 3-phenyl, and R 8 is methyl, and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0284] Table A-14: Compounds of formula (Ia-A-14) (wherein R is the formula) 1 , R 7 , R 8 and R 9 (These are defined in Tables A-14a to A-14f, and G is defined in Table Z above.) [ka]

[0285] Table A-14a: This subtable lists nine compounds of formula (Ia-A-14) A-14a.01 to A-14a.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 7 and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0286] Table A-14b: This subtable lists nine compounds of formula (Ia-A-14) A-14b.01 to A-14b.12 (where R is used in the formula). 1 It is 3-(trifluoromethyl)phenyl, and R7 and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0287] Table A-14c: This subtable lists nine compounds of formula (Ia-A-14) A-14c.01 to A-14c.12 (where R is used in the formula). 1 It is 5-cyanopyridine-3-yl, and R 7 and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0288] Table A-14d: This subtable lists nine compounds of formula (Ia-A-14) A-14d.01 to A-14d.12 (where R is used in the formula). 1 It is 3-cyclopropylphenyl, and R 7 and R 9 (where is hydrogen, and substituent G is as defined in Table Z above).

[0289] Table A-14e: This subtable lists nine compounds of formula (Ia-A-14) A-14e.01 to A-14e.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 7 is methyl, and R 9 (where is methyl, and substituent G is as defined in Table Z above).

[0290] Table A-14f: This subtable lists nine compounds of formula (Ia-A-14) A-14f.01 to A-14f.12 (where R is used in the formula). 1 It is 3-phenyl, and R 7 is hydrogen, R 9 (where is methyl, and substituent G is as defined in Table Z above).

[0291] Table A-15: Compounds of formula (Ia-A-15) (wherein R is the formula) 1 , R 7 , R 8 and R 9 (These are defined in Tables A-15a to A-15f, and G is defined in Table Z above.) [ka]

[0292] Table A-15a: This subtable lists nine compounds of formula (Ia-A-15) A-15a.01 to A-15a.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 7 and R 8 (where is hydrogen, and substituent G is as defined in Table Z above).

[0293] Table A-15b: This subtable lists nine compounds of formula (Ia-A-15) A-15b.01 to A-15b.12 (where R is used in the formula). 1 It is 3-(trifluoromethyl)phenyl, and R 7 and R 8 (where is hydrogen, and substituent G is as defined in Table Z above).

[0294] Table A-15c: This subtable lists nine compounds of formula (Ia-A-15) A-15c.01 to A-15c.12 (where R is used in the formula). 1 It is 5-cyanopyridine-3-yl, and R 7 and R 8 (where is hydrogen, and substituent G is as defined in Table Z above).

[0295] Table A-15d: This subtable lists nine compounds of formula (Ia-A-15) A-15d.01 to A-15d.12 (where R is used in the formula). 1 It is 5-(cyclopropyl)pyridine-3-yl, and R 7 and R 8 (where is hydrogen, and substituent G is as defined in Table Z above).

[0296] Table A-15e: This subtable lists nine compounds of formula (Ia-A-15) A-15e.01 to A-15e.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 7 is hydrogen, R8 (where is fluoro, and substituent G is as defined in Table Z above).

[0297] Table A-15f: This subtable lists nine compounds of formula (Ia-A-15) A-15f.01 to A-15f.12 (where R is used in the formula). 1 It is 3-cyclopropylphenyl, and R 7 is methyl, and R 8 (where is hydrogen, and substituent G is as defined in Table Z above).

[0298] Table A-16: Compounds of formula (Ia-A-16) (wherein R 1 , R 7 , R 8 and R 9 (These are defined in Tables A-16a to A-16c, and G is defined in Table Z above.) [ka]

[0299] Table A-16a: This subtable lists nine compounds of formula (Ia-A-16) A-16a.01 to A-16a.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 7 (where is hydrogen, and substituent G is as defined in Table Z above).

[0300] Table A-16b: This subtable lists nine compounds of formula (Ia-A-16) A-16b.01 to A-16b.12 (where R is used in the formula). 1 It is 3-(trifluoromethyl)phenyl, and R 7 (where is hydrogen, and substituent G is as defined in Table Z above).

[0301] Table A-16c: This subtable lists nine compounds of formula (Ia-A-16) A-16c.01 to A-16c.12 (where R is used in the formula). 1 It is 5-cyanopyridine-3-yl, and R 7(where is hydrogen, and substituent G is as defined in Table Z above).

[0302] Table A-17: Compounds of formula (Ia-A-17) (wherein R 1 , R 7 , R 8 and R 9 (These are defined in Tables A-17a to A-17c, and G is defined in Table Z above.) [ka]

[0303] Table A-17a: This subtable lists nine compounds of formula (Ia-A-17) A-17a.01 to A-17a.12 (where R is used in the formula). 1 It is 3-cyclopropyl-2-fluorophenyl, and R 8 (where is hydrogen, and substituent G is as defined in Table Z above).

[0304] Table A-17b: This subtable lists nine compounds of formula (Ia-A-17) A-17b.01 to A-17b.12 (where R is used in the formula). 1 It is 3-(trifluoromethyl)phenyl, and R 8 (where is hydrogen, and substituent G is as defined in Table Z above).

[0305] Table A-17c: This subtable lists nine compounds of formula (Ia-A-17) A-17c.01 to A-17c.12 (where R is used in the formula). 1 This is a 3-trill, and R 8 (where is hydrogen, and substituent G is as defined in Table Z above).

[0306] Some of these are novel, formulas (IC-1), (IC-2), and (IC-3): [ka] (In the formula, R 1 Q a Q b Q c Q7 Q 8 Q 9 And G are as defined for the compound of formula (I); X a X 3 or X 4 and; X b and X c Both are hydrogen, or X b is hydrogen, and X c is a protecting group selected from tert-butyloxycarbonyl, benzylcarbonyl, 9-fluorenylmethylcarbonyl, trifluoroacetyl, benzyl, triphenylmethyl, benzylidenyl and p-toluenesulfonyl, or X b and X c Xb and Xc are either the same or different protecting groups, or Xb and Xc together with the nitrogen to which they are bonded form a protecting group, the protecting group being selected from tert-butyloxycarbonyl, benzylcarbonyl, 9-fluorenylmethylcarbonyl, trifluoroacetyl, benzyl, triphenylmethyl, benzylidenyl, p-toluenesulfonyl, phthalimide, or succinimide; X d is H or -CH2-C(O)-CH2-G; X 3 is a leaving group selected from fluoro, chloro, bromo, iodine, BF3K, B(OH)2, and B(pinacol); X 4 is OH or -OR 1 (is) Specific intermediate compounds are also provided.

[0307] As can be seen from the formulas of the intermediate compounds of the above formulas (IC-1), (IC-2), and (IC-3), a heterobicyclic group [ka] corresponds to group A defined for the compound of formula (Ia), where ## is X in the intermediate compound of formulas (IC-1) and (IC-2). aThis indicates a bond to the amide group in the intermediate compound of formula (IC-1), a bond to the -5,6-dihydro-4H-1,2,4-oxadiazine-3-yl-G moiety in the intermediate compound of formula (IC-2), or a bond to the amidine group in the intermediate compound of formula (IC-3).

[0308] In the intermediate compounds of formulas (IC-1), (IC-2), and (IC-3), group A may be as defined in Tables 1 and 2. Preferably, A is A-1, A-2, A-3, A-5, A-14, or A-15. More preferably, A is A-3, A-5, or A-15. In particular, A and R 1 A and R are defined in Tables A-1 to A-17 and their respective subtables, and G is defined in Table Z. Preferably, A and R 1 A and R are defined as in Tables A-1, A-2, A-3, A-5, A-14 or A-15 and their respective subtables, and G is defined as in Table Z. More preferably, A and R 1 G is defined as in Tables A-3, A-5, or A-15 and their respective subtables, and G is defined as in Table Z.

[0309] For example, specific intermediate compounds of formulas (II), (X), and (XV) are provided. They correspond to the intermediate compounds of formula (IC-1), where X b and X c Both are hydrogen, and X a In the compound of formula (II), OR 1 In the compound of formula (X), X 3 Or, in compounds of formula (XV), it is OH: [ka] (In the formula, R 1 Q a Q b Q c Q 7 Q 8 Q 9And G are as defined for the compound of formula (I), and X3 is a leaving group selected from fluoro, chloro, bromo, iodine, BF3K, B(OH)2 and B(pinacol). In particular, G is as defined in Table Z.

[0310] Other specific intermediate compounds of formulas (III), (IX), and (XIV) are also provided. They correspond to the intermediate compounds of formula (IC-1), where X a In the compound of formula (III), OR 1 In the compound of formula (IX), X 3 Or, in compounds of formula (XIV), it is OH, and X b and X c These are X 1 and X 2 is: [ka] (In the formula, R 1 Q a Q b Q c Q 7 Q 8 Q 9 And G are as defined for the compound of formula (I), and in particular G is as defined in Table Z; X 1 H is X 2 is a protecting group, or X 1 and X 2 are either the same or different protecting groups, or X 1 and X 2 These atoms form protecting groups together with the nitrogen atoms to which they are bonded. Examples of protecting groups include, for example, tert-butyloxycarbonyl, benzylcarbonyl, 9-fluorenylmethylcarbonyl, trifluoroacetyl, benzyl, triphenylmethyl, benzylidenyl, p-trienesulfonyl, phthalimide, or succinimide.

[0311] Other specific intermediate compounds of formulas (VIII), (XIII), and (XVII) are also provided. They correspond to the intermediate compounds of formula (IC-2), where X aIn the compound of formula (VIII), X 3 , in compounds of formula (XIII), OH or in compounds of formula (XVII), X 4 is: [ka] (In the formula, R 1 Q a Q b Q c Q 7 Q 8 Q 9 And G are as defined for the compound of formula (I), and in particular G is as defined in Table Z; X 3 is a leaving group selected from fluoro, chloro, bromo, iodine, BF3K, B(OH)2 and B(pinacol); X 4 is OH or -OR 1 (That is.)

[0312] Other specific intermediate compounds of formulas (XXII) and (XXIII) are also provided. They correspond to the intermediate compounds of formula (IC-3), where X d In compounds of formula (XXII), this is -CH2-C(O)-CH2-G, or in compounds of formula (XXIII), it is H: [ka] (In the formula, R 1 Q a Q b Q c Q 7 Q 8 Q 9 And G are as defined for the compound of formula (I); in particular, G is as defined in Table Z; X 4 is OH or -OR 1 (That is.)

[0313] In the intermediate compounds of formulas (II), (III), (VIII), (IX), (X), (XIII), (XIV), (XV), (XVII), (XXII), and (XXIII), group A may be as defined in Tables 1 and 2. Preferably, A is A-1, A-2, A-3, A-5, A-14, or A-15. More preferably, A is A-3, A-5, or A-15. In particular, A and R 1 A and R are defined in Tables A-1 to A-17 and their respective subtables, and G is defined in Table Z. Preferably, A and R 1 A and R are defined as in Tables A-1, A-2, A-3, A-5, A-14 or A-15 and their respective subtables, and G is defined as in Table Z. More preferably, A and R 1 This is as defined in Tables A-3, A-5, or A-15 and their respective subtables, and G is as defined in Table Z. a , X b , X c , X d , X 3 and X 4 This is as defined for the compounds of formulas (IC-1), (IC-2), and (IC-3) above.

[0314] For example, the following intermediate compounds are provided, some of which are novel. - Compound of formula (II) (wherein R 1 And A is as defined in Tables A-1 to A-17 and any one of their subtables, and G is as defined in Table Z): [ka] More specifically, compounds of formulas (II-A-1i) to (II-A-17i) as shown in Table II below (where R is used in the formulas) 1 , R 7 , R 8 and R 9 (The definitions of G are as defined in Tables A-1 to A-17 and any one of their subtables, and G is as defined in Table Z.) Table II [ka] - Compound of formula (III) (wherein X 1 and X 2 is the same or different protecting group selected from tert-butyloxycarbonyl, benzylcarbonyl, 9-fluorenylmethylcarbonyl, trifluoroacetyl, benzyl, phthalyl, triphenylmethyl, benzylidenyl and p-toluenesulfonyl, or X 1 and X 2 They form a protective ring together with the nitrogen to which they are bound; R 1 And A is as defined in Tables A-1 to A-17 and any one of their subtables, and G is as defined in Table Z): [ka] More specifically, compounds of formulas (III-A-1i) to (III-A-17i) as shown in Table III below (where R is used in the formulas) 1 , R 7 , R 8 and R 9 (The definitions of G are as defined in Tables A-1 to A-17 and any one of their subtables, and G is as defined in Table Z.) Table III [ka] - Compound of formula (VIII) (wherein X 3 A is a suitable leaving group such as fluoro, chloro, bromo, iodine, BF3K, B(OH)2, or B(pinacol), A is as defined in Tables A-1 to A-17 and any one of their subtables, and G is as defined in Table Z): [ka] More specifically, compounds of the formulas (VIII-A-1i) to (VIII-A-17i) as shown in Table VIII below (where R is used in the formulas) 7 , R8 and R 9 (The definitions of G are as defined in Tables A-1 to A-17 and any one of their subtables, and G is as defined in Table Z.) Table VIII [ka] - Compound of formula (IX) (wherein X 1 and X 2 is the same or different protecting group selected from tert-butyloxycarbonyl, benzylcarbonyl, 9-fluorenylmethylcarbonyl, trifluoroacetyl, benzyl, phthalyl, triphenylmethyl, benzylidenyl and p-toluenesulfonyl, or X 1 and X 2 They form a protective ring together with the nitrogen to which they are bound; X 3 A is a suitable leaving group such as fluoro, chloro, bromo, iodine, BF3K, B(OH)2, or B(pinacol), A is as defined in Tables A-1 to A-17 and any one of their subtables, and G is as defined in Table Z): [ka] More specifically, compounds of the formulas (IX-A-1i) to (IX-A-17i) as shown in Table IX below (where R is used in the formulas) 7 , R 8 and R 9 (The definitions of G are as defined in Tables A-1 to A-17 and any one of their subtables, and G is as defined in Table Z.) Table IX [ka] - Compound of formula (X) (wherein X 3 A is a suitable leaving group such as fluoro, chloro, bromo, iodine, BF3K, B(OH)2, or B(pinacol), A is as defined in Tables A-1 to A-17 and any one of their subtables, and G is as defined in Table Z): [ka] More specifically, compounds of formulas (XA-1i) to (XA-17i) as shown in Table X below (where R is used in the formulas) 7 , R 8 and R 9 (The definitions of G are as defined in Tables A-1 to A-17 and any one of their subtables, and G is as defined in Table Z.) Table X [ka] - Compound of formula (XIII) (wherein A is as defined in Tables A-1 to A-17 and their respective subtables, and G is as defined in Table Z): [ka] More specifically, compounds of the formulas (XIII-A-1i) to (XIII-A-17i) as shown in Table XIII below (where R is used in the formulas) 7 , R 8 and R 9 (The definitions of G are as defined in Tables A-1 to A-17 and any one of their subtables, and G is as defined in Table Z.) Table XIII [ka] - Compound of formula (XIV) (wherein X 1 and X 2 is the same or different protecting group selected from tert-butyloxycarbonyl, benzylcarbonyl, 9-fluorenylmethylcarbonyl, trifluoroacetyl, benzyl, phthalyl, triphenylmethyl, benzylidenyl and p-toluenesulfonyl, or X 1 and X 2 They form a protective ring with the nitrogen to which they are bound; A is as defined in Tables A-1 to A-17 and any one of their respective subtables, and G is as defined in Table Z): [ka] More specifically, compounds of the formulas (XIV-A-1i) to (XIV-A-17i) as shown in Table XIV below (where R is used in the formulas). 7 , R 8 and R 9 (The definitions of G are as defined in Tables A-1 to A-17 and any one of their subtables, and G is as defined in Table Z.) Table XIV [ka] - Compounds of formula (XV) (wherein A is as defined in Tables A-1 to A-17 and their respective subtables, and G is as defined in Table Z): [ka] More specifically, compounds of the formulas (XV-A-1i) to (XV-A-17i) as shown in Table XV below (where R is used in the formulas) 7 , R 8 and R 9 (The definitions of G are as defined in Tables A-1 to A-17 and any one of their subtables, and G is as defined in Table Z.) Table XV [ka] - Compound of formula (XVII) (wherein A and R 1 (The definitions of G are as defined in Tables A-1 to A-17 and any one of their subtables, and G is as defined in Table Z.) [ka] More specifically, compounds of formulas (XVII-A-1i) to (XVII-A-17i) as shown in Table XVII below (where R is used in the formulas) 1 , R 7 , R 8 and R 9(The definitions of G are as defined in Tables A-1 to A-17 and any one of their subtables, and G is as defined in Table Z.) Table XVII [ka] - Compound of formula (XXII) (wherein X 4 is OH or -OR 1 A is as defined in Tables A-1 to A-17 and any one of their subtables, and G is as defined in Table Z): [ka] More specifically, compounds of the formulas (XXII-A-1i) to (XXII-A-17i) as shown in Table XXII below (where R is used in the formulas) 7 , R 8 and R 9 (The definitions of G are as defined in Tables A-1 to A-17 and any one of their subtables, and G is as defined in Table Z.) Table XXII [ka] - Compound of formula (XXIII) (wherein X 4 is OH or -OR 1 A is as defined in Tables A-1 to A-17 and any one of their subtables, and G is as defined in Table Z): [ka] More specifically, compounds of the formulas (XXIII-A-1i) to (XXIII-A-17i) as shown in Table XXIII below (where R is used in the formulas). 7 , R 8 and R 9 (The definitions of G are as defined in Tables A-1 to A-17 and any one of their subtables, and G is as defined in Table Z.) Table XXIII [ka]

[0315] In a further aspect, the present invention thus provides intermediate compounds of formula (IC-1), (IC-2) and (IC-3), for example compounds of formula (II), (III), (VIII), (IX), (X), (XIII), (XIV), (XV), (XVII), (XXII) and (XXIII), in each case, R 1 , Q a , Q b , Q c , Q 7 , Q 8 , Q 9 and G (R 7 , R 8 and R 9 included) are as defined for the compounds of formula (I) in either the first aspect or any of the above embodiments; X a is X 3 or X 4 ; X b and X c are both hydrogen, or X b is hydrogen, X c is a protecting group, or X b and X c are the same or different protecting groups, or X b and X c form a protecting group together with the nitrogen to which they are attached, said one or more protecting groups being selected from tert-butyloxycarbonyl, benzylcarbonyl, 9-fluorenylmethylcarbonyl, trifluoroacetyl, benzyl, triphenylmethyl, benzylidene, p-toluenesulfonyl, phthalimide and succinimide; X d is H or -CH2-C(O)-CH2-G; X 3 is a leaving group selected from fluoro, chloro, bromo, iodo, BF3K, B(OH)2 and B(pinacol); X 4 is OH or -O-R 1 ; In particular, Q a , Q b , Q c , Q7 Q 8 Q 9 This is as defined in Table 1 or Table 2, and preferably Q a Q b Q c Q 7 Q 8 Q 9 Q has the definitions given for A-1, A-2, A-3, A-5, A-14 or A-15, and more preferably Q a Q b Q c Q 7 Q 8 Q 9 This has the definition given for A-3, A-5, or A-15. [Examples]

[0316] The following examples are for illustrative purposes only and are not intended to limit the present invention.

[0317] The compounds of the present invention can be distinguished from known compounds by their high efficacy at low doses, which can be verified by those skilled in the art using the experimental methods outlined in the examples, with the application of low doses such as 60 ppm, 20 ppm, or 2 ppm as needed.

[0318] Compounds of formula (I) may have many advantages, particularly those related to their use as advantageous levels of biological activity or agrochemical active ingredients for protecting plants from fungal diseases (e.g., high biological activity, a favorable range of activity, a high safety profile (including improved crop tolerance), improved physicochemical properties, or high biodegradability).

[0319] Throughout this specification, temperatures are given in degrees Celsius, and "mp" signifies the melting point. LC-MS means liquid chromatography-mass spectroscopy, and the apparatus and method are described below.

[0320] 1 1H NMR and 19F NMR measurements were recorded using a Bruker 400MHz spectrometer, and chemical shifts were measured using TMS standards. 1 H) and CFCl3( 19 F) Values ​​are expressed in ppm relative to the standard. Spectra were measured in the deuterated solvent as described. One of the following LC-MS methods was used to characterize the compounds. Characteristic LC-MS values ​​obtained for each compound were recorded as retention time ("Rt", recorded in minutes) and molecular ion (M+H). + or (MH) - It was a measured value.

[0321] Example formulation

[0322] [Table 3]

[0323] This combination is thoroughly mixed with an auxiliary agent, and the mixture is thoroughly ground in a suitable mill to obtain a wettable powder, which is then diluted with water to obtain a suspension of the desired concentration.

[0324] [Table 4]

[0325] This combination, when thoroughly mixed with the auxiliary agent and the mixture is thoroughly ground in a suitable mill, yields a powder that can be used directly for seed treatment.

[0326] emulsifiable concentrate Active ingredient 10% Octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3% Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (35 mol ethylene oxide) 4% Cyclohexanone 30% Xylene mixture 50%

[0327] Emulsions of any required dilution ratio, which can be used for plant protection, can be obtained from this concentrate by dilution with water.

[0328] [Table 5]

[0329] Ready-to-use powders are obtained by mixing them with a carrier and grinding the mixture in a suitable mill. Such powders for scattering can also be used for drying and coating seeds.

[0330] Extruded granules Active ingredient 15% Sodium lignosulfonate 2% Carboxymethylcellulose 1% Kaolin 82%

[0331] This combination is mixed with an auxiliary agent, ground, and the mixture is wetted with water. This mixture is then extruded and dried with an airflow.

[0332] Coated granules Active ingredient 8% Polyethylene glycol (molecular weight 200) 3% Kaolin 89%

[0333] This pulverized mixture is uniformly applied to kaolin moistened with polyethylene glycol in a mixer. In this way, dust-free coated granules are obtained.

[0334] 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%

[0335] A finely ground combination can be completely mixed with an auxiliary agent to obtain a suspension concentrate, which can then be diluted with water to obtain a suspension of any desired dilution. Using such dilutions, living plants and plant propagation materials can be treated and protected from microbial ectoparasitism by spraying, pouring, or immersion.

[0336] Fluid concentrate for seed treatment Active ingredient 40% Propylene glycol 5% Copolymer Butanol PO / EO 2% Tristyrenephenol + 10-20 molar 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%

[0337] A finely ground combination can be completely mixed with an auxiliary agent to obtain a suspension concentrate, which can then be diluted with water to obtain a suspension of any desired dilution. Using such dilutions, living plants and plant propagation materials can be treated and protected from microbial ectoparasitism by spraying, pouring, or immersion.

[0338] Sustained-release capsule suspension Mix 28 parts of the combination with 2 parts of aromatic solvent and 7 parts of toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). Emulsify this mixture 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. Add a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water to this emulsion. Stir this mixture until the polymerization reaction is complete. Stabilize the resulting capsule suspension by adding 0.25 parts of thickener and 3 parts of dispersant. This capsule suspension formulation contains 28% active ingredient. The medium capsule diameter is 8-15 microns. The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for this purpose.

[0339] Examples of formulation types include emulsion concentrates (EC), suspension concentrates (SC), suspension emulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifying 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), industrial concentrates (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG), or any technically preferred formulations combined with agriculturally acceptable auxiliaries.

[0340] Abbreviation Abbreviations used in synthesis schemes and preparation examples ACN (AcN or MeCN) Acetonitrile aq. Water-based Boc t-Butoxycarbonyl CDCl3 (deuterated chloroform) DBU 1,8-Diazabicyclo[5.4.0]Undeca-7-Ene DCM Dichloromethane DDQ 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone DMSO (Dimethyl Sulfoxide) DMSO-d6 Deuterated Dimethyl Sulfoxide DPEN (Diphenylethylenediamine) Et3N triethylamine HCl ethyl acetate HATU 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium-3-oxide-hexafluorophosphate HCl (hydrochloric acid) h / hrs time MeCN acetonitrile MeOH ethanol Ms Methanesulfonyl (Mesyl) n-Bu n-butyl NHC N-heterocyclic carbene NPhth Phthalimido-1-yl OMs Mesylate group OTf triflate group OTs tosylate group PdCl2dppf 1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride rt room temperature T3P, also known as 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphospholinane-2,4,6-trioxide, is a propanephosphonic anhydride. TBME tert-butylmethyl ether TEA (Triethylamine) TEMPO(2,2,6,6-tetramethylpiperidine-1-yl)oxydanyl Tf Trifluoromethanesulfonyl (Trifuryl) TFA (Trifluoroacetic Acid) THF (Tetrahydrofuran) TLC (Thin-Layer Chromatography) Ts p-toluenesulfonyl(tosyl) X-Phos 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl

[0341] Preparation example The compound of formula (I) according to the present invention can be prepared using the synthesis techniques described above and below.

[0342] "Mp" stands for melting point (°C). Free radical represents a methyl group. 1 H and 19 F NMR measurements were recorded using a Bruker 400 MHz spectrometer (or a 600 MHz spectrometer as shown), and the chemical shift was measured using TMS. 1 H) Standard and CFCl3 19 F) Values ​​are expressed in ppm relative to the standard. Spectra were measured in the deuterated solvent as described. One of the following LC-MS methods was used to characterize the compounds. Characteristic LC-MS values ​​obtained for each compound were recorded as retention time ("Rt", recorded in minutes) and molecular ion (M+H). + or (MH) - It was a measured value.

[0343] Unless otherwise instructed, 1 The H NMR spectrum was recorded at 400 MHz. 19 The 1F NMR spectrum is recorded at 377 MHz, and the chemical shift is recorded in ppm. The following abbreviations are used: s = singlet; s = broad singlet; d = doublet; d = broad doublet; dd = double doublet; dt = double triplet; t = triplet; tt = triple triplet; q = quartet; quin = quintuplet; sept = septet; m = multiplet.

[0344] Throughout this specification, temperatures are expressed in degrees Celsius (°C). "MP" stands for melting point. "Rt" stands for retention time. LC / MS stands for liquid chromatography-mass spectrometry. The LC / MS apparatus and method are as follows:

[0345] LC-MS Method A: Spectra were recorded using an Agilent Technologies mass spectrometer (6410 triple quadrupole mass spectrometer) equipped with an electrospray source (positive and negative polarity switches, capillary (kV) 4.00, scan type MS2 scan, fragmenter (V) 100.00, gas temperature (°C) 350, gas flow rate (L / min) 11, nebulizer gas (psi) 45, mass range: 110~1000 Da), and an Agilent 1200 series HPLC was used: DAD wavelength range: 210~400 nm, column: KINETEX EVO C18, column length: 50 mm, column inner diameter: 4.6 mm, particle size: 2.6 μm, column oven temperature: 40°C.

[0346] Gradient conditions: Solvent A: Water containing 0.1% formic acid: Acetonitrile: 95: 5 volumes / volume Solvent B: Acetonitrile containing 0.1% formic acid

[0347] [Table 6]

[0348] If necessary, the enantiomerically pure final compound can be obtained from the racemic material, as needed, via standard physical separation techniques such as reversed-phase chiral chromatography or stereoselective synthesis techniques, for example, by using chiral starting materials.

[0349] LC-MS Method B: Spectra were recorded using an Agilent Technologies mass spectrometer (6410 triple quadrupole mass spectrometer) equipped with an electrospray source (positive and negative polarity switches, capillary (kV) 7.00, scan type MS2 scan, fragmenter (V) 120.00, gas temperature (°C) 350, gas flow rate (L / min) 11, nebulizer gas (psi) 40, mass range: 110~650 Da), and an Agilent 1200 series HPLC was used: DAD wavelength: 254 nm, column: KINETEX EVO C18, column length: 50 mm, column inner diameter: 4.6 mm, particle size: 2.6 μm, column oven temperature: 40°C.

[0350] Gradient conditions: Solvent A: Water containing 0.1% formic acid: Acetonitrile: 95: 5 volumes / volume Solvent B: Acetonitrile containing 0.1% formic acid

[0351] [Table 7]

[0352] If necessary, the enantiomerically pure final compound can be obtained from the racemic material, as needed, via standard physical separation techniques such as reversed-phase chiral chromatography or stereoselective synthesis techniques, for example, by using chiral starting materials.

[0353] LC-MS method C: Spectra were recorded using a Waters mass spectrometer (Acquity QDA mass spectrometer) equipped with an electrospray source (positive and negative polarity switch, capillary (kV) 0.8, cone voltage (V) 25.00, full scan, source temperature (°C) 120, desolvation gas flow rate (L / Hr) 1000, desolvation temperature (°C) 600, cone gas flow rate (L / hour) 50, mass range: 110~850 Da). HPLC: DAD wavelength range: 230~400 nm, column: Acquity UPLC HSS T3 C18, column length: 30 mm, column inner diameter: 2.1 mm, particle size: 1.8 μm, column oven temperature: 40°C.

[0354] Gradient conditions: Solvent A: Water containing 0.1% formic acid: Acetonitrile: 95: 5 volumes / volume Solvent B: Acetonitrile containing 0.05% formic acid

[0355] [Table 8]

[0356] If necessary, the enantiomerically pure final compound can be obtained from the racemic material, as needed, via standard physical separation techniques such as reversed-phase chiral chromatography or stereoselective synthesis techniques, for example, by using chiral starting materials.

[0357] LC-MS method D: Spectra were recorded using a Waters mass spectrometer equipped with an electrospray source (Acquity SDQ mass spectrometer) (positive and negative polarity switch, capillary (kV) 3.0, full scan, cone voltage (V) 41.0, source temperature (°C) 150, desolvation temperature (°C) 500, desolvation temperature (°C) 500, cone gas flow rate (L / hour) 50, mass range: 110~800 Da). HPLC "H" class: DAD, wavelength range: 210~400 nm, column: Acquity UPLC HSS T3 C18, column length: 30 mm, column inner diameter: 2.1 mm, particle size: 1.8 μm, column oven temperature: 40°C.

[0358] Gradient conditions: Solvent A: Water containing 0.1% formic acid: Acetonitrile: 95: 5 volumes / volume Solvent B: Acetonitrile containing 0.05% formic acid

[0359] [Table 9]

[0360] If necessary, the enantiomerically pure final compound can be obtained from the racemic material, as needed, via standard physical separation techniques such as reversed-phase chiral chromatography or stereoselective synthesis techniques, for example, by using chiral starting materials.

[0361] Example P1: Preparation of 3-[6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (Compound 1.1 in Table T1) [ka] a) Preparation of ethyl 2-(3-cyclopropylphenoxy)acetate In a round-bottom flask with a single neck, cesium carbonate (5.82 g, 17.8 mmol) was added to a solution of 3-cyclopropylphenol (2.0 g, 14.9 mmol) in acetonitrile (22 mL). Ethyl 2-bromoacetate (2.98 g, 17.8 mmol) was then added, and the resulting reaction mixture was stirred at room temperature for 4 hours. The progress of the reaction was monitored by LC-MS. The reaction mixture was then diluted with water and extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain the crude residue. The obtained crude residue was purified by silica gel chromatography (cyclohexane / ethyl acetate) to obtain ethyl 2-(3-cyclopropylphenoxy)acetate (1.7 g, 41%). LCMS (Method B): Retention time 1.48 min, 221(M+H)

[0362] b) Preparation of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate In a sealed glass reactor, ethyl 2-(3-cyclopropylphenoxy)acetate (1.5 g, 6.8 mmol) and 1-tert-butoxy-N,N,N',N',-tetramethylmethanediamine (9.2 g, 48.0 mmol) were heated at 90°C for 2 hours. The reaction was monitored by LC-MS. The reaction mixture was then diluted with water and extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain the crude residue. The crude residue was purified by silica gel chromatography (cyclohexane / ethyl acetate) to obtain ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)propa-2-enoate (1.47 g, 78%). LCMS (Method B): Retention time 1.52 min, 276(M+H)

[0363] c) Preparation of 6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidine-7one In a round-bottom flask with a single neck, a mixture of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)propa-2-enoate (1.0 g, 3.63 mmol), 3H-pyrazole-3-amine (0.30 g, 3.63 mmol), and sodium acetate (0.30 g, 3.63 mmol) was stirred in acetic acid (2 mL) at 90°C for 24 hours. The progress of the reaction was monitored by LC-MS. After the completion of the reaction, the reaction mixture was concentrated under reduced pressure and distilled twice with toluene under reduced pressure to obtain a crude mixture. This was purified by silica gel chromatography (cyclohexane / ethyl acetate) to obtain 6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidine-7-one (0.58 g, 59%) as a brown solid. LCMS (Method B): Retention time 1.24 min, 268 (M+H)

[0364] d) Preparation of 7-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine N,N-dimethylaniline (1.95 g, 15.3 mmol) was added at 0°C to a round-bottom flask containing a mixture of 6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidine-7-one (1.0 g, 3.74 mmol) and phosphorus(V) oxychloride (26.5 mL, 284 mmol). The reaction mixture was stirred at 85°C for 12 hours. The progress of the reaction was monitored by LC-MS. After the reaction was complete, the reaction mixture was evaporated to the minimum volume, diluted with ice water, and extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain the crude residue. The crude residue was purified by silica gel chromatography (cyclohexane / ethyl acetate) to obtain 7-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine (0.6 g, 53%). LCMS (Method B): Retention time 1.52 min, 286(M+H)

[0365] e) Preparation of methyl 6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate An autoclave vessel was packed with 7-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine (0.2 g, 0.70 mmol), triethylamine (0.2 mL, 0.56 mmol), Pd(dppf)Cl2CH2Cl2 (0.14 g, 0.17 mmol), and methanol (20 mL). The reactor was then flushed three times with carbon monoxide and packed with carbon monoxide under a pressure of 10 bar. The reaction mixture was heated at 80°C for 5 hours. The progress of the reaction was monitored by LCMS. After the reaction was complete, 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 to obtain the crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / ethyl acetate) to obtain methyl 6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate (0.13 g, 60%) as a yellow solid. LCMS (Method D): Retention time 1.19 min, 310 (M+H)

[0366] f) Preparation of lithium 6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate Lithium hydroxide (0.024 g, 0.96 mmol) was added to a solution of methyl 6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate (100 mg, 0.32 mmol) in tetrahydrofuran (4 mL) and water (2 mL). The reactants were stirred at room temperature for 1 hour. The progress of the reaction was monitored by TLC and LCMS. After the reaction was complete, the reaction mixture was concentrated under reduced pressure to obtain lithium 6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate (95 mg, 97%) as a grayish-white solid, which was used directly in the next step. LCMS (Method C): Retention time 0.96 min, 296(M+H)

[0367] g) Preparation of 6-(3-cyclopropylphenoxy)-N-[1-[(2,4-dichlorophenyl)methyl]-2-(1,3-dioxoisoindorin-2-yl)oxyethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide Lithium 6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate (0.10 g, 0.33 mmol) was added to anhydrous N,N-dimethylformamide (4 mL) with 1-[(2,4-dichlorophenyl)methyl]-2-(1,3-dioxoisoindorin-2-yl)oxyethyl]ammonium;2,2,2-trifluoroacetate (0.19 g, 0.39 mmol), followed by the addition of HATU (0.26 g, 0.66 mmol). The reaction mixture was stirred at room temperature for 12 hours. The progress of the reaction was monitored by TLC and LCMS. After completion, the reaction mixture was diluted with water to precipitate the solid from the reactants, filtered, washed with water and methyl tert-butyl ether, and finally dried under vacuum to obtain 6-(3-cyclopropylphenoxy)-N-[1-[(2,4-dichlorophenyl)methyl]-2-(1,3-dioxoisoindorin-2-yl)oxyethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (0.15 g, 66%). LCMS (Method D): Retention time 1.22 minutes, 640.0 (MH)

[0368] h) Preparation of N-[1-(aminooxymethyl)-2-(2,4-dichlorophenyl)ethyl]-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxamide 6-(3-cyclopropylphenoxy)-N-[1-[(2,4-dichlorophenyl)methyl]-2-(1,3-dioxoisoindorin-2-yl)oxyethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (100 mg, 0.15 mmol) was added to tetrahydrofuran (6 mL) with hydrazine monohydrate (46.7 μl, 0.93 mmol). The reaction mixture was stirred at room temperature for 1 hour. A precipitate formed during the reaction. After completion, the reaction mixture was diluted with methyl tert-butyl ether and ethyl acetate (8:2, 15 mL) and filtered through a funnel. The filtrate was washed with water, dried over sodium sulfate, and concentrated under reduced pressure to obtain N-[1-(aminooxymethyl)-2-(2,4-dichlorophenyl)ethyl]-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxamide (80 mg, 90%), which was used directly in the next step. LCMS (Method D): Retention time 1.39 min, 512.0 (M+H)

[0369] i) Preparation of 3-[6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine N-[1-(aminooxymethyl)-2-(2,4-dichlorophenyl)ethyl]-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxamide (350 mg, 0.68 mmol) was dissolved in dichloromethane (5 mL). To this solution, phosphorus pentachloride (213 mg, 1.02 mmol) was added, and the mixture was stirred at room temperature for 1.5 hours. The progress of the reaction was monitored by TLC and LC-MS. After completion, the reaction mixture was quenched with saturated sodium bicarbonate solution, diluted with water, and extracted with ethyl acetate (15 mL x 2). The organic layers were combined, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue obtained was purified by silica gel chromatography (cyclohexane / ethyl acetate) to obtain 3-[6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (55 mg, 16%). 1 H NMR(400MHz,acetonitrile-d3)δ ppm 8.32(s,1H),8.08(d,J=2.5Hz,1H),7.35(d,J=2.3Hz,1H),7.10-7.20(m,2H),7.06(dd,J=8. 3,2.1Hz,1H),6.77(d,J=7.4Hz,1H),6.73(dd,J=2.6,0.9Hz,1H),6.70-6.72(m,1H),6.68(br s,1H),5.84(br d,J=3.4Hz,1H),3.73-3.84(m,1H),3.66-3.73(m,2H),2.78-2.91(m,2H),1.74-1.84(m,1H),0.80-0.93(m,2H),0.50-0.65(m,2H) LCMS (Method B): Retention time 2.98 min, 494 (M+H)

[0370] Example P2: Preparation of 3-[3-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (Compound 1.2, Table T1) Note: N-[1-(aminooxymethyl)-2-(2,4-dichlorophenyl)ethyl]-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxamide was prepared as described in Example 1 (steps a-h). [ka] a) Preparation of 3-[3-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine N-[1-(aminooxymethyl)-2-(2,4-dichlorophenyl)ethyl]-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxamide (80 mg, 0.15 mmol) was dissolved in dichloromethane (3 mL). To this solution, phosphorus pentachloride (97.5 mg, 0.46 mmol) was added, and the mixture was stirred at room temperature for 12 hours. The progress of the reaction was monitored by TLC and LCMS. After completion, the reaction mixture was quenched with saturated sodium bicarbonate solution, diluted with water, and extracted with ethyl acetate (15 mL x 2). The organic layers were combined, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue obtained was purified by reverse-phase column chromatography (70% acetonitrile / water) to obtain 3-[3-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (16 mg, 19%). 1 H NMR(400MHz,CDCl3)δ ppm 8.46(s,1H),8.08(s,1H),7.38(s,1H),7.21(t,J=7.0Hz,1H),7.08-7.16(m,2H),6.84(br d,J=7.8Hz,1H),6.71-6.80(m,2H),5.71(br s,1H),3.84-4.00(m,3H),2.91-3.08(m,2H),1.81-1.92(m,1H),0.92-1.04(m,2H),0.61-0.77(m,2H) LCMS (Method D): Retention time 1.24 min, 528(M+H)

[0371] Example P3: Preparation of 3-[6-(3-cyclopropylphenoxy)-2-fluoro-pyrazolo[1,5-a]pyrimidine-7-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (Compound 1.3 in Table T1) [ka] a) Preparation of 6-(3-cyclopropylphenoxy)-2-fluoro-4H-pyrazolo[1,5-a]pyrimidine-7-one In a round-bottom flask with a single neck, a mixture of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)propa-2-enoate (0.5 g, 1.73 mmol), 5-fluoro-1H-pyrazole-3-amine (0.17 g, 1.73 mmol), and sodium acetate (0.14 g, 1.73 mmol), prepared as in Example 1, steps a) and b) (see above), in acetic acid (5 mL) was stirred at 100 °C for 16 hours. The progress of the reaction was monitored by LC-MS. After the completion of the reaction, the reactants were cooled to room temperature, diluted with ice-cold water to precipitate a grayish-white solid, filtered over a Buchner funnel, washed with cold water, and dried to obtain 6-(3-cyclopropylphenoxy)-2-fluoro-4H-pyrazolo[1,5-a]pyrimidine-7-one (0.45 g, 82%) as a grayish-white solid. LCMS (Method B): Retention time 1.32 min, 284(MH)

[0372] b) Preparation of 7-chloro-6-(3-cyclopropylphenoxy)-2-fluoropyrazolo[1,5-a]pyrimidine In a round-bottom flask with a single neck, a mixture of 6-(3-cyclopropylphenoxy)-2-fluoro-4H-pyrazolo[1,5-a]pyrimidine-7-one (1.5 g, 5.25 mmol) and phosphorus(V) oxychloride (37.3 mL, 399 mmol), along with pyridine (1.71 mL, 21.0 mmol), was added at 0°C. The reaction mixture was stirred at 85°C for 12 hours. The progress of the reaction was monitored by LC-MS. After the completion of the reaction, the reaction mixture was concentrated to the minimum volume and diluted with ice water. The desired substance was extracted with ethyl acetate, the organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain the crude residue. The obtained crude residue was purified by silica gel chromatography (cyclohexane / ethyl acetate) to obtain 7-chloro-6-(3-cyclopropylphenoxy)-2-fluoro-pyrazolo[1,5-a]pyrimidine (0.9 g, 53%) as a pale yellow solid. LCMS (Method B): Retention time 1.70 min, 304(M+H)

[0373] c) Preparation of methyl 6-(3-cyclopropylphenoxy)-2-fluoropyrazolo[1,5-a]pyrimidine-7-carboxylate An autoclave solution was packed with 7-chloro-6-(3-cyclopropylphenoxy)-2-fluoropyrazolo[1,5-a]pyrimidine (0.7 g, 2.30 mmol), triethylamine (0.65 mL, 4.61 mmol), and Pd(dppf)Cl2.CH2Cl2 (0.47 g, 0.57 mmol) in methanol (69.1 mL). The reactor was flushed three times with carbon monoxide gas, and then packed with carbon monoxide under a pressure of 10 bar. The reaction mixture was heated at 80°C for 3 hours. The progress of the reaction was monitored by LC-MS. After the reaction was complete, the reaction mixture was diluted with water, and the desired substance was extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain a crude residue. This residue was purified by silica gel chromatography (cyclohexane / ethyl acetate) to obtain methyl 6-(3-cyclopropylphenoxy)-2-fluoropyrazolo[1,5-a]pyrimidine-7-carboxylate (0.40 g, 50%) as a yellow gummy mass. LCMS (Method B): Retention time 1.65 min, 328(M+H)

[0374] d) Preparation of lithium 6-(3-cyclopropylphenoxy)-2-fluoropyrazolo[1,5-a]pyrimidine-7-carboxylate Lithium hydroxide (57.7 mg, 2.29 mmol) was added to a solution of methyl 6-(3-cyclopropylphenoxy)-2-fluoropyrazolo[1,5-a]pyrimidine-7-carboxylate (250 mg, 0.76 mmol) in tetrahydrofuran (3 mL) and water (1 mL). The reactants were stirred at room temperature for 2 hours. The progress of the reaction was monitored by TLC and LC-MS. After the reaction was complete, the reaction mixture was concentrated under reduced pressure and subsequently distilled twice with toluene (10 mL) to obtain lithium 6-(3-cyclopropylphenoxy)-2-fluoropyrazolo[1,5-a]pyrimidine-7-carboxylate (225 mg, 92%) as a solid, which was used directly in the next step. LCMS (Method B): Retention time 1.47 min, 314(M+H)

[0375] e) Preparation of 6-(3-cyclopropylphenoxy)-N-[1-[(2,4-dichlorophenyl)methyl]-2-(1,3-dioxoisoindorin-2-yl)oxyethyl]-2-fluoropyrazolo[1,5-a]pyrimidine-7-carboxamide Lithium 6-(3-cyclopropylphenoxy)-2-fluoropyrazolo[1,5-a]pyrimidine-7-carboxylate (225 mg, 0.70 mmol) was added to anhydrous N,N-dimethylformamide (4.5 mL) with [1-[(2,4-dichlorophenyl)methyl]-2-(1,3-dioxoisoindorin-2-yl)oxyethyl]ammonium; 2,2,2-trifluoroacetate (405 mg, 0.84 mmol), followed by the addition of 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxidehexafluorophosphate (HATU) (0.56 g, 1.41 mmol). The reaction mixture was stirred at room temperature for 12 hours. The progress of the reaction was monitored by TLC and LCMS. After completion, the reaction mixture was diluted with water to precipitate the solid from the reactants. The precipitate was filtered off, washed with water and methyl tert-butyl ether, and dried under vacuum to obtain 6-(3-cyclopropylphenoxy)-N-[1-[(2,4-dichlorophenyl)methyl]-2-(1,3-dioxoisoindorin-2-yl)oxyethyl]-2-fluoropyrazolo[1,5-a]pyrimidine-7-carboxamide (0.37 g, 75%) as a white solid. LCMS (Method D): Retention time 1.28 min, 660 (M+H)

[0376] f) Preparation of N-[1-(aminooxymethyl)-2-(2,4-dichlorophenyl)ethyl]-6-(3-cyclopropylphenoxy)-2-fluoropyrazolo[1,5-a]pyrimidine-7-carboxamide 6-(3-cyclopropylphenoxy)-N-[1-[(2,4-dichlorophenyl)methyl]-2-(1,3-dioxoisoindolin-2-yl)oxyethyl]-2-fluoropyrazolo[1,5-a]pyrimidine-7-carboxamide (200 mg, 0.30 mmol) was added to tetrahydrofuran (6 mL) with hydrazine monohydrate (90.8 μl, 1.81 mmol). The reaction mixture was stirred at room temperature for 2 hours. The progress of the reaction was monitored by TLC and LC-MS. After completion, the precipitated solid was filtered through a Buchner funnel. The filtrate was diluted with ethyl acetate (15 mL), washed with water, dried over sodium sulfate, and concentrated under reduced pressure to obtain N-[1-(aminooxymethyl)-2-(2,4-dichlorophenyl)ethyl]-6-(3-cyclopropylphenoxy)-2-fluoropyrazolo[1,5-a]pyrimidine-7-carboxamide (150 mg, 84%), which was used directly in the next step. LCMS (Method xy / QDA): Retention time 1.31 min, 530(M+H)

[0377] g) Preparation of 3-[6-(3-cyclopropylphenoxy)-2-fluoro-pyrazolo[1,5-a]pyrimidine-7-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine N-[1-(aminooxymethyl)-2-(2,4-dichlorophenyl)ethyl]-6-(3-cyclopropylphenoxy)-2-fluoropyrazolo[1,5-a]pyrimidine-7-carboxamide (0.15 g, 0.28 mmol) was dissolved in dichloromethane (4.5 mL), phosphorus pentachloride (88.3 mg, 0.42 mmol) was added, and the mixture was stirred at room temperature for 2 hours. The progress of the reaction was monitored by TLC and LCMS. The reaction mixture was then quenched with saturated sodium bicarbonate solution, diluted with water, and extracted twice with ethyl acetate (30 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue obtained was purified by reverse-phase chromatography (water / acetonitrile) to obtain 3-[6-(3-cyclopropylphenoxy)-2-fluoro-pyrazolo[1,5-a]pyrimidine-7-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (26 mg, 18%). 1 H NMR(400MHz,CDCl3)δ ppm 8.45(s,1H),7.40(d,J=1.83Hz,1H),7.15-7.25(m,3H),6.85(d,J=7.95Hz,1H),6.73-6.80(m,2H),6.33(d,J=5.14Hz,1H),5.55(br d,J=3.18Hz,1H),3.88-3.99(m,3H),2.95-3.08(m,2H),1.84-1.92(m,1H),0.97-1.03(m,2H),0.66-0.76(m,2H) LCMS (Method B): Retention time 1.80 min, 512 (M+H)

[0378] Example P4: Preparation of 3-[2-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (compound 1.4 in Table T1) [ka] a) Preparation of 2-chloro-6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidine-7-one In a round-bottom flask with a single neck, a mixture of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)propa-2-enoate (0.5 g, 2.00 mmol), 3-chloro-1H-pyrazole-5-amine (0.2 g, 2.00 mmol), and sodium acetate (0.2 g, 2.00 mmol) prepared in Example 1, steps a) and b) (see above) in acetic acid (10 mL) was stirred at 110 °C for 4 hours. The progress of the reaction was monitored by LC-MS. After the completion of the reaction, the reactants were cooled to room temperature, diluted with ice-cold water to precipitate a grayish-white solid, filtered over a Buchner funnel, washed with cold water, and dried to obtain 2-chloro-6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidine-7-one (0.49 g, 90%) as a grayish-white solid. LCMS (Method B): Retention time 1.38 min, 302 (M+H)

[0379] b) Preparation of 2,7-dichloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine In a round-bottom flask with a single neck, a mixture of 2-chloro-6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidine-7-one (0.2 g, 0.66 mmol) and phosphorus(V) oxychloride (4.70 mL, 50.4 mmol), along with pyridine (0.21 mL, 2.65 mmol), was added at 0°C. The reaction mixture was stirred at 90°C for 4 hours. The progress of the reaction was monitored by LC-MS. After the completion of the reaction, the reaction mixture was concentrated to the minimum volume and diluted with ice water. The desired substance was extracted with ethyl acetate, the organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain the crude residue. The obtained crude residue was purified by silica gel chromatography (cyclohexane / ethyl acetate) to obtain 2,7-dichloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine (0.22 g, 74%) as a yellow solid. LCMS (Method B): Retention time 1.77 min, 320 (M+H)

[0380] c) Preparation of methyl 2-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate An autoclave vessel was packed with 2,7-dichloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine (0.5 g, 1.56 mmol), triethylamine (0.44 mL, 3.12 mmol), and Pd(dppf)Cl2.CH2Cl2 (0.32 g, 0.39 mmol) in methanol (20 mL). The reactor was flushed three times with carbon monoxide, and then packed with carbon monoxide under a pressure of 10 bar. The reaction mixture was heated at 80°C for 2 hours. The progress of the reaction was monitored by LC-MS. After the reaction was complete, the reaction mixture was diluted with water, and the desired substance was extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain a crude residue. This residue was purified by silica gel chromatography (cyclohexane / ethyl acetate 0-50%) to obtain methyl 2-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate (0.38 g, 71%) as a yellow gummy mass. LCMS (Method B): Retention time 1.70 min, 344(M+H)

[0381] d) Preparation of lithium 2-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate Lithium hydroxide (97.1 mg, 2.27 mmol) was added to a solution of methyl 2-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate (260 mg, 0.76 mmol) in tetrahydrofuran (1 mL) and water (0.5 mL). The reactants were stirred at room temperature for 6 hours. The progress of the reaction was monitored by TLC and LCMS. After the completion of the reaction, the reaction mixture was concentrated under reduced pressure and subsequently subjected to two consecutive co-distillations with toluene (2 × 10 mL) to obtain lithium 2-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate (362 mg, 96%) as a solid, which was used directly in the next step. LCMS (Method B): Retention time 1.57 min, 330 (M+H)

[0382] e) Preparation of 2-chloro-6-(3-cyclopropylphenoxy)-N-[1-[(2,4-dichlorophenyl)methyl]-2-(1,3-dioxoisoindorin-2-yl)oxyethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide Lithium 2-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate (0.35 g, 0.73 mmol) was added to anhydrous N,N-dimethylformamide (2.19 mL) with [1-[(2,4-dichlorophenyl)methyl]-2-(1,3-dioxoisoindorin-2-yl)oxyethyl]ammonium;2,2,2-trifluoroacetate (0.41 g, 0.87 mmol), followed by the addition of 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxidehexafluorophosphate (HATU) (0.33 g, 0.87 mmol). The reaction mixture was stirred at room temperature for 1 hour. The progress of the reaction was monitored by TLC and LCMS. After the completion of the reaction, the reaction mixture was diluted with water, and the solid was precipitated from the reactants. The precipitate was filtered off, washed with water and methyl tert-butyl ether, and dried under vacuum to obtain 2-chloro-6-(3-cyclopropylphenoxy)-N-[1-[(2,4-dichlorophenyl)methyl]-2-(1,3-dioxoisoindorin-2-yl)oxyethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (0.5 g, 81%) as a yellow solid. LCMS (Method B): Retention time 1.91 min, 676(M+H)

[0383] f) Preparation of N-[1-(aminooxymethyl)-2-(2,4-dichlorophenyl)ethyl]-2-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxamide 2-chloro-6-(3-cyclopropylphenoxy)-N-[1-[(2,4-dichlorophenyl)methyl]-2-(1,3-dioxoisoindolin-2-yl)oxyethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (100 mg, 0.14 mmol) was added to tetrahydrofuran (2 mL) with hydrazine monohydrate (11 μl, 0.22 mmol). The reaction mixture was stirred at room temperature for 2 hours. The progress of the reaction was monitored by TLC and LC-MS. After completion, a solid precipitate formed and was filtered through a Buchner funnel. The filtrate was diluted in ethyl acetate (15 mL), washed with water, dried over sodium sulfate, and concentrated under reduced pressure to obtain N-[1-(aminooxymethyl)-2-(2,4-dichlorophenyl)ethyl]-2-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxamide (80 mg, 79%), which was used directly in the next step. LCMS (Method B): Retention time 1.69 min, 546(M+H)

[0384] g) Preparation of 3-[2-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine N-[1-(aminooxymethyl)-2-(2,4-dichlorophenyl)ethyl]-2-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxamide (80.0 mg, 0.15 mmol) was dissolved in dichloromethane (5 mL), phosphorus pentachloride (46 mg, 0.22 mmol) was added, and the mixture was stirred at room temperature for 1 hour. The progress of the reaction was monitored by TLC and LC-MS. The reaction mixture was then quenched with saturated sodium bicarbonate solution, diluted with water, and extracted twice with ethyl acetate (30 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue obtained was purified by reverse-phase chromatography (water / acetonitrile) to obtain 3-[2-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (15 mg, 77%). 1 H NMR(400MHz,CDCl3)δ ppm 8.43(s,1H),7.39(d,J=2.08Hz,1H),7.24-7.30(m,2H),7.16-7.23(m,2H),6.83(d,J=7.70Hz,1H),6.76(d,J=2.57Hz,1H),6.73(s,1H),5.68(br d,J=3.42Hz,1H),3.95(m,3H),2.95-3.09(m,2H),1.82-1.94(m,1H),0.93-1.02(m,2H),0.65-0.73(m,2H) LCMS (Method B): Retention time 1.85 min, 528(M+H)

[0385] Example P5: Preparation of 3-[7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazin-8-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (Compound 1.5 in Table T1) [ka] a) Preparation of 2-[(2-bromoimidazole-1-yl)methoxy]ethyl-trimethyl-silane Sodium hydride (0.65 g, 16 mmol, 60% by mass) was added to a solution of 2-bromo-1H-imidazole (2.0 g, 14 mmol) in tetrahydrofuran (5 mL) at 0°C, and the reaction mixture was stirred for 30 minutes. Then, 2-(trimethylsilyl)ethoxymethyl chloride (2.8 mL, 15 mmol) was added at 0°C, and the resulting reaction mixture was stirred at room temperature for 2 hours. The progress of the reaction was monitored by TLC and LCMS. After completion, the reaction mixture was diluted with water, extracted with ethyl acetate, washed with brine, dried over sodium sulfate, filtered, and concentrated under reduced pressure. The resulting crude residue was purified by silica gel chromatography (cyclohexane / ethyl acetate) to obtain 2-[(2-bromoimidazole-1-yl)methoxy]ethyl-trimethyl-silane (2.6 g, 69%) as a pale yellow liquid. 1 H NMR(400MHz,CDCl3)δ ppm 7.11(d,J=1.63Hz,1H),7.05(d,J=1.38Hz,1H),5.27(s,2H),3.53(dd,J=8.69,7.69Hz,2H),0.87-0.99(m,2H),-0.02(s,9H)

[0386] b) Preparation of 2-(3-cyclopropylphenoxy)-1-[1-(2-trimethylsilylethoxymethyl)imidazole-2-yl]ethenone In a two-necked round-bottom flask, 2-[(2-bromoimidazole-1-yl)methoxy]ethyl-trimethyl-silane (2.35 g, 8.50 mmol) was dissolved in tetrahydrofuran (42 mL) and cooled to 0°C. To this, isopropylmagnesium chloride lithium chloride complex solution (1.3 mol / L) in THF (6.5 mL, 8.50 mmol) was added dropwise, and the mixture was stirred for 30 minutes. Then, 2-(3-cyclopropylphenoxy)-N-methoxy-N-methyl-acetamide (prepared separately as described in the following three steps) (1.0 g, 4.25 mmol) was dissolved in tetrahydrofuran. The reaction mixture was stirred at room temperature for 1 hour. The progress of the reaction was monitored by TLC and LCMS. After the completion of the reaction, the reaction mixture was quenched with saturated ammonium chloride solution, 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 resulting crude residue was purified by silica gel chromatography (cyclohexane / ethyl acetate) to obtain 2-(3-cyclopropylphenoxy)-1-[1-(2-trimethylsilylethoxymethyl)imidazole-2-yl]ethenone (1.63 g, 92%) as a pale yellow liquid. LCMS (Method B): Retention time 1.69 min, 373(M+H)

[0387] c) Preparation of 2-(3-cyclopropylphenoxy)-1-(1H-imidazole-2-yl)ethanone In a round-bottom flask, 2-(3-cyclopropylphenoxy)-1-[1-(2-trimethylsilylethoxymethyl)imidazole-2-yl]ethanone (0.25 g, 0.47 mmol) was dissolved in methanol (2 mL), and hydrochloric acid (1.4 mL, 5.63 mmol) was added. The reaction mixture was stirred at 80°C for 3 hours. The progress of the reaction was monitored by TLC and LCMS. After completion, the reaction mixture was concentrated under reduced pressure, diluted with water, and extracted with ethyl acetate. The organic layer was washed with sodium bicarbonate. The combined organic layers were dried under reduced pressure to obtain 2-(3-cyclopropylphenoxy)-1-(1H-imidazole-2-yl)ethanone (0.06 g, 50%), and the crude product was used directly in the next step. LCMS (Method C): Retention time 1.03 min, 243(M+H)

[0388] d) Preparation of 2-(3-cyclopropylphenoxy)-3-(dimethylamino)-1-(1H-imidazole-2-yl)prop-2-en-1-one In a sealed glass reactor, 2-(3-cyclopropylphenoxy)-1-(1H-imidazole-2-yl)ethanone (0.60 g, 2.0 mmol) and 1-tert-butoxy-N,N,N',N',-tetramethylmethanediamine (5.0 g, 20.0 mmol) were heated at 90°C for 2 hours. The progress of the reaction was monitored by 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 to obtain the crude residue. The obtained crude residue was purified by silica gel chromatography (cyclohexane / ethyl acetate) to obtain 2-(3-cyclopropylphenoxy)-3-(dimethylamino)-1-(1H-imidazole-2-yl)prop-2-en-1-one (0.3 g, 40%). LCMS (Method B): Retention time 1.05 min, 298 (M+H)

[0389] e) Preparation of 7-(3-cyclopropylphenoxy)-5H-imidazo[1,2-b]pyridazine-8one In a round-bottom flask, 2-(3-cyclopropylphenoxy)-3-(dimethylamino)-1-(1H-imidazole-2-yl)propa-2-en-1-one (0.03 g, 0.10 mmol) was dissolved in N-methyl-2-pyrrolidone (1 mL), and potassium tert-butoxide (0.012 g, 0.10 mmol) was added as a solution in N-methyl-2-pyrrolidone (0.5 mL). The resulting reaction mixture was stirred at room temperature for 30 minutes. Amino-4-nitrobenzoate (0.022 g, 0.12 mmol) was added as a solution in N-methyl-2-pyrrolidone (1 mL), and the reaction mixture was stirred at room temperature for 16 hours. The progress of the reaction was monitored by LC-MS. After completion, the reactants were diluted with water and extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to obtain the crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / ethyl acetate) to obtain a mixture (60 mg) of 1-(1-aminoimidazole-2-yl)2-(3-cyclopropylphenoxy)-3-(dimethylamino)propa-2-en-1-one and 7-(3-cyclopropylphenoxy)-5H-imidazo[1,2-b]pyridazine-8-one. This mixture was used directly in the next step. LCMS (Method B): Retention time 0.28 min, 313 (M+H) and 1.9 min, 268 (M+H)

[0390] f) Preparation of 8-chloro-7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine A mixture of 1-(1-aminoimidazole-2-yl)2-(3-cyclopropylphenoxy)-3-(dimethylamino)propa-2-en-1-one and 7-(3-cyclopropylphenoxy)-5H-imidazo[1,2-b]pyridazine 8-one (0.4 g), N,N-dimethylaniline (0.7 mL, 5 mmol) and phosphorus(V) oxychloride (8 mL, 90 mmol) (8 mL, 90 mmol) was stirred at 90°C for 12 hours. The progress of the reaction was monitored by 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 to obtain the crude residue. The obtained crude residue was purified by silica gel chromatography (cyclohexane / ethyl acetate) to obtain 8-chloro-7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine (0.3 g, 30%) as a brown gummy mass. LCMS (Method B): Retention time 1.47 min, 286 (M+H)

[0391] g) Preparation of methyl 7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine-8-carboxylate An autoclave vessel was packed with 8-chloro-7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine (0.13 g, 0.45 mmol), triethylamine (0.13 mL, 0.91 mmol), and Pd(dppf)Cl2.CH2Cl2 (0.093 g, 0.11 mmol) in methanol (20 mL). The reactor was flushed three times with carbon monoxide and then packed with carbon monoxide under a pressure of 10 bar. The reaction mixture was heated at 80°C for 5 hours. The progress of the reaction was monitored by LC-MS. After the reaction was complete, 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 to obtain the crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / ethyl acetate) to obtain methyl 7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine-8-carboxylate (0.075 g, 53%) as a yellow solid. LCMS (Method B): Retention time 2.03 min, 310(M+H)

[0392] h) Preparation of lithium 7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine-8-carboxylate Lithium hydroxide monohydrate (20 mg, 0.48 mmol) was added to a solution of methyl 7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine-8-carboxylate (0.05 g, 0.16 mmol) in tetrahydrofuran (1 mL) and water (0.05 mL). The reactants were stirred at room temperature for 16 hours. The progress of the reaction was monitored by TLC and LCMS. After completion, the reaction mixture was concentrated under reduced pressure at 30°C and subsequently co-distilled twice in succession with toluene (2 × 10 mL) to obtain lithium 7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine-8-carboxylate (50 mg crude product), which was used directly in the next step. LCMS (Method B): Retention time 0.51 min, 296(M+H)

[0393] i) Preparation of 7-(3-cyclopropylphenoxy)-N-[1-[(2,4-dichlorophenyl)methyl]-2-(1,3-dioxoisoindorin-2-yl)oxyethyl]imidazo[1,2-b]pyridazine-8-carboxamide [1-[(2,4-dichlorophenyl)methyl]-2-(1,3-dioxoisoindorin-2-yl)oxyethyl]ammonium 2,2,2-trifluoroacetate (0.41 g, 0.86 mmol) was added to lithium 7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine-8-carboxylate (0.24 g, 0.71 mmol) in anhydrous N,N-dimethylformamide (2.14 mL), followed by the addition of 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxidehexafluorophosphate (HATU) (0.32 g, 0.86 mmol). The reaction mixture was stirred at room temperature for 1 hour. The progress of the reaction was monitored by TLC and LCMS. After the completion of the reaction, the reaction mixture was diluted with water, and the solid was precipitated from the reactants. The precipitate was filtered off, washed with water and methyl tert-butyl ether, and dried under vacuum to obtain 7-(3-cyclopropylphenoxy)-N-[1-[(2,4-dichlorophenyl)methyl]-2-(1,3-dioxoisoindorin-2-yl)oxyethyl]imidazo[1,2-b]pyridazine-8-carboxamide (0.47 g, 82%) as a grayish-white solid. LCMS (Method B): Retention time 1.68 min, 642(M+H)

[0394] j) Preparation of N-[1-(aminooxymethyl)-2-(2,4-dichlorophenyl)ethyl]-7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine-8-carboxamide 7-(3-cyclopropylphenoxy)-N-[1-[(2,4-dichlorophenyl)methyl]-2-(1,3-dioxoisoindorin-2-yl)oxyethyl]imidazo[1,2-b]pyridazine-8-carboxamide (460 mg, 0.71 mmol) was added to tetrahydrofuran (2 mL) with hydrazine monohydrate (52.7 μl, 0.22 mmol). The reaction mixture was stirred at room temperature for 2 hours. The progress of the reaction was monitored by TLC and LC-MS. After completion, the precipitated solid was filtered through a Buchner funnel. The filtrate was diluted in ethyl acetate (15 mL), washed with water, dried over sodium sulfate, and concentrated under reduced pressure to obtain N-[1-(aminooxymethyl)-2-(2,4-dichlorophenyl)ethyl]-7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine-8-carboxamide (370 mg, 91%), which was used directly in the next step. LCMS (Method B): Retention time 1.37 min, 512 (M+H)

[0395] k) Preparation of 3-[7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazin-8-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine N-[1-(aminooxymethyl)-2-(2,4-dichlorophenyl)ethyl]-7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine-8-carboxamide (190 mg, 0.37 mmol) was dissolved in dichloromethane (5 mL), phosphorus pentachloride (116 mg, 0.55 mmol) was added, and the mixture was stirred at room temperature for 1 hour. The progress of the reaction was monitored by TLC and LCMS. After completion, the reaction mixture was then quenched with saturated sodium bicarbonate solution, diluted with water, and extracted twice with ethyl acetate (30 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude residue obtained was purified by reverse-phase chromatography (water / acetonitrile) to obtain 3-[7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazin-8-yl]-5-[(2,4-dichlorophenyl)methyl]-5,6-dihydro-4H-1,2,4-oxadiazine (27 mg, 14%). 1 H NMR(400MHz,CDCl3)δ ppm 8.14(s,1H),7.89(d,J=1.38Hz,1H),7.65(d,J=1.25Hz,1H),7.50(br s,1H),7.40(d,J=2.00Hz,1H),7.21-7.25(m,2H),7.17(d,J=2.13Hz,1H),6.87(d,J=7.75Hz,1H),6.78(br d,J=1.63Hz,2H),3.91-4.04(m,2H),3.77-3.89(m,1H),3.00-3.10(m,2H),1.85-1.90(m,1H),0.94-0.98(m,2H),0.66-0.74(m,2H) LCMS (Method B): Retention time 1.48 min, 494(M+H)

[0396] Example P6: Preparation of 2-(3-cyclopropylphenoxy)-N-methoxy-N-methylacetamide Step 1: Preparation of methyl 2-(3-cyclopropylphenoxy)acetate In a round-bottom flask, cesium carbonate (2.76 g, 8.50 mmol) was added to 3-cyclopropylphenyl (1.0 g, 7.08 mmol) in acetonitrile (10 mL). Methyl 2-bromoacetate (1.29 g, 8.50 mmol) was added to this reaction mixture, and the resulting reaction mixture was stirred at room temperature for 12 hours. The progress of the reaction was monitored by LC-MS. After the reaction was complete, 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 to obtain a crude residue, which was purified by silica gel chromatography (cyclohexane / ethyl acetate) to obtain methyl 2-(3-cyclopropylphenoxy)acetate (1.6 g, 98%). LCMS (Method B): Retention time 1.41 min, 207(M+H)

[0397] Step 2: Preparation of 2-(3-cyclopropylphenoxy)acetic acid Lithium hydroxide (0.83 g, 19.40 mmol) was added to a solution of methyl 2-(3-cyclopropylphenoxy)acetate (1.48 g, 6.46 mmol) in tetrahydrofuran (9 mL) and water (4.5 mL). The reactants were stirred at room temperature for 1 hour. The progress of the reaction was monitored by TLC and LC-MS. After the reaction was complete, the mixture was diluted with water and washed with ethyl acetate. The aqueous layer was then acidified with 2N HCl and extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under vacuum to obtain 2-(3-cyclopropylphenoxy)acetic acid (1.30 g, 99%) as a beige solid. 1 H NMR(400MHz,CDCl3)δ ppm 7.19(t,J=7.73Hz,1H),6.76(d,J=7.63Hz,1H),6.64-6.73(m,2H),4.68(s,2H),1.84-1.92(m,1H),0.92-1.02(m,2H),0.64-0.76(m,2H). LCMS (Method B): Retention time 1.24 min, 190.8 (MH)

[0398] Step 3: Preparation of 2-(3-cyclopropylphenoxy)-N-methoxy-N-methylacetamide Methoxy(methyl)ammonium chloride (0.97 g, 9.93 mmol) was added to 2-(3-cyclopropylphenoxy)acetic acid (1.34 g, 6.62 mmol) in ethyl acetate (27 mL), followed by the addition of 1-propanephosphonic anhydride solution (T3P, 50% in ethyl acetate, 4.64 g, 7.29 mmol) and N,N-diisopropylethylamine (2.59 g, 19.9 mmol). The reaction mixture was stirred at room temperature for 12 hours. The progress of the reaction was monitored by TLC and LCMS. After completion, the reaction mixture was diluted with ethyl acetate, poured into water, and the desired substance was extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude residue was purified by silica gel chromatography (ethyl acetate / cyclohexane) to obtain 2-(3-cyclopropylphenoxy)-N-methoxy-N-methyl-acetamide (1.26 g, 76%) as a gummy mass. 1 H NMR(400MHz,CDCl3)δ ppm 7.16(t,J=7.74Hz,1H),6.69-6.73(m,3H),4.79(s,2H),3.76(s,3H),3.25(s,3 H),1.82-1.92(m,1H),1.67-1.67(m,1H),0.88-1.02(m,2H),0.65-0.74(m,2H). LCMS (Method B): Retention time 1.32 min, 236 (M+H)

[0399] [Table 10]

[0400] Biological Examples and Test Methods General description of the test method Leaf pieces or leaf fragments from various plant species are cut from plants grown in a greenhouse. The cut leaf pieces or leaf fragments are placed on agar plates in a multi-well plate (24-well type). The test solution is sprayed onto the leaf pieces either before (preventively) or after (curatively) inoculation. The compound to be tested is prepared as a DMSO solution (maximum 10 mg / mL) and diluted to the appropriate concentration with 0.025% Tween20 immediately before spraying. The inoculated leaf pieces or leaf fragments are incubated under restrictive conditions (temperature, relative humidity, light, etc.) according to each test system. A single assessment of disease level is performed 3 to 14 days after inoculation, according to the pathogen response system. The disease control rate is then calculated by comparing it with an untreated reference leaf piece or leaf fragment.

[0401] A freshly prepared or chilled fungal mycelial fraction or conidial suspension from a fungal liquid medium is directly mixed with a nutrient solution. A DMSO solution of the test compound (maximum 10 mg / mL) is diluted 50-fold with 0.025% Tween20, and 10 μl of this solution is pipettered into a microtiter plate (96-well type). Then, the nutrient solution containing fungal spores / mycelium is added to obtain the final concentration of the test compound. The test plate is incubated in the dark at 24°C and 96% relative humidity. The inhibition of fungal growth is measured photometrically after 2-7 days according to the pathogen response system, and the antifungal activity percentage is calculated by comparing it with an untreated comparison.

[0402] Example B1: Alternaria solani (summer blight on tomatoes) A portion of a tomato leaf (cv. Baby) is placed on agar in a multi-well plate (24-well type), and the formulated test compound, diluted with water, is sprayed onto it. Two days after application, the leaf is inoculated with a suspension of fungal spores. The inoculated leaf is incubated in a climate cabinet under a 12 / 12 hour (illuminated / dark) light environment at 23°C / 21°C (day / night) and 80% relative humidity. Once an appropriate level of disease damage has occurred on an untreated test disc-shaped leaf (5-7 days after application), the effectiveness of the compound is evaluated as the disease control rate compared to the untreated sample.

[0403] The following compounds in Table T1 provided control of at least 80% of Alternaria solani at 200 ppm compared to an untreated control under the same conditions that showed widespread disease development: 1.1.

[0404] Example B2: Botryotinia fuckeliana (synonym) Botrytis cinerea (grape gray mold) Fungal conidia stored at low temperature are directly mixed into a nutrient solution medium (Vogels liquid medium). After adding a (DMSO) solution of the test compound to a microtiter plate (96-well type), the nutrient solution medium containing the fungal spores is added. The test plate is incubated at 24°C, and the inhibition of growth is measured by photometry 3-4 days after application.

[0405] The following compounds in Table T1 provided control of at least 80% of Botryotinia fuckeliana at 20 ppm compared to an untreated control under the same conditions that showed widespread disease development: 1.1, 1.2, 1.3, 1.4, 1.5.

[0406] Example B3: Glomerella lagenarium (synonym) Colletotrichum lagenarium (anthracnose in cucurbitaceae plants) Conidia of the fungus from the cold storage facility are directly mixed into a nutrient solution medium (PDB potato dextrose liquid medium). After adding a solution of the test compound (DMSO) to a microtiter plate (96-well type), the nutrient solution medium containing the fungal spores is added. The test plate is incubated at 24°C, and the inhibition of growth is measured by photometry 3-4 days after application.

[0407] The following compounds in Table T1 provided at least 80% control of Glomerella lagenarium at 20 ppm compared to an untreated control under the same conditions exhibiting widespread disease development: 1.1, 1.5.

[0408] Example B4: Monographella nivalis (synonym), Microdochium nivale, Fusarium nivale (snow mold, bottom rot of cereals) Conidia of the fungus from the cold storage facility are directly mixed into a nutrient solution medium (PDB potato dextrose liquid medium). After adding a solution of the test compound (DMSO) to a microtiter plate (96-well type), the nutrient solution medium containing the fungal spores is added. The test plate is incubated at 24°C, and the inhibition of growth is measured by photometry 4-5 days after application.

[0409] The following compounds in Table T1 showed widespread disease development and, compared to an untreated control under the same conditions, provided at least 80% control of 20 ppm of Monographella nivalis: 1.5.

[0410] Example B5: Pyrenophora teres (Barley netting disease) Place barley leaf fragments (cv. Hasso) on agar in a multi-well plate (24-well type) and spray with the formulated test compound diluted with water. Two days after application, inoculate the leaf fragments with a suspension of fungal spores. Incubate the inoculated leaf fragments in a climate cabinet at 20°C and 65% relative humidity under a 12-hour light / 12-hour darkness environment. Once an appropriate level of disease damage has occurred in the untreated test leaf fragments (5-7 days after application), evaluate the effectiveness of the compound as a disease control agent compared to the untreated leaf fragments.

[0411] The following compounds in Table T1 provided control of at least 80% of Pyrenophora teres at 200 ppm compared to an untreated control under the same conditions that showed widespread disease development: 1.1.

[0412] Example B6: Sclerotinia sclerotiorum (Rapeseed cotton rot) Mycelial fragments from a newly cultured fungal liquid culture are directly mixed into a nutrient solution medium (PDB potato glucose liquid medium). A solution of the test compound (DMSO) is placed in a microtiter plate (96-well type), and the nutrient solution medium containing the fungal material is added. The test plate is incubated at 24°C, and the inhibition of growth is measured by photometry 3-4 days after application.

[0413] The following compounds in Table T1 provided control of at least 80% of Sclerotinia sclerotiorum at 20 ppm compared to an untreated control under the same conditions that showed widespread disease development: 1.1, 1.5.

[0414] Example B7: Exemplary wheat leaf sp...

Claims

1. Equation (I) 【Chemistry 1】 (In the formula, Q a N is Q b C is C, and Q c is CH; or Q a C is Q b N is N, and Q c is N or CH; Q 7 is N or C-R 7 ; Q 8 is N or C-R 8 ; and Q 9 is N or C-R 9 ; Q 7 , Q 8 and Q 9 one or two of which are N; provided that if Q a is N, Q 7 and Q 8 are not N simultaneously; R 1 R is one, two, or three independently selected substituents. 11 A phenyl which may be optionally substituted with; or R 1 is a five-membered or six-membered monocyclic heteroaryl ring containing one, two, or three heteroatoms independently selected from N, O, and S, wherein the heteroaryl ring has one or two independently selected substituents R 11 It may be arbitrarily replaced with; R 11 These are hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, prop-2-inoxy, prop-1-inoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, or cyclopropyloxy; G is selected from G-1, G-2, G-3, and G-4. G-1 is phenyl or phenoxy, and the phenyl or phenoxy is a substituent R selected from 1, 2, or 3 independently selected substituents. G1 It may be arbitrarily replaced with; G-2 is a five-membered or six-membered monocyclic heteroaryl or heteroaryl-oxy; the heteroaryl comprises one, two, or three heteroatoms independently selected from N, O, and S; and the heteroaryl comprises one or two independently selected substituents R G2 It may be arbitrarily replaced with; G-3 is a nine- or ten-membered heterobicyclic ring system containing one, two, or three heteroatoms independently selected from N, O, and S; the heterobicyclic ring system is saturated, partially unsaturated, or aromatic; and the heterobicyclic ring system contains one or two independently selected substituents R G3 It may be arbitrarily replaced with; G-4 is a 9-membered or 10-membered carbon bicyclic ring system; the carbon bicyclic ring system is saturated, partially unsaturated, or aromatic; the carbon bicyclic ring system has one or two independently selected substituents R G4 It may be arbitrarily replaced with; R G1 , R G2 , R G3 and R G4 These are independently hydroxyl, halogen, mercapto, amino, cyano, and C. 1-4 Alkyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy, allyloxy, prop-2-inoxy, prop-1-inoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, or cyclopropyloxy; R 7 , R 8 and R 9 These are hydrogen, fluoro, chloro, bromo, iodine, and C. 1-4 Alkyl, allyl, propargyl, cyclopropylmethyl, cyclopentyl, cyclohexyl, -C(=O)OCH 3 , -C(=O)N(CH 3 ) 2 (Independently selected from 2-(dimethylamino)-2-oxoethyl, 2-(methylamino)-2-oxoethyl, difluoromethyl, trifluoromethyl, methylsulfonyl, methylsulfanyl, methoxy, ethoxy, cyano, hydroxyl, mercapto, and amino) Compounds of the above formula (I), or agriculturally acceptable salts, stereoisomers, enantiomers, and N-oxides of the compound of formula (I).

2. Q a Q b Q c Q 7 Q 8 and Q 9 The following applies: a) Q a C is Q b N is Q c is CH and Q 7 Q 8 and Q 9 One of them is N; or b) Q a C is Q b N is Q c CH and Q 7 is N or CR 7 Q 8 CR 8 And Q 9 is N; or c) Q a N is Q b C is Q c CH and Q 7 CR 7 And Q 8 and Q 9 One of them is N; or d) Q a C is Q b N is Q c CH and Q 7 CR 7 Q 8 CR 8 And Q 9 is N; or e) Q a C is Q b N is Q c CH and Q 7 N is Q 8 CR 8 And Q 9 is N; or f) Q a N is Q b C is Q c CH and Q 7 CR 7 Q 8 CR 8 And Q 9 The compound according to claim 1, wherein is N.

3. a) Q a is C, and Q b is N, and Q c is CH, and Q 7 is CR 7 and Q 8 is CR 8 and Q 9 is N; or b) Q a C is Q b N is Q c CH and Q 7 N is Q 8 CR 8 And Q 9 is N; or c) Q a N is Q b C is Q c CH and Q 7 CR 7 Q 8 CR 8 And Q 9 The compound according to claim 1 or 2, wherein is N.

4. R 1 The compound according to any one of claims 1 to 3, wherein is phenyl, or phenyl substituted with a single substituent selected from methyl, trifluoromethyl, ethynyl, chloro, and cyclopropyl; or 3-cyclopropyl-2-fluorophenyl; or pyridinyl substituted with a single substituent selected from cyano and cyclopropyl.

5. The compound according to any one of claims 1 to 4, wherein G is 2,4-dimethylphenyl, 2,4-dichlorophenyl, 4-bromo-2-methylphenyl, 4-bromo-2-chlorophenyl, 2,6-dichloro-3-pyridyl, 4,6-dichloro-3-pyridyl, 3,5-dichloro-2-pyridyl, 3,5-dichlorothienyl, 3,5-dimethylthienyl, 3,4-dimethylphenyl, 2-chloro-4-methylphenyl, 2-bromo-4-chlorophenyl, 4-chloro-2-fluorophenyl, or 2-chloro-4-fluorophenyl.

6. Independent of each other, R 7 is hydrogen, chloro, or methyl; R 8 is hydrogen, chloro, fluoro, or methyl; R 9 is hydrogen or methyl; however, Q 7 Q 8 and Q 9 If only one of them is N, then R 7 , R 8 and R 9 The compound according to any one of claims 1 to 5, wherein at least one of them is hydrogen.

7. Q 7 Q 8 and Q 9 Only one of them is N; and if there is R 7 is hydrogen, chloro, or methyl; R 8 is hydrogen, chloro, or fluoro; R 9 is hydrogen or methyl; however, R 7 , R 8 and R 9 The compound according to any one of claims 1 to 5, wherein at least one of them is hydrogen.

8. Q 7 Q 8 and Q 9 The two are nitrogen, and R 7 and R 9 is hydrogen or methyl, and R 8 The compound according to any one of claims 1 to 5, wherein is hydrogen or fluoro.

9. A pesticide composition comprising a fungicidally effective amount of the compound described in any one of claims 1 to 8.

10. The composition according to claim 9, further comprising at least one additional active ingredient and / or an agriculturally chemistry-acceptable diluent or carrier.

11. A method for controlling or preventing ectoparasitism of useful plants by plant pathogenic microorganisms, comprising applying a fungicidal amount of a compound according to any one of claims 1 to 8, or a composition containing the compound as an active ingredient, to the plant, a part thereof, or its habitat.

12. Use of the compound according to any one of claims 1 to 8 as a fungicide.

13. Plant propagation material such as seeds that includes, is treated with, or is attached to a compound according to any one of claims 1 to 8, or a composition containing the compound as an active ingredient.

14. Formulas (IC-1), (IC-2), or (IC-3): 【Chemistry 2】 (In the formula, X a is, X 3 or X 4 And; X b and X c Both are hydrogen, or X b is hydrogen, and X c is a protecting group, or X b and X c are either the same or different protecting groups, or X b and X c These groups, together with the nitrogen to which they are bonded, form a protecting group, and the one or more protecting groups are selected from tert-butyloxycarbonyl, benzylcarbonyl, 9-fluorenylmethylcarbonyl, trifluoroacetyl, benzyl, triphenylmethyl, benzylidenyl, and p-toluenesulfonyl, phthalimide, and succinimide; X d is H or -CH 2 -C(O)-CH 2 -G is; X 3 Fluoro, chloro, bromo, iodine, BF 3 K, B (OH) 2 A leaving group selected from B (pinacol); X 4 is OH or -O-R 1 And; R 1 Q a Q b Q c Q 7 Q 8 Q 9 (and G are defined in any one of claims 1 to 8 for the compound of formula (I)) A compound of [this].

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