Microbicidal bicyclic heterocyclic carboxamide derivatives

Abstract

Compounds of formula (I) in which the substituents are as defined in claim 1, which are useful as pesticides, in particular fungicides. TIFF2025525366000110.tif33160

Description

[Technical Field]

[0001] The present invention relates to unsaturated N-bridged bicyclic heterocyclic derivatives, e.g., as active ingredients, having microbicidal, especially fungicidal, activity. The present invention also relates to pesticide compositions comprising at least one of the carboxamide derivatives, processes for preparing these compounds, and the use of the carboxamide derivatives or compositions in agriculture or horticulture to control or prevent infestation of plants, harvested food crops, seeds, or non-living materials by phytopathogenic microorganisms, preferably fungi. [Background technology]

[0002] Many plant protection compounds have been developed to prevent or reduce plant diseases caused by microorganisms, such as fungi. For example, WO 2021 / 233861 discloses azabicyclo(thio)amides as fungicidal compounds, and WO 2021 / 249995 discloses azabicyclyl-substituted heterocycles as fungicides. The azabicyclo compounds disclosed therein are C-bridged. Summary of the Invention [Means for solving the problem]

[0003] Thus, in a first aspect, the present invention provides a compound of formula (I) [ka] (In the formula, R 1 is unsubstituted or contains one, two, or three independently selected substituents R 11 or R 1 is a 5- or 6-membered monocyclic heteroaryl ring containing 1, 2, or 3 heteroatoms each independently selected from N, O, and S, said heteroaryl ring being unsubstituted or containing 1 or 2 independently selected substituents R 11 is replaced by R 11is hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, isopropyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl or cyclopropyloxy, L 1 represents a direct bond, -O- or -OC(R L1A )(R L1B )-, and R L1A and R L1B are independently selected from hydrogen and methyl, or R L1A and R L1B together with the carbon atom to which they are attached form a cyclopropyl, or L 1 is -NR 10 -(CR 2 R 3 ) m - represents R 10 is selected from hydrogen or methyl, and m=0 or 1; or L 1 teeth, [ka] where # indicates the bond to the nitrogen atom and the zigzag line indicates the bond to the group G, R 2 and R 3 is independently selected from hydrogen and methyl, and n is 0 or 1; R 4 and R 5 are independently selected from hydrogen, hydroxy, fluoro, methyl, cyano or methoxy; R 4 and R 5 together with the carbon atom to which they are attached form a carbonyl group, a cyclopropyl group, or a cyclobutyl group, G is selected from G-1, G-2, G-3 or G-4; G-1 is phenyl or phenoxy, wherein said phenyl or phenoxy is unsubstituted or contains one, two or three independently selected substituents R G1 is replaced by G-2 is a 5- or 6-membered monocyclic heteroaryl or heteroaryl-oxy, wherein the heteroaryl contains 1, 2, or 3 heteroatoms each independently selected from N, O, and S, and the heteroaryl is unsubstituted or contains 1 or 2 independently selected substituents R G2 is replaced by G-3 is a 9- or 10-membered heterobicyclic ring system containing 1, 2, or 3 heteroatoms each independently selected from N, O, and S, said heterobicyclic ring system being saturated, partially unsaturated, or aromatic, said heterobicyclic ring system being unsubstituted or containing 1 or 2 independently selected substituents R G3 is replaced by G-4 is a 9- or 10-membered carbobicyclic ring system, said carbobicyclic ring system being saturated, partially unsaturated or aromatic, said carbobicyclic ring system being unsubstituted or containing one or two independently selected substituents R G4 is replaced by R G1 , R G2 , R G3 and R G4 are independently hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, iso-propyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, iso-propyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl or cyclopropyloxy; A is selected from A-1 to A-17;

[0004] [Table 1]

[0005] ## means -OR1 indicates a bond to -C(O)-N(H)-L 1 -G, and R 7 , R 8 , R 9 are independently selected from hydrogen, fluoro, chloro, bromo, iodo, methyl, ethyl, propyl, isopropyl, allyl, propargyl, cyclopropylmethyl, cyclopentyl, cyclohexyl, -C(=O)OCH3, -C(=O)N(CH3), 2-(dimethylamino)-2-oxo-ethyl, 2-(methylamino)-2-oxo-ethyl, difluoromethyl, trifluoromethyl, methylsulfonyl, methylsulfanyl, methoxy, ethoxy, cyano, hydroxyl, mercapto, or amino. or agriculturally acceptable salts, stereoisomers, enantiomers and N-oxides of the compounds of formula (I).

[0006] The present invention also provides processes for preparing compounds of formula (I) and intermediate compounds useful in the preparation of compounds of formula (I).

[0007] It has now been surprisingly found that the novel compounds of formula (I) have a very advantageous level of biological activity in fact in the protection of plants against diseases caused by fungi.

[0008] According to a second aspect of the present invention there is provided an agricultural composition comprising a fungicidally effective amount of a compound of formula (I). Such agricultural compositions may further comprise at least one additional active ingredient and / or an agriculturally acceptable diluent or carrier.

[0009] According to a third aspect of the present invention there is provided a method for controlling or preventing infestation of useful plants by phytopathogenic microorganisms, which comprises applying a fungicidally effective amount of a compound of formula (I) or a composition comprising this compound as an active ingredient to the plant, a part thereof or its habitat.

[0010] According to a fourth aspect of the present invention, there is provided the use of a compound of formula (I) as a fungicide. According to this particular aspect of the present invention, the use may exclude methods of treating the human or animal body by surgery or therapy.

[0011] According to a fifth aspect, the present invention provides plant propagation material, such as seeds, comprising, treated with or having attached thereto a compound of formula (I) or a composition comprising such a compound. DETAILED DESCRIPTION OF THE INVENTION

[0012] As used herein, the term "hydroxyl" or "hydroxy" refers to an --OH group.

[0013] As used herein, the term "mercapto" means a -SH group.

[0014] As used herein, the term "cyano" refers to a -CN group.

[0015] As used herein, amino refers to the group —NH 2 .

[0016] As used herein, nitro refers to the group —NO 2 .

[0017] As used herein, oxo means a ═O group (such as in a carbonyl (C═O) group).

[0018] As used herein, the term "halogen" or "halo" refers to fluorine (fluoro), chlorine (chloro), bromine (bromo) or iodine (iodo), preferably fluorine, chlorine or bromine. This also applies correspondingly to halogen in combination with other meanings, such as haloalkyl.

[0019] As used herein, "C 1-4The term "alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from 1 to 4 carbon atoms, and attached to the rest of the molecule by a single bond. 1-3 Alkyl should be construed accordingly. 1-4 Examples of alkyl include, but are not limited to, methyl, ethyl, and isopropyl.

[0020] As used herein, "C 2-3 The term "alkenyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, having two or three carbon atoms, containing at least one double bond which may be in either the (E) or (Z) configuration, attached to the rest of the molecule by a single bond. 2-3 Examples of alkenyl include, but are not limited to, vinyl (ethenyl), prop-1-enyl, and allyl (prop-2-enyl).

[0021] As used herein, "C 2-3 The term "alkynyl" refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having two or three carbon atoms and attached to the rest of the molecule by a single bond. 2-3 Examples of alkynyl include, but are not limited to, prop-1-ynyl and propargyl (prop-2-ynyl).

[0022] As used herein, "C 1-4 haloalkyl", "C 2-3 haloalkenyl" and "C 2-3 The term "haloalkynyl" refers to any C as defined above, each substituted by one or more of the same or different halogen atoms. 1-4 Alkyl, C 2-3 Alkenyl and C 2-3 Refers to an alkynyl group. 1-4Examples of haloalkyl include, but are not limited to, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, and 2,2,2-trifluoroethyl.

[0023] As used herein, "C 1-3 The term "fluoroalkyl" refers to a C, as generally defined above, substituted by one or more fluorine atoms. 1-3 Refers to alkyl groups. 1-3 Examples of fluoroalkyl include, but are not limited to, difluoromethyl and trifluoromethyl.

[0024] As used herein, "C 1-3 The term "alkoxy" refers to a group of the formula R a O- refers to the group R a is the C generally defined above. 1-3 It is an alkyl group. 1-3 Examples of alkoxy include, but are not limited to, methoxy, ethoxy, and iso-propoxy.

[0025] As used herein, "C 1-3 The term "fluoroalkoxy" refers to a C group, as generally defined above, substituted by one or more fluorine atoms. 1-3 Refers to an alkoxy group. 1-3 Examples of fluoroalkoxy include, but are not limited to, trifluoromethoxy.

[0026] As used herein, "C 3-4 The term "cycloalkyl" refers to a stable monocyclic ring group that is saturated and contains 3 or 4 carbon atoms.

[0027] As used herein, "C 1-3 The term "alkylsulfanyl" refers to a group of the formula -SR a R refers to the group a is the C generally defined above. 1-3 It is an alkyl group.

[0028] As used herein, "C 1-3 The term "alkylsulfonyl" refers to a group of the formula -S(O)R a R refers to the group a is the C generally defined above. 1-3 It is an alkyl group.

[0029] The term "heteroaryl" as used herein refers to a 5- or 6-membered aromatic monocyclic ring having 1 to 3 heteroatoms independently selected from N, O, and S. Examples of heteroaryls include J-1 to J-43 shown in Table J below. The zigzag line of heteroaryls J-1 to J-43 represents the point of attachment to the remainder of the compound. Preferred heteroaryls include pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, and thiazolyl, preferably pyridinyl and thiazolyl.

[0030] [Table 2-1] [Table 2-2]

[0031] The term "heterocyclyl" as used herein refers to a 3-, 4-, 5-, or 6-membered saturated monocyclic ring 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 zigzag lines of heterocyclyls K-1 to K-26 represent the points of attachment to the remainder of the compound. Some of the heterocyclyls shown below contain asymmetric carbons, meaning that compounds containing them may exist in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. Preferred heterocyclyls include pyrrolidinyl, piperidinyl, piperazinyl, and tetrahydropyranyl, with pyrrolidinyl, piperazinyl, and tetrahydropyranyl being preferred.

[0032] [Table 3]

[0033] As used herein, the term "optionally substituted" means that the referenced group is either unsubstituted or substituted with a specified substituent; for example, "C3-C4 cycloalkyl optionally substituted with 1 or 2 halo atoms" means C3-C4 cycloalkyl, C3-C4 cycloalkyl substituted with 1 halo atom, and C3-C4 cycloalkyl substituted with 2 halo atoms. Furthermore, as used herein, the term "optionally substituted" means that the referenced group is unsubstituted or substituted. The term "optionally substituted" can be used interchangeably with "unsubstituted or substituted."

[0034] As used herein, the term "optionally in the presence" means that a particular process is carried out in the presence or absence of a referenced reagent; for example, "a process is optionally carried out in the presence of a base" means that the process can be carried out with or without a base.

[0035] As used herein, for example, the zigzag lines in the heteroaryls shown in Table J and the heterocyclyls shown in Table K represent points of connection / attachment to the remainder of the compound.

[0036] As used herein, the term "control" refers to reducing the number of pests so as to reduce damage to plants or plant-derived products, eliminating pests, and / or preventing further pest damage.

[0037] As used herein, the term "pest" refers to insects and mollusks found in agriculture, horticulture, forestry, the storage of products of plant origin (such as fruit, grain, and timber), and pests associated with damage to man-made structures. The term pest encompasses all stages of the pest life cycle.

[0038] As used herein, the term "effective amount" refers to the amount of a compound or salt thereof that provides a desired effect upon single or multiple applications.

[0039] An effective amount can be readily determined by one skilled in the art using known techniques and by observing results obtained under analogous circumstances. In determining an effective amount, many factors are taken into consideration, including, but not limited to, the type of plant or derived product to which it is applied, the pest and its life cycle to be controlled, the particular compound applied, the type of application, and other relevant circumstances.

[0040] As used herein, the terms "room temperature," or "RT," or "rt" refer to a temperature of about 15° C. to about 35° C. For example, rt can refer to a temperature of about 20° C. to about 30° C.

[0041] The possible presence of one or more asymmetric carbon atoms in the compounds of formula (I) means that the compounds can exist in chiral isomeric forms, i.e., enantiomeric or diastereomeric forms. Restricted rotation about a single bond can also result in astrogenic isomers. Formula (I) is intended to include all these possible isomeric forms and mixtures thereof. The present invention includes all these possible isomeric forms and mixtures thereof of the compounds of formula (I). Similarly, formula (I) is intended to include all possible tautomers, if present (including lactam-lactim tautomers and keto-enol tautomers). The present invention includes all possible tautomeric forms of the compounds of formula (I).

[0042] The compounds of formula (I) having at least one basic center can form, for example, acid addition salts with strong inorganic acids, such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrohalic acids, strong organic carboxylic acids, for example C1-C4 alkanecarboxylic acids which are unsubstituted or substituted, for example, by halogens, for example acetic acid, saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid or benzoic acid, or organic sulfonic acids, for example C1-C4 alkane or arylsulfonic acids which are unsubstituted or substituted, for example, by halogens, for example methane or p-toluenesulfonic acid. Compounds of formula (I) having at least one acidic group can, for example, form salts with bases, for example inorganic 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.

[0043] The compounds of formula (I) according to the invention also include the hydrates which may be formed during salt formation.

[0044] In each case, the compounds of formula (I) according to the invention may be in the free form, in the oxidized form as an N-oxide, in a covalently hydrated form or in a salt form, e.g. an agriculturally usable or agrochemically acceptable salt form.

[0045] N-oxides are oxidized forms of tertiary amines or nitrogen-containing aromatic heterocyclic compounds, as described, for example, in the book "Heterocyclic N-oxides", A. Albini and S. Pietra, CRC Press, Boca Raton 1991.

[0046] Throughout this specification: [ka] are respectively -(CR 2 R 3 ) n -CR 4 R 5 -and-CR 2 R 3 -CR 4 R 5 - can also be written as

[0047] The following list refers to the compounds of formula (I) of the present invention and defines the substituents A, G, L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , R 7 , R 11 , R G1 , R G2 , R G3 and R G4 For any one of these substituents, any of the definitions set forth below may be combined with any other substituent definition set forth below or elsewhere in this specification.

[0048] In one embodiment of each aspect of the invention, L 1 teeth, A. Direct bond, -NR 10 -CR 2 R 3 -or-CR 2 R 3 -CR 4 R 5 -(In the formula, R 10 is selected from hydrogen and methyl, R 2 and R 3 are independently selected from hydrogen and methyl; R 4 and R 5 are independently selected from hydrogen, hydroxy, fluoro, methyl, cyano, and methoxy, or R 4 and R 5together with the carbon atom to which they are attached form a carbonyl group, a cyclopropyl group, or a cyclobutyl group), or B.-NR 10 -CR 2 R 3 -(In the formula, R 10 is selected from hydrogen and methyl, R 2 and R 3 are independently selected from hydrogen and methyl, or C.-NR 10 -CR 2 R 3 -(In the formula, R 10 is selected from hydrogen and methyl, R 2 and R 3 are both hydrogen), or D.-NR 10 -CR 2 R 3 -(In the formula, R 10 is hydrogen and R 2 and R 3 are both hydrogen), or E.-CR 2 R 3 -CR 4 R 5 -(In the formula, R 2 and R 3 are independently selected from hydrogen and methyl; R 4 and R 5 are independently selected from hydrogen, hydroxy, fluoro, methyl, cyano, hydroxy, and methoxy, or R 4 and R 5 together with the carbon atom to which they are attached form a carbonyl group, a cyclopropyl group, or a cyclobutyl group), or F.-CR 2 R 3 -CR 4 R 5 -(In the formula, R 2 and R 3 is hydrogen and R 4 and R 5 are independently selected from hydrogen and fluoro, or R 4 and R 5together with the carbon atom to which they are attached form cyclopropyl), or G.-CR 2 R 3 -CR 4 R 5 -(In the formula, R 2 and R 3 is hydrogen and R 4 and R 5 are independently selected from hydrogen and fluoro, or H-CH2-CHF- or -CH2-CH2-, or I. Direct binding is.

[0049] In one embodiment of each aspect of the invention, R 1 teeth, A. unsubstituted or containing one, two, or three independently selected substituents R 11 , for example, one or two independently selected substituents R 11 , preferably one substituent R 11 phenyl substituted with (wherein R 11 is selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, iso-propyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, iso-propyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl and cyclopropyloxy), or B. One or two substituents R 11 , for example one substituent R 11 phenyl substituted with (wherein R 11 is selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl), or C. phenyl substituted with one or two substituents independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynylmethoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl, for example, one substituent; or D. Phenyl, unsubstituted or substituted with one or two substituents independently selected from chloro, fluoro, cyano, methyl, methoxy, and cyclopropyl, for example, with one substituent; or E. Phenyl substituted with a single substituent selected from methyl and cyclopropyl, or F. Cyclopropylphenyl, e.g., 3-cyclopropylphenyl is.

[0050] In one embodiment of each aspect of the invention, R 1 teeth, a 5- or 6-membered monocyclic heteroaryl ring containing 1, 2 or 3 heteroatoms, which may be the same or different, independently selected from AN, O and S, wherein said heteroaryl ring is unsubstituted or contains 1 or 2 independently selected substituents R 11 ), or B. 6-membered monocyclic heteroaryl rings containing 1, 2, or 3 nitrogen atoms, wherein the heteroaryl ring is unsubstituted or contains 1 or 2 independently selected substituents R 11 ), or C. Pyridine, pyrimidine, pyridazine or 1,2,4-triazine, wherein any of said pyridine, pyrimidine, pyridazine or 1,2,4-triazine is unsubstituted or substituted with one or two substituents independently selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, iso-propyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, iso-propyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl and cyclopropyloxy, or D. Pyridine substituted with one or two substituents independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethylmethoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or E. Pyridine substituted with a single substituent selected from chloro, fluoro, cyano, methyl, methoxy, difluoromethoxy and cyclopropyl, or F. Pyridines substituted with a single substituent selected from chloro, cyano, and methyl But it's possible.

[0051] In one embodiment of each aspect of the invention, R 1 teeth, A. Each of the groups is unsubstituted or contains one or two independently selected substituents R 11 phenyl, pyridyl, pyrimidyl or pyridazinyl substituted with 11 is selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, iso-propyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, iso-propyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl and cyclopropyloxy), or B. each unsubstituted or one or two independently selected substituents R 11 phenyl, pyridyl or pyrimidyl substituted with 11 is selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethylmethoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl), or C. each unsubstituted or one or two independently selected substituents R 11 phenyl or pyridyl substituted with (wherein R 11 is selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethylmethoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl), or D. each unsubstituted or one or two independently selected substituents R 11 phenyl or pyridyl substituted with (wherein R 11 is selected from chloro, fluoro, cyano, methyl, methoxy, difluoromethoxy and cyclopropyl, or E. each unsubstituted or one or two independently selected substituents R 11 phenyl or pyridyl substituted with (wherein R 11 is selected from chloro, cyano, methyl and cyclopropyl, or F. each unsubstituted or one or two independently selected substituents R 11 phenyl or pyridyl substituted with (wherein R 11 is selected from chloro, cyano and cyclopropyl is.

[0052] In one embodiment of each aspect of the invention, R 11 teeth, A. hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, isopropyloxy, tert-butoxy, propynoxy, 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. Chloro, fluoro, cyano, methoxy, allyloxy, trifluoromethoxy, cyclopropyl and cyclobutyl, or G. halogen, cyano, methoxy, allyloxy, trifluoromethoxy and cyclopropyl, or H. Chloro, fluoro, cyano, cyclopropyl and cyclobutyl, or I. Chloro, Cyano, Cyclopropyl and Methyl is selected from.

[0053] In one embodiment of each aspect of the invention, G is G-1: phenyl or phenoxy, wherein said phenyl or phenoxy is unsubstituted or contains one, two, or three independently selected substituents R G1 For example, G-1 is substituted with A. phenyl, unsubstituted or substituted with one or two substituents independently selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, iso-propyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, iso-propyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, or cyclopropyloxy; or B. Phenyl that is unsubstituted or substituted with one or two substituents independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethylmethoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or C. Phenyl that is unsubstituted or substituted with 1, 2, or 3 substituents, for example 2 or 3 substituents, each independently selected from chloro, fluoro, methyl, and methoxy; or D. phenyl substituted with one or two substituents selected from chloro and methyl, for example, one substituent; or E. Phenyl substituted with two substituents independently selected from chloro and methyl, or F. 2,4-disubstituted phenyl, wherein each substituent is independently selected from chloro and methyl; or G. 2,4-Dichlorophenyl is.

[0054] In one embodiment of each aspect of the invention, G is G-2: a 5- or 6-membered monocyclic heteroaryl or heteroaryl-oxy, wherein the heteroaryl contains 1, 2, or 3 heteroatoms each independently selected from N, O, and S, and the heteroaryl is unsubstituted or contains 1 or 2 independently selected substituents R G2 For example, G-2 is substituted with A. pyridine, pyrimidine, pyridazine or 1,2,4-triazine, wherein said pyridine, pyrimidine, pyridazine, 1,2,4-triazine is unsubstituted or substituted with one or two substituents independently selected from hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, iso-propyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, iso-propyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl and cyclopropyloxy, or B. Pyridine, pyrimidine or pyridazine substituted with one or two substituents independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethylmethoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl and cyclobutyl, or C. Pyrimidine or pyridazine substituted with one or two substituents independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethylmethoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl, or D. pyridine substituted with one, two or three substituents, for example two or three substituents, each independently selected from chloro, fluoro, cyano, methyl and methoxy; or E. Pyridine substituted with one or two substituents selected from chloro and methyl, for example one substituent. is.

[0055] In one embodiment of each aspect of the invention, G is a G-3:9 or 10 membered heterobicyclic ring system containing 1, 2 or 3 heteroatoms each independently selected from N, O and S, said heterobicyclic ring system being saturated, partially unsaturated or aromatic, said heterobicyclic ring system being unsubstituted or containing 1 or 2 independently selected substituents R G3For example, G-3 is substituted with A. 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, benzothiazol-2-yl, benzothiazol-5-yl, benzothiazol-6-yl, benzoxazol-2-yl, benzoxazol-5-yl, benzoxazol-6-yl, benzofuran-2-yl, benzofuran-3-yl, benzofuran-5-yl, benzofuran-6-yl, benzothiophen-2-yl, benzothiophen-3-yl, benzothiophen-5-yl, benzothiophen-6-yl, or unsubstituted or substituted with 1, 2 or 3 substituents, e.g., 1 or 2 substituents each independently selected from chloro, fluoro, cyano, methyl and methoxy; B. 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, benzothiazol-2-yl, benzothiazol-5-yl, benzothiazol-6-yl, benzoxazol-2-yl, benzofuran-2-yl, benzofuran-3-yl, or benzothiophen-2-yl, benzothiophen-3-yl, all of which are substituted with one substituent selected from chloro, fluoro, cyano, methyl, and methoxy; or C. chroman-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 D. 1,3-benzodioxol-5-yl, benzothiazol-2-yl, benzothiazol-5-yl, benzothiazol-6-yl, benzoxazol-2-yl, benzofuran-2-yl, benzofuran-3-yl, benzothiophen-2-yl or benzothiophen-3-yl is.

[0056] In one embodiment of each aspect of the invention, G is a G-4:9 or 10-membered carbobicyclic ring system, said carbobicyclic ring system being saturated, partially unsaturated or aromatic, said carbobicyclic ring system being unsubstituted or containing one or two independently selected substituents R G4 For example, G-4 is substituted with A. naphthalen-2-yl, tetralin-1-yl, tetralin-2-yl, tetralin-6-yl, indan-1-yl, indan-2-yl or indan-5-yl, each optionally substituted with one, two or three substituents, for example one or two substituents, independently selected from chloro, fluoro, cyano, methyl and methoxy, or B. 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 C. Tetralin-1-yl or indan-1-yl substituted with one substituent selected from chloro, fluoro, cyano, methyl and methoxy is.

[0057] In one embodiment of each aspect of the invention, R G1 , R G2 , R G3 and R G4 are independently selected from: A. hydroxyl, halogen, such as chloro and fluoro, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, isopropyloxy, tert-butoxy, propynoxy, 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, trifluoromethylmethoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl and cyclobutyl, or D. Chloro, fluoro, cyano, methyl and methoxy, or E. Chloro and methyl.

[0058] In one embodiment of each aspect of the invention, A is selected from: AA-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 BA-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 CA-13, A-14, A-15, A-16 and A-17, or DA-1, A-2, A-3, A-4, A-5 and A-6, or 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-7, A-8, A-9, A-13, A-14 and A-15, or KA-4, A-5, A-6, A-10, A-11, A-12, A-16 and A-17, or LA-1, A-3, A-5, A-13 and A-15, or MA-1, A-3 and A-5, or NA-1, A-3 and A-13, or OA-1, A-3 and A-15, or PA-1 and A-3, or QA-1 and A-5, or RA-3 and A-5, SA-3.

[0059] In one embodiment of each aspect of the present invention, A is selected from A-1 to A-17; R 7 , R 8 and R 9 are independently selected from: A. hydrogen, fluoro, chloro, bromo, iodo, 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, or B. hydrogen, fluoro, chloro, methyl, ethyl, isopropyl, cyclopropyl, -C(=O)OCH3, -C(=O)N(CH3)2, 2-(dimethylamino)-2-oxo-ethyl, 2-(methylamino)-2-oxo-ethyl, difluoromethyl, trifluoromethyl, methylsulfonyl, methoxy and cyano, or C. hydrogen, fluoro, chloro, methyl, ethyl, cyclopropyl, 2-(methylamino)-2-oxo-ethyl, methylsulfonyl, methoxy and cyano, or D. hydrogen, fluoro, chloro, methyl, cyclopropyl and cyano, or E. hydrogen, fluoro, chloro, methyl and cyano, or F. hydrogen, fluoro, chloro and methyl, or G. Hydrogen, chloro and methyl, or H. Hydrogen, chloro and fluoro.

[0060] In one embodiment of each aspect of the present invention, A is selected from A-1 to A-17; R 7 , R 8 and R 9 At least one of is hydrogen and the others, if present, are selected from: A. hydrogen, fluoro, chloro, methyl, ethyl, cyclopropyl, 2-(methylamino)-2-oxo-ethyl, methylsulfonyl, methoxy and cyano, or B. hydrogen, fluoro, chloro, methyl, cyclopropyl and cyano, or C. hydrogen, fluoro, chloro, methyl and cyano, or D. hydrogen, fluoro, chloro and methyl, or E. Hydrogen, chloro and methyl, or F. hydrogen, chloro and cyano, or G. Hydrogen, chloro and fluoro, or H. Hydrogen and chloro.

[0061] A preferred embodiment 1 of each aspect of the present invention is a compound represented by formula (IA-1), (IA-3), (IA-5), (IA-13) and (IA-15): [ka] (In the formula, G, L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 is as defined for compounds of formula (I) or a pesticidally acceptable salt, stereoisomer, enantiomer and N-oxide thereof.

[0062] A preferred embodiment 2 of each aspect of the present invention is L 1 is a direct bond or -CR 2 R 3 -CR4 R 5 - and R 2 and R 3 are independently selected from hydrogen and methyl; R 4 and R 5 is independently selected from hydrogen, hydroxy, fluoro, methyl, cyano and methoxy.

[0063] A preferred embodiment 3 of each aspect of the present invention is L 1 Ga-CR 2 R 3 -CR 4 R 5 - and R 2 and R 3 is hydrogen and R 4 and R 5 is independently selected from hydrogen, hydroxy, fluoro, methyl, cyano and methoxy, preferably hydrogen and fluoro.

[0064] A preferred embodiment 4 of each aspect of the present invention is L 1 is -CH2-CHF- or -CH2-CH2- (i.e., R 2 and R 3 is hydrogen and R 4 or R 5 is fluoro and the other is hydrogen), compounds according to any one of preferred embodiments 1, 2 or 3 are provided.

[0065] A preferred embodiment 5 of each aspect of the invention is R 1 is one or two substituents R each independently selected from halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethylmethoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; 11 The present invention provides a compound according to any one of preferred embodiments 1, 2, 3 or 4, wherein R is phenyl, pyridyl or pyrimidyl optionally substituted with R.

[0066] A preferred embodiment 6 of each aspect of the present invention is R 1 is one or two substituents R each independently selected from chloro, fluoro, cyano, methyl, methoxy, difluoromethoxy and cyclopropyl; 11 is phenyl or pyridyl optionally substituted with

[0067] A preferred embodiment 7 of each aspect of the invention is R 1 is one substituent R selected from chloro, fluoro, cyano, methyl, methoxy, difluoromethoxy and cyclopropyl, preferably chloro, cyano, methyl and cyclopropyl 11 The present invention provides a compound according to any one of preferred embodiments 1, 2, 3, 4, 5 or 6, wherein R is phenyl optionally trisubstituted by R.

[0068] A preferred embodiment 8 of each aspect of the invention is R 1 is one or two substituents R independently selected from chloro, fluoro, cyano, methyl, methoxy, difluoromethoxy and cyclopropyl; 11 The compound according to any one of preferred embodiments 1, 2, 3, 4, 5 or 6 is pyridyl, preferably pyrid-3-yl, optionally substituted with

[0069] A preferred embodiment 9 of each aspect of the invention is R 1 is one substituent R selected from chloro, cyano, methyl and cyclopropyl, preferably cyano 11 The compound according to preferred embodiment 8 is pyrid-3-yl pentasubstituted with

[0070] A preferred embodiment 10 of each aspect of the invention is where G is phenyl or phenoxy, and said phenyl or phenoxy is selected from one, two or three substituents R independently selected from hydroxyl, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethylmethoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl and cyclobutyl. G1 In accordance with any one of preferred embodiments 1, 2, 3, 4, 5, 6, 7, 8 or 9, optionally substituted with

[0071] A preferred embodiment 11 of each aspect of the invention is where G is selected from one or two substituents R independently selected from chloro, fluoro, methyl, and methoxy. G1 The present invention provides a compound according to any one of preferred embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, wherein R is phenyl optionally substituted with R.

[0072] A preferred embodiment 12 of each aspect of the invention provides a compound according to any one of preferred embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or 11, wherein G is phenyl substituted with two substituents independently selected from chloro and methyl, preferably G is 2,4-dichlorophenyl.

[0073] A preferred embodiment 13 of each aspect of the invention is R 7 , R 8 and R 9is independently selected from hydrogen, fluoro, chloro, bromo, iodo, methyl, ethyl, propyl, isopropyl, allyl, propargyl, cyclopropylmethyl, cyclopropyl, cyclopentyl, cyclohexyl, —C(═O)OCH, —C(═O)N(CH), 2-(dimethylamino)-2-oxo-ethyl, 2-(methylamino)-2-oxo-ethyl, difluoromethyl, trifluoromethyl, methylsulfonyl, methylsulfanyl, thiomethoxy, methoxy, ethoxy, cyano, hydroxyl, mercapto, and amino.

[0074] A preferred embodiment 14 of each aspect of the invention is R 7 , R 8 and R 9 is independently selected from hydrogen, fluoro, chloro, methyl, cyclopropyl, and cyano.

[0075] A preferred embodiment 15 of each aspect of the invention is R 7 , R 8 and R 9 is hydrogen and the others, if present, are selected from hydrogen, fluoro, chloro, methyl, ethyl, cyclopropyl, 2-(methylamino)-2-oxo-ethyl, methylsulfonyl, methoxy and cyano.

[0076] A sixteenth preferred embodiment of each aspect of the invention is R 7 , R 8 and R 9is hydrogen and the others, if present, are selected from hydrogen, fluoro, chloro, methyl and cyano, preferably hydrogen, fluoro, chloro and methyl.

[0077] A preferred embodiment 17 of each aspect of the invention provides compounds of formula (IA-1), (IA-3) and (IA-5) according to any one of preferred embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16.

[0078] A preferred embodiment 18 of each aspect of the invention provides compounds of formula (IA-1) and (IA-3) according to any one of preferred embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16.

[0079] A preferred embodiment 19 of each aspect of the invention is R 8 is selected from hydrogen, fluoro, chloro, methyl and cyano, preferably hydrogen, fluoro, chloro and methyl; R 9 is hydrogen.

[0080] A preferred embodiment 20 of each aspect of the invention is R 7 and R 8 is hydrogen and the others are selected from hydrogen, fluoro, chloro, methyl and cyano.

[0081] A preferred embodiment 21 of each aspect of the invention is R 7 is selected from hydrogen, chloro and methyl; R 8 is selected from hydrogen, fluoro, chloro, cyano and methyl; R7 and R 8 is hydrogen.

[0082] A preferred embodiment 22 of each aspect of the invention is R 8 is selected from hydrogen, fluoro, chloro and methyl, preferably R 8 is selected from hydrogen and methyl.

[0083] A preferred embodiment 23 of each aspect of the invention is R 1 is one substituent R selected from chloro, cyano, methyl and cyclopropyl 11 The compound according to any one of preferred embodiments 17, 18, 19, 20, 21 or 22 is phenyl trisubstituted by

[0084] A preferred embodiment 24 of each aspect of the invention is 1 Ga-CR 2 R 3 -CR 4 R 5 - and R 2 and R 3 is hydrogen and R 4 and R 5 is independently selected from hydrogen and fluoro.

[0085] A preferred embodiment 25 of each aspect of the invention is where G is one or two substituents R independently selected from chloro, fluoro, methyl, and methoxy. G1 25. A compound according to any one of preferred embodiments 17, 18, 19, 20, 21, 22, 23 or 24, wherein R is phenyl optionally substituted with R.

[0086] A preferred embodiment 26 of each aspect of the invention is where G is a substituted or unsubstituted hydroxyl group containing two substituents R independently selected from chloro, fluoro, methyl and methoxy, preferably selected from chloro, fluoro and methyl. G1 The present invention provides a compound according to any one of preferred embodiments 17, 18, 19, 20, 21, 22, 23, 24 or 25, wherein the phenyl is 2,4 disubstituted by

[0087] In one embodiment, 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-17.

[0088] In another embodiment, the compound of formula (I) according to the present invention is selected from the compounds listed in Table T1 (below).

[0089] In another embodiment of the invention, the compound of formula (I) is selected from the group consisting of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]imidazo[1,2-a]pyrimidine-5-carboxamide (P-1.1); 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxamide (P-1.2); 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxamide (P-1.3); 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxamide (P-1.4); )-2-fluoro-ethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (P-1.3); 7-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]imidazo[1,2-b]pyridazine-8-carboxamide (P-1.4); 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxamide (P-1.5); 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxamide 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2-methyl-imidazo[1,2-a]pyrimidine-5-carboxamide (P-1.6); 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2-methyl-imidazo[1,2-a]pyrimidine-5-carboxamide (P-1.7); 2-cyano-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (P-1.8); 3-chloro-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide )-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (P-1.9); 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2-fluoro-pyrazolo[1,5-a]pyrimidine-7-carboxamide (P-1.10); 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-3-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxamide (P-1.11); 2-chloro-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (P-1.12); 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxamide (P-1.13); 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxamide (P-1.14) 3-chloro-6-(3-cyclopropylphenoxy)-N-[(2R)-2-(2,4-dichlorophenyl)-2-fluoro-ethyl]pyrazolo[1,5-b]pyridazine-4-carboxamide (P-1.15); 3-chloro-6-(3-cyclopropylphenoxy)-N-[(2R)-2-(2,4-dichlorophenyl)-2-fluoro-ethyl]pyrazolo[1,5-b]pyridazine-4-carboxamide (P-1.16); Pyrazolo[1,5-a]pyrimidine-7-carboxamide (P-1.16); 3-chloro-6-(3-cyclopropylphenoxy)-N-[(2S)-2-(2,4-dichlorophenyl)-2-fluoro-ethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (P-1.17); 3-cyano-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2-methoxy-pyrazolo[1,5-a]pyrimidine-7-carboxamide 3-chloro-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxamide (P-1.18); 3-chloro-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxamide (P-1.19); or 3-cyano-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxamide (P-1.20).

[0090] The presence of one or more possible asymmetric carbon atoms in a compound selected from the compounds of formula (I) according to the present invention, or in a compound selected from the compounds listed in Tables A-1 to A-17, or in any of the compounds listed in Table T1 (below), means that the compound can occur in chiral isomeric forms, i.e. in enantiomeric or diastereomeric forms.

[0091] Compounds of formula (I) can be prepared by one skilled in the art as shown in Schemes 1-29 below, where A, G, L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 and R 11 are as defined for compounds of formula (I) unless otherwise specified. Specific stereocenters have not been specified for the sake of clarity and are not intended to limit the teaching of the schemes in any way.

[0092] As shown in Scheme 1, compounds of formula (I) can be obtained by an amide coupling conversion between a compound of formula (II) and an amine compound of formula (III) by activating the carboxylic acid functionality of the compound of formula (II) by converting the -OH of the carboxylic acid into a good leaving group such as a chloride group, for example by using (COCl) or SOCl, prior to treatment with a compound of formula (III), preferably in a suitable solvent (e.g., N-methylpyrrolidone, acetonitrile, dimethylacetamide, dichloromethane or tetrahydrofuran), at a temperature preferably between 25°C and 60°C, optionally in the presence of a base such as triethylamine or N,N-diisopropylethylamine, or alternatively optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine), in a suitable solvent (e.g., acetonitrile), under conditions typically described in the literature for amide coupling such as 1-propanephosphonic acid cyclic anhydride (T3P). See, for example, Chem.Soc.Rev. 2009, 38, 606 and Chem.Soc.Rev. 2011, 40, 5084. Compounds of formula (III) are known or commercially available. [ka] Scheme 1

[0093] As shown in Scheme 2, compounds of formula (I) can be prepared by catalyzing the nucleophilic compound of formula (IV) with X in the presence of a base (e.g., K0-t-Bu, K3PO4, K2CO3, triethylamine, or Cs2CO3) in a suitable solvent (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, or dimethyl sulfoxide) at a temperature between 10°C and 90°C, preferably using a metal catalyst complex (e.g., Cu or Pd). 2With an electrophilic compound of formula (V), where is a suitable leaving group, such as fluoro, chloro, bromo, iodo, 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 (IV) are known or commercially available. [ka] Scheme 2

[0094] As shown in Scheme 3, compounds of formula (II) can be prepared by the reaction of X with an alkali metal hydroxide (e.g., NaOH, LiOH) in a suitable solvent or mixture of solvents, typically tetrahydrofuran, methanol, water, 2-methyl-tetrahydrofuran, or acetonitrile, at temperatures between 20°C and 100°C. 1 is C1-C4-alkoxy, such as methoxy or ethoxy. For relevant examples, see WO 2008 / 133192 or J. Med. Chem. 2021, 64, 12322.

[0095] X 1 Compounds of formula (VII), wherein X is C1-C4-alkoxy, such as methoxy or ethoxy, can be prepared by reacting nucleophilic compounds of formula (IV) with X in the presence of a base (e.g., K0-t-Bu, K3PO4, K2CO3, triethylamine or Cs2CO3) in a suitable solvent or mixture of solvents (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, dimethyl sulfoxide) using preferably a metal catalyst complex (e.g., Cu or Pd) at a temperature between 20°C and 110°C. 1 is C1-C4-alkoxy such as methoxy or ethoxy, and X 2The compound of formula (IV) can be prepared by reacting with an electrophilic compound of formula (VI) where B is a suitable leaving group such as fluoro, chloro, bromo, iodo, 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; WO 2008 / 110313 and WO 2012 / 136604. Compounds of formula (IV) are known or commercially available. [ka] Scheme 3

[0096] As shown in Scheme 4, X 2 Compounds of formula (V) can be prepared by reacting X with X, where X is a suitable leaving group such as fluoro, chloro, bromo, iodo, BF3K, B(OH)2 or B(pinacol). 2is a suitable leaving group such as fluoro, chloro, bromo, iodo, BFK, B(OH) or B(pinacol), and by amide coupling transformation with an amine compound of formula (III) by activating the carboxylic acid functionality of the compound of formula (VIII), typically by converting the -OH of the carboxylic acid to a good leaving group such as a chloride group, for example using (COCl) or SOCl, preferably in a suitable solvent (e.g., N-methylpyrrolidonedimethylacetamide, dichloromethane or tetrahydrofuran) at a temperature preferably between 25°C and 60°C, optionally in the presence of a base such as triethylamine or N,N-diisopropylethylamine, or alternatively in a suitable solvent (e.g., acetonitrile), optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine), under conditions described in the literature for amide coupling, such as 1-propanephosphonic cyclic anhydride (T3P). See, for example, Chem.Soc.Rev. 2009, 38, 606 and Chem.Soc.Rev. 2011, 40, 5084. Compounds of formula (III) are known or commercially available. [ka] Scheme 4

[0097] As shown in Scheme 5, X 3 Compounds of formula (VII) in which X is OH or C1-C4-alkoxy, for example methoxy or ethoxy, 3Nucleophilic compounds of formula (X), wherein X is OH or C1-C4-alkoxy, such as methoxy or ethoxy, can be oxidized in a suitable solvent (e.g., dichloromethane, 1,2-dichloromethane, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, N-methylpyrrolidone, dimethylacetamide) at a temperature of 40°C to 80°C with a metal source (e.g., Cu(OAc)2), preferably in the presence of an oxidizing agent such as O2 or a suitable palladium pre-catalyst, e.g., RockPhos Pd G3, in the presence of a base (e.g., K3PO4) and a solvent (e.g., dimethyl ether or toluene) at a temperature of 20°C to 80°C to form X 2 The compounds of formula (IX) can also be prepared by reacting with an electrophilic compound of formula (IX) where B is a suitable leaving group such as fluoro, chloro, bromo, iodo, 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 (IX) are known or commercially available. [ka] Scheme 5

[0098] Alternatively, as shown in Scheme 6, compounds of formula (I) can be prepared by reacting a nucleophilic compound of formula (XI) with a nucleophilic compound of formula (XI) 2is a suitable leaving group such as fluoro, chloro, bromo, iodo, BF3K, B(OH)2 or B(pinacol) with a metal source (e.g., Cu(OAc)2) in a suitable solvent (e.g., dichloromethane, 1,2-dichloromethane, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran) at a temperature between 40°C and 80°C, optionally in the presence of an oxidant such as O2 or a suitable palladium pre-catalyst such as RockPhos Pd G3, in the presence of a base (e.g., K3PO4) and a suitable solvent (e.g., dimethyl ether or toluene) at a temperature between 20°C and 80°C. 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 (IX) are known or commercially available. [ka] Scheme 6

[0099] As shown in Scheme 7, X 5 Compounds of formula (XIV) where is OH or halogen can be obtained from compounds of formula (XIII) by hydrolysis in a similar manner as described for the conversion of compounds of formula (VII) to compounds of formula (II) in Scheme 3. 3 is OH or C1-C4-alkoxy, for example methoxy or ethoxy, and X 5 Compounds of formula (XIII) where is OH or halogen can be converted to X by oxidation using a suitable oxidizing agent, such as KMnO or a cobalt(II) salt and trihydroxyisocyanuric acid (THICA), in a suitable solvent, such as acetic acid, at a temperature between 25°C and 200°C. 5It can be obtained from a compound of formula (XII) in which is OH or halogen. For relevant examples, see Can. J. Chem. 1978, 56, 1273 and WO 2021 / 160470. Compounds of formula (XII) are known or can be prepared as described in Bulletin de la Société Chimique de France 1972, 8, 3198. [ka] Scheme 7

[0100] As shown in Scheme 8, X 1 Compounds of formula (VII), where R is C1-C4-alkoxy, such as methoxy or ethoxy, can be obtained from compounds of formula (XV) 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 WO 2021 / 160470. Compounds of formula (XV) can be prepared as described in Bulletin de la Société Chimique de France 1972, 8, 3198.

[0101] Furthermore, the compound of formula (XV) can be prepared by reacting a nucleophilic compound of formula (IV) with X 2is a suitable leaving group such as fluoro, chloro, bromo, iodo, BF3K, B(OH)2, or B(pinacol) with an electrophilic compound of formula (XVI) in the presence of a base (e.g., KO-t-Bu, K3PO4, K2CO3, triethylamine, or Cs2CO3) in a suitable solvent (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, dimethyl sulfoxide) at a temperature between 25°C and 100°C, optionally using a metal catalyst and a ligand complex (e.g., CuI,N,N-dimethylglycine). For relevant examples, see Eur. J. Org. Chem. 2011, 18, 3353; J. Org. Chem. 2009, 74, 7951; Tetrahedron Lett. 2012, 53, 5318; WO 2008 / 110313 and WO 2012 / 136604. Compounds of formula (IV) are known or commercially available. [ka] Scheme 8

[0102] As shown in Scheme 9, X 3 Compounds of formula (VII), in which is OH or C1-C4-alkoxy, can also be prepared by reaction of compounds of formula (XVII) in aqueous solvent mixtures such as isopropanol or ethanol, optionally in alkaline medium at temperatures between 90° C. and 110° C. For relevant examples, see J. Med. Chem. 2012, 55, 10118. [ka] Scheme 9

[0103] Compounds of formula (XVII) are either known or can be prepared by the reaction of X 6is chloro, bromo, iodo or trifluoromethanesulfonyl-O-, at a temperature of 50°C to 120°C, preferably 80°C to 110°C, from a metal source such as XPhos Pd G1 ((2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2-aminoethyl)phenyl]palladium(II) chloride or (XPhos) palladium(II) phenethylamine chloride or chloro(2-dicyclohexylphosphino-2',4',6'-triisopropyl-1,1'-biphenyl)[2-(2-aminoethyl)phenyl)]palladium(II) or XPhos palladacycle or XPhos precatalyst) can be obtained in the presence of a cyanide source such as potassium ferrocyanide, copper cyanide, zinc cyanide or potassium cyanide and a base such as KOAc in a suitable solvent or mixture of solvents such as dioxane, water, toluene, tetrahydrofuran, 2-methyl-tetrahydrofuran, xylene). For relevant examples, see J. Org. Chem. 2018, 83, 4922 and Org. Lett. 2006, 8, 1189. [ka] Scheme 10

[0104] As shown in Scheme 11a, X 3 Compounds of formula (VII) in which X is OH or C1-C4-alkoxy are 6It can also be obtained from a compound of formula (XVIII) where R is chloro, bromo, iodo, or trifluoromethanesulfonyl-O- using a metal source such as XPhos Pd G1 in a pressure vessel, typically a stainless steel autoclave charged with carbon monoxide at a pressure of 1 to 50 bar, more preferably 5 to 15 bar, in the presence of an organic base such as triethylamine or diisopropylethylamine and a suitable solvent (e.g., methanol or ethanol) at a temperature of 20°C to 130°C, preferably 70°C to 110°C. For relevant examples, see J. Med. Chem. 2014, 57, 2692 and Adv. Synth. Catal. 2006, 348, 1255. [ka] Scheme 11a

[0105] Alternatively, as shown in Scheme 11b, X 7 Compounds of formula (II) can also be obtained by reacting compounds of formula (XIX) where is chloro, bromo, or iodo with a lithium reagent (e.g., n-butyllithium, sec-butyllithium, tert-butyllithium, or lithium diisopropylamine) in a suitable solvent such as hexane, diethyl ether, or tetrahydrofuran at a temperature of −78° C. to −30° C., followed by the addition of carbon dioxide. For related examples, see J.Am.Chem.Soc. 2018, 140, 9140 and J.Am.Chem.Soc. 2021, 143, 1539. [ka] Scheme 11b

[0106] As shown in Scheme 12, X 7Compounds of formula (XIX) in which is chloro, bromo, or iodo are known or can be prepared by reacting compounds of formula (XX) with an electrophilic halogen reagent such as bromine, dibromohydantoin, N-bromo-, or N-chloro-succinimide, optionally with a base, typically lithium diisopropylamine or n-butyllithium, in a suitable solvent (e.g., chloroform, methyltetrahydrofuran, or dimethylformamide) at a temperature of −78° C. to 10° C. For relevant examples, see Tetrahedron Lett. 2003, 44, 823; J. Am. Chem. Soc. 2010, 132, 8858, and Synthesis 2005, 16, 2782. [ka] Scheme 12

[0107] As shown in Scheme 13, compounds of formula (II) can also be prepared by reacting compounds of formula (XX) 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), optionally in the presence of a catalyst (e.g., potassium tert-butoxide), at a temperature of -78°C to 10°C, followed by the addition of carbon dioxide. Compounds of formula (XX) are known or commercially available. For relevant examples, see Bioorg.Med.Chem.2004,12,5579; J.Am.Chem.Soc.2010,132,8858, and Synthesis 2005,16,2782. [ka] Scheme 13

[0108] As shown in Scheme 14, X 7Compounds of formula (XIX) in which is chloro, bromo, or iodo are known or can be obtained from the tautomeric compounds of formulas (XXI) and (XXII) by treating with a phosphorus compound such as phosphorus oxychloride, phosphorus pentachloride, or phosphorus tribromide in a suitable solvent (e.g., toluene, acetonitrile, dichloromethane, or chloroform), optionally in the presence of a substoichiometric 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. [ka] Scheme 14

[0109] As shown in Scheme 15, compounds of formula (XXI) in equilibrium with compounds of formula (XXII) are either known or can be prepared by reacting X with a suitable solvent, preferably ethanol, isopropanol, dimethylformamide, acetic acid, or acetonitrile, at a temperature between 50° C. and 110° C., optionally in the presence of a base (e.g., potassium carbonate, triethylamine). 8 are C1-C4 alkyl or C5-C6 cycloalkyl, or together with the nitrogen to which they are attached form a saturated heterocycle, and X 3 Compounds of formula (XXIII) in which X is OH or C1-C4-alkoxy and 9 and independently R as defined for compounds of formula (I). 7 , R 8 or R 9 is a carbon atom or nitrogen atom substituted with X 10It can be prepared by one-pot nucleophilic addition followed by cyclization using a compound of formula (XXIV) where is H or a protecting group (e.g., tetrahydropyran, 2-(trimethylsilyl)ethoxymethyl, or benzyl). For relevant examples, see U.S. Patent Application Publication No. 2018 / 0230157, Synthesis 2006, 1, 59, and WO 2010 / 016005. Compounds of formula (XXIV) are known or commercially available. [ka] Scheme 15

[0110] As shown in Scheme 16, a compound of formula (XXI) in equilibrium with a compound of formula (XXII) can be prepared by the reaction of X 8 are C1-C4 alkyl or C5-C6 cycloalkyl, or together with the nitrogen to which they are attached form a saturated heterocyclic ring, and X 9 and independently R as defined for compounds of formula (I). 7 , R 8 or R 9 It can be prepared by intramolecular cyclization of a compound of formula (XXV), wherein the carbon atom or nitrogen atom is substituted with. For relevant examples, see WO 2005 / 012262. [ka] Scheme 16

[0111] As shown in Scheme 17, compounds of formula (XXI) are in equilibrium with compounds of formula (XXII), and X 8 are C1-C4 alkyl or C5-C6 cycloalkyl, or together with the nitrogen to which they are attached form a saturated heterocyclic ring, and X 9 and independently R as defined for compounds of formula (I). 7 , R 8 or R 9 is a carbon atom or nitrogen atom substituted with X 10The compounds of formula (XXVI), wherein is H or a protecting group (e.g., tetrahydropyran, 2-(trimethylsilyl)ethoxymethyl, or benzyl), can be prepared by amination and direct cyclization with an aminating reagent (e.g., amino 4-nitrobenzoic acid, N-(tert-butoxycarbonyl)-2-nitrobenzenesulfonamide, hydroxylamine-O-sulfonic acid, or sodium diformylamide) in a suitable solvent, such as dimethyl sulfoxide, dimethylformamide, dichloromethane, N-methyl-2-pyrrolidone, or ethanol, at a temperature of 0°C to 110°C, more preferably 20°C to 50°C, optionally in the presence of a base (e.g., KOH, NaOH). For relevant examples, see J. Med. Chem. 1996, 39, 582; Organometallics 2014, 33, 4035, and Chem. Eur. J. 2019, 25, 1963. [ka] Scheme 17

[0112] As shown in Scheme 18, X 8 are C1-C4 alkyl or C5-C6 cycloalkyl, or together with the nitrogen to which they are attached form a saturated heterocyclic ring, and X 9 and independently R as defined for compounds of formula (I). 7 , R 8 or R 9 The compound of formula (XXV), wherein the carbon atom or nitrogen atom is substituted with X, can be prepared by reaction in a suitable solvent such as dimethyl sulfoxide, N-methyl-2-pyrrolidone or dimethylacetamide at a temperature of 20°C to 120°C. 8 are C1-C4 alkyl or C5-C6 cycloalkyl, or together with the nitrogen to which they are attached form a saturated heterocyclic ring, and X 9 and independently R as defined for compounds of formula (I). 7 , R 8 or R 9For relevant examples, see Dalton Trans. 2016, 45, 15644, J. Med. Chem. 1996, 39, 582 or Chem. Eur. J. 2019, 25, 1963. [ka] Scheme 18

[0113] As shown in Scheme 19, X 8 are C1-C4 alkyl or C5-C6 cycloalkyl, or together with the nitrogen to which they are attached form a saturated heterocyclic ring, and X 9 and independently R as defined for compounds of formula (I). 7 , R 8 or R 9 is a carbon atom or nitrogen atom substituted with X 10 Compounds of formula (XXVI) where X is H or a protecting group (e.g., tetrahydropyran, 2-(trimethylsilyl)ethoxymethyl or benzyl) can be prepared by 9 and independently R as defined for compounds of formula (I). 7 , R 8 or R 9 is a carbon atom or nitrogen atom substituted with X 10 It can be obtained from a compound of formula (XVVIII), where is H or a protecting group (e.g., tetrahydropyran, 2-(trimethylsilyl)ethoxymethyl, or benzyl), by reacting with a formamide equivalent, such as dimethylformamide dimethyl acetal or 1-(dimethoxymethyl)pyrrolidine, either neat or in a suitable solvent (e.g., toluene, dimethylformamide), at a temperature of 50° C. to 120° C. For relevant examples, see WO 2021 / 2296621; WO 2008 / 149379, and Bioorg.Med.Chem.Lett. 2022, 61, 128552. [ka] Scheme 19

[0114] As shown in Scheme 20, X can be prepared by using an organometallic reagent (e.g., methyl magnesium bromide, isopropyl magnesium chloride, lithium chloride, butyl lithium, tert-butyl lithium, or phenyl magnesium 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. 8 are C1-C4 alkyl or C5-C6 cycloalkyl, or form a saturated heterocycle together with the nitrogen to which they are attached, and X 9 and independently R as defined for compounds of formula (I). 7 , R 8 or R 9 is a carbon atom or nitrogen atom substituted with X 10 Compounds of formula (XXVI) where X is H or a protecting group (e.g., tetrahydropyran, 2-(trimethylsilyl)ethoxymethyl or benzyl) can be prepared by 7 is chloro, bromo or iodo, and X 9 and independently R as defined for compounds of formula (I). 7 , R 8 or R 9 is a carbon atom or nitrogen atom substituted with X 10 can be prepared from compounds of formula (XXIX) and compounds of formula (XXX), where is H or a protecting group (e.g., tetrahydropyran, 2-(trimethylsilyl)ethoxymethyl, or benzyl). For relevant examples, see WO 2009 / 130193 and WO 2015 / 057205. [ka] Scheme 20

[0115] As shown in Scheme 21, compounds of formula (XXIX) are known or can be obtained by reacting compounds of formula (XXXI) with N,O-dimethylhydroxylamine hydrochloride in a suitable solvent or mixture of solvents (e.g., dimethylformamide, dichloromethane, or 2-methyltetrahydrofuran) in the absence of a mixture of oxalyl chloride or thionyl chloride and dimethylformamide at temperatures between −10° C. and 80° C., more preferably between 0° C. and 30° C., or in the presence of a coupling agent (e.g., T3P, HATU, COMU) in a suitable solvent or mixture of solvents (e.g., dimethylformamide, dichloromethane, trichloromethane, tetrahydrofuran, methyltetrahydrofuran) at temperatures between 0° C. and 80° C. For relevant examples, see International Publication No. 2011 / 023706 and J. Med. Chem. 2004, 47, 2405. Compounds of formula (XXXI) are known or commercially available. [ka] Scheme 21

[0116] As shown in Scheme 22, X 3 is OH or C1-C4-alkoxy, and X 8 is C1-C4 alkyl or C5-C6 cycloalkyl, or forms both a saturated heterocycle with the nitrogen to which it is attached, can be reacted with X 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) or in a suitable solvent or mixture of solvents (e.g., dimethylformamide, 2-methyltetrahydrofuran) at a temperature between 25°C and 120°C. 3The compound of formula (XXXII) can be prepared by reacting a compound of formula (XXXII) in which is OH or C1-C4 alkoxy. For relevant examples, see Tetrahedron 1998, 54, 9799; J. Het. Chem. 2014, 51, 954 and Synth. Commun. 2021, 51, 2160. Compounds of formula (XXXII) are known or commercially available. [ka] Scheme 22

[0117] As shown in Scheme 23a, a compound of formula (XXI) is in equilibrium with a compound of formula (XXII), and a nucleophilic compound of formula (XXXIII) in equilibrium with a compound of formula (XXXIV) and X 2 where R is a suitable leaving group such as fluoro, chloro, bromo, iodo, BF3K, B(OH)2 or B(pinacol) with an electrophilic compound of formula (IX) in a suitable solvent (e.g., dichloromethane, 1,2-dichloromethane, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, N-methylpyrrolidone, dimethylacetamide) at a temperature between 40°C and 80°C using a catalyst (e.g., Cu(OAc)2), preferably in the presence of an oxidizing agent such as O2, or alternatively, using a suitable palladium pre-catalyst such as RockPhos Pd G3 in the presence of a base (e.g., K3PO4) and a suitable solvent (e.g., dimethyl ether or toluene) at a temperature between 20°C and 80°C. 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. [ka] Scheme 23a

[0118] Alternatively, as shown in Scheme 23b, the compound of formula (XXI) in equilibrium with the compound of formula (XXII) can be reacted with X7 may be prepared from a compound of formula (XXXV) in equilibrium with a compound of formula (XXXVI) where is chloro, bromo or iodo, by reacting with a compound of formula (IX) optionally in the presence of a base (e.g., K0-t-Bu, K3PO4, K2CO3, triethylamine or Cs2CO3) in a suitable solvent or mixture of solvents (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, dimethyl sulfoxide) at a temperature between 50°C and 110°C, preferably using a metal catalyst complex (e.g., Cu or Pd). For relevant examples, see Eur. J. Org. Chem. 2011, 18, 3353; J. Org. Chem. 2009, 74, 7951; Tetrahedron Lett. 2012, 53, 5318; WO 2008 / 110313 and WO 2012 / 136604. Compounds of formula (IX) are known or commercially available. [ka] Scheme 23b

[0119] As shown in Scheme 24, compounds of formula (XXXV) are in equilibrium with compounds of formula (XXXVI), and X 7 It can be obtained from a compound of formula (XXXVII) in equilibrium with a compound of formula (XXXVIII) where is chloro, bromo or iodo, by treatment with hydrochloric acid or hydrogen bromide, optionally in the presence of a transition metal (e.g., zinc, palladium) or sodium nitrite, followed by the addition of a copper salt, such as bromide or chloride, in a suitable solvent or mixture of solvents (e.g., water, acetonitrile, ethanol) at a temperature between 0° C. and 50° C. For relevant examples, see Mendeleev Commun. 2017, 27, 285. [ka] Scheme 24

[0120] As shown in Scheme 25, compounds of formula (XXXVII) are in equilibrium with compounds of formula (XXXVIII) and can be converted to X after treatment with sodium or potassium nitrite, sodium hypochloride, or sodium azide in the presence of a strong acid (e.g., hydrochloric acid, trifluoroacetic acid, sulfuric acid, nitric acid) in a suitable solvent, typically water or acetonitrile, at temperatures between 10°C and 30°C. 9 and independently R as defined for compounds of formula (I). 7 , R 8 or R 9 is a carbon atom or nitrogen atom substituted with X 10 The diazonium salt can be obtained from a compound of formula (XXXIX) in which ≡H is 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 is reacted with a nitro compound (e.g., 4-(2-nitroethenyl)morpholine, 2-nitroacetaldehyde, 2-nitropropanediol, 1,3-diethyl 2-nitropropanedioate) in a suitable solvent or mixture of solvents, such as water or ethanol, at a temperature between 0°C and 60°C, optionally in the presence of a base (e.g., NaCO3, KCO3, KOH) or optionally in the presence of a strong acid (e.g., nitric acid, hydrochloric acid). For relevant examples, see Mendeleev Commun. 2017, 27, 285; WO 2017 / 144708 or Khimiya Geterotsiklicheskikh Soedinenii 1986, 5, 662. Compounds of formula (XXXIX) are known or commercially available. [ka] Scheme 25

[0121] As shown in Scheme 26, X 3 Compounds of formula (VII) in which X is OH or C1-C4-alkoxy are 3is OH or C1-C4-alkoxy, 11 is a leaving group, e.g., chloro, bromo, iodo, O-mesyl, O-tosyl, and X 12 The compound of formula (XLI) can be obtained by reacting the compound of formula (XLI) where X is a carbonyl or a carbonyl equivalent, such as an aldehyde, acetal, acyl chloride or bromide, ester, or orthoester, with a suitable solvent or mixture of solvents (e.g., dimethylformamide, dimethyl sulfoxide, toluene, ethanol, isopropanol, water) at a temperature of 30°C to 125°C, optionally in the presence of a catalyst such as hydrogen bromide or sodium carbonate, in a microwave reactor. For relevant examples, see J. Med. Chem. 2021, 64, 1197; Tetrahedron Lett. 2017, 58, 4816, and Chem. Pharm. Bull. 1992, 40, 1170. The compound of formula (XLI) is known or commercially available. [ka] Scheme 26

[0122] As shown in Scheme 27, R 1 is as defined for compounds of formula (I), and X 3 In the compound of formula (XL) where is OH or C1-C4-alkoxy, OH or C1-C4-alkoxy is obtained, and X 13

[0043] The nucleophilic substitution of the sulfone of the compound of formula (XLII), wherein R is an alkyl or cycloalkyl group, can be obtained with an aminating reagent (e.g., NHOH, NH, NHOAc) and an alkyl or cycloalkyl group, such as methyl, ethyl, or cyclohexyl, optionally in the presence of a base, such as triethylamine, in a suitable solvent or solvent mixture (e.g., dimethyl sulfoxide, water, tetrahydrofuran, 1,4-dioxane, isopropanol, ethanol, methanol, dichloromethane). For relevant examples, see Tetrahedron 2009, 65, 1697; Heterocycles 1977, 8, 299 and Org. Biomol. Chem. 2015, 13, 10620. [ka] Scheme 27

[0123] As shown in Scheme 28, R 1 is as defined for compounds of formula (I), and X 3 is OH or C1-C4-alkoxy, and X 13 Compounds of formula (XLII) where R is an alkyl or cycloalkyl group, for example, methyl, ethyl, or cyclohexyl, can be prepared by oxidizing R in the presence of an oxidizing agent (e.g., 3-chloroperbenzoic acid, hydrogen peroxide, oxone, chlorine) at a temperature between −10° C. and 50° C. in a suitable solvent or mixture of solvents, for example, dichloromethane, acetonitrile, chloroform, water, toluene, or 2-methyl-tetrahydrofuran. 1 , X 3 and X 13 can be obtained by oxidation of a compound of formula (XLIII), wherein is as defined for the compound of formula (XLII). 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 28

[0124] As shown in Scheme 29, R 1 is as defined for compounds of formula (I), and X 3 is OH or C1-C4-alkoxy, for example methoxy, and X 13 Compounds of formula (XLIII) where X is an alkyl or cycloalkyl group, such as methyl, ethyl, or cyclohexyl, can be converted to X by the reaction of X with a base (e.g., K0-t-Bu, K3PO4, K2CO3, triethylamine, or Cs2CO3) in a suitable solvent (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, dimethyl sulfoxide) at a temperature between 25°C and 110°C under reflux, optionally using a metal catalyst and a ligand complex (e.g., CuI,N,N-dimethylglycine). 3 and X 13 is as defined for compounds of formula (XLIV), and X 15 is a suitable leaving group such as a halogen, can be obtained by reacting a compound of formula (XLIV). For relevant examples, see Eur. J. Org. Chem. 2011, 18, 3353; J. Org. Chem. 2009, 74, 7951; Tetrahedron Lett. 2012, 53, 5318; WO 2008 / 110313 and WO 2012 / 136604. Compounds of formula (XLIV) are known or commercially available. [ka] Scheme 29

[0125] As already indicated, it has now been surprisingly found that the compounds of formula (I) of the present invention have a very advantageous level of biological activity in the protection of plants against diseases caused by fungi in fact.

[0126] The compounds of formula (I) can be used in the agricultural sector and related fields of use, for example, as active ingredients for controlling plant pests or non-living materials, and for controlling spoilage microorganisms or organisms potentially harmful to humans. The novel compounds are distinguished by their excellent activity at low application rates, good plant tolerance, and environmental safety. They possess highly useful curative, preventive, and systemic properties and can be used to protect numerous cultivated plants. The compounds of formula (I) can be used to inhibit or eliminate pests that occur on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of different crops of useful plants, while simultaneously protecting these parts of later-developing plants from, for example, phytopathogenic microorganisms.

[0127] The present invention further relates to a method for controlling or preventing infestation of susceptible plants or plant propagation material and / or harvested food crops by treating the plants or plant propagation material and / or harvested food crops, wherein an effective amount of a compound of formula (I) is applied to the plant, its part or its habitat.

[0128] The compounds of formula (I) can also be used as fungicides. As used herein, the term "fungicide" refers to a compound that controls, modifies, or prevents the growth of fungi. As used herein, the term "fungicidally effective amount" refers to the amount of such a compound or a combination of such compounds that can have an effect on the growth of fungi. Control or modification effects include any deviation from natural development, such as killing, retardation, etc., and prevention includes the formation of a barrier or other defense in plants to prevent infection by fungi.

[0129] It may also be possible to use the compounds of formula (I) as a dressing to treat plant propagation material, such as seeds of fruits, tubers, or grains, or plant cuttings, for protection against fungal infections and phytopathogenic fungi occurring in the soil. The propagation material can be treated with a composition containing a compound of formula (I) before planting. For example, seeds can be dressed before being sown. The active compound of formula (I) can also be applied to grains (coatings) by impregnating the seeds in a liquid formulation or coating the seeds with a solid formulation. The composition can be applied to the planting site when the propagation material is planted, or, for example, to the sowing furrow during sowing. The present invention also relates to a method for treating such plant propagation material and to the plant propagation material treated in this way.

[0130] Furthermore, the compounds of formula (I) may be used for the control of fungi in related fields such as the protection of industrial materials, including wood and wood-based industrial products, food storage and hygiene control.

[0131] In addition, the present invention may be used to protect non-living materials such as timber, wallboard and paint from fungal attack.

[0132] The compounds of formula (I) and compositions containing such compounds are effective, for example, in controlling a wide range of plant diseases, including foliar and / or soil-borne pathogens of ornamental plants, turfgrass, plants, fields, cereals, and fruit crops, such as fungi and fungal vectors of diseases, and plant pathogenic bacteria and viruses. These pathogens may include: Phytophthora cactorum, Phytophthora capsici, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora, Phytophthora erythroseptica, Phytophthora fragariae, Phytophthora infestans, Phytophthora nicotianae, Phytophthora porri, and Phytophthora sojae. sojae; Pythium species such as Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythium irregulare, and Pythium ultimum; other Peronosporales such as Bremia lactucae, Hyaloperonospora parasitica, Sclerophthora macrospora, and Sclerospora graminicola; Peronospora destructor destructor, Peronospora farinosa f.sp. spinaciae and Peronospora viciae f.sp. pisi.Peronospora spp., including Plasmopara halstedii and Plasmopara viticola; Pseudoperonospora spp., including Pseudoperonospora cubensis and Pseudoperonospora humili; Peronosclerospora maydis, Peronosclerospora philippinensis, and Peronosclerospora sorgi. Peronosclerospora species, including Albugo candida, Albugo occidentalis, and Albugo tragopogonis; Saprolegniales, including Aphanomyces species, including Aphanomyces cochliodes; Cercospora species including Actinothyrium graminis, Asperisporium caricae, Cercospora arachidicola, Cercospora beticola, Cercospora brassicicola, Cercospora canescens, Cercospora cf. flagellaris, Cercospora janseana, Cercospora kikuchii, Cercospora lagenariae, Cercospora sogynae Ascomycetes, including Cercospora sojinae, Cercospora sorghi, and Cercospora zeae-maydis; Mycosphaerella species, including Dothistroma septosporum, Fulvia fulva, Mycosphaerella pomi, and Mycosphaerella linicola;Neopseudocercosporella brassicae, Neopseudocercosporella capsellae, Nothopassalora personata, Nothophaeocrytopus gaeumannii, Passalora bataticola, Passalora koepkei, Pseudocercospora griseola, Pseudocercospora vitis, Pseudocercospora fijiensis, Ramularia veticola Ramularia species, including Ramulariopsis gossypii, Ramulariopsis pseudoglycines, Ramulispora sorghi, Septoria species, including Scolecostigmina palmivora, Septoria apiicola, Septoria glycines, and Septoria lycopersici; Septoria species, including Zasmidium citri-griseum and Zymosepotria tritici. tritici); Helotiales, e.g., Botrytis species including Blumeriella jaapii, Botrytis cinerea and Botrytis fabae;Monilinia, including Cadophora gregata, Civorinia allii, Claireedia homoeocarpa, Diplocarpon coronariae, Drepanopeziza campestris, Gloeotinia temulenta, Hymenoscyphus fraxineus, Leptotrochila medicaginis, Marssonina graminicola, Monilinia fructigena, and Monilinia laxa; Neofabraea perenans Pyrenopeziza species including Pseudopeziza medicaginis, Pseudopeziza tracheiphila, and Pyrenopeziza brassicae; Rhabdocline pseudotsugae; Rhynchosporium species including Rhynchosporium secalis; Sclerotinia minor; Sclerotinia borealis. Sclerotinia species, including Sclerotinia borealis and Sclerotinia sclerotiorum;Hypocreales, such as Acremonium strictum, Albifimbria verrucaria, Claviceps africana, Claviceps purpurea, Fusarium avenaceum, Fusarium culmorum, Fusarium fujikuroi, Fusarium graminearum, Fusarium incarnatum, Fusarium langsethiae, Fusarium moniliforme, Fusarium oxysporum oxysporum, Fusarium oxysporum f.sp. cubense, Fusarium poae, Fusarium proliferatum, Fusarium pseudograminearum, Fusarium subglutinans, Fusarium sulphureum, Fusarium tricinctum and Fusarium verticillioides;Gliocladium species, Neocosmospora phaseoli, Neocosmospora solani, Neonectria candida, Paramyrothecium roridum, Sarocladium oryzae, Trichoderma species such as Trichoderma harzianum, Trichoderma pseudokoningii and Trichoderma viride; Trichothecium roseum and Ustilaginoidea virens); Magnaporthales, e.g., Pyricularia species including Gaeumannomyces avenae, Gaeumannomyces graminis, Gaeumannomyces graminis tritici, Gaeumannomyces wongoonoo, Magnaporthiopsis poae, Pyricularia grisea and Pyricularia oryzae;Pleosporales, e.g., Alternaria species including Alternaria allii, Alternaria alternata, Alternaria arachidis, Alternaria brassicae, Alternaria brassicicola, Alternaria dauci, Alternaria grandisi, Alternaria helianthicola, Alternaria mali, Alternaria porri, Alternaria solani, and Alternaria tomato; Boeremia Locust species including Ascochyta coffeae, Ascochyta pisi, and Ascochyta rabiei; Bipolaris maydis, Bipolaris oryzae; Curvularia species, including Bipolaris sorokiniana, Cochliobolus species, Corynespora cassiicola, Curvularia australiensis, Curvularia cactivora, and Curvularia lunata; Didymella species, including Didymella pinodella and Didymela pinodes; Drechslera species, including Drechslera glycine; Epicoccum nigrum, Exserohilum tursicum, and turcicum, Helminthosporium species including Helminthosporium solani;Hendersonia creberrima, Leptosphaerulina crassiasca, Neocamarosporium betae, Ophiosphaerella agrostidis, Ophiosphaerella herpotricha, Ophiosphaerella korrae, Ophiosphaerella narmari, Parastagonospora nodorum, Phaeosphaeria herpotrichoides, Phaeosphaeria maydis maydis, Phoma spp., Plenodomus lindquistii, Plenodomus lingam, Pleospora spp., Pyrenophora spp. including Pseudopyrenochaeta lycopersici, Pyrenophora poae, Pyrenophora teres, and Pyrenophora tritici-repentis; Remotididymella destructiva, Stagonospora thainanensis, Stemphylium species, including Stemphylium tainanensis, Stagonosporopsis cucurbitacearum, Stemphylium botryosum, Stemphylium solani, and Stemphylium vesicarium;Diaporthales such as Anisogramma anonmala, Apiognomonia errabunda, Cytospora platani, Diaporthe spp., Diaporthe amygdali, Diaporthe helianthin, Diaporthe neoviticola and Diaporthe phaseolorum; Diaporthe spp., Discula destructiva, Gnomoniopsis fructicola, Greeneria ubicola uvicola, Euglanconia juglandina, Ophiognomonia clavigignenti-juglandacearum, Stenocarpella maydis and Tubakia dryina; the Aureobasidiales, e.g., Aureobasidium spp., including Aureobasidium pullulans; Discosphaerina fulvida; the Erysiphe genus, including Blumeria graminis, Brasiliomyces malachrae, Erysiphe betae, Erysiphe cruciferarum, Erysiphe diffusa, Erysiphe heraclei, Erysiphe necator, and Erysiphe pisi; the Golovinomyces cichoracearum, Golovinomyces orontii, Leveillula taurica, Oidium arachidisi, Phyllactinia guttata, Podosphaera fuliginea, Podosphaera fusca, Podosphaera leucotricha, Podosphaera macularis, Podosphaera mors-uvae, Podosphaera pannosa, Podosphaera tridactyla Podosphaera species, including Podosphaera tridactyla and Podosphaera xanthii;Colletotrichum acutatum, Colletotrichum cereale, Colletotrichum chrysanthemi, Colletotrichum cliviicola, Colletotrichum coccodes, Colletotrichum fragariae, Colletotrichum gloeosporioides, Colletotrichum graminicola, Colletotrichum lentis, Colletotrichum lindemuthianum, Colletotrichum musae Glomerelles such as Colletotrichum species including Glomerella musae, Colletotrichum orbiculare, Colletotrichum siamense, and Colletotrichum truncatum; Verticillium species including Glomerella cingluata, Glomerella gossypii, Musicillium theobromae, Plectosphaerella cucumerina, and Verticillium dahlia; Venturia carpophila, Venturia efsae, and Venturia Venturia species, including Venturia effusa, Venturia inaequalis, Venturia oleaginea, and Venturia pyrina;The Chirales, such as Eutypa lata, Microdochium albescens, Microdochium majus, Microdochium nivale, Microdochium paspali, Microdochium sorghi, Physalospora abdita, Rosellinia spp., and Seimatosporium mariae; the Botryosphaeriales, such as Botryosphaeria species including Botryosphaeria dothidea; and Diplodia seriata. seriata, Dothiorella aromatica, Lasiodiplodia theobromae, Macrophoma theicola, Macrophomina phaseolina, Phyllosticta ampelicida, and Phyllosticta cucurbitacearum; Aspergillus flavus, Aspergillus fumigatus, Aspergillus niger, and Aspergillus terreus Eurotiales, such as Aspergillus species, including Aspergillus terreus; Penicillium species, including Penicillium digitatum, Penicillium expansum, and Penicillium italicum;Microaskers such as Ceratocystis species, including Berkeleyomyces basicola, Thielaviopsis paradoxa, Ceratocystis fimbriata, Ceratocystis manginecans, and Ceratocystis platani; Scedosporium species, including Scedosporium apiospermum and Scedosporium prolificans; Elsinoe ampelina and Elsinoe perseae; Myriangiales, such as Elsinoe species including Leptographium lundbergii, Leptographium microsporum, Ophiostoma novo-ulmi, Ophiostoma piceae, and Sporothrix species; Pezizomycetes, such as Phymatotrichopsis omnivore and Polyscytalum pustulans; Gibellina cerealis, Phyllachora maydis, and others. Phyllocoralles such as Maydis and Phyllachora pomigena;Amphisphaeriales, such as Griphosphaeria corticola, Lepteutypa cupressi, and Pestalotia rhododendri; Chaetothyriales, such as Capnodium ramosum and Schizothyrium pomi; Cladosporiales, such as Cladosporium spp., including Cladosporium oxysporum; Lophodermium seditiosum and Naemacyclus spp. Rhytismatales, such as Cephaloascus spp.; Saccharomycetales, such as Cephaloascus spp., including Cephaloascus fragrans; Candida spp., including Geotrichum candidum, Candida glabrata, Candida krusei, Candida lusitaniae, Candida parapsilosis, Candida albicans, and Candida tropicalis; Chaetomium spp., Monosporascus cannonballus, Sordariales such as Wongia garrettii and Wongia griffinii; Taphrina bullata; Taphrinales, such as Taphrina deformans; Onygenales, such as Coccidioides species, including Ajellomyces capsulatus, Blastomyces dermatitidis, and Coccidioides immitis; Epidermophyton species, Histoplasma species, Microsporum species, Trichophyton species, and Paracoccidioides species, including Paracoccioides brasiliensis; others, such as Hymenula cerealis. cerealis, Petriellidum spp., Septocyta ruborum; Basidiomycetes, including Hemileia species, including Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Cronartium ribicola, Gymnosporangium juniperi-virginianae, Gymnosporangium sabinae, and Hemileia vastatrix; Melampsora medusae, Melampsora lini, and Phakopsora ampelopsidis; ampelopsidis, Phakopsora pachyrhizi, Phragmidium mucronatum, Puccinia allii, Puccinia arachidis, Puccinia asparagi, Puccinia coronata, Puccinia graminis, Puccinia helianthi, Puccinia hieracii, Puccinia hordei, Puccinia horiana, Puccinia melanocephala, Puccinia polysora polysora), Puccinia porri, Puccinia recondita, Puccinia sorghi, Puccinia striiformis, Puccinia striiformis f.sp.hordei, Puccinia striiformis f.sp. tritici, and Puccinia triticina; Uromyces species including Pucciniastrum coryli, Tranzschelia discolor, Uromyces betae, Uromyces pisi, and Uromyces viciae-fabae; Tilleteria species such as Neovossia moliniae, Tilletia species including Tilletia caries and Tilletia controversa; Ustilago maydis maydis, Sporisorium reilianum and Ustilago spp. including Ustilago segetum var. nuda, Ustilago segetum var. tritici and Ustilago striiformis; Urocystidales such as Urocystis spp. including Urocystis agropyri; Marasmiellus inoderma, Mycena spp., Moniliophthora roreri, Moniliophthora perniciosa perniciosa and other acarid pests; Sclerotium spp.Cantharellales such as Typhula spp. and Typhula spp. including Typhula incarnata and Typhula ishikariensis; Ceratobasidiales such as Waitea circinata and Rhizoctonia spp. including Rhizoctonia cerealis, Rhizoctonia solani and Rhizoctonia theobromae; Atheliales such as Athelia rolfsii; Corticium invisum and Laetisaria fusiformis. Corticiales such as Itersonilia fuciformis; Cystodilobasidiales such as Itersonilia perplexans; Entylomatales such as Entyloma calendulae f.sp. dahliae and Entylomella microspore; Exobasidium vexans; Hymenochaetales such as Phellinus igniarius; Stereum hirsutum; Tremella species such as Cryptococcus species, including Cryptococcus neoformans. Mucorales, such as Choanephora cucurbitarum, Mucor spp., Rhizopus oryzae, Absidia corymbifera, and Rhizomucor pusillus; Blastocladiomycetes, including Physoderma maydis; and Diseases caused by other species and genera closely related to those listed above.

[0133] In addition to their fungicidal activity, the compounds of formula (I) and compositions containing such compounds have been shown to be effective against Actinobacteria, such as Streptomyces scabiei; Proteobacteria, such as Erwinia amylovora, Pectobacterium carotovorum, Xanthomonas species (including Xanthomonas axonopodis, Xanthomonas campestris, Xanthomonas oryzae, and Xanthomonas vesicatoria); Pseudomonas species, including Pseudomonas syringae; Polymyxa bettae; They may also have activity against diseases caused by black spot animals such as Polymyxa betae, Polymyxa graminis, Spongospora subterranea; Labyrinthula zosterae, and other species and genera closely related to those listed above.

[0134] The compounds of formula (I) may be used, for example, in turf, ornamental crops such as flowers, shrubs, broadleaf or evergreen trees such as conifers and tree injections, pest control, and the like.

[0135] Within the scope of the present invention, the target crops and / or useful plants to be protected are typically berry plants, such as blackberries, blueberries, cranberries, raspberries and strawberries; cereals, such as barley, maize (corn), millet, oats, rice, rye, sorghum, triticale and wheat; fiber plants, such as cotton, flax, hemp, jute and sisal; field crops, such as sugar and fodder beet, coffee, hops, mustard, rapeseed (canola), poppy, sugarcane, sunflower, tea and tobacco; fruit trees, such as apple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pear and plum; herbs such as basil, borage, chives, coriander, lavender, lovage, mint, oregano, parsley, rosemary, sage and thyme; legumes such as beans, lentils, peas and soybeans; nuts such as almonds, cashews, groundnuts, hazelnuts, peanuts, pecans, pistachios and walnuts; palms such as oil palm; ornamental plants such as flowers, shrubs and trees; other trees such as cocoa, coconut, olive and rubber; vegetables such as asparagus, eggplant, broccoli, cabbage, carrots, cucumber, garlic, lettuce, squash, melon, okra, onion, pepper, potato, pumpkin, rhubarb, spinach and tomato; and perennial and annual crops such as vines.

[0136] The term "useful plants" should also be understood to include useful plants that have been rendered tolerant to herbicides such as bromoxynil or to certain classes of herbicides (e.g., HPPD inhibitors, ALS inhibitors such as primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyroyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen oxidase) inhibitors) by conventional breeding or genetic engineering methods. An example of a crop that has been rendered tolerant to imidazolinones, such as imazamox, by conventional breeding methods (mutagenesis) is Clearfield® summer rapeseed (canola). Examples of crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-tolerant corn varieties commercially available under the trade names RoundupReady®, Herculex I®, and LibertyLink®.

[0137] The term "useful plants" should also be understood to include useful plants that have been transformed using recombinant DNA techniques with the ability to synthesize one or more selectively acting toxins, such as those known to be derived from toxin-producing bacteria, particularly those from the genus Bacillus.

[0138] Examples of such plants are YieldGard® (a corn variety expressing a CryIA(b) toxin); YieldGard Rootworm® (a corn variety expressing a CryIIIB(b1) toxin); YieldGard Plus® (a corn variety expressing CryIA(b) and CryIIIB(b1) toxins); Starlink® (a corn variety expressing a Cry9(c) toxin); Herculex I® (a corn variety expressing a CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety expressing a CryIA(c) toxin); Bollgard I® (a cotton variety expressing a CryIA(c) toxin); Bollgard II® (a cotton variety expressing CryIA(c) and CryIIA(b) toxins); VIPCOT® (a cotton variety expressing VIP toxin); NewLeaf® (a potato variety expressing CryIIIA toxin); NatureGard® Agrisure® GT Advantage (GA21 glyphosate-tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), Agrisure® RW (corn rootworm trait), and Protecta®.

[0139] The term "crop plant" should also be understood to include crop plants that have been transformed using recombinant DNA techniques to have the ability to synthesize one or more selectively acting toxins, such as those known to be derived from toxin-producing bacteria, particularly bacteria of the genus Bacillus.

[0140] Toxins that can be expressed by such transformed plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as d-endotoxins, e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or vegetative insecticidal proteins (Vip), e.g., Vip1, Vip2, Vip3, or Vip3A; or insecticidal proteins from bacteria, such as Photorhabdus spp. or Xenorhabdus spp., e.g., Photorhabdus luminescens, Xenorhabdus nematophilus, etc. insecticidal proteins of nematode-symbiotic bacteria such as Azotoxins; toxins produced by animals such as scorpion toxins, spider toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi such as Streptomycete toxins, plant lectins such as pea lectin, barley lectin or snowdrop lectin; agglutinins; proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ricin, Ribosome-inactivating proteins (RIPs) such as maize-RIP, abrin, ruffin, saporin or bryodin; steroid metabolic enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers such as sodium or calcium blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

[0141] Furthermore, in the context of the present invention, d-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or trophic insecticidal proteins (Vip), such as Vip1, Vip2, Vip3, or Vip3A, are understood to also refer to, inter alia, hybrid toxins, truncated toxins, and modified toxins. Hybrid toxins are produced recombinantly by combining different domains of these proteins in a new way (see, for example, WO 02 / 15701). For example, truncated toxins, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the natural toxin are replaced. In such amino acid substitutions, a non-naturally occurring protease recognition sequence is preferably inserted into the toxin, e.g., in the case of Cry3A055, a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see WO 03 / 018810).

[0142] Examples of such toxins or transformed plants capable of synthesizing such toxins are disclosed, for example, in EP 0 374 753, WO 93 / 07278, WO 95 / 34656, EP 0 427 529, EP 451 878 and WO 03 / 052073.

[0143] Processes for the preparation of such transformed plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP 0 367 474, EP 0 401 979 and WO 90 / 13651.

[0144] The toxins contained in the transformed plants confer resistance to harmful insects on the plants, which can be from any taxonomic group of insects, but are particularly commonly found in beetles (Coleoptera), two-winged insects (Diptera), and butterflies (Lepidoptera).

[0145] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known, and some are commercially available. Examples of such plants include: YieldGard® (a corn variety expressing the Cry1Ab toxin); YieldGard Rootworm® (a corn variety expressing the Cry3Bb1 toxin); YieldGard Plus® (a corn variety expressing the Cry1Ab and Cry3Bb1 toxins); Starlink® (a corn variety expressing the Cry9C toxin); Herculex I® (a corn variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety expressing the Cry1Ac toxin); Bollgard I® (a cotton variety expressing the Cry1Ac toxin); Bollgard II® (a cotton variety expressing Cry1Ac and Cry2Ab toxins); VipCot® (a cotton variety expressing Vip3A and Cry1Ab toxins); NewLeaf® (a potato variety expressing Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait), and Protecta®.

[0146] Further examples of such transformed crops are: 1. Bt11 corn, registration number C / FR / 96 / 05 / 10, manufactured by Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France. Genetically engineered corn (Zea mays) resistant to European corn borers (Ostrinia nubilalis and Sesamia nonagrioides) through transgenic expression of a truncated Cry1Ab toxin. Bt11 corn also achieves tolerance to the herbicide glufosinate ammonium through transgenic expression of the enzyme PAT.

[0147] 2. Bt176 maize, registration number C / FR / 96 / 05 / 10, manufactured by Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France. Genetically engineered maize (Zea mays) that confers resistance to European corn borers (Ostrinia nubilalis and Sesamia nonagrioides) through transgenic expression of the Cry1Ab toxin. Bt176 maize also achieves tolerance to the herbicide glufosinate-ammonium through transgenic expression of the enzyme PAT.

[0148] 3. MIR604 maize, registration number C / FR / 96 / 05 / 10, manufactured by Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France. Maize conferred insect resistance by transgenic expression of a modified Cry3A toxin. The toxin is Cry3A055 modified by the insertion of a cathepsin-G-proteinase recognition sequence. The preparation of such transformed maize plants is described in WO 03 / 018810.

[0149] 4. MON863 maize, registration number C / DE / 02 / 9, manufactured by Monsanto Europe SA270-272 Avenue de Tervuren, B-1150 Brussels, Belgium. MON863 expresses the Cry3Bb1 toxin and confers resistance to certain coleopteran insects.

[0150] 5. IPC531 Cotton, registration number C / ES / 96 / 02, manufactured by Monsanto Europe SA270-272 Avenue de Tervuren, B-1150 Brussels, Belgium.

[0151] 6. 1507 corn, registration number C / NL / 00 / 10, manufactured by Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium. Maize genetically engineered for expression of the protein Cry1F to achieve resistance to certain lepidopteran insects and for expression of the PAT protein to achieve tolerance to the herbicide glufosinate ammonium.

[0152] 7. NK603 x MON810 corn, registration number C / GB / 02 / M3 / 03, manufactured by Monsanto Europe SA270-272 Avenue de Tervuren, B-1150 Brussels, Belgium. This conventional hybrid corn variety is the result of crossing the genetically engineered varieties NK603 and MON810. NK603 x MON810 corn transgenicly expresses the CP4 EPSPS protein from Agrobacterium sp. strain CP4, which confers resistance to the Roundup® herbicide (containing glyphosate), and also transgenicly expresses the Cry1Ab toxin from Bacillus thuringiensis subsp. kurstaki, which confers resistance to certain Lepidoptera, including the European corn borer.

[0153] The compounds of formula (I) can be used to control or prevent phytopathogenic diseases caused in particular by phytopathogenic fungi such as Botrytis cinerea on Rosaceae, Vitaceae, Solanaceae, Cucurbitaceae and Fabaceae; Glomerella lagenarium on Cucurbitaceae plants; Sclerotinia sclerotiorum on Leguminosae, Brassicaceae and Asteraceae plants, for example soybean, rapeseed and sunflower respectively; Alternaria solani on Solanaceae plants, such as tomato and potato; Monographella nivalis on Grassaceae plants; or Pyrenophora teres on Grassaceae plants, such as barley.

[0154] As used herein, the term "habitat" means the field in which the plant is growing, or the field in which the seeds of the cultivated plant are sown, or the field in which the seeds will be sown in the soil. It includes the soil, the seeds and seedlings, and the established vegetation.

[0155] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, seedlings, roots, tubers, stems, stalks, foliage, and fruits.

[0156] The term "plant propagation material" is understood to refer to reproductive parts of plants, such as seeds, that can be used for their propagation, as well as vegetative bodies, such as cuttings or tubers, e.g., potatoes. For example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes, and plant parts may be mentioned. Also included are sprouted plants and shoots that will be transplanted after germination or emergence from the soil. These shoots may be protected by a complete or partial treatment by immersion before transplantation. Preferably, "plant propagation material" is understood to refer to seeds.

[0157] The compounds of formula (I) can be used in their pure form or, preferably, together with adjuvants conventionally employed in the formulation art. For this purpose, they can be conveniently formulated in a known manner into emulsifiable concentrates, coating pastes, directly sprayable or dilutable solutions or suspensions, diluted emulsions, wettable powders, soluble powders, dusts, granules, and capsules, for example, in polymeric materials. The application method, such as spraying, atomizing, dusting, scattering, coating, or pouring, as well as the type of composition, are selected depending on the intended purpose and the current situation. The composition may also contain further adjuvants, such as stabilizers, antifoaming agents, viscosity modifiers, binders or adhesives, and fertilizers, trace element sources, or other compounds for achieving special effects.

[0158] Suitable carriers and adjuvants, for example for use in agriculture, can be solid or liquid and are substances useful in formulation technology, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers. Such carriers are described, for example, in WO 97 / 33890.

[0159] Suspension concentrates are aqueous formulations in which fine solid particles of the active compound are suspended. Such formulations contain anti-settling and dispersing agents and may further contain wetting agents, as well as anti-foaming and crystal growth inhibitors to enhance activity. When used, these concentrates are diluted in water and typically applied by spray to the area to be treated. The amount of active ingredient can range from 0.5% to 95% of the concentrate.

[0160] Wettable powders are in the form of fine particles that disperse readily in water or other liquid carriers. These particles contain the active ingredient held in a solid matrix. Typical solid matrices include Fuller's earth, kaolin clay, silica, and other readily wet organic or inorganic solids. Wettable powders usually contain 5% to 95% of the active ingredient and small amounts of wetting agents, dispersing agents, or emulsifying agents.

[0161] Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquids. They may consist solely of the active compound and a liquid or solid emulsifier, or may contain a liquid carrier such as xylene, high-boiling aromatic naphtha, isophorone, and other nonvolatile organic solvents. When used, these concentrates are dispersed in water or other liquid and typically applied by spraying to the area to be treated. The amount of active ingredient can range from 0.5% to 95% of the concentrate.

[0162] Granular formulations include both extrudates and relatively coarse particles and are usually applied undiluted to the area where treatment is required. Typical carriers for granular formulations include sand, Fuller's earth, attapulgite clay, bentonite clay, montmorillonite clay, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster of Paris, wood flour, ground corn cobs, ground peanut shells, sugar, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate, and other organic or inorganic materials that can absorb or be coated with the active compound. Granular formulations typically contain 5% to 25% active ingredient, which may include surfactants or vegetable oils such as high-boiling aromatic naphtha, kerosene and other petroleum fractions; and / or spreading agents such as dextrin, glue, or synthetic resins.

[0163] Dusts are free-flowing admixtures of the active ingredient and finely divided solids such as talc, clays, powders and other organic and inorganic solids which act as dispersants and carriers.

[0164] Microcapsules are typically small droplets or granules of an active ingredient enclosed in an inert, porous shell that allows the encapsulated material to be released into the environment at a controlled rate. The encapsulated droplets are typically 1 to 50 microns in diameter. The encapsulated liquid typically comprises 50 to 95% of the capsule's weight and may contain a solvent in addition to the active compound. Encapsulated granules are generally porous granules with a porous membrane that seals the pore openings of the granule, retaining the active species in liquid form within the pores of the granule. Granules typically range in diameter from 1 millimeter to 1 centimeter, preferably 1 to 2 millimeters. Granules are formed by extrusion, agglomeration, or prilling, or are natural. Examples of such materials are vermiculite, calcined clay, kaolin, attapulgite clay, sawdust, and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes, and starch xandates.

[0165] Other useful formulations for pesticide applications include simple solutions of the active ingredient in solvents such as acetone, alkylated naphthalenes, xylene, and other organic solvents, in which complete dissolution at the desired concentration is achieved. Pressurized sprayers can also be used, in which the active ingredient is dispersed in finely divided form as the low-boiling dispersant solvent carrier evaporates.

[0166] Suitable agricultural adjuvants and carriers useful in formulating the compositions of the present invention in the formulation types described above are well known to those skilled in the art.

[0167] Suitable liquid carriers include, for example, water, toluene, xylene, petroleum naphtha oil, crop oil, acetone, methyl ethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, divinyl glycol, divinyl glycol abietate, divinyl glycol butyl ether, divinyl glycol ethyl ether, divinyl 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, vinyl carbonate, 1,1,1-Trichloroethane, 2-heptanone, α-pinene, d-limonene, vinyl glycol, vinyl glycol butyl ether, vinyl glycol methyl ether, γ-butyrolactone, glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropyl benzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, vinyl chloride, m-xylene, n-hexane, n-octylamine, kutade Examples of suitable solvents include citric acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyvinyl glycol (PEG 400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, trivinyl glycol, xylene sulfonic acid, paraffin, mineral oil, trichlorovinyl, perchlorovinyl, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol and amyl alcohol, tetrahydrofurfuryl alcohol, high molecular weight alcohols such as hexanol, octanol, etc., vinyl glycol, propylene glycol, glycerin, and N-methyl-2-pyrrolidinone. For dilution of concentrates, water is typically the carrier of choice.

[0168] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, Kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, Fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut hulls, and lignin.

[0169] A wide range of surfactants are advantageously employed in both the liquid and solid compositions, particularly those designed to be diluted with a carrier before application. These surfactants, when used, typically comprise from 0.1% to 15% by weight of the formulation. They may be anionic, cationic, nonionic, or polymeric in nature and may be used as emulsifying agents, wetting agents, suspending agents, or for other purposes. Typical surfactants include alkyl sulfates such as diethanolammonium lauryl sulfate; alkylaryl sulfonate salts such as calcium dodecylbenzene sulfonate; alkylphenol-alkylene oxide adducts such as nonylphenol-C.18 ethoxylate; alcohol-alkylene oxide adducts such as tridecyl alcohol-C.16 ethoxylate; soaps such as sodium stearate; alkylnaphthalene sulfonates such as sodium dibutylnaphthalene sulfonate; dialkyl esters of sulfosuccinates such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters such as sorbitol oleate; quaternary amines such as lauryltrimethylammonium chloride; polyvinyl glycol esters of fatty acids such as polyvinyl glycol stearate; block copolymers of vinyl oxide and propylene oxide; and salts of mono- and di-alkyl phosphate esters.

[0170] Other adjuvants commonly utilized in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray size regulators, pigments, antioxidants, foaming agents, antifoaming agents, light-blocking agents, compatibilizers, defoamers, sequestering agents, neutralizing agents and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetration aids, trace elements, emollients, lubricants, and adhesives.

[0171] In addition, other biocidal active ingredients or compositions can be combined with the composition of the present invention, used in the method of the present invention, and applied simultaneously or sequentially with the composition of the present invention.When applied simultaneously, these additional active ingredients can be formulated together with the composition of the present invention, or can be mixed together, for example, in a spray tank.These additional biocidal active ingredients can be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and / or plant growth regulators.

[0172] Pesticides referred to herein using common names are known, for example, from "The Pesticide Manual", 15th Ed., British Crop Protection Council 2009.

[0173] Additionally, the compositions of the present invention may be applied in conjunction with one or more systemic acquired resistance inducers ("SAR" inducers). SAR inducers are known and are described, for example, in U.S. Patent No. 6,919,298, and include, for example, salicylates and the commercially available SAR inducer acibenzolar-S-methyl.

[0174] The compounds of formula (I) are usually used in the form of agrochemical compositions, and can be applied to the crop area or plants to be treated simultaneously or sequentially with other compounds.These additional compounds can be, for example, fertilizers or trace element donors or other preparations that affect plant growth.They can also be selective or non-selective herbicides, as well as insecticides, fungicides, bactericides, nematicides, molluscicides, or mixtures of several of these preparations, optionally with additional carriers, surfactants or application-promoting adjuvants that are conventionally used in the field of formulation.

[0175] The compounds of formula (I) may be used in the form of a composition for the control or protection against phytopathogenic microorganisms, comprising as active ingredient at least one compound of formula (I), or in the form of at least one preferred individual compound as defined herein, in free form or in the form of an agrochemically usable salt, and at least one of the adjuvants described above.

[0176] The present invention therefore provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I), an agriculturally acceptable carrier, and optionally an adjuvant. An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural carriers are well known in the art. Preferably, the composition may comprise, in addition to the compound of formula (I), at least one or more pesticidal active compounds, for example, additional fungicidal active ingredients.

[0177] The following mixtures of compounds of formula (I) with active ingredients are preferred (wherein the abbreviation "TX" means "one compound selected from the compounds defined in Tables A-1 to A-17 and their subtables or a compound selected from P-1.1 to P-1.19 listed in Table T1 (below)"): A compound selected from the group of substances consisting of: 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, aldoxicarb + TX, amidithione + TX, amidothioate + TX, amiton + TX, amiton hydrogen oxalate + TX, amitraz + TX, alamite + TX, arsenic oxide + TX, azobenzene + TX, azotoate + T X, Benomyl + TX, Benoxafos + TX, Benzyl Benzoate + TX, Bixafen + TX, Brofenvalerate + TX, Bromocyclen + TX, Bromophos + TX, Bromopropylate + TX, Buprofezin + TX, Butocarboxim + TX, Butoxycarboxim + TX, Butylpyridaben + TX, Calcium Polysulfide + TX, Camphorchlor + TX, Carbanolate + TX, Carbophenothion + TX, Cymiazole + TX, Chinomethionate + TX, Chlorbenside + TX, Chlordimeform + TX, Chlordimeform Hydrochloride + T X, chlorphenetole + TX, chlorfenson + TX, chlorfensulfide + TX, chlorobenzilate + TX, chlormebform + TX, chloromethiuron + TX, chloropropylate + TX, chlorthiophos + TX, cinerin I + TX, cinerin II + TX, cinerin + TX, closantel + TX, coumaphos + TX, crotamiton + TX, crotoxifos + TX, cuflaneb + 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, Dichlofluanid+TX, Dichlorvos+TX, Diglifos+TX, Dienochlor+TX, Dimefox+TX, Zinex+TX, Zinex-Diclexin+TX, Dinocap-4+TX, Dinocap-6+TX, Dinocton+TX, Dinopenton+TX, Dinosulfone+TX, Dinotervone+TX, Dioxathion+TX, Diphenylsulfone+TX, Disulfiram+TX, DNOC+TX,Dofenapine +TX, Doramectin +TX, Endothion +TX, Eprinomectin +TX, Ethoate methyl +TX, Etrimphos +TX, Fenazaflor +TX, Fenbutatin oxide +TX, Fenothiocarb +TX, Fenpyrad +TX, Fenpyroximate +TX, Fenpyrazamine +TX, Fenson +TX, Fentrifanil +TX, Flubenzimine +TX, Flucycloxuron +TX, Fluentil +TX, Fluorobenside +TX, FMC1137 +TX, Formetanate +TX, Formetanate hydrochloride +TX, Forparane ate + TX, gamma-HCH + TX, gliodin + TX, halfrenprox + TX, hexadecylcyclopropanecarboxylate + TX, isocarbophos + TX, jasmolin I + TX, jasmolin II + TX, iodofenphos + TX, lindane + TX, malonoven + TX, mecarbam + TX, mefosorane + TX, mesulfen + TX, methacrifos + TX, methyl bromide + TX, metolcarb + TX, mexacarbate + TX, milbemycin oxime + TX, mipafox + TX, monocrotophos + TX, morphothion + TX, moxidectin +TX, naled +TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one +TX, nifururizide +TX, nikkomycin +TX, nitrilacarb +TX, nitrilacarb 1:1 zinc chloride complex +TX, omethoate +TX, oxydeprophos +TX, oxydisulfoton +TX, pp'-DDT +TX, parathion +TX, permethrin +TX, fencapton +TX, phosalone +TX, phospholan +TX, phosphamidon +TX, polychloroterpenes +TX, polynaphthalene Chin + TX, Proclonol + TX, Promacyl + TX, Propoxur + TX, Protidathion + TX, Protoate + TX, Pyrethrin I + TX, Pyrethrin II + TX, Pyrethrin + TX, Pyridaphenthion + TX, Pirimitate + TX, Quinalphos + TX, Quinthiofos + TX, R-1492 + TX, Phosglycine + TX, Rotenone + TX, Schladan + TX, Cebufos + TX, Selamectin + TX, Sofamide + TX, SSI-121 + TX, Sulfiram + TX, Sulfuramide + TX, Sulfotep + TX, Sulfur + TX, Diflobidazine + TX,Tau-fluvalinate + TX, TEPP + TX, Terbam + TX, Tetradifon + TX, Tetrasul + TX, Thiafenox + TX, Thiocarboxim + TX, Thiofanox + TX, Thiometon + TX, Thioquinox + TX, Thuringensin + TX, Triamiphos + TX, Triatene + TX, Triazophos + TX, Triazuron + TX, Trifenofos + TX, Trinactin + TX, Vamidothion + TX, Vaniliprole + TX, Bethoxazin +TX, copper dioctanoate +TX, copper sulfate +TX, sibutrin +TX, dichloren +TX, dichlorophen +TX, endothal +TX, fentin +TX, hydrated lime +TX, nabam +TX, quinoclamine +TX, quinonamide +TX, simazine +TX, triphenyltin acetate +TX, triphenyltin hydroxide +TX, crufomate +TX, piperazine +TX, thiophanate +TX, chloralose +TX, fenthion +TX, pyridin-4-amine +TX, Strychnine + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide + TX, 8-hydroxyquinoline sulfate + TX, bronopol + TX, copper hydroxide + TX, cresol + TX, dipyrithione + TX, dodisin + TX, fenaminosulf + TX, formaldehyde + TX, hydralgafen + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel bicarbonate Dimethyldithiocarbamate + TX, Nitropyrine + TX, Octilinone + TX, Oxolinic Acid + TX, Oxytetracycline + TX, Potassium Hydroxyquinoline Sulfate + TX, Probenazole + TX, Streptomycin + TX, Streptomycin Sesquisulfate + TX, Tecloftalam + TX, Thiomersal + TX, Adoxophyes orana GV + TX, Agrobacterium radiobacter + TX, Amblyseius species + 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 formosa + TX, Eretmocerus eremicus + TX, Heterorhabditis bacteriophora and H. megidis + TX, Hippodamia convergens + TX, Leptomastix dactylopii + TX, Macrolophus caliginosus + TX, Mamestra brassicae NPV + TX, Metaphycus helvolus + TX, Metarhizium anisopliae var. acridum + TX, Metarhizium anisopliae var. anisopliae anisopliae var. anisopliae) + TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, Orius spp. + TX,Paecilomyces fumosoroseus + TX, Phytoseiulus persimilis + TX, Steinernema bibionis + TX, Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Trichogramma spp.) + TX, Typhlodromus occidentalis + TX, Verticillium lecanii lecanii) + TX, afolate + TX, bisazir + TX, busulfan + TX, dimatif + TX, hemel + TX, hempa + TX, metepa + TX, methiotepa + TX, methyl afolate + TX, molzide + TX, penfluron + TX, tepa + TX, thiohempa + TX, thiotepa + TX, tretamine + TX, uredepa + TX, (E)-dec-5-en-1-yl acetate + TX with (E)-dec-5-en-1-ol, (E)-tridec-4-en-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E,Z)-tetradec-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-icos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX, (9Z, 11E)-Tetradeca-9,11-dien-1-yl acetate + TX, (9Z,12E)-Tetradeca-9,12-dien-1-yl acetate + TX, 14-methyloctadec-1-ene + TX, 4-methylnonan-5-ol with 4-methylnonan-5-one, α-multistriatin + TX, Brevicomin + TX, Chodralure + TX, Chodramon + TX, Curar + TX, Disparlua + TX, Dodec-8-en-1-yl acetate + TX, Dodec-9-en-1-yl acetate + TX, Dodec-8 + TX, 10-dien-1- Ile Acetate + TX, Dominical Lure + TX, Ethyl 4-Methyloctanoate + TX, Eugenol + TX, Frontalin + TX, Gran Lure + TX, Gran Lure I + TX, Gran Lure II + TX, Gran Lure III + TX, Gran Lure IV + TX, Hexal Lure + TX, Ipsdienol + TX, Ipsenol + TX, Japonyl Lure + TX, Lineatin + TX, Little Lure + TX, Loop Lure + TX, Medi Lure + TX, Megaatomic Acid + TX, Methyl Eugenol + TX, Muscal Lure + TX, Octadeca-2,13-di En-1-yl acetate + TX, Octadeca-3,13-dien-1-yl acetate + TX, Olfrulure + TX, Orictalure + TX, Ostramon + TX, Sigluure + TX, Soldigin sulcatol + TX, Tetradec-11-en-1-yl acetate + TX, Trimedlure + TX, Trimedlure A + TX, Trimedlure B1 + TX, Trimedlure B2 + TX, Trimedlure C + TX, trunc-call + TX, 2-(octylthio)ethanol + TX, Butopyronoxyl + TX, Butoxy(polypropylene glycol) + TX,Dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, diethyl toluamide + TX, dimethylcarbate + TX, dimethyl phthalate + TX, ethyl hexanediol + TX, hexamide + TX, methoquin-butyl + TX, methyl neodecanoamide + TX, oxamate + TX, picaridin + TX, 1-dichloro-1-nitroethane + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane + TX, 1,2-dichloropropane with 1,3-dichloropropene + TX, 1-bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethyl carbamate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methyl carbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazoline Don + TX, 2-isovalerylindan-1,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenyl methyl carbamate + TX, 2-thiocyanatoethyl laurate + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-methyl-1-phenylpyrazol-5-yl dimethyl carbamate + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylyl methyl carbamate + TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethyl carbamate + TX, acetone + TX, acrylonitrile + TX, Aldrin +TX, allosamidin +TX, allylxycarb +TX, alpha-ecdysone +TX, aluminum phosphide +TX, aminocarb +TX, anabasine +TX, azidathion +TX, azamethiphos +TX, Bacillus thuringiensis delta-endotoxin +TX, barium hexafluorosilicate +TX, polysulfide +TX, bartholin +TX, Bayer 22 / 190 +TX, Bayer 22408 +TX, beta-cyfluthrin +TX, beta-cypermethrin +TX, bioethanomethrin +TX, biopermethrin +TX,Bis(2-chloroethyl) ether + TX, Borax + TX, Bromfen-infufos + 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, Cevadine + TX, Chlorbicyclen + TX, Chlordane + TX, Chlordecone + TX, Chloroform + TX, Chloropicrin + TX, Chlorphoxim + TX, Chlorprazophos + TX, Cis-Resmethrin + TX, Simetry methionine + TX, clocitrin + TX, copper acetoanite + TX, copper arsenate + TX, copper oleate + TX, cumisoate + TX, cryolite + TX, CS708 + TX, cyanofenphos + TX, cyanophos + TX, cyclethrin + TX, cythioate + TX, d-tetramethrin + TX, DAEP + TX, dazomet + TX, decarbofuran + TX, diamidaphos + TX, dikapton + TX, diclofenthion + TX, dicresyl + TX, dicyclanil + TX, dieldrin + TX, diethyl 5-methylpyrazol-3-yl phosphate + TX, dilol + TX, di Mefluthrin + TX, Dimethane + TX, Dimethryn + TX, Dimethylvinphos + TX, Dimethylan + TX, Dinoprop + TX, Zinam + TX, Dinoseb + TX, Diofenolan + TX, Dioxabenzophos + TX, Dicyclophos + TX, DSP + TX, Ecdysterone + TX, EI1642 + TX, EMPC + TX, EPBP + TX, Ethaphos + TX, Ethiofencarb + TX, Ethyl formate + TX, Ethylene dibromide + TX, Ethylene dichloride + TX, Ethylene oxide + TX, EXD + TX, Fenchlorphos + TX, Fenetacarb + T X, fenitrothion +TX, fenoxacrim +TX, fenpyrithrin +TX, fensulfothion +TX, fenthion ethyl +TX, flucofuron +TX, fosmisilan +TX, hospirate +TX, fostietan +TX, furathiocarb +TX, fretolin +TX, guazatine +TX, guazatine acetate +TX, sodium tetrathiocarbonate +TX, halfpenprox +TX, HCH +TX, HEOD +TX, heptachlor +TX, heterophos +TX, HHDN +TX, hydrogen cyanide +TX, hikincarb +TX, IPSP +TX,Isazophos + TX, Isobenzan + TX, Isodrin + TX, Isofenphos + TX, Isolane + TX, Isoprothiolane + TX, Isoxathion + TX, Juvenile Hormone I + TX, Juvenile Hormone II + TX, Juvenile Hormone III + TX, Kelan + TX, Kinoprene + TX, Lead Arsenate + TX, Leptophos + TX, Silimphos + TX, Litathion + TX, m-Cumenylmethylcarbamate + TX, Magnesium Phosphide + TX, Magidox + TX, Mecarfone + TX, Menasone + TX, Mercurous Chloride + TX, Mesulfenphos + TX, Metam + TX, Metakalium +TX, methasodium +TX, methanesulfonyl fluoride +TX, methocrotophos +TX, methoprene +TX, methotrin +TX, methoxychlor +TX, methyl isothiocyanate +TX, methyl chloroform +TX, methylene chloride +TX, methoxadiazone +TX, Mirex +TX, naphthalophos +TX, naphthalene +TX, NC-170 +TX, nicotine +TX, nicotine sulfate +TX, nithiazine +TX, nornicotine +TX, O-5-dichloro-4-iodophenyl O-ethylphosphonothioate +TX, O,O-diethyl O-4-methyl- 2-Oxo-2H-chromen-7-yl phosphorothioate + TX, O,O-Diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate + TX, O,O,O',O'-Tetrapropyldithiopyrophosphate + TX, Oleic acid + TX, paradichlorobenzene + TX, parathion-methyl + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH60-38 + TX, Fenkapton + TX, Fosniclor + TX, Phosphine + TX, Phoximmethyl + TX, Pyrimetaphos + TX, Polychlorodisil Lopentadiene isomers + TX, potassium arsenite + TX, potassium thiocyanate + TX, precocene I + TX, precocene II + TX, precocene III + TX, primidophos + TX, profluthrin + TX, promecarb + TX, prothiofos + TX, pyrazophos + TX, pyresmethrin + TX, cassia + TX, quinafos-methyl + TX, quinothione + TX, lafoxanide + TX, resmethrin + TX, rotenone + TX, cadetrin + TX, ryania + TX, ryanodine + TX, sabadila + TX, shradan + TX, cebufos + TX, SI-0009 + TXTiapronil +TX, Sodium arsenite +TX, Sodium cyanide +TX, Sodium fluoride +TX, Sodium hexafluorosilicate +TX, Sodium pentachlorophenoxide +TX, Sodium selenate +TX, Sodium thiocyanate +TX, Sulcofuron +TX, Sulcofuron-sodium +TX, Sulfuryl fluoride +TX, Sulprofos +TX, Tal oil +TX, Tadinecarb +TX, TDE +TX, Tebupirimfos +TX, Temephos +TX , teralethrin + TX, tetrachloroethane + TX, cyclofos + TX, thiocyclam + TX, thiocyclam hydrogen oxalate + TX, thionazine + TX, thiosultap + TX, thiosultap-sodium + TX, tralomethrin + TX, transpermethrin + TX, triazamate + TX, trichloromethos-3 + TX, trichloronate + TX, trimethacarb + TX, tolprocarb + TX, triclopyricarb + TX, triplen + TX, veratrizol thoron + TX, veratrine + TX, XMC + TX, zetamethrin + TX, zinc phosphate + TX, zolaprofos + 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-dichloropropene + TX, 3 ,4-Dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, anicifluprine + TX, benclothiaz + TX, cytokinin + TX, DCIP + TX, furfural + TX, isamidophos + TX, kinetin + TX, Myrothecium verrucaria composition + TX, tetrachlorothiophene + TX, xylenol + TX, zeatin + TX, potassium ethylxanthate + TX, acibenzolar + TX, acibenzolar-S-methyl + TX, Reynoutria sachalinensis extract + TX, α-chlorohydrin + TX, antu + TX,Barium carbonate +TX, bisthiosemi +TX, brodifacoum +TX, bromadiolone +TX, bromethalin +TX, chlorophacinone +TX, cholecalciferol +TX, coumachlor +TX, coumafuryl +TX, coumatetralyl +TX, crimidine +TX, difenacoum +TX, difethialone +, TX, diphacinone + TX, ergocalciferol + TX, flocoumafen + TX, fluoroacetamide + TX, flupropazine + TX, flupropazine hydrochloride + TX, norbormide + TX, fosacetim + TX, phosphorus + TX, pindone + TX, pyrinuron + TX, sciliroside + TX, sodium fluoroacetate + TX, thallium sulfate + TX, warfarin + TX, 2-(2-butoxyethoxy)ethyl piperonylate + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, nerolidol + TX Farnesol, Verbutin +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, Thiram +TX, Zinc naphthenate +TX, Ziram +TX, Imanin +TX, Ribavirin +TX, Chlorinconazide +TX, Mercury oxide +TX, Thiophanate methyl +TX, Azaconazole +TX, Bitertanol +TX, Bromoconazo ol + TX, cyproconazole + TX, difenoconazole + TX, diconazole + TX, epoxiconazole + TX, fenbuconazole + TX, fluquinconazole + TX, flusilazole + TX, flutriafol + TX, furametapyr + TX, hexaconazole + TX, imazalil + TX, imibenconazole + TX, ipconazole + TX, metconazole + TX, myclobutanyl + TX, paclobutrazol + TX, pefurazoate + TX, penconazole + TX, prothioconazole + TX, pyrifenox + TX, prochloraz + TX , propiconazole + TX, pyrisoxazole + TX, simeconazole + TX, tebuconazole + TX, tetraconazole + TX, triadimefon + TX, triadimenol + TX, triflumizole + TX, triticonazole + TX, ancymidol + TX, fenarimol + TX, nuarimol + TX, bupirimate + TX, dimethirimol + TX, ethirimol + TX, dodemorph + TX, fenpropidin + TX, fenpropimorph +, spiroxamine + TX, tridemorph + TX, cyprodinil + TX, mepanipyrim + TX, pyrimethanil + TX,Fenpiclonil + TX, fludioxonil + TX, benalaxyl + TX, furalaxyl + TX, metalaxyl + TX, R-metalaxyl + TX, ofrace + TX, oxadixyl + TX, carbendazim + TX, debacarb + TX, fuberidazole + TX, thiabendazole + TX, chlozolinate + TX, dichlozolin + TX, mycrozolin + TX, procymidone + TX, vinclozolin + TX, boscalid + TX, carboxin + TX, Fenfuram + TX, Flutolanil + TX, Mepronil + TX, Oxycarboxin + TX, Penthiopyrad +, Thifluzamide + TX, Dodine + TX, Iminoctadine + TX, Azoxystrobin + TX, Dimoxystrobin + TX, Estrogen + TX, Phenaminestrobin + TX, Flufenoxystrobin + TX, Fluoxastrobin + TX, Kresoxim-methyl + TX, Metominostrobin + TX, Trifloxystrobin + TX, Orysastrobin + TX, Picoxystrobin + TX, Pyraclostrobin + TX, Pyrametstrobin Bin + TX, pyraoxystrobin + TX, ferbam + TX, mancozeb + TX, maneb + TX, metiram + TX, propineb + TX, zineb + TX, captafol + TX, captan + TX, fluoroimide + TX, folpet + TX, tolylfluanid + TX, Bordeaux mixture + TX, copper oxide + TX, copper manate + TX, copper oxine + TX, nitrothalisopropyl + TX, edifenphos + TX, iprobenfos + TX, phosdifen + TX, tolclofos-methyl + TX, anilazine + TX, benthiavalicarb + TX, blasticidin-S +TX, chloroneb +TX, chlorothalonil +TX, cyflufenamid +TX, cymoxanil +TX, cyclobutrifluram +TX, diclocymet +TX, diclomedine +TX, dicloran +TX, diethofencarb +TX, dimethomorph +TX, flumorph +TX, dithianon +TX, ethaboxam +TX, etridiazole +TX, famoxadone +TX, fenamidone +TX, fenoxanil +TX, ferimzone +TX, fluazinam +TX, flumethylsulfolim +TX, fluopicolide +TX, fluoxytioconazole +TX, flu Sulfamide + TX, fluxapyroxad + TX, fenhexamid + TX, fosetyl-aluminum + TX, hymexazole + TX, iprovalicarb + TX, cyazofamid + TX, metasulfocarb + TX, metrafenone + TX, pencycuron + TX, phthalide + TX, polyoxin + TX, propamocarb + TX, pyribencarb + TX, proquinazid + TX, pyroquilon + TX, pyriophenone + TX, quinoxyfen + TX, quintozene + TX, tiadinil + TX, triazoxide + TX, tricyclazole + TX, triforine + TX,Validamycin + TX, Valifenalate + TX, Zoxamide + TX, Mandipropamide + TX, Fluvenetam + TX, Isopyrazam + TX, Sedaxane + TX, Benzovindiflupyr + TX, Pydiflumetofen + TX, 3-Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, Isoflucipram + TX, Isotianil + TX, Dipimethitrone + TX, 6-Ethyl-5,7-dioxo-pyrrole[4,5][1,4]dithiino[1,2-c]isothiazo 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile + TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide + TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazole 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine + TX, fluindapyr + TX, koumethoxystrobin (jiaxiangjunzhi) + TX, lvbenmixianan + TX, diclobenziazox + TX, mandestrobin + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolone] (1-methyltetrazol-5-yl)-phenyl]propan-2-ol + TX, oxathiapiproline + TX, tert-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, pyraziflumide + TX, impirflusam + TX, trolprocarb + TX, mefentrifluconazole + TX, ipfentrifluconazole + TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX,N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl]methanesulfonate + TX, but-3-ynyl N -[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, pyridaclomethyl + TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole- 4-Carboxamide + TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one + TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one + TX, aminopyrifen + TX, ametoctrazine + TX, amisulbrom + TX, penflufen + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazole-3- [yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX, florylpicoxamide + TX, fenpicoxamide + TX, methallylpicoxamide + TX, tebufloquine + TX, ipflufenoquine + TX, quinofumelin + TX, isofetamide + TX, isofetamide + ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate + TX (which can be prepared from the method described in WO 2020 / 056090),Ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enoxy]phenyl]methyl]pyrazole-3-carboxylate + TX (which can be prepared from the method described in WO 2020 / 056090), methyl N-[[4-[1-(4-cyclopropyl-2,6-difluorophenyl)pyrazol-4-yl]-2-methylphenyl]methyl]carbamate + TX (which can be prepared from the method described in WO 2020 / 097012), methyl N-[[4-[1-(2,6-difluoro-4-isopropyl

[0033] 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide + TX (which can be prepared from the method described in WO 2020 / 109391), 6-chloro-N-[2-(2-chloro-4-methyl-phenyl)-2,2-difluoro- ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide + TX (which can be prepared from the method described in WO 2020 / 109391), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide + TX (which can be prepared from the method described in WO 2020 / 109391), N-[2-[2,4-dichloro-phenoxy]phenyl] -3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide + TX, benzothiostrobin + TX, fenamacryl + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, fluopyram + TX, flufenoxadiazam + TX, flutianil + TX, fluopimomide + TX, pyrapropoin + 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-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, Methyltetraprole + TX, 2-(Difluoromethyl)-N-(3-ethyl-1,1-dimethylindan-4-yl)pyridine-3-carboxamide + TX, (fluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidinemethanol + TX, fluoxapiprolin + TX, enoxastrobin + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop-2-enoate + TX, methyl (Z)- 3-Methoxy-2-[2-methyl-5-(4-propyltriazol-2-yl)phenoxy]prop-2-enoate + TX, methyl (Z)-2-[5-(3-isopropylpyrazol-1-yl)-2-methyl-phenoxy]-3-methoxy-prop-2-enoate + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-(3-propylpyrazol-1-yl)phenoxy]prop-2-enoate + TX, methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl) pyrazol-1-yl]phenoxy]prop-2-enoate + TX (these compounds can be prepared from the method described in WO 2020 / 079111), methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate + TX, methyl (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate + TX (these compounds can be prepared from the method described in WO 2020 / 193387),4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propylpyrazole]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-, 1,1-Difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, Trinexapac + TX, Cumoxystrobin + TX, Zongenmycin + TX, Thiodiazole copper + TX, Zincthiazole + TX, Amectotractin + TX, Iprodione + TX, Sebooctylamine + TX; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]oxy]benzonitrile + TX, Trinexapac + TX, Cumoxystrobin + TX, Zongenmycin + TX, Thiodiazole copper + TX, Zincthiazole + TX, Amectotractin + TX, Iprodione + TX, Sebooctylamine + TX; N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-ethyl- N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds can be prepared according to the method described in WO 2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared according to 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 from the method described in WO 2018 / 228896);N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine + TX (these compounds can be prepared by the method described in WO 2019 / 110427); N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3 -carboxamide + TX, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro 8-Fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-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 N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX (these compounds can be prepared by the method described in WO 2017 / 153380);1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline + TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX (these compounds were prepared by the method described in WO 2017 / 025510). 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline + TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline + TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline + TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole + TX (these compounds can be prepared by the method described in WO 2016 / 156085);N-Methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N,2-Dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, N-Ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX phenyl]phenyl]methyl]propanamide + TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea + TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2 ,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one + TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate + TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine + TX. The compounds of this paragraph can be prepared from the methods described in WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 093348 and WO 2017 / 118689;2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound can be prepared from the method described in WO 2017 / 029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol + TX (this compound can be prepared from the method described in WO 2017 / 029179); 3 -[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile + TX (this compound can be prepared from the method described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile + TX (this compound can be prepared from the method described in WO 2016 / 156290); (4-phenoxyphen N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbazole (N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzoate + TX (this compound can be prepared by the method described in WO 2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone + TX (this compound can be prepared by the method described in WO 2011 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbazole (N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzoate + TX) (this compound can be prepared by the method described in WO 2011 / 138281); pyrothioamide + TX; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX (this compound can be prepared from the method described in WO 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX;N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared from the method described in WO 2016 / 202742); 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX (this compound can be prepared from the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methasone + TX, (3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-;

[0033] 1,2,4-oxadiazol-3-yl]phenyl]methasone + TX (these compounds can be prepared from the method described in WO 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX (this compound can be prepared from the method described in WO 2018 / 065414); ethyl 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylate + TX (this compound can be prepared from the method described in WO 2018 / 158365); 2,2-difluoro- N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX, N-[N-methoxy-C-methyl-carbonimidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide + TX (these compounds can be prepared from the method described in WO 2018 / 202428).

[0178] The reference in parentheses after the active ingredient, e.g., [3878-19-1], refers to the Chemical Abstracts Registry number. The above-mentioned mixing partners are publicly known. When the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; Thirteenth Edition; Editor: CDS TomLin; The British Crop Protection Council], they are listed therein under the entry number indicated in parentheses above for the particular compound; for example, the compound "abamectin" is listed under entry number (1). When "[CCN]" is added above to a particular compound, the compound in question is included in the "Compendium of Pesticide Common Names," which is accessible on the Internet [A. Wood; Compendium of Pesticide Common Names, Copyright c 1995-2004]. For example, the compound "acetoprole" is listed under the Internet address http: / / www.alanwood.net / pesticides / acetoprole.html.

[0179] Most of the active ingredients mentioned above are herein referred to as so-called "common names" above, with the relevant "ISO common name" or another "common name" being used in individual cases. If the designation is not a "common name", the nature of the designation used instead is given in parentheses for the particular compound. In that case, the IUPAC name, IUPAC / Chemical Abstracts name, "chemical name", "conventional name", "compound name" or "development code" is used, or if none of these names is a "common name", an "alternative name" is used. "CAS Reg. No" means Chemical Abstracts Registry Number.

[0180] The active ingredient mixtures of compounds of formula (I) are selected from one of the compounds shown in Tables A-1 to A-17 and their subtables (below) or from the compounds selected from P-1.1 to P-1.19 listed in Table T1 (below), preferably in a mixing ratio of 100:1 to 1:6000, in particular 50:1 to 1:50, more in particular 20:1 to 1:20, even more in particular 10:1 to 1:10, very in particular 5:1 and 1:5, with ratios of 2:1 to 1:2 being particularly preferred, and ratios of 4:1 to 2:1 being equally preferred, in particular 1:1, or 5:1, or 5:2, or 5:3, or 5:4. 4, or 4:1, or 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. These mixing ratios are by weight.

[0181] The mixtures described above can be used in methods of controlling pests, which methods include applying a composition comprising the mixture to the pest or its environment, with the exception of methods of treating the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body.

[0182] Mixtures comprising the compounds shown in Tables A-1 to A-17 and their subtables (below) or the compounds P-1.1 to P-1.19 listed in Table T1 (below) and one or more of the active ingredients described above can be applied, for example, in a single "ready-mix" form, as combination spray mixtures composed of separate formulations of a single active ingredient, such as "tank mixes," and in combined use of the single active ingredients when applied sequentially, i.e., one after the other within a reasonably short period of time, such as a few hours or days. The order in which the compounds shown in Tables A-1 to A-17 and their subtables (below) above or the compounds P-1.1 to P-1.19 listed in Table T1 (below) and the active ingredients are applied is not essential to the practice of the invention.

[0183] The compounds of the present invention may also be used in combination with anthelmintic drugs. Such anthelmintics include compounds selected from the macrocyclic lactone class of compounds, such as ivermectin, avermectin, abamectin, emamectin, epinomectin, doramectin, selamectin, moxidectin, nemadectin, and milbemycin derivatives, as described in EP 357460, EP 444964, and EP 594291. Additional anthelmintic drugs include semisynthetic and biosynthetic avermectin / milbemycin derivatives, such as those described in U.S. Pat. No. 5,015,630, WO 9,415,944, and WO 9,522,552. Additional anthelmintic drugs include benzimidazoles, such as albendazole, cambandazole, fenbendazole, flubendazole, mebendazole, oxifendazole, oxibendazole, parbendazole, and other members of this class. Additional anthelmintics include imidazothiazoles and tetrahydropyrimidines such as tetramisole, levamisole, pyrantel pamoate, oxantel, or morantel. Additional anthelmintics include fluoxides such as triclabendazole and clorsulon, and cestosides such as praziquantel and epsiprantel.

[0184] The compounds of the present invention may be used in combination with derivatives and analogues of the paraherquamide / marcfortine class of anthelmintics and antiparasitic oxazolines such as those disclosed in U.S. Pat. No. 5,478,855, U.S. Pat. No. 4,639,771 and German Patent No. 19,520,936.

[0185] The compounds of the invention may be used in combination with derivatives and analogues of the general class of dioxomorpholine antiparasitic agents described in WO 96 / 15121, and with anthelmintic active cyclic depsipeptides such as those described in WO 96 / 11945, WO 93 / 19053, WO 93 / 25543, EP 0 626 375, EP 0 382 173, WO 94 / 19334, EP 0 382 173 and EP 0 503 538.

[0186] The compounds of the invention may be used in combination with other ectoparasiticides, for example fipronil, pyrethroids, organophosphates, insect growth regulators such as lufenuron, ecdysone agonists such as tebufenozide, neonicotinoids such as imidacloprid.

[0187] The compounds of the present invention may be used in combination with terpene alkaloids, such as those described in WO 95 / 19363 or WO 04 / 72086, in particular the compounds disclosed therein.

[0188] Other examples of such biologically active compounds with which the compounds of the present invention may be used in combination include, but are not limited to: Organophosphates: Acephate, Azamethiphos, Azinphos-ethyl, Azinphos-methyl, Bromophos, Bromophos-ethyl, Cadusafos, Chlorethoxyphos, Chlorpyrifos, Chlorfenvinphos, Chlormephos, Demeton, Demeton-S-methyl, Demeton-S-methylsulfone, Dialifos, Diazinon, Dichlorvos, Dicrotophos, Dimethoate, Disulfoton, Ethion, Ethoprophos, Etrimphos, Fanfur, Fenamiphos, Fenitrothion, Fensulfothion, Fenthion, Flupyrazophos, Fonophos, Formothion, Fosthiazate, Heptenophos, Isazophos, Isothioate, Isoxathio phenthoate, malathion, methacrifos, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, paraoxon, parathion, parathion-methyl, phenthoate, phosalone, phospholane, phosphocarb, phosmet, phosphamidon, phorate, phoxim, pirimiphos, pirimiphos-methyl, profenofos, propafos, proethamfos, prothiofos, pyraclofos, pyridapenthione, quinalphos, sulprofos, temephos, terbufos, tebupirimphos, tetrachlorvinphos, thimeton, triazophos, trichlorfon, vamidothion.

[0189] Carbamates: alanycarb, aldicarb, 2-sec-butylphenyl methylcarbamate, benfuracarb, carbaryl, carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801, isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-cumenylbutyryl (methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, UC-51717.

[0190] Pyrethroids: acrinatin, allethrin, alphamethrin, 5-benzyl-3-furylmethyl (E)-(1R)-cis-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, bifenthrin, β-cyfluthrin, cyfluthrin, α-cypermethrin, β-cypermethrin, bioallethrin, bioallethrin ((S)-cyclopentyl isomer), bioresmethrin, bifenthrin, NCI-85193, cycloprothrin, cyhalothrin , cycythrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (D isomer), imiprothrin, cyhalothrin, λ-cyhalothrin, permethrin, fenothrin, prallethrin, pyrethrins (natural products), resmethrin, tetramethrin, transfluthrin, θ-cypermethrin, silafluofen, t-fluvalinate, tefluthrin, tralomethrin, ζ-cypermethrin.

[0191] Arthropod growth regulators: a) Chitin synthesis inhibitors: Benzoylureas: Chlorfluazuron, Diflubenzuron, Fluazuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novaluron, Teflubenzuron, Triflumuron, Buprofezin, Diofenolan, Hexythiazox, Etoxazole, Chlorfentadine; b) Ecdysone antagonists: Halofenozide, Methoxyfenozide, Tebufenozide; c) Juvenoids: Pyriproxyfen, Methoprene (including S-Methoprene), Fenoxycarb; d) Lipid biosynthesis inhibitors: Spirodiclofen.

[0192] Other antiparasitic drugs: acequinocyl, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis thuringiensis), bensultap, bifenazate, binapacryl, bromopropylate, BTG-504, BTG-505, camphechlor, cartap, chlorobenzilate, chlordimeform, chlorfenapyr, chromafenozide, clothianidine, cyromazine, diacloridene, diafenthiuron, DBI-3204, dinactin, dihydroxymethyldihydroxypyrrolidine, dinobuton, dinocap, endosulfan, ethiprole, etofenprox, fenazaquin, flumite, MTI-800, fenpyroximate, fluacrypyrim, flubenzimine, flubrocythrinate, flufenzin, flufenprox, fluproxifen, halofenprox ofenprox, hydramethylnon, IKI-220, Kanemite, NC-196, Niemgard, Nidinolterfuran, Nitenpyram, SD-35651, WL-108477, pyridalyl, propargite, protrifenbut, pymethrozine, pyridaben, pyrimidifen, NC-1111, R-195, RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601, silafluofen, cyromazine, spinosad, tebufenpyrad, tetradifon, tetranactin, thiacloprid, thiocyclam, thiamethoxam, tolfenpyrad, triazamate, triethoxyspinosyn, trinactin, belbutin, Bertarec, YI-5301.

[0193] Biological agents: Bacillus thuringiensis ssp aizawai, kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, entomopathogenic bacteria, viruses and fungi.

[0194] Fungicides: chlortetracycline, oxytetracycline, streptomycin.

[0195] Other biological agents: enrofloxacin, febantel, penetamate, moroxicam, cephalexin, kanamycin, pimobendan, clenbuterol, omeprazole, tiamulin, benazepril, pyriprole, cefquinome, florfenicol, buserelin, cefovecin, tulathromycin, ceftiour, carprofen, metaflumizone, praziquarantel, triclabendazole.

[0196] The compositions according to the invention may also comprise further solid or liquid auxiliaries, such as, for example, stabilizers, such as unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soybean oil), antifoaming agents, for example silicone oils, preservatives, viscosity regulators, binders and / or adhesives, fertilizers or other active ingredients for achieving a particular effect, such as, for example, fungicides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0197] The compositions according to the invention are prepared in a manner known per se, for example by powdering, screening and / or compressing the solid active ingredient in the absence of auxiliaries, and by intimately mixing and / or powdering the active ingredient with one or more auxiliaries in the presence of at least one auxiliary agent. These preparation processes for the compositions and the use of compound (I) for preparing these compositions are also the subject of the present invention.

[0198] Another aspect of the present invention relates to the use of a compound of formula (I) or a preferred individual compound as defined herein, a composition comprising at least one compound of formula (I) or at least one preferred individual compound as defined above, or a fungicidal or insecticidal mixture comprising at least one compound of formula (I) or at least one preferred individual compound as defined above, in admixture with other fungicides or insecticides as defined above, for controlling or preventing infestation on plants, e.g. useful plants such as crop plants, their propagation material, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living material by phytopathogenic microorganisms, e.g. insects or preferably fungal organisms.

[0199] A further aspect of the present invention relates to a method for controlling or preventing infestation on plants, e.g. useful plants such as crop plants, their propagation material, e.g. seeds, harvested crops, e.g. harvested food crops, or non-living material by plant pathogenic or spoilage microorganisms or organisms that are potentially harmful to humans, such as insects or especially fungal organisms, which method comprises the step of applying a compound of formula (I) or a preferred individual compound as defined above as an active ingredient to the plant, to parts of the plant or its habitat, to its propagation material or to any part of the non-living material.

[0200] Control or prevention means reducing infestation by plant pathogenic or spoilage microorganisms or organisms that are potentially harmful to humans, particularly fungal organisms, to a level that demonstrates improvement.

[0201] A preferred method for controlling or preventing infestation of crop plants by phytopathogenic microorganisms, especially fungal organisms, or insects, which involves the application of a compound of formula (I) or an agrochemical composition containing at least one of said compounds, is foliar treatment. The frequency and amount of application will depend on the risk of infestation by the corresponding pathogen or insect. However, the compound of formula (I) can also be introduced into the plant through the roots via the soil (systemic action) by drenching the plant habitat with a liquid formulation or by applying the compound to the soil in solid form, for example, in granular form (soil application). In the case of rice crops, such granules can be applied to flooded rice fields. The compound of formula (I) can also be applied to seeds (coating) by impregnating the seeds or tubers with a liquid formulation of the fungicide or coating them with a solid formulation.

[0202] Formulations, e.g., compositions containing a compound of formula (I) and, optionally, a solid or liquid adjuvant or monomer that encapsulates the compound of formula (I), can be prepared in a known manner, typically by homogeneously mixing and / or grinding the compounds together with extenders, e.g., solvents, solid carriers and, optionally, surface-active compounds (surfactants).

[0203] Advantageous application rates are usually 5g to 2kg of active ingredient (ai) per hectare (ha), preferably 10g to 1kg ai / ha, most preferably 20g to 600g ai / ha. When used as a seed drench, a convenient dosage is 10mg to 1g of active substance per kg of seed.

[0204] When the combinations of the invention are used for seed treatment, an amount of 0.001 to 50 g of a compound of formula (I) per kg of seed, preferably 0.01 to 10 g per kg of seed, will generally be sufficient.

[0205] Preferably, the composition comprising the compound of formula (I) according to the present invention is applied prophylactically, meaning before the onset of disease, or therapeutically, meaning after the onset of disease.

[0206] The compositions of the present invention may be in any conventional form, such as a two-part system, dry seed treatment powder (DS), seed treatment emulsion (ES), seed treatment flowable concentrate (FS), seed treatment solution (LS), seed treatment water dispersible powder (WS), seed treatment capsule suspension (CF), seed treatment gel (GF), emulsion concentrate (EC), suspension concentrate (SC), suspoemulsion (SE), capsule suspension (CS), water dispersible granules (WG), emulsifiable granules, etc. They may be employed in the form of granules (EG), emulsions, water-in-oil (EO), emulsions, oil-in-water (EW), microemulsions (ME), oil dispersions (OD), oil-miscible fluids (OF), oil-miscible liquids (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume liquids (UL), technical concentrates (TK), dispersible concentrates (DC), wettable powders (WP) or any technically desirable formulation in combination with agriculturally acceptable adjuvants.

[0207] Such compositions can be prepared in a conventional manner, for example, by mixing the active ingredient with suitable inert ingredients (diluents, solvents, fillers, and optionally other ingredients such as surfactants, biocides, antifreeze agents, spreading agents, thickeners, and compounds providing adjuvant activity). Conventional slow-release formulations can also be employed when long-lasting efficacy is intended. In particular, formulations applied in spray form, such as water-dispersible concentrates (e.g., EC, SC, DC, OD, SE, EW, EO, etc.), wettable powders, and granules, can contain surfactants such as wetting and dispersing agents and other compounds providing adjuvant effects, such as, for example, condensates of formaldehyde and naphthalenesulfonates, alkylarylsulfonates, ligninsulfonates, fatty alkyl sulfates, and ethoxylated alkylphenols and ethoxylated fatty alcohols.

[0208] The seed dressing formulation is applied to seeds in a manner known per se, and utilizes the combination and diluent of the present invention in a suitable seed dressing formulation form, such as an aqueous suspension or a dry powder form with good adhesion to the seeds. Such seed dressing formulations are known in the art. The seed dressing formulation may contain a single active ingredient or a combination of active ingredients in encapsulated form, for example, as slow-release capsules or microcapsules.

[0209] Typically, the formulations contain 0.01 to 90% by weight of an active agent, 0 to 20% by weight of an agriculturally acceptable surfactant, and 10 to 99.99% by weight of solid or liquid inert compounding agents and adjuvants. The active agent is composed of at least a compound of formula (I), optionally together with other active agents, particularly fungicides or preservatives. Concentrated forms of the compositions generally contain about 2 to 80% by weight, preferably about 5 to 70% by weight, of the active agent. Application forms of the formulations may contain, for example, 0.01 to 20% by weight, preferably 0.01 to 5% by weight, of the active agent. While commercial products are preferably formulated as concentrates, end users will typically utilize diluted formulations.

[0210] Although it is preferred to formulate commercial products as concentrates, end users will typically dilute the formulations before use.

[0211] The compounds listed in the following Tables A-1 to A-17 can be prepared according to the above methods. The following examples are intended to illustrate the present invention and to show preferred compounds of formula (Ia). [ka]

[0212] Table A: Formula (Ia) (wherein, R 1 , R 7 , R 8 and R 9 is defined in Tables A-1 to A-17, and NH-L 1 -G is as defined in Table Z below

[0213] [Table 4]

[0214] Table A-1: Formula (Ia-A-1) (where R 1 , R 7 , R 8 and R 9 is defined in Tables A-1a to A-1j, and NH-L 1 -G is as defined in Table Z above: [ka] Ia-A-1

[0215] Table A-1a: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 8 and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0216] Table A-1b: This subtable is 1 is 3-(trifluoromethyl)phenyl, and R 8 and R 9 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-1b.01 to A-1b.23 of formula (Ia-A-1), wherein G is as defined in Table Z above.

[0217] Table A-1c: This subtable is 1 is 3-ethynylphenyl, and R 8 and R 9 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-1c.01 to A-1c.23 of formula (Ia-A-1), wherein G is as defined in Table Z above.

[0218] Table A-1d: This subtable is 1 is 3-chlorophenyl, and R8 and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0219] Table A-1e: This subtable is 1 is 5-cyanopyridin-3-yl, and R 8 and R 9 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-1e.01 to A-1e.23 of formula (Ia-A-1), wherein G is as defined in Table Z above.

[0220] Table A-1f: This subtable is 1 is 3-cyclopropylphenyl, and R 8 and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0221] Table A-1g: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 8 is methyl and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0222] Table A-1h: This subtable is 1 is 3-(trifluoromethyl)phenyl, and R 8 is chloro and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0223] Table A-1i: This subtable is 1is 5-cyanopyridin-3-yl, and R 8 is hydrogen and R 9 is chloro and the substituent NH-L 1 - Provided are 23 compounds A-1i.01 to A-1i.23 of formula (Ia-A-1), wherein G is as defined in Table Z above.

[0224] Table A-1j: This subtable is 1 is 3-cyclopropylphenyl, and R 8 is methyl and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0225] Table A-2: Formula (Ia-A-2) (where R 1 , R 7 , R 8 and R 9 is defined in Tables A-2a to A-2k and NH-L1-G is as defined in Table Z above: [ka] Ia-A-2

[0226] Table A-2a: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 7 and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0227] As an example, compound A-2a.01 is: [ka]

[0228] Table A-2b: This subtable is 1is 3-(trifluoromethyl)phenyl, and R 7 and R 9 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-2b.01 to A-2b.23 of formula (Ia-A-2), wherein G is as defined in Table Z above.

[0229] Table A-2c: This subtable is 1 is 3-ethynylphenyl, and R 7 and R 9 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-2c.01 to A-2c.23 of formula (Ia-A-2), wherein G is as defined in Table Z above.

[0230] Table A-2d: This subtable is 1 is 3-chlorophenyl, and R 7 and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0231] Table A-2e: This subtable is 1 is 5-cyanopyridin-3-yl, and R 7 and R 9 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-2e.01 to A-2e.23 of formula (Ia-A-2), wherein G is as defined in Table Z above.

[0232] Table A-2f: This subtable is 1 is 5-(cyclopropyl)pyridin-3-yl, and R 7 and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0233] Table A-2g: This subtable is 1is 3-cyclopropylphenyl, and R 7 and R 9 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-2g.01 to A-2g.23 of formula (Ia-A-2), wherein G is as defined in Table Z above.

[0234] Table A-2h: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 7 is hydrogen and R 9 is methyl and the substituent NH-L 1 -G is as defined in Table Z above.

[0235] Table A-2i: This subtable is 1 is 3-(trifluoromethyl)phenyl, and R 7 is hydrogen and R 9 is methyl and the substituent NH-L 1 -G is as defined in Table Z above.

[0236] Table A-2j: This subtable is 1 is 5-cyanopyridin-3-yl, and R 7 is hydrogen and R 9 is methyl and the substituent NH-L 1 -G is as defined in Table Z above.

[0237] Table A-2k: This subtable is 1 is 3-cyclopropylphenyl, and R 7 is hydrogen and R 9 is methyl and the substituent NH-L 1 -G is as defined in Table Z above.

[0238] Table A-3: Formula (Ia-A-3) (where R 1 , R 7 , R 8 and R 9 is defined in Tables A-3a to A-3k, and NH-L 1 -G is as defined in Table Z above: [ka] Ia-A-3

[0239] Table A-3a: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 7 and R 8 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0240] Table A-3b: This subtable is 1 is 3-(trifluoromethyl)phenyl, and R 7 and R 8 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-3b.01 to A-3b.23 of formula (Ia-A-3), wherein G is as defined in Table Z above.

[0241] Table A-3c: This subtable is 1 is 3-ethynylphenyl, and R 7 and R 8 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0242] Table A-3d: This subtable is 1 is 3-chlorophenyl, and R 7 and R 8 is hydrogen and the substituent NH-L 1-G is as defined in Table Z above.

[0243] Table A-3e: This subtable is 1 is 5-cyanopyridin-3-yl, and R 7 and R 8 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-3e.01 to A-3e.23 of formula (Ia-A-3), wherein G is as defined in Table Z above.

[0244] Table A-3f: This subtable is 1 is 5-(cyclopropyl)pyridin-3-yl, and R 7 and R 8 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0245] Table A-3g: This subtable is 1 is 3-cyclopropylphenyl, and R 7 and R 8 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0246] Table A-3h: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 7 is methyl and R 8 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0247] Table A-3i: This subtable is 1 is 3-(trifluoromethyl)phenyl, and R 7 is chloro and R 8is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0248] As an example, compound A-3i-15 is: [ka]

[0249] Table A-3j: This subtable is 1 is 5-cyanopyridin-3-yl, and R 7 is hydrogen and R 8 is chloro and the substituent NH-L 1 -G is as defined in Table Z above.

[0250] Table A-3k: This subtable is 1 is 3-cyclopropylphenyl, and R 7 is hydrogen and R 8 is fluoro and the substituent NH-L 1 -G is as defined in Table Z above.

[0251] Table A-4: Formula (Ia-A-4) (where R 1 , R 7 , R 8 and R 9 is defined in Tables A-4a to A-4d, and NH-L 1 -G is as defined in Table Z above: [ka] Ia-A-4

[0252] Table A-4a: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 9 is hydrogen and the substituent NH-L1 -G is as defined in Table Z above.

[0253] Table A-4b: This subtable is 1 is 3-(trifluoromethyl)phenyl, and R 9 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-4b.01 to A-4b.23 of formula (Ia-A-4), wherein G is as defined in Table Z above.

[0254] Table A-4c: This subtable is 1 is 5-cyanopyridin-3-yl, and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0255] Table A-4d: This subtable is 1 is 3-cyclopropylphenyl, and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0256] Table A-5: Formula (Ia-A-5) (where R 1 , R 7 , R 8 and R 9 is defined in Tables A-5a to A-5d, and NH-L 1 -G is as defined in Table Z above: [ka] Ia-A-5

[0257] Table A-5a: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 8 is hydrogen and the substituent NH-L 1-G is as defined in Table Z above.

[0258] Table A-5b: This subtable is 1 is 3-(trifluoromethyl)phenyl, and R 8 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0259] Table A-5c: This subtable is 1 is 5-(cyclopropyl)pyridin-3-yl, and R 8 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0260] Table A-5d: This subtable is 1 is 3-cyclopropylphenyl, and R 8 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0261] Table A-6: Formula (Ia-A-6) (where R 1 , R 7 , R 8 and R 9 is defined in Tables A-6a to A-6c, and NH-L 1 -G is as defined in Table Z above: [ka] Ia-A-6

[0262] Table A-6a: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 7 is hydrogen and the substituent NH-L 1-G is as defined in Table Z above.

[0263] Table A-6b: This subtable is 1 is 3-(trifluoromethyl)phenyl, and R 7 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0264] Table A-6c: This subtable is 1 is 3-cyclopropylphenyl, and R 7 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0265] As an example, compound A-6c.02 is: [ka]

[0266] Table A-7: Formula (Ia-A-7) (where R 1 , R 7 , R 8 and R 9 is defined in Tables A-7a to A-7f, and NH-L 1 -G is as defined in Table Z above: [ka] Ia-A-7

[0267] Table A-7a: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 8 and R 9 is hydrogen and the substituent NH-L 1-G is as defined in Table Z above.

[0268] Table A-7b: This subtable is 1 is 3-(trifluoromethyl)phenyl, and R 8 and R 9 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-7b.01 to A-7b.23 of formula (Ia-A-7), wherein G is as defined in Table Z above.

[0269] Table A-7c: This subtable is 1 is 3-cyclopropylphenyl, and R 8 and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0270] Table A-7d: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 8 is chloro and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0271] As an example, compound A-7d.03 is: [ka]

[0272] Table A-7e: This subtable is 1 is 3-(trifluoromethyl)phenyl, and R 8 is hydrogen and R 9 is chloro and the substituent NH-L 1- Provided are 23 compounds A-7e.01 to A-7e.23 of formula (Ia-A-7), wherein G is as defined in Table Z above.

[0273] Table A-7f: This subtable is 1 is 3-cyclopropylphenyl, and R 8 is methyl and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0274] Table A-8: Formula (Ia-A-8) (where R 1 , R 7 , R 8 and R 9 is defined in Tables A-8a to A-8h, and NH-L 1 -G is as defined in Table Z above: [ka] Ia-A-8

[0275] Table A-8a: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 7 and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0276] Table A-8b: This subtable is 1 is 3-(trifluoromethyl)phenyl, and R 7 and R 9 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-8b.01 to A-8b.23 of formula (Ia-A-8), wherein G is as defined in Table Z above.

[0277] Table A-8c: This subtable is 1is 5-cyanopyridin-3-yl, and R 7 and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0278] Table A-8d: This subtable is 1 is 5-(cyclopropyl)pyridin-3-yl, and R 7 and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0279] Table A-8e: This subtable is 1 is 3-cyclopropylphenyl, and R 7 and R 9 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-8e.01 to A-8e.23 of formula (Ia-A-8), wherein G is as defined in Table Z above.

[0280] Table A-8f: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 7 is hydrogen and R 9 is methyl and the substituent NH-L 1 -G is as defined in Table Z above.

[0281] Table A-8g: This subtable is 1 is 3-(trifluoromethyl)phenyl, and R 7 is hydrogen and R 9 is methyl and the substituent NH-L 1 - Provided are 23 compounds A-8g.01 to A-8g.23 of formula (Ia-A-8), wherein G is as defined in Table Z above.

[0282] Table A-8h: This subtable is 1 is 3-cyclopropylphenyl, and R 7 is hydrogen and R 9 is methyl and the substituent NH-L 1 - Provided are 23 compounds A-8h.01 to A-8h.23 of formula (Ia-A-8), wherein G is as defined in Table Z above.

[0283] As an example, compound A-8h.22 is: [ka]

[0284] Table A-9: Formula (Ia-A-9) (where R 1 , R 7 , R 8 and R 9 is defined in Tables A-9a to A-9h, and NH-L 1 -G is as defined in Table Z above: [ka] Ia-A-9

[0285] Table A-9a: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 7 and R 8 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0286] Table A-9b: This subtable is for R 1 is 3-(trifluoromethyl)phenyl, and R 7 and R 8 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0287] Table A-9c: This subtable is 1 is 5-cyanopyridin-3-yl, and R 7 and R 8 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0288] As an example, compound A-9c.19 is: [ka]

[0289] Table A-9d: This subtable is 1 is 3-cyclopropylphenyl, and R 7 and R 8 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0290] Table A-9e: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 7 is chloro and R 8 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-9e.01 to A-9e.23 of formula (Ia-A-9), wherein G is as defined in Table Z above.

[0291] Table A-9f: This subtable is 1 is 3-(trifluoromethyl)phenyl, and R 7 is hydrogen and R 8 is chloro and the substituent NH-L 1 -G is as defined in Table Z above.

[0292] Table A-9g: This subtable is 1 is 5-cyanopyridin-3-yl, and R7 is hydrogen and R 8 is fluoro and the substituent NH-L 1 - Provided are 23 compounds A-9g.01 to A-9g.23 of formula (Ia-A-9), wherein G is as defined in Table Z above.

[0293] Table A-9h: This subtable is 1 is 3-cyclopropylphenyl, and R 7 is hydrogen and R 8 is methyl and the substituent NH-L 1 -G is as defined in Table Z above.

[0294] Table A-10: Formula (Ia-A-10) (where R 1 , R 7 , R 8 and R 9 is defined in Tables A-10a to A-10c, and NH-L 1 -G is as defined in Table Z above: [ka] Ia-A-10

[0295] Table A-10a: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0296] Table A-10b: This subtable is 1 is 3-(trifluoromethyl)phenyl, and R 9 is hydrogen and the substituent NH-L 1 - 23 compounds A-10b.01 to A-10b.23 of formula (Ia-A-10), wherein G is as defined in Table Z above, are provided.

[0297] As an example, compound A-10b.21 is: [ka]

[0298] Table A-10c: This subtable is 1 is 3-cyclopropylphenyl, and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0299] Table A-11: Formula (Ia-A-11-1) (where R 1 , R 7 , R 8 and R 9 is defined in Tables A-11a to A-11c, and NH-L 1 -G is as defined in Table Z above: [ka] Ia-A-11

[0300] Table A-11a: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 7 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-11a.01 to A-11a.23 of formula (Ia-A-11), wherein G is as defined in Table Z above.

[0301] Table A-11b: This subtable is 1 is 3-(trifluoromethoxy)phenyl, and R 7 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-11b.01 to A-11b.23 of formula (Ia-A-11), wherein G is as defined in Table Z above.

[0302] Table A-11c: This subtable is 1is 3-cyclopropylphenyl, and R 7 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-11c.01 to A-11c.23 of formula (Ia-A-11), wherein G is as defined in Table Z above.

[0303] Table A-12: Formula (Ia-A-12) (where R 1 , R 7 , R 8 and R 9 is defined in Tables A-12a to A-12c, and NH-L 1 -G is as defined in Table Z above: [ka] Ia-A-12

[0304] Table A-12a: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 8 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0305] Table A-12b: This subtable is 1 is 3-(trifluoromethyl)phenyl, and R 8 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-12b.01 to A-12b.23 of formula (Ia-A-12), wherein G is as defined in Table Z above.

[0306] Table A-12c: This subtable is 1 is 3-cyclopropylphenyl, and R 8 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0307] Table A-13: Formula (Ia-A-13) (where R 1 , R 7 , R 8 and R 9 is defined in Table A-13a, and NH-L 1 -G is as defined in Table Z above: [ka] Ia-A-13

[0308] Table A-13a: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 8 and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0309] Table A-14: Formula (Ia-A-14) (where R 1 , R 7 , R 8 and R 9 is defined in Tables A-14a to A-14f, and NH-L 1 -G is as defined in Table Z above: [ka] Ia-A-14

[0310] Table A-14a: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 7 and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0311] Table A-14b: This subtable is 1 is 3-(trifluoromethyl)phenyl, and R 7 and R 9is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-14b.01 to A-14b.23 of formula (Ia-A-14), wherein G is as defined in Table Z above.

[0312] Table A-14c: This subtable is 1 is 5-cyanopyridin-3-yl, and R 7 and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0313] Table A-14d: This subtable is 1 is 3-cyclopropylphenyl, and R 7 and R 9 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0314] Table A-14e: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 7 is hydrogen and R 9 is methyl and the substituent NH-L 1 - Provided are 23 compounds A-14e.01 to A-14e.23 of formula (Ia-A-14), wherein G is as defined in Table Z above.

[0315] Table A-14f: This subtable is 1 is 3-(trifluoromethyl)phenyl, and R 7 is hydrogen and R 9 is methyl and the substituent NH-L 1 - Provided are 23 compounds A-14f.01 to A-14f.23 of formula (Ia-A-14), wherein G is as defined in Table Z above.

[0316] Table A-15: Formula (Ia-A-15) (where R 1 , R7 , R 8 and R 9 is defined in Tables A-15a to A-15f, and NH-L 1 -G is as defined in Table Z above: [ka] Ia-A-15

[0317] Table A-15a: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 7 and R 8 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0318] Table A-15b: This subtable is 1 is 3-(trifluoromethyl)phenyl, and R 7 and R 8 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0319] Table A-15c: This subtable is 1 is 5-cyanopyridin-3-yl, and R 7 and R 8 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0320] Table A-15d: This subtable is for R 1 is 5-(cyclopropyl)pyridin-3-yl, and R 7 and R 8 is hydrogen and the substituent NH-L 1-G is as defined in Table Z above, and 23 compounds A-15d.01 to A-15d.23 of formula (Ia-A-15) are provided.

[0321] Table A-15e: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 7 is chloro and R 8 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-15e.01 to A-15e.23 of formula (Ia-A-15), wherein G is as defined in Table Z above.

[0322] Table A-15f: This subtable is for R 1 is 3-cyclopropylphenyl, and R 7 is methyl and R 8 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0323] Table A-16: Formula (Ia-A-16) (where R 1 , R 7 , R 8 and R 9 is defined in Tables A-16a to A-16e, and NH-L 1 -G is as defined in Table Z above: [ka] Ia-A-16

[0324] Table A-16a: This subtable is 1 is 3-cyclopropyl-2-fluorophenyl, and R 7 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0325] Table A-16b: This subtable is 1is 3-(trifluoromethyl)phenyl, and R 7 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-16b.01 to A-16b.23 of formula (Ia-A-16), wherein G is as defined in Table Z above.

[0326] Table A-16c: This subtable is 1 is 5-cyanopyridin-3-yl, and R 7 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0327] Table A-16d: This subtable is 1 is 5-(cyclopropyl)pyridin-3-yl, and R 7 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0328] Table A-16e: This subtable is 1 is 3-cyclopropylphenyl, and R 7 is hydrogen and the substituent NH-L 1 - Provided are 23 compounds A-16e.01 to A-16e.23 of formula (Ia-A-16), wherein G is as defined in Table Z above.

[0329] Table A-17: Formula (Ia-A-17) (where R 1 , R 7 , R 8 and R 9 is defined in Tables A-17a to A-17c, and NH-L 1 -G is as defined in Table Z above: [ka] Ia-A-17

[0330] Table A-17a: This subtable is1 is 3-cyclopropyl-2-fluorophenyl, and R 8 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0331] Table A-17b: This subtable is 1 is 3-(trifluoromethyl)phenyl, and R 8 is hydrogen and the substituent NH-L 1 - 23 compounds A-17b.01 to A-17b.23 of formula (Ia-A-17), wherein G is as defined in Table Z above, are provided.

[0332] Table A-17c: This subtable is 1 is 3-cyclopropylphenyl, and R 8 is hydrogen and the substituent NH-L 1 -G is as defined in Table Z above.

[0333] Certain intermediate compounds of formulae (II), (V), (VI) and (XVIII) are also provided, some of which are novel, for example: -R 1 and compounds of formula (II) wherein A is as defined in any one of Tables A-1 to A-17 and their subtables: [ka] More specifically, the compounds of formulae (II-A-1i) to (II-A-17i) shown in Table II below (wherein R 1 , R 7 , R 8 and R 9 is as defined in any one of Tables A-1 to A-17 and their respective subtables).

[0334] [Table 5]

[0335] X 2 is a suitable leaving group such as fluoro, chloro, bromo, iodo, BF3K, B(OH)2 or B(pinacol), A is as defined in any one of Tables A-1 to A-17 and their respective subtables, and NH-L 1 - a compound of formula (V) wherein G is as defined in Table Z: [ka] More specifically, the compounds of formulae (VA-1i) to (VA-17i) shown in Table V below (wherein X 2 is a suitable leaving group such as fluoro, chloro, bromo, iodo, BF3K, B(OH)2, or B(pinacol), and R 7 , R 8 and R 9 is as defined in any one of Tables A-1 to A-17 and their respective subtables, and NH-L 1 -G is as defined in Table Z).

[0336] [Table 6]

[0337] X 1 is C1-C4-alkoxy, and X 2 Compounds of formula (VI) wherein is a suitable leaving group such as fluoro, chloro, bromo, iodo, BF3K, B(OH)2 or B(pinacol), and A is as defined in any one of Tables A-1 to A-17 and their respective subtables: [ka] More specifically, the compounds of formulae (VI-A-1i) to (VI-A-17i) shown in Table VI below (wherein X 1 is C1-C4-alkoxy such as methoxy or ethoxy, and X 2is a suitable leaving group such as fluoro, chloro, bromo, iodo, BF3K, B(OH)2, or B(pinacol), and R 7 , R 8 and R 9 is as defined in any one of Tables A-1 to A-17 and their respective subtables).

[0338] [Table 7]

[0339] X 6 is chloro, bromo, iodo, trifluoromethanesulfonyl-O-, and R 1 and compounds of formula (XVIII) wherein A is as defined in any one of Tables A-1 to A-17 and their subtables: [ka] More specifically, the compounds of formulae (XVIII-A-1i) to (XVIII-A-17i) shown in Table XVIII below (wherein X 6 is chloro, bromo, iodo, trifluoromethanesulfonyl-O-, and R 1 , R 7 , R 8 and R 9 is as defined in any one of Tables A-1 to A-17 and their respective subtables).

[0340] [Table 8]

[0341] Thus, in a further aspect, the present invention provides compounds of formula (II), (V), (VI) and (XVIII), where applicable, R 1 , R 2 , R 3 , R 4 , R 5 , L 1 , G and A(R 7 , R 8 and R 9) is as defined for formula (I) of the first aspect, and X 2 is a suitable leaving group such as fluoro, chloro, bromo, iodo, BF3K, B(OH)2, or B(pinacol). X 3 is OH or C1-C4-alkoxy, and X 6 is chloro, bromo, iodo, trifluoromethanesulfonyl-O-. Furthermore, the corresponding embodiments exemplified for formula (I) also apply to compounds of formulas (II), (V), (VI) and (XVIII). [Example]

[0342] The following examples serve to illustrate the invention and are not meant to limit it in any way.

[0343] The compounds of the present invention can be distinguished from known compounds by their higher efficacy at low application rates, which can be verified by one skilled in the art using the experimental procedures outlined in the Examples and using lower application rates, such as 60 ppm, 20 ppm or 2 ppm, if necessary.

[0344] The compounds of formula (I) may have a number of benefits, including, inter alia, advantageous levels of biological activity for the protection of plants against diseases caused by fungi or superior properties for use as active pesticide ingredients (e.g., high biological activity, advantageous spectrum of activity, high safety profile (including improved crop tolerance), improved physicochemical properties or high biodegradability).

[0345] Throughout this specification, temperatures are given in degrees Celsius (°C) and "mp" means melting point. LC / MS, or LC-MS, or LCMS means liquid chromatography mass spectroscopy, and a description of the equipment and methods follows.

[0346] 1 H NMR and 19 F NMR measurements were recorded on a Bruker 400 MHz spectrometer, and chemical shifts were expressed in terms of TMS ( 1 H) and CFCl3 (19 F) are shown in ppm relative to standards. Spectra were measured in deuterated solvents as indicated. Compounds were characterized using one of the following LCMS methods. The characteristic LCMS values obtained for each compound are the retention time ("Rt", recorded in minutes) and the observed molecular ion (M+H). + or (MH) - It was.

[0347] Method A: Spectra were recorded on an Agilent Technologies 6410 triple quadrupole mass spectrometer equipped with an electrospray source (positive and negative polarity switch, capillary (kV) 4.00, scan type MS2 scan, fragmentor (V) 100.00, gas temperature (°C) 350, gas flow rate (L / min) 11, nebulizer gas (psi) 45, mass range: 110 to 1000 Da) and an Agilent 1200 series HPLC: DAD wavelength range: 210 to 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.

[0348] Gradient conditions: Solvent A: Water with 0.1% formic acid:Acetonitrile:95:5 v / v Solvent B: acetonitrile containing 0.1% formic acid

[0349] [Table 9]

[0350] If desired, enantiomerically pure final compounds can be obtained from racemic material, if desired, via standard physical separation techniques such as reverse-phase chiral chromatography or via stereoselective synthesis techniques, for example, by using chiral starting materials.

[0351] Method B: Spectra were recorded on an Agilent Technologies 6410 triple quadrupole mass spectrometer equipped with an electrospray source (positive and negative polarity switch, capillary (kV) 7.00, scan type MS2 scan, fragmentor (V) 120.00, gas temperature (°C) 350, gas flow rate (L / min) 11, nebulizer gas (psi) 40, mass range: 110 to 650 Da) and an Agilent 1200 series HPLC: 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.

[0352] Gradient conditions: Solvent A: Water with 0.1% formic acid:Acetonitrile:95:5 v / v Solvent B: acetonitrile containing 0.1% formic acid

[0353] [Table 10]

[0354] If desired, enantiomerically pure final compounds can be obtained from racemic material, if desired, via standard physical separation techniques such as reverse-phase chiral chromatography or via stereoselective synthesis techniques, for example, by using chiral starting materials.

[0355] Method C: Spectra were recorded on a Waters 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 (L / Hr) 1000, desolvation temperature (°C) 600, gas flow at cone (L / Hr) 50, mass range: 110 to 850 Da) and HPLC: DAD wavelength range: 230 to 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.

[0356] Gradient conditions: Solvent A: Water with 0.1% formic acid:Acetonitrile:95:5 v / v Solvent B: acetonitrile containing 0.05% formic acid

[0357] [Table 11]

[0358] If desired, enantiomerically pure final compounds can be obtained from racemic material, if desired, via standard physical separation techniques such as reverse-phase chiral chromatography or via stereoselective synthesis techniques, for example, by using chiral starting materials.

[0359] Method D: Spectra were recorded on a Waters Acquity SDQ mass spectrometer equipped with an electrospray source (positive and negative polarity switch, capillary (kV) 3.0, full scan, cone voltage (V) 41.0, source temperature (°C) 150, desolvation temperature 500°C, gas flow rate at cone (L / Hr) 50, mass range: 110 to 800 Da) and HPLC "H" class: DAD wavelength range: 210 to 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.

[0360] Gradient conditions: Solvent A: Water with 0.1% formic acid:Acetonitrile:95:5 v / v Solvent B: acetonitrile containing 0.05% formic acid

[0361] [Table 12]

[0362] Method E: Spectra were recorded on a Waters mass spectrometer (QDa) (polarity: positive and negative ions), detector gain: 1, temperature probe: 500 °C, cone voltage: 10 V, ESI capillary positive voltage: 0.8–negative voltage: 0.8, sampling frequency: 5 Hz, mass range: 100–850 Da.

[0363] Chiral column (for analysis) SFC: Waters Acquity UPC 2 / QDa PDA Detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® AY, 3 μm, 0.3 cm x 10 cm, 40°C Mobile phase: A: CO2 B: IPA Isocratic: 25% B ABPR: 1800 psi Flow rate: 2.0 ml / min Detection: 240 nm Sample concentration in MeOH / ACN: 1 mg / mL Injection: 2 μL

[0364] Formulation example The following examples serve to illustrate the invention.

[0365] [Table 13]

[0366] The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill to give wettable powders which can be diluted with water to give a suspension of the desired concentration.

[0367] [Table 14]

[0368] The active ingredient is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to obtain a powder which can be used directly for seed treatment.

[0369] [Table 15]

[0370] Emulsions of any required dilution that can be used for plant protection can be obtained from this concentrate by dilution with water.

[0371] [Table 16]

[0372] Ready-to-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used as dry dressings for seeds.

[0373] [Table 17]

[0374] The active ingredient is mixed and ground with the adjuvants, the mixture is moistened with water, the mixture is extruded and then dried in a stream of air.

[0375] [Table 18]

[0376] The finely ground active ingredient is evenly coated in a mixer onto kaolin moistened with polyvinyl glycol, thus obtaining non-dusty coated granules.

[0377] [Table 19]

[0378] The finely ground active ingredient is mixed homogeneously with adjuvants to give a suspension concentrate, which can be diluted with water to give any desired concentration, and can be used to treat and protect living plants and plant propagation material from microbial infestation by spraying, pouring or dipping.

[0379] [Table 20]

[0380] The finely ground active ingredient is mixed homogeneously with adjuvants to give a suspension concentrate, which can be diluted with water to give any desired concentration, and can be used to treat and protect living plants and plant propagation material from microbial infestation by spraying, pouring or dipping.

[0381] Slow-release capsule suspension 28 parts of the combined compounds of formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polyvinyl-polyphenylisocyanate mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of a defoamer, and 51.6 parts of water until the desired particle size is achieved. A mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water is added to the emulsion. The mixture is stirred until the polymerization reaction is complete.

[0382] The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% of the active ingredient. The average capsule size is 8-15 microns.

[0383] The resulting formulation is applied to the seeds as an aqueous suspension in an apparatus suitable for the purpose.

[0384] List of abbreviations: Abbreviations used in the synthetic schemes and preparations ACN Acetonitrile Boc t-butoxycarbonyl DBU 1,8-diazabicyclo[5.4.0]undec-7-ene DCM dichloromethane DDQ 2,3-dichloro-5,6-dicyano-1,4-benzoquinone DMSO dimethyl sulfoxide DMSO-d 6 Deuterated dimethyl sulfoxide DPEN Diphenylvinyldiamine Et3N Triethylamine EtOAc ethyl acetate hr / hrs hours / hours MeCN acetonitrile MeOH Ethanol Ms methanesulfonyl (mesyl) n-Bu n-butyl NHC N-heterocyclic carbene NPhth phthalimide-1-yl OMs mesylate group OTf triflate group OTs Tosylate group PdCl2dppf 1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride TBME tert-butyl methyl ether TEA Triethylamine TEMPO (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl Tf Trifluoromethanesulfonyl (triflyl) TFA trifluoroacetic acid THF tetrahydrofuran Ts p-Toluenesulfonyl (tosyl) X-Phos 2-Dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl aq. aqueous solution ℃ Celsius equiv. h time LC / MS or LC-MS Liquid Chromatography Mass Spectrometry M mol MHz Megahertz min mp or MP melting point NMR nuclear magnetic resonance ppm parts per million RT or rt room temperature Rt retention time RBF Round Bottom Flask

[0385] Preparation example The following examples further illustrate, but do not limit, the present invention. Those skilled in the art will readily recognize appropriate variations from the procedures, both as to reactants and reaction conditions and techniques.

[0386] Unless otherwise specified, 1 H NMR spectra were recorded at 400 MHz. 19 F NMR spectra were recorded at 377 MHz and chemical shifts are reported in ppm. The following abbreviations are used: s = singlet; br s = broad singlet; d = doublet; br d = broad doublet; dd = double doublet; dt = double triplet; t = triplet, tt = triple triplet, q = quartet, quin = quintuplet, sept = septet; m = multiplet.

[0387] Throughout this description, temperatures are given in degrees Celsius (°C). "MP" means melting point. "Rt" means retention time. LC / MS means liquid chromatography mass spectrometry. The LC / MS equipment and methods are as follows:

[0388] If desired, enantiomerically pure final compounds can be obtained from racemic material, if desired, via standard physical separation techniques such as reverse-phase chiral chromatography or via stereoselective synthesis techniques, for example, by using chiral starting materials.

[0389] Example P1: This example illustrates the preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]imidazo[1,2-a]pyrimidine-5-carboxamide (compound 1.1 of Table T1). [ka] (Compound P-1.1 in Table T1)

[0390] a) Preparation of ethyl 2-(3-cyclopropylphenoxy)acetate In a single-neck round-bottom flask, 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). To this was added 2-bromoethyl acetate (2.98 g, 17.8 mmol), and the resulting reaction mixture was stirred at room temperature for 4 hours. The progress of the reaction was monitored by LCMS. The reaction mixture was then diluted with water and extracted with EtOAc. 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 / EtOAc) to give ethyl 2-(3-cyclopropylphenoxy)acetate. LCMS (Method B): Retention time 1.48 min, 221(M+H)

[0391] b) Preparation of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate A solution of ethyl 2-(3-cyclopropylphenoxy)acetate (1.5 g, 6.8 mmol) and 1-tert-butoxy-N,N,N',N'-tetramethyl-methanediamine (9.2 g, 48.0 mmol) was heated to 90 °C for 2 h in a sealed glass reactor. The progress of the reaction was monitored by LCMS. The reaction mixture was then diluted with water and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate. LCMS (Method B): Retention time 1.52 min, 276(M+H)

[0392] c) Preparation of 6-(3-cyclopropylphenoxy)-8H-imidazo[1,2-a]pyrimidin-5-one A mixture of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate (1.0 g, 3.63 mmol), 2H-imidazol-2-amine (0.30 g, 3.63 mmol), and sodium acetate (0.30 g, 3.63 mmol) in acetic acid (10 mL) was stirred in a round-bottom flask at 110 °C for 4 h. The reaction progress was monitored by LCMS. The reaction mixture was then concentrated under reduced pressure, followed by two successive co-distillations with toluene under reduced pressure to give a crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give 6-(3-cyclopropylphenoxy)-8H-imidazo[1,2-a]pyrimidin-5-one as a brown solid. LCMS (Method B): Retention time 1.24 min, 268 (M+H)

[0393] d) Preparation of 5-chloro-6-(3-cyclopropylphenoxy)imidazo[1,2-a]pyrimidine A mixture of 6-(3-cyclopropylphenoxy)-8H-imidazo[1,2-a]pyrimidin-5-one (0.40 g, 1.49 mmol), N,N-dimethylaniline (0.78 g, 6.13 mmol), and phosphorus(V) oxychloride (10.6 mL, 113 mmol) was stirred in a round-bottom flask at 90 °C for 12 hours. The reaction progress was monitored by LCMS. Upon completion, the reaction mixture was diluted with ice water and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give 5-chloro-6-(3-cyclopropylphenoxy)imidazo[1,2-a]pyrimidine. LCMS (Method B): Retention time 1.42 min, 286(M+H)

[0394] e) Preparation of methyl 6-(3-cyclopropylphenoxy)imidazo[1,2-a]pyrimidine-5-carboxylate An autoclave vessel was charged with 5-chloro-6-(3-cyclopropylphenoxy)imidazo[1,2-a]pyrimidine (0.08 g, 0.28 mmol), triethylamine (0.08 mL, 0.56 mmol), Pd(dppf)Cl2CH2Cl2 (0.057 g, 0.07 mmol), and methanol (20 mL). The reactor was flushed with carbon monoxide gas three times and then charged with 10 bar of carbon monoxide. The reaction mixture was heated to 80 °C for 1.5 h. The reaction progress was monitored by LCMS. The reaction mixture was then diluted with water and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give methyl 6-(3-cyclopropylphenoxy)imidazo[1,2-a]pyrimidine-5-carboxylate as a yellow solid. LCMS (Method B): Retention time 1.36 min, 310(M+H)

[0395] f) Preparation of lithium 6-(3-cyclopropylphenoxy)imidazo[1,2-a]pyrimidine-5-carboxylate To a solution of methyl 6-(3-cyclopropylphenoxy)imidazo[1,2-a]pyrimidine-5-carboxylate (0.10 g, 0.32 mmol) in tetrahydrofuran (0.45 mL) and water (0.22 mL) was added lithium hydroxide monohydrate (0.041 g, 0.96 mmol). The reaction was allowed to proceed at room temperature for 2 hours. The reaction progress was monitored by TLC and LCMS. The reaction mixture was then concentrated under reduced pressure at 30 °C, followed by two successive co-distillations with toluene to give lithium 6-(3-cyclopropylphenoxy)imidazo[1,2-a]pyrimidine-5-carboxylate, which was used directly in the next step. LCMS (Method B): Retention time 0.45 min, 296(M+H)

[0396] g) Preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]imidazo[1,2-a]pyrimidine-5-carboxamide (compound P-1.1, Table T1) To lithium 6-(3-cyclopropylphenoxy)imidazo[1,2-a]pyrimidine-5-carboxylate (0.10 g, 0.27 mmol), 2-(2,4-dichlorophenyl)-2-fluoroethanamine (0.067 g, 0.32 mmol) in EtOAc (1.35 mL) was added 1-propanephosphonic anhydride solution (T3P, 50% in EtOAc, 0.48 mL, 0.81 mmol) and triethylamine (0.08 mL, 0.59 mmol) at 0 °C. The reaction mixture was stirred at room temperature for 2 hours. The progress of the reaction was monitored by TLC and LCMS. Upon completion, the reaction mixture was diluted with water and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The crude residue obtained was purified by silica gel chromatography (cyclohexane / EtOAc) to give 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]imidazo[1,2-a]pyrimidine-5-carboxamide as a yellow solid. 1 H NMR (400 MHz, CDCl3) δ ppm 8.79(d,J=1.38Hz,1H),8.36(s,1H),7.95(d,J=1.38Hz,2H),7.36-7.38(m,1 H),7.29-7.34(m,1H),7.19-7.25(m,1H),7.07-7.12(m,1H),6.94-6.99(m,1H ),6.79-6.84(m,1H),6.73-6.77(m,1H),5.85-6.00(m,1H),4.06-4.21(m,1H) ,3.83-3.98(m,1H),1.88-1.95(m,1H),1.00-1.08(m,2H),0.70-0.75(m,2H). LCMS (Method B): Retention time 1.55 min, 485(M+H)

[0397] Example P2: This example illustrates the preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.2 of Table T1). [ka] (Compound P-1.2 in Table T1)

[0398] Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate was prepared as described in Example 1, steps a) and b).

[0399] a) Preparation of 6-(3-cyclopropylphenoxy)-4H-[1,2,4]triazolo[1,5-a]pyrimidin-7-one Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate (3 g, 10.35 mmol) and 4H-1,2,4-triazol-3-amine (0.96 g, 10.35 mmol) were dissolved in acetic acid (30 mL) in a round-bottom flask equipped with a nitrogen balloon. To this was added sodium acetate (0.86 g, 10.35 mmol) and stirred at 90 °C under nitrogen for 18 h. Progress was monitored by TLC and LCMS analysis. After complete consumption of the starting material, the reaction mixture was cooled to room temperature, diluted with ice-cold water, and extracted with EtOAc. The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure. The resulting crude residue was purified by silica gel chromatography (0–30% EtOAc in cyclohexane) to afford 6-(3-cyclopropylphenoxy)-4H-[1,2,4]triazolo[1,5-a]pyrimidin-7-one as a white solid. 1 H NMR(400MHz,DMSO-d6)δ ppm 8.29-8.34(m,2H)7.15(t,J=7.86Hz,1H)6.78(s,1H)6.78(d,J=7.70Hz,2 H)6.72(d,J=7.39Hz,1H)1.89(s,1H)0.88-0.96(m,2H)0.59-0.72(m,2H) LCMS (Method B): Retention time 1.21 min, 269(M+H)

[0400] b) Preparation of 7-chloro-6-(3-cyclopropylphenoxy)-[1,2,4]triazolo[1,5-a]pyrimidine In a round-bottom flask equipped with a nitrogen balloon and condenser, 6-(3-cyclopropylphenoxy)-4H-[1,2,4]triazolo[1,5-a]pyrimidin-7-one (0.95 g, 3.38 mmol) was added to phosphorus oxychloride (24 mL, 257 mmol). To this was added N,N-dimethylaniline (1.77 g, 13.88 mmol), and the resulting reaction mixture was stirred at 85 °C for 12 h. The reaction progress was monitored by TLC and LCMS analysis. Upon completion, the reaction mixture was cooled to room temperature, added to crushed ice in one portion, and extracted with EtOAc. The combined organic layers were dried over sodium sulfate and concentrated in vacuo to give a crude residue, which was then purified by silica gel chromatography (0–20% EtOAc in cyclohexane) to give 7-chloro-6-(3-cyclopropylphenoxy)-[1,2,4]triazolo[1,5-a]pyrimidine as a pale yellow solid. 1 H NMR(400MHz,CDCl3)δ ppm 8.70(s,1H),8.59(d,J=1.50Hz,1H),7.22-7.29(m,1H),6.88(d,J=7.75Hz,1H ),6.70-6.77(m,2H),1.82-1.94(m,1H),0.93-1.06(m,2H),0.64-0.76(m,2H). LCMS (Method B): Retention time 1.43 min, 287(M+H)

[0401] c) Preparation of methyl 6-(3-cyclopropylphenoxy)-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxylate An autoclave vessel was charged with 7-chloro-6-(3-cyclopropylphenoxy)-[1,2,4]triazolo[1,5-a]pyrimidine (0.85 g, 2.82 mmol), triethylamine (0.57 g, 5.63 mmol), Pd(dppf)Cl2CH2Cl2 (0.58 g, 0.70 mmol), and methanol (30 mL). The reactor was flushed with carbon monoxide gas three times and then charged with 10 bar of carbon monoxide. The reaction mixture was heated to 80 °C for 1.5 h. The reaction progress was monitored by LCMS. Upon completion, the reaction mixture was cooled to room temperature and filtered through Celite. The filtrate was then evaporated under reduced pressure. The crude compound was purified by silica gel chromatography (0-20% EtOAc in cyclohexane) to give methyl 6-(3-cyclopropylphenoxy)-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxylate as a pale yellow gum. 1 H NMR(400MHz,CDCl3)δ ppm 8.65(s,1H),8.48(s,1H),7.14-7.22(m,1H),6.83(d,J=7.75Hz,1H),6.67-6.7 5(m,2H),3.96(s,3H),1.77-1.85(m,1H),0.83-1.01(m,2H),0.59-0.65(m,2H). LCMS (Method B): Retention time 1.4 min, 311(M+H)

[0402] d) Preparation of 6-(3-cyclopropylphenoxy)-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxylic acid To a solution of methyl 6-(3-cyclopropylphenoxy)-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxylate (0.30 g, 0.93 mmol) in tetrahydrofuran (1.3 mL) and water (0.6 mL) was added lithium hydroxide (0.12 g, 2.80 mmol). The reaction mixture was stirred at 10 °C for 1 hour. The progress of the reaction was monitored by TLC and LCMS. After completion of the reaction, the reaction mixture was diluted with water and washed with EtOAc. The aqueous layer was then acidified with 2N HCl at 0 °C and extracted with EtOAc. The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure to give 2-(3-cyclopropylphenoxy)imidazo[1,5-b]pyridazine-3-carboxylic acid as a beige solid. LCMS (Method B): Retention time 1.12 min, 297(M+H)

[0403] e) 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.2, Table T To 6-(3-cyclopropylphenoxy)-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxylic acid (0.3 g, 0.91 mmol) in EtOAc (4.5 mL) was added 2-(2,4-dichlorophenyl)-2-fluoroethanamine (0.23 g, 1.1 mmol), followed by 1-propanephosphonic anhydride solution (T3P, 50% in EtOAc, 1.74 g, 2.73 mmol) and triethylamine (0.58 g, 5.47 mmol). The reaction mixture was stirred at room temperature for 18 hours. The reaction progress was monitored by TLC and LCMS. Upon completion, the reaction mixture was diluted with water, extracted with EtOAc, and 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 (0-30% EtOAc in cyclohexane) to afford 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxamide as a white solid. 1H NMR(400MHz,CDCl3)δ ppm 8.99(br s,1H),8.74(s,1H),8.58(s,1H),7.46(br d,J=8.44Hz,1H),7.41(s,1H),7.26(br t,J=8.50Hz,2H),6.90(br d,J=7.46Hz,1H),6.75-6.81(m,2H),6.07-5.94(m,1H),4.12-4.29(m,1H),3.76-3.91(m,1H),1.83-1.93(m,1H),1.00(m,2H),0.71(m,2H). LCMS (Method C): Retention time 1.22 min, 486.2 (M+H)

[0404] Example P3: This example illustrates the preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.3 of Table T1). [ka] (Compound P-1.3 in Table T1)

[0405] Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate was prepared as described in Example 1, steps a) and b).

[0406] a) Preparation of 6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidin-7-one In a single-neck round-bottom flask, a mixture of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate (1.0 g, 3.63 mmol), 3H-pyrazol-3-amine (0.30 g, 3.63 mmol), and sodium acetate (0.30 g, 3.63 mmol) in acetic acid (2 mL) was stirred at 90 °C for 24 h. The reaction progress was monitored by LCMS. The reaction mixture was then concentrated under reduced pressure, and after two successive co-distillations with toluene under reduced pressure, a crude residue was obtained. The resulting residue was finally purified by silica gel chromatography (cyclohexane / EtOAc) to give 6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidin-7-one as a brown solid. LCMS (Method B): Retention time 1.24 min, 268 (M+H)

[0407] b) Preparation of 7-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine To a mixture of 6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidin-7-one (0.33 g, 1.23 mmol) and phosphorus(V) oxychloride (8.76 mL, 93.83 mmol) in a round-bottom flask was added N,N-dimethylaniline (0.64 g, 5.06 mmol) at 0 °C. The reaction mixture was heated at 90 °C for 12 h. The progress of the reaction was monitored by LCMS. The reaction mixture was then diluted with ice water and extracted with EtOAc. 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 / EtOAc) to give 7-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine. LCMS (Method B): Retention time 2.53 min, 286(M+H)

[0408] c) Preparation of methyl 6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate An autoclave vessel was charged with 7-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine (0.08 g, 0.28 mmol), triethylamine (0.08 mL, 0.56 mmol), Pd(dppf)Cl2CH2Cl2 (0.057 g, 0.07 mmol), and methanol (20 mL). The reactor was flushed with carbon monoxide gas three times and charged with 10 bar of carbon monoxide. The reaction mixture was heated to 80 °C for 1.5 h. The reaction progress was monitored by LCMS. The reaction mixture was then diluted with water and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give methyl 6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate as a yellow solid. LCMS (Method D): Retention time 1.10 min, 310 (M+H)

[0409] d) Preparation of lithium 6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate To a solution of methyl 6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate (30 mg, 0.096 mmol) in tetrahydrofuran (2 mL) and water (1 mL) was added lithium hydroxide (0.012 g, 0.29 mmol). The reaction was allowed to proceed at room temperature for 12 hours. The reaction progress was monitored by TLC and LCMS. After completion of the reaction, the reaction mixture was concentrated in vacuo to afford lithium 6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate as an off-white solid, which was used directly in the next step. LCMS (Method B): Retention time 1.37 min, 296 (M+H)

[0410] e) Preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.3, Table T1) To lithium 6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate (0.02 g, 0.06 mmol) in EtOAc (2 mL) was added 2-(2,4-dichlorophenyl)-2-fluoroethanamine (0.016 g, 0.08 mmol), followed by the addition of 1-propanephosphonic anhydride solution (T3P, 50% in EtOAc, 0.12 g, 0.19 mmol) and triethylamine (0.015 g, 0.14 mmol) at 0 °C. The reaction mixture was stirred at room temperature for 24 hours. The progress of the reaction was monitored by TLC and LCMS. Upon completion, the reaction mixture was diluted with water and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The crude residue obtained was purified by silica gel chromatography (cyclohexane / EtOAc) to give 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide. 1 H NMR(400MHz,CDCl3)δ ppm 9.64(br s,1H),8.43(s,1H),8.19(d,J=2.50Hz,1H),7.48(d,J=8.38Hz,1H),7.3 6-7.43(m,1H),7.18-7.26(m,2H),6.88(d,J=2.50Hz,1H),6.83(d,J=7. 88Hz,1H),6.72-6.79(m,2H),6.05-5.93(m,1H),4.14-4.24(m,1H),3.8 0-3.82(m,1H),1.85-1.89(m,1H),0.96-0.98(m,2H),0.67-0.72(m,2H). LCMS (Method C): Retention time 1.29 min, 485(M+H)

[0411] Example P4: This example illustrates the preparation of 7-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]imidazo[1,2-b]pyridazine-8-carboxamide (compound P-1.4 of Table T1). [ka] (Compound P-1.4 in Table T1)

[0412] a) Preparation of 2-[(2-bromoimidazol-1-yl)methoxy]ethyl-trimethyl-silane To a solution of 2-bromo-1H-imidazole (2.0 g, 14 mmol) in tetrahydrofuran (5 mL) was added sodium hydride (60% by weight, 0.65 g, 16 mmol) at 0° C. The reaction mixture was stirred for 30 minutes, and then 2-(trimethylsilyl)ethoxymethyl chloride (2.8 mL, 15 mmol) was added at 0° C. The resulting reaction mixture was stirred at room temperature for 2 hours. The reaction progress was monitored by TLC and LCMS. Upon completion, the reaction mixture was diluted with water and extracted with EtOAc. The organic layer was then washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to afford 2-[(2-bromoimidazol-1-yl)methoxy]ethyl-trimethyl-silane 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)

[0413] b) Preparation of 2-(3-cyclopropylphenoxy)-1-[1-(2-trimethylsilylethoxymethyl)imidazol-2-yl]ethenone In a two-necked round-bottom flask, 2-[(2-bromoimidazol-1-yl)methoxy]ethyl-trimethyl-silane (2.35 g, 8.50 mmol) was dissolved in tetrahydrofuran (42 mL) and cooled to 0 °C. A solution of isopropylmagnesium chloride lithium chloride complex (1.3 mol / L in THF, 6.5 mL, 8.50 mmol) was added dropwise and stirred for 30 minutes. Then, 2-(3-cyclopropylphenoxy)-N-methoxy-N-methyl-acetamide (1.0 g, 4.25 mmol) was added as a solution in tetrahydrofuran (2 mL). The reaction mixture was stirred at room temperature for 1 hour. The reaction progress was monitored by TLC and LCMS. Upon completion, the reaction mixture was quenched with a saturated solution of ammonium chloride and diluted with water. The desired organic material was extracted with EtOAc, dried over sodium sulfate, and concentrated under reduced pressure. The crude residue obtained was purified by silica gel chromatography (cyclohexane / EtOAc) to give 2-(3-cyclopropylphenoxy)-1-[1-(2-trimethylsilylethoxymethyl)imidazol-2-yl]ethenone as a pale yellow liquid. LCMS (Method B): Retention time 1.69 min, 373(M+H)

[0414] The 2-(3-cyclopropylphenoxy)-N-methoxy-N-methyl-acetamide used in step b) was prepared as follows:

[0415] i. 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 (9.0 mL) and water (4.5 mL). The reaction was allowed to proceed at room temperature for 1 hour. The reaction progress was monitored by TLC and LCMS. Upon completion, the reaction mixture was diluted with water and washed with ethyl acetate. The aqueous layer was then acidified with 2N HCl and extracted with EtOAc. The combined organic layers were dried over sodium sulfate and concentrated in vacuo to afford 2-(3-cyclopropylphenoxy)acetic acid as a beige solid. 1H 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)

[0416] ii. Preparation of 2-(3-cyclopropylphenoxy)-N-methoxy-N-methyl-acetamide To 2-(3-cyclopropylphenoxy)acetic acid (1.34 g, 6.62 mmol) in EtOAc (26.8 mL) was added methoxy(methyl)ammonium chloride (0.97 g, 9.93 mmol), followed by 1-propanephosphonic anhydride solution (T3P, 50% in EtOAc, 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 h. The reaction progress was monitored by TLC and LCMS. Upon completion, the reaction mixture was diluted with water and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The crude residue was purified by silica gel chromatography (10–30% EtOAc in cyclohexane) to give 2-(3-cyclopropylphenoxy)-N-methoxy-N-methyl-acetamide as a gum. 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)

[0417] c) Preparation of 2-(3-cyclopropylphenoxy)-1-(1H-imidazol-2-yl)ethenone In a round-bottom flask, 2-(3-cyclopropylphenoxy)-1-[1-(2-trimethylsilylethoxymethyl)imidazol-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 reaction progress was monitored by TLC and LCMS. Upon completion, the reaction mixture was concentrated under reduced pressure, diluted with water, and extracted with EtOAc. The organic layer was washed with sodium bicarbonate. The combined organic layers were dried under reduced pressure to give 2-(3-cyclopropylphenoxy)-1-(1H-imidazol-2-yl)ethanone. The crude residue obtained was used directly in the next step. LCMS (Method C): Retention time 1.03 min, 243(M+H)

[0418] d) Preparation of 2-(3-cyclopropylphenoxy)-3-(dimethylamino)-1-(1H-imidazol-2-yl)prop-2-en-1-one In a sealed glass reactor, 2-(3-cyclopropylphenoxy)-1-(1H-imidazol-2-yl)ethanone (0.60 g, 2.0 mmol) and 1-tert-butoxy-N,N,N',N'-tetramethyl-methanediamine (5.0 g, 20.0 mmol) were heated to 90 °C for 2 h. The reaction progress was monitored by LCMS. The reaction mixture was then diluted with water and extracted with EtOAc. 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 / EtOAc) to give 2-(3-cyclopropylphenoxy)-3-(dimethylamino)-1-(1H-imidazol-2-yl)prop-2-en-1-one. LCMS (Method B): Retention time 1.05 min, 298 (M+H)

[0419] e) Preparation of 7-(3-cyclopropylphenoxy)-5H-imidazo[1,2-b]pyridazin-8-one In a round-bottom flask, 2-(3-cyclopropylphenoxy)-3-(dimethylamino)-1-(1H-imidazol-2-yl)prop-2-en-1-one (0.03 g, 0.10 mmol) was dissolved in N-methyl-2-pyrrolidone (1 mL). Potassium tert-butoxide (0.012 g, 0.10 mmol) was then added as a suspension in N-methyl-2-pyrrolidone (0.5 mL). The resulting reaction mixture was stirred at room temperature for 30 minutes. A solution of amino 4-nitrobenzoic acid (0.022 g, 0.12 mmol) in N-methyl-2-pyrrolidone (1 mL) was then added, and the reaction mixture was stirred at room temperature for 18 hours. The progress of the reaction was monitored by LCMS. The reaction mixture was then diluted with water and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give a mixture of 1-(1-aminoimidazol-2-yl)-2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-en-1-one and 7-(3-cyclopropylphenoxy)-5H-imidazo[1,2-b]pyridazin-8-one, which was used directly in the next step. LCMS (Method B): Retention time 0.28 min, 313 (M+H) and retention time 1.9 min, 268 (M+H)

[0420] f) Preparation of 8-chloro-7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine A mixture of 1-(1-aminoimidazol-2-yl)-2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-en-1-one and 7-(3-cyclopropylphenoxy)-5H-imidazo[1,2-b]pyridazin-8-one (0.4 g), N,N-dimethylaniline (0.7 mL, 5 mmol), and phosphorus(V) oxychloride (8 mL, 90 mmol) was stirred at 90 °C for 12 h. The reaction progress was monitored by LCMS. The reaction mixture was then diluted with ice water and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give 8-chloro-7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine as a brown gum. LCMS (Method B): Retention time 1.47 min, 286(M+H)

[0421] g) Preparation of methyl 7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine-8-carboxylate An autoclave was charged with 8-chloro-7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine (0.13 g, 0.45 mmol), triethylamine (0.13 mL, 0.91 mmol), Pd(dppf)Cl2CH2Cl2 (0.093 g, 0.11 mmol), and methanol (20 mL). The reactor was flushed with carbon monoxide gas three times and then charged with 10 bar of carbon monoxide. The reaction mixture was heated to 80 °C for 1.5 h. The reaction progress was monitored by LCMS. The reaction mixture was then diluted with water and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The crude residue obtained was purified by silica gel chromatography (cyclohexane / EtOAc) to give methyl 7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine-8-carboxylate as a yellow solid. LCMS (Method B): Retention time 2.03 min, 310(M+H)

[0422] h) Preparation of lithium 7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine-8-carboxylate 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) was added lithium hydroxide monohydrate (20 mg, 0.48 mmol). The reaction was allowed to proceed at room temperature for 18 hours. The reaction progress was monitored by TLC and LCMS. After completion of the reaction, the reaction mixture was concentrated under reduced pressure at 30 °C, followed by two successive co-distillations with toluene to afford lithium 7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine-8-carboxylate, which was used directly in the next step. LCMS (Method B): Retention time 0.51 min, 296(M+H)

[0423] i) Preparation of 7-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]imidazo[1,2-b]pyridazine-8-carboxamide (compound P-1.4, Table T1) To lithium 7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine-8-carboxylate (0.0.5 g, 0.16 mmol) in EtOAc (0.83 mL) was added 2-(2,4-dichlorophenyl)-2-fluoroethanamine (0.041 g, 0.19 mmol), followed by 1-propanephosphonic anhydride solution (T3P, 50% in EtOAc, 0.3 mL, 0.50 mmol) and triethylamine (0.05 mL, 0.36 mmol) at 0 °C. The reaction mixture was then stirred at room temperature for 2 hours. The reaction progress was monitored by TLC and LCMS. Upon completion, the reaction mixture was diluted with water, extracted with EtOAc, and 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 / EtOAc) to afford 7-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]imidazo[1,2-b]pyridazine-8-carboxamide as a white solid. 1 H NMR (400 MHz, CDCl3) δ ppm 10.15-10.23(m,1H),8.15(s,1H),7.92(d,J=1.34Hz,1H),7.73(d,J=1.34Hz, 1H),7.52(d,J=8.44Hz,1H),7.38-7.41(m,1H),7.31-7.35(m,1H),7.27(m,1H) ,6.89(d,J=7.83Hz,1H),6.78-6.81(m,2H),6.10-5.95(m,1H),4.10-4.25(m,1 H),3.72-3.84(m,1H),1.85-1.92(m,1H),0.84-1.01(m,2H),0.68-0.72(m,2H) LCMS (Method B): Retention time 1.48 min, 485(M+H)

[0424] Example P5: This example illustrates the preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.5 of Table T1). [ka] (Compound P-1.5 in Table T1)

[0425] 6-(3-Cyclopropylphenoxy)-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxylic acid was prepared as described in Example 2, steps a) to d).

[0426] a) Preparation of 6-(3-cyclopropylphenoxy)-[1,2,4]triazolo[1,5-a]pyrimidine-7-carbonyl chloride To a solution of 6-(3-cyclopropylphenoxy)-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxylic acid (0.07 g, 0.22 mmol) in dichloromethane (1.4 mL) was added dropwise oxalyl chloride (0.03 mL, 0.34 mmol) under an argon atmosphere. One drop of dry N,N-dimethylformamide was then added to the reaction mixture. Gas evolution was observed. The reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was concentrated in vacuo under nitrogen, and the resulting brown residue of 6-(3-cyclopropylphenoxy)-[1,2,4]triazolo[1,5-a]pyrimidine-7-carbonyl chloride was used immediately in the next step.

[0427] b) Preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.5, Table T1) To a mixture of 2-(2,4-dichlorophenyl)ethanamine (0.04 g, 0.21 mmol) and pyridine (0.04 mL, 0.53 mmol) in acetonitrile (0.85 mL) was slowly added a solution of 6-(3-cyclopropylphenoxy)-[1,2,4]triazolo[1,5-a]pyrimidine-7-carbonyl chloride (0.07 g, 0.21 mmol) in acetonitrile (0.85 mL). The reaction mixture was stirred at room temperature overnight for 12 hours. The reaction progress was monitored by TLC and LCMS. Upon completion, the reaction mixture was diluted with water, extracted with EtOAc, and the organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude residue was purified by reverse phase chromatography (0 to 70% acetonitrile in water) to give 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxamide as a white solid. 1H NMR(400MHz,CDCl3)δ ppm 8.55(s,1H),8.35(s,1H),8.29(br t,J=5.07Hz,1H),7.22(d,J=2.13Hz,1H),7.04-7.16(m,2H),6.95(dd,J=8.13,2.13Hz,1H),6.76(d,J=7.75Hz,1H),6 .58-6.66(m,2H),3.63-3.72(m,2H),2.95(t,J=6.94Hz,2H),1.70-1.80(m,1H),0.80-0.93(m,2H),0.51-0.62(m,2H). LCMS (Method C): Retention time 1.24 min, 468.3 (M+H)

[0428] Example P6: This example illustrates the preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]imidazo[1,2-a]pyrimidine-5-carboxamide (compound P-1.6, Table T1). [ka] (Compound P-1.6 in Table T1)

[0429] a) Preparation of 5-bromo-N-[2-(2,4-dichlorophenyl)ethyl]-2-methylsulfanyl-pyrimidine-4-carboxamide To 5-bromo-2-methylsulfanyl-pyrimidine-4-carboxylic acid (2.0 g, 8.02 mmol) in EtOAc (20 mL) was added 2-(2,4-dichlorophenyl)ethanamine (1.67 g, 8.83 mmol), followed by the addition of 1-propanephosphonic anhydride solution (T3P, 50% in EtOAc, 14.3 mL, 24.0 mmol) and triethylamine (2.25 mL, 16.0 mmol) at 0 °C. The reaction mixture was stirred at room temperature for 2 h. The reaction progress was monitored by TLC and LCMS. Upon completion, the reaction mixture was diluted with water and extracted with EtOAc. 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 / EtOAc) to give 5-bromo-N-[2-(2,4-dichlorophenyl)ethyl]-2-methylsulfanyl-pyrimidine-4-carboxamide. LCMS (Method C): Retention time 1.18 min, 419.8 (M+H)

[0430] b) Preparation of 5-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]-2-methylsulfanyl-pyrimidine-4-carboxamide In a round-bottom flask, 5-bromo-N-[2-(2,4-dichlorophenyl)ethyl]-2-methylsulfanyl-pyrimidine-4-carboxamide (1.3 g, 3.1 mmol) and 3-cyclopropylphenol (0.50 g, 3.7 mmol) were dissolved in dimethyl sulfoxide. The reaction mixture was purged with argon for 15 minutes. Potassium phosphate tribasic (1.3 g, 6.2 mmol), cuprous iodide (0.059 g, 0.31 mmol), and N-benzyl-N'-(2-methyl-1-naphthyl)oxamide (0.098 g, 0.31 mmol) were added, and the reaction mixture was flushed with argon. The round-bottom flask was placed in a preheated block, and the reaction mixture was stirred at 110 °C for 15 minutes. The mixture was diluted with ice water (30 mL) and extracted with EtOAc (20 mL). The combined organic layers were washed with water (20 mL) followed by brine (30 mL). The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure. The crude residue was purified by silica gel chromatography (cyclohexane / Et0Ac) to give 5-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]-2-methylsulfanyl-pyrimidine-4-carboxamide. LCMS (Method D): Retention time 1.29 min, 474(M+H)

[0431] c) Preparation of 5-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]-2-methylsulfonyl-pyrimidine-4-carboxamide A mixture of 5-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]-2-methylsulfanyl-pyrimidine-4-carboxamide (1.0 g, 2.10 mmol) in dichloromethane (10 mL) was stirred in a round-bottom flask at 0 °C. To this solution was added 3-chlorobenzenecarboperoxoic acid (1.82 g, 6.32 mmol) in portions. The resulting reaction mixture was stirred at room temperature for 4 hours. The progress of the reaction was monitored by TLC and LCMS. After completion of the reaction, the reaction mixture was quenched with sodium thiosulfate solution (the amount of peroxide was monitored with starch paper), diluted with water, and extracted with EtOAc. The organic layer was washed with sodium bicarbonate solution, brine solution, and dried over sodium sulfate. The crude residue obtained was purified by silica gel chromatography (cyclohexane / EtOAc) to give 5-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]-2-methylsulfonyl-pyrimidine-4-carboxamide. LCMS (Method C): Retention time 1.18 min, 507(M+H)

[0432] d) Preparation of 2-amino-5-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]pyrimidine-4-carboxamide A premixed pressure reactor was charged with 5-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]-2-methylsulfonyl-pyrimidine-4-carboxamide (0.3 g, 0.6 mmol) and tetrahydrofuran (0.2 mL). To this was added ammonia in 1,4-dioxane (0.5 mol / L, 10 mL), and the reaction was heated at 90° C. for 5 hours. The reaction progress was monitored by LCMS. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, diluted with water, and extracted twice with EtOAc. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give 2-amino-5-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]pyrimidine-4-carboxamide. LCMS (Method C): Retention time 1.22 min, 443.3 (M+H)

[0433] e) Preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]imidazo[1,2-a]pyrimidine-5-carboxamide (compound P-1.6, Table T1) A microwave vessel was charged with 2-amino-5-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]pyrimidine-4-carboxamide (0.16 g, 0.36 mmol), ethanol (2 mL), and 2-chloroacetaldehyde (0.085 g, 1.1 mmol). The reaction was irradiated at 98 °C for 12 hours. The reaction progress was monitored by LCMS. Upon completion, the reaction mixture was concentrated under reduced pressure, diluted with water, and extracted twice with EtOAc. The combined organic layers were washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]imidazo[1,2-a]pyrimidine-5-carboxamide (0.045 g, 27%) and 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]imidazo[1,2-a]pyrimidine-7-carboxamide. 1 H NMR(400MHz,CDCl3)δ ppm 8.83(s,1H),8.30(s,1H),7.94(s,1H),7.64(br s,1H),7.26-7.28(m,2H),7.02(d,J=8.13Hz,1H),6.91-6.97(m,2H),6.62-6.75(m,2H),3.7 8-3.86(m,2H),2.96-3.12(m,2H),1.86-1.97(m,1H),1.03-1.05(m,2H),0.70-0.72(m,2H). LCMS (Method D): Retention time 1.15 min, 467.0 (M+H)

[0434] Example P7: This example illustrates the preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]-2-methyl-imidazo[1,2-a]pyrimidine-5-carboxamide (compound P-1.7, Table T1). [ka] (Compound P-1.7 in Table T1)

[0435] Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate was prepared as described in Example 1, steps a) and b).

[0436] a) Preparation of 6-(3-cyclopropylphenoxy)-2-methyl-8H-imidazo[1,2-a]pyrimidin-5-one In a single-neck round-bottom flask, ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate (2.00 g, 6.90 mmol), 5-methyl-1H-imidazol-2-amine; hydrochloride (0.92 g, 6.90 mmol) in acetic acid (20 mL), and sodium acetate (0.57 g, 6.90 mmol) were stirred at 100 °C for 18 h. The reaction progress was monitored by LCMS. After completion of the reaction, the reaction mixture was cooled to room temperature, diluted with ice-cold water, and extracted with EtOAc. The organic layer was dried over sodium sulfate and concentrated in vacuo to give a crude residue, which was purified by silica gel chromatography (cyclohexane / EtOAc) to give 6-(3-cyclopropylphenoxy)-2-methyl-8H-imidazo[1,2-a]pyrimidin-5-one as a white solid. LCMS (Method B): Retention time 1.31 min, 282(M+H)

[0437] b) Preparation of 5-chloro-6-(3-cyclopropylphenoxy)-2-methyl-imidazo[1,2-a]pyrimidine In a single-neck round-bottom flask, pyridine (1 mL) was added to a mixture of 6-(3-cyclopropylphenoxy)-2-methyl-8H-imidazo[1,2-a]pyrimidin-5-one (1.00 g, 3.55 mmol) and phosphorus(V) oxychloride (25 mL) at 0 °C under stirring. The mixture was allowed to warm to room temperature and then stirred at 70 °C for 5 h. The reaction progress was monitored by LCMS. After completion of the reaction, the reaction mixture was concentrated in vacuo and quenched by adding it to crushed ice. The organic layer was washed with 150 mL of saturated sodium bicarbonate solution, 150 mL of water, and finally with brine solution, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The resulting crude residue was purified by silica gel chromatography (0–20% EtOAc in cyclohexane) to give 5-chloro-6-(3-cyclopropylphenoxy)-2-methyl-imidazo[1,2-a]pyrimidine as a pale yellow gum. LCMS (Method C): Retention time 1.12 min, 300 (M+H)

[0438] c) Preparation of methyl 6-(3-cyclopropylphenoxy)-2-methyl-imidazo[1,2-a]pyrimidine-5-carboxylate An autoclave vessel was charged with 5-chloro-6-(3-cyclopropylphenoxy)-2-methyl-imidazo[1,2-a]pyrimidine (0.48 g, 1.60 mmol), triethylamine (0.45 mL, 3.20 mmol), and Pd(dppf)Cl2CH2Cl2 (0.33 g, 0.40 mmol) in methanol (32 mL). The vessel was flushed with carbon monoxide gas three times and then charged with 10 bar of carbon monoxide. The reaction mixture was heated to 80 °C for 3 h. The progress of the reaction was monitored by LCMS. After completion of the reaction, the reaction mixture was diluted with water and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The crude residue obtained was purified by silica gel chromatography (0-30% EtOAc in cyclohexane) to give methyl 6-(3-cyclopropylphenoxy)-2-methyl-imidazo[1,2-a]pyrimidine-5-carboxylate as a yellow gum. LCMS (Method D): Retention time 1.09 min, 324(M+H)

[0439] d) Preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]-2-methyl-imidazo[1,2-a]pyrimidine-5-carboxamide (compound P-1.7, Table T1) A 10 mL microwave vial was charged with methyl 6-(3-cyclopropylphenoxy)-2-methyl-imidazo[1,2-a]pyrimidine-5-carboxylate (0.10 g, 0.30 mmol) and 2-(2,4-dichlorophenyl)-2-fluoro-ethanamine (0.06 g, 0.30 mmol), the vial was sealed, and microwaved at 100 °C for 2 h under stirring. The reaction progress was monitored by TLC and LCMS. Upon completion, the reaction mixture was diluted with water and extracted with EtOAc. The resulting organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude residue was purified by reverse-phase Combiflash by using 0–70% acetonitrile in water as the eluent to give 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]-2-methyl-imidazo[1,2-a]pyrimidine-5-carboxamide as a yellow solid. 1 H NMR(400MHz,chloroform-d)δ ppm 8.52(s,1H),8.28(s,1H),7.96(br s,1H),7.20-7.37(m,3H),7.09(dd,J=8.38,2.02Hz,1H),6.93-6.97(m,1H),6.88(m,1H),6.72-6.81(m,1H),5.81-6.0 4(m,1H),4.04-4.18(m,1H),3.84-3.97(m,1H),2.55(s,3H),1.76-2.04(m,1H),1.00-1.06(m,2H),0.69-0.74(m,2H). LCMS (Method C): Retention time 1.22 min, 499(M+H)

[0440] Example P8: This example illustrates the preparation of 2-cyano-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.8, Table T1). [ka] (Compound P-1.8 in Table T1)

[0441] Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate was prepared as described in Example 1.

[0442] a) Preparation of 2-bromo-6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidin-7-one In a single-neck round-bottom flask, a mixture of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate (0.5 g, 3.45 mmol), 3-bromo-1H-pyrazol-5-amine (0.57 g, 3.45 mmol), and sodium acetate (0.28 g, 3.45 mmol) in acetic acid (10 mL) was stirred at 100 °C for 1 h. The reaction mixture was cooled to 60 °C, magnesium chloride (0.65 g, 6.90 mmol) was added, and the mixture was heated to 120 °C for approximately 4 h. The progress of the reaction was monitored by LCMS analysis. The reaction mixture was cooled to room temperature, and water (30 mL) was added. The resulting precipitate was filtered to give 2-bromo-6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidin-7-one. LCMS (Method A): Retention time 0.87 min, 348(M+3H)

[0443] b) Preparation of 6-(3-cyclopropylphenoxy)-7-oxo-4H-pyrazolo[1,5-a]pyrimidine-2-carbonitrile A 30 mL vial was charged with zinc cyanide (0.43 g, 3.65 mmol), Pd2(dba)3 (1.57 g, 1.66 mmol), Pd(dppf)Cl2 (0.25 g, 0.332 mmol), and Zn powder (54.4 mg, 0.83 mmol). A solution of 2-bromo-6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidin-7-one (1.15 g, 3.32 mmol) in dry DMA (17 mL) was added. The mixture was purged with argon. The vial was closed, and the reaction mixture was heated to 120 °C and stirred for 2 h. The reaction progress was monitored by LCMS. The reaction mixture was then quenched with water, filtered through a pad of Celite, and diluted with EtOAc. The organic layer was washed with water (5 × 40 mL). Chromatography on 120 g of C18 (water / 20-70% acetonitrile) was carried out to give 6-(3-cyclopropylphenoxy)-7-oxo-4H-pyrazolo[1,5-a]pyrimidine-2-carbonitrile. LCMS (Method A): Retention time 0.85 min, 293(M+H)

[0444] c) Preparation of 7-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-2-carbonitrile A 100 mL round-bottom flask was taken, and 6-(3-cyclopropylphenoxy)-7-oxo-4H-pyrazolo[1,5-a]pyrimidine-2-carbonitrile (0.32 g, 1.1 mmol) and POCl3 (16 mL, 170 mmol) were added to it under stirring. Pyridine (0.18 mL, 2.2 mmol) was slowly added at room temperature, and the mixture was stirred at 90 °C for 20 h. The reaction progress was monitored by LCMS, which showed complete conversion of the product. The reaction mixture was concentrated to dryness in vacuo, then diluted with EtOAc, washed three times with water and once with brine, then dried over magnesium sulfate, filtered, and concentrated on a rotary evaporator. The crude product, 7-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-2-carbonitrile, was carried on to the next step without further purification. LCMS (Method A): Retention time 1.13 min, 311(M+H)

[0445] d) Preparation of methyl 2-cyano-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate An autoclave vessel was charged with 7-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-2-carbonitrile (0.35 g, 1.10 mmol), triethylamine (0.32 mL, 4.61 mmol), and Pd(dppf)Cl2CH2Cl2 (0.19 g, 0.23 mmol) in methanol (23 mL). The reactor was flushed with nitrogen gas, then flushed twice with carbon monoxide gas, and then charged with 10 bar of carbon monoxide. The reaction mixture was heated to 80 °C for 2 h. The reaction progress was monitored by LCMS. After completion of the reaction, the reaction mixture was diluted with water and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The crude residue obtained was purified by silica gel chromatography (cyclohexane / EtOAc) to give methyl 2-cyano-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate. LCMS (Method A): Retention time 1.08 min, 335(M+H)

[0446] e) Preparation of Lithium; 2-Cyano-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate To a solution of methyl 2-cyano-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate (0.20 g, 0.60 mmol) in tetrahydrofuran (18 mL) and water (6 mL) was added lithium hydroxide hydrate (51 mg, 1.2 mmol). The reaction mixture was stirred at room temperature for 1 hour. The reaction progress was monitored by LCMS and TLC. After completion of the reaction, the reaction mixture was concentrated under reduced pressure at 30 °C and then concentrated twice by co-distillation with toluene. The crude lithium 2-cyano-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate salt was used directly in the next step. LCMS (Method A): Retention time 0.75 min, 321(M+H)

[0447] f) Preparation of 2-cyano-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.8, Table T1) A solution of lithium; 2-cyano-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate salt (0.20 g, 0.613 mmol), (1-cyano-2-ethoxy-2-oxoethylideneaminooxy)dimethylamino-morpholino-carbenium hexafluorophosphate (0.32 g, 0.74 mmol) was stirred in EtOAc (6 mL) at room temperature. Diisopropylethylamine (0.32 mL, 1.84 mmol) was added, followed by 2-(2,4-dichlorophenyl)-2-fluoroethan-1-amine (0.14 g, 0.67 mmol). The reaction progress was monitored by LCMS and TLC. After completion of the reaction, the reaction mixture was diluted with water. It was then extracted twice with EtOAc. The combined organic layers were washed once with brine, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure at 60 °C. The resulting crude residue was purified by chromatography on C18 40 g (30–80% ACN in water + 0.1% formic acid) to give 2-cyano-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide. 1 H NMR(400MHz,CDCl3)δ ppm 8.1-8.53(m,1H),8.7-8.27(m,1H),7.1-7.42(m,2H),7.32(dd,J=49.59,8.54Hz,1H),7 .3-7.22(m,3H),6.7-6.95(m,2H),5.90(ddd,J=46.32,6.72,3.27Hz,1H),4.1-4.20(m,1 H),3.8-3.85(m,1H),3.6-3.50(m,1H),2.3-2.96(m,1H),2.9-2.82(m,1H),1.2-2.04(m ,1H),1.81(tt,J=8.36,5.09Hz,1H),1.4-1.28(m,2H),0.4-1.00(m,2H)0.3-0.72(m,2H) LCMS (Method A): Retention time 1.19 min, 510 (M+H)

[0448] Example P9: This example illustrates the preparation of 3-chloro-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.9, Table T1). [ka] (Compound P-1.9 in Table T1)

[0449] Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate was prepared as described in Example 1.

[0450] a) Preparation of 3-chloro-6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidin-7-one In a single-neck round-bottom flask, a mixture of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate (1.50 g, 5.20 mmol), 4-chloro-1H-pyrazol-3-amine (0.61 g, 5.20 mmol), and sodium acetate (0.43 g, 5.20 mmol) in acetic acid (15 mL) was stirred at 100 °C for 12 h. The reaction progress was monitored by LCMS. Upon completion, the reaction mixture was diluted with ice-cold water and stirred for 15 min. The resulting solid was filtered through a Buchner funnel and dried under vacuum to give 3-chloro-6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidin-7-one as a brown solid. LCMS (Method B): Retention time 1.34 min, 302 (M+H)

[0451] b) Preparation of 3,7-dichloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine In a single-neck round-bottom flask, a mixture of 3-chloro-6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidin-7-one (0.80 g, 2.65 mmol) and phosphorus(V) oxychloride (18.8 mL, 201 mmol) was added. The reaction mixture was cooled to 0°C, and pyridine (0.86 mL, 10.6 mmol) was added dropwise via syringe at 0°C. The resulting reaction mixture was stirred at room temperature and then at 85°C for 16 hours. The reaction progress was monitored by LCMS. Upon completion, the reaction mixture was cooled to room temperature, concentrated in vacuo to a minimum volume, quenched by adding it to crushed ice, and the organic desired material was extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give 3,7-dichloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine as a yellow gum. LCMS (Method B): Retention time 1.73 min, 320(M+H)

[0452] c) Preparation of methyl 3-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate An autoclave vessel was charged with 3,7-dichloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine (0.50 g, 1.56 mmol), triethylamine (0.44 mL, 3.12 mmol), and Pd(dppf)Cl2CH2Cl2 (0.32 g, 0.39 mmol) in methanol (46.8 mL). The reactor was flushed with carbon monoxide gas three times and then charged with 10 bar of carbon monoxide. The reaction mixture was heated to 80 °C for 3 h. The reaction progress was monitored by LCMS. Upon completion, the reaction mixture was diluted with water and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The crude residue obtained was purified by silica gel chromatography (cyclohexane / EtOAc) to give methyl 3-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate as a yellow gum. LCMS (Method B): Retention time 1.67 min, 344(M+H)

[0453] d) Preparation of 3-chloro-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.9, Table T1) A 10 mL microwave vial was charged with methyl 3-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate (110 mg, 0.32 mmol) and 2-(2,4-dichlorophenyl)-2-fluoroethanamine (133 mg, 0.64 mmol). The vial was then sealed and microwaved at 90 °C for 2 hours with stirring. The reaction progress was monitored by TLC and LCMS. Upon completion, the reaction mixture was diluted with water and extracted with EtOAc. The resulting 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 / EtOAc as eluent) to give 3-chloro-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide as an off-white solid. 1 H NMR(400MHz,CDCl3)δ ppm 9.02(br s,1H),8.47(s,1H),8.16(s,1H),7.45(d,J=8.44Hz,1H),7.40(s,1H),7.20-7.27(m,2H),6.86(d,J=7.83Hz,1H),6.71-6.7 7(m,2H),5.81-6.11(m,1H),4.12-4.26(m,1H),3.74-3.87(m,1H),1.83-1.91(m,1H),0.95-1.01(m,2H),0.66-0.73(m,2H) 19 F NMR(377MHz,CDCl3)δ ppm 188.27(s,1F) LCMS (Method C): Retention time 1.25 min, 517(MH)

[0454] The analytical sample rac-3-chloro-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide was analyzed by chiral phase column chromatography.

[0455] Method: SFC: Waters Acquity UPC 2 / QDa PDA Detector Waters Acquity UPC 2 Column: Daicel SFC CHIRALPAK® AY, 3 μm, 0.3 cm x 10 cm, 40°C Mobile phase: A: CO2 B: IPA Isocratic: 25% B ABPR: 1800 psi Flow rate: 2.0 ml / min Detection: 240 nm Sample concentration: 1 mg / mL MeOH / ACN injection: 2 μl.

[0456] This gave the first eluting isomer 3-chloro-6-(3-cyclopropylphenoxy)-N-[(2R)-2-(2,4-dichlorophenyl)-2-fluoro-ethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (retention time 3.39 min) and the second eluting isomer 3-chloro-6-(3-cyclopropylphenoxy)-N-[(2S)-2-(2,4-dichlorophenyl)-2-fluoro-ethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (reset time 5.59 min). A preparative sample was obtained on a preparative chiral column: Preparation method: Sepiatec Prep SFC100; Column: Daicel CHIRALPAK (registered trademark) AY, 5 μm, 2.0 cm x 25 cm Mobile phase: A:CO2B:EtOH Isocratic: 25%B; Back pressure: 150 bar; GLS: -; Flow rate: 60 ml / min, Detection: UV 240 nm; Sample concentration: 1 g in 33 ml IPA / ACN / DCM (10 / 10 / 13); Injection: 950 μl

[0457] The first eluting peak (retention time approximately 2.5 min) corresponds to 3-chloro-6-(3-cyclopropylphenoxy)-N-[(2R)-2-(2,4-dichlorophenyl)-2-fluoro-ethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide, while the second eluting peak (retention time 3.9 min) corresponds to 3-chloro-6-(3-cyclopropylphenoxy)-N-[(2S)-2-(2,4-dichlorophenyl)-2-fluoro-ethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide. The analytical ee of the Beaute sample measured on the analytical column described above was >98%.

[0458] Example P10: This example illustrates the preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]-2-fluoro-pyrazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.10, Table T1). [ka] (Compound P-1.10 in Table T1)

[0459] Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate was prepared as described in Example 1.

[0460] a) Preparation of 6-(3-cyclopropylphenoxy)-2-fluoro-4H-pyrazolo[1,5-a]pyrimidin-7-one In a single-neck round-bottom flask, a mixture of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate (0.5 g, 1.73 mmol) (prepared in Example 1), 5-fluoro-1H-pyrazol-3-amine (0.17 g, 1.73 mmol), and sodium acetate (0.14 g, 1.73 mmol) in acetic acid (5 mL) was stirred at 100° C. for 16 hours. The reaction progress was monitored by LCMS. Upon completion, the reaction mixture was cooled to room temperature and diluted with ice-cold water. The resulting solid compound was then precipitated, filtered through a Buchner funnel, washed with cold water, and dried to give 6-(3-cyclopropylphenoxy)-2-fluoro-4H-pyrazolo[1,5-a]pyrimidin-7-one as an off-white solid. LCMS (Method B): Retention time 1.32 min, 284(MH)

[0461] b) Preparation of 7-chloro-6-(3-cyclopropylphenoxy)-2-fluoro-pyrazolo[1,5-a]pyrimidine In a single-neck round-bottom flask, pyridine (1.71 mL, 21.0 mmol) was added to a mixture of 6-(3-cyclopropylphenoxy)-2-fluoro-4H-pyrazolo[1,5-a]pyrimidin-7-one (1.5 g, 5.25 mmol) and phosphorus(V) oxychloride (37.3 mL, 399 mmol) at 0 °C. The reaction mixture was stirred at 85 °C for 12 h. The reaction progress was monitored by LCMS. Upon completion, the reaction mixture was concentrated to a minimum volume, then diluted with ice water and extracted with EtOAc. The resulting organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give 7-chloro-6-(3-cyclopropylphenoxy)-2-fluoro-pyrazolo[1,5-a]pyrimidine as a pale yellow solid. LCMS (Method B): Retention time 1.70 min, 304(M+H)

[0462] c) Preparation of methyl 6-(3-cyclopropylphenoxy)-2-fluoro-pyrazolo[1,5-a]pyrimidine-7-carboxylate An autoclave vessel was charged with 7-chloro-6-(3-cyclopropylphenoxy)-2-fluoro-pyrazolo[1,5-a]pyrimidine (0.7 g, 2.30 mmol), triethylamine (0.65 mL, 4.61 mmol), and Pd(dppf)Cl2CH2Cl2 (0.47 g, 0.57 mmol) in methanol (69 mL). The reactor was flushed with carbon monoxide gas three times and then charged with 10 bar of carbon monoxide. The reaction mixture was heated to 80 °C for 3 h. The reaction progress was monitored by LCMS. Upon completion, the reaction mixture was diluted with water and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The crude residue obtained was purified by silica gel chromatography (cyclohexane / EtOAc) to give methyl 6-(3-cyclopropylphenoxy)-2-fluoro-pyrazolo[1,5-a]pyrimidine-7-carboxylate as a yellow gum. LCMS (Method B): Retention time 1.65 min, 328(M+H)

[0463] d) Preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]-2-fluoro-pyrazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.10, Table T1) A 10 mL microwave vial was charged with methyl 3-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate (100 mg, 0.30 mmol) and 2-(2,4-dichlorophenyl)-2-fluoroethanamine (127 mg, 0.61 mmol). The vial was then sealed and microwaved at 90 °C for 2 hours with stirring. The reaction progress was monitored by TLC and LCMS. Upon completion, the reaction mixture was diluted with water and extracted with EtOAc. The resulting 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 / EtOAc as eluent) to give 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]-2-fluoro-pyrazolo[1,5-a]pyrimidine-7-carboxamide as a white solid. 1 H NMR(400MHz,CDCl3)δ ppm 8.39-8.52(m,2H),7.49(d,J=8.38Hz,1H),7.37-7.44(m,1H),7.21-7.28(m,2H),6.86(d,J=7.75Hz,1H),6.71-6.78(m,2H),6.40(d,J=5 .13Hz,1H),5.89-6.04(m,1H),4.13-4.26(m,1H),3.76-3.89(m,1H),1.89(tt,J=8.41,5.03Hz,1H),0.89-1.05(m,2H),0.67-0.74(m,2H) 19 F NMR(377MHz,CDCl3)δ ppm 117.63(s,1F),-188.54(s,1F) LCMS (Method C): Retention time 1.29 min, 503(M+H)

[0464] Example P11: This example illustrates the preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]-3-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.11, Table T1). [ka] (Compound P-1.11 in Table T1)

[0465] Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate was prepared as described in Example 1.

[0466] a) Preparation of 6-(3-cyclopropylphenoxy)-3-methyl-4H-pyrazolo[1,5-a]pyrimidin-7-one In a single-neck round-bottom flask, a mixture of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate (0.30 g, 1.09 mmol), 4-methyl-1H-pyrazol-3-amine (0.73 g, 7.59 mmol), and sodium acetate (90.3 mg, 1.09 mmol) in acetic acid (3 mL) was stirred at 100 °C for 16 h. The reaction progress was monitored by LCMS. Upon completion, the reaction mixture was cooled to room temperature and diluted with ice-cold water. The resulting solid was filtered and dried in vacuo to give 6-(3-cyclopropylphenoxy)-3-methyl-4H-pyrazolo[1,5-a]pyrimidin-7-one as a brown solid. LCMS (Method B): Retention time 1.28 min, 282 (M+H) +

[0467] b) Preparation of 7-chloro-6-(3-cyclopropylphenoxy)-3-methyl-pyrazolo[1,5-a]pyrimidine In a single-neck round-bottom flask, a mixture of 6-(3-cyclopropylphenoxy)-2-methyl-4H-pyrazolo[1,5-a]pyrimidin-7-one (170 mg, 0.60 mmol) and phosphorus(V) oxychloride (4.3 mL, 45.9 mmol) was cooled to 0 °C, and pyridine (19.7 μL, 2.41 mmol) was added dropwise via syringe at 0 °C. The resulting reaction mixture was stirred at 80 °C for 2 h. The reaction progress was monitored by LCMS. Upon completion, the reaction mixture was concentrated under reduced pressure, and the reaction mixture was diluted with ice water and extracted with EtOAc. The resulting organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give 7-chloro-6-(3-cyclopropylphenoxy)-3-methyl-pyrazolo[1,5-a]pyrimidine as a pale yellow gum. LCMS (Method B): Retention time 1.79 min, 300 (M+H)

[0468] c) Preparation of methyl 6-(3-cyclopropylphenoxy)-3-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxylate An autoclave vessel was charged with 7-chloro-6-(3-cyclopropylphenoxy)-3-methyl-pyrazolo[1,5-a]pyrimidine (0.14 g, 0.46 mmol), triethylamine (0.13 mL, 0.93 mmol), and Pd(dppf)Cl2CH2Cl2 (93.3 mg, 0.11 mmol) in methanol (20 mL). The reactor was flushed with carbon monoxide gas three times and then charged with 10 bar of carbon monoxide. The reaction mixture was heated to 80 °C for 5 h. The reaction progress was monitored by LCMS. Upon completion, the reaction mixture was cooled, filtered through Celite, and concentrated in vacuo to give a crude red-brown residue. The crude residue obtained was purified by silica gel chromatography (cyclohexane / EtOAc) to give methyl 6-(3-cyclopropylphenoxy)-3-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxylate as a yellow gum. LCMS (Method B): Retention time 1.63 min, 324(M+H)

[0469] d) Preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]-3-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.11, Table T1) A 10 mL microwave vial was charged with methyl 6-(3-cyclopropylphenoxy)-3-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxylate (70.0 mg, 0.22 mmol) and 2-(2,4-dichlorophenyl)-2-fluoro-ethanamine (45.0 mg, 0.22 mmol). The vial was then sealed and microwaved at 100 °C for 2 hours with stirring. The reaction progress was monitored by TLC and LCMS. Upon completion, the reaction mixture was diluted with water and extracted with EtOAc. The resulting 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 / EtOAc as eluent) to give 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]-3-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxamide. 1 H NMR(400MHz,CDCl3)δ ppm 9.77(br s,1H),8.28(s,1H),7.94(s,1H),7.39(d,J=8.31Hz,1H),7.28-7.35(m, 1H),7.17-7.22(m,1H),7.12(t,J=7.95Hz,1H),6.74(d,J=7.82Hz,1H),6 .61-6.68(m,2H),5.96-5.85(m,1H),4.00-4.19(m,1H),3.72-3.80(m,1 H),2.36(s,3H),1.75-1.82(m,1H),0.75-0.92(m,2H),0.57-0.66(m,2H) 19 F NMR(377MHz,CDCl3)δ ppm 187.91(s,1F) LCMS (Method B): Retention time 1.80 min, 499(M+H)

[0470] Example P12: This example illustrates the preparation of 2-chloro-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.12, Table T1). [ka] (Compound P-1.12 in Table T1)

[0471] Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate was prepared as described in Example 1, steps a) and b).

[0472] a) Preparation of 2-chloro-6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidin-7-one In a single-neck round-bottom flask, a mixture of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate (0.50 g, 2.00 mmol), 5-chloro-3H-pyrazol-3-amine (0.20 g, 2.00 mmol), and sodium acetate (0.20 g, 2.00 mmol) in acetic acid (10 mL) was stirred at 110 °C for 4 hours. The reaction progress was monitored by LCMS. After completion of the reaction, the reaction mixture was concentrated under reduced pressure and water was added. The resulting solid was filtered and dried to give 2-chloro-6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidin-7-one as a brown solid. LCMS (Method B): Retention time 1.38 min, 302 (M+H)

[0473] b) Preparation of 2,7-dichloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine In a single-neck round-bottom flask, a mixture of 2-chloro-6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidin-7-one (0.20 g, 0.66 mmol), pyridine (0.2 mL, 2.65 mmol), and phosphorus(V) oxychloride (5.0 mL, 50.3 mmol) was stirred at 90 °C for 4 h. The reaction progress was monitored by LCMS. After completion of the reaction, the reaction mixture was diluted with ice water and extracted with EtOAc. The resulting organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / ethyl acetate) to give 2,7-dichloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine as a yellow solid. LCMS (Method B): Retention time 1.77 min, 320 (M+H)

[0474] c) Preparation of methyl 2-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate An autoclave vessel was charged with 2,7-dichloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine (0.08 g, 0.25 mmol), triethylamine (0.07 mL, 0.50 mmol), and Pd(dppf)Cl2CH2Cl2 (0.051 g, 0.06 mmol) in ethanol (20 mL). The reactor was flushed with carbon monoxide gas three times and then charged with 10 bar of carbon monoxide. The reaction mixture was heated to 80 °C for 2 h. The progress of the reaction was monitored by LCMS. After completion of the reaction, the reaction mixture was diluted with water and extracted with EtOAc. The resulting organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The crude residue obtained was purified by silica gel chromatography (cyclohexane / EtOAc) to give methyl 2-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate as a yellow gum. LCMS (Method B): Retention time 2.92 min, 344(M+H)

[0475] d) Preparation of 2-chloro-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.12, Table T1) In a microwave vial, a mixture of methyl 2-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate (0.06 g, 0.14 mmol) and 2-(2,4-dichlorophenyl)-2-fluoro-ethanamine (0.029 g, 0.14 mmol) was stirred at 80 °C for 2 hours. The reaction progress was monitored by TLC and LCMS. Upon completion, the reaction mixture was diluted with water and extracted with EtOAc. The resulting organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give 2-chloro-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide as a brown solid. 1 H NMR(400MHz,CDCl3)δ ppm 8.72(br s,1H),8.43(s,1H),7.51(d,J=8.38Hz,1H),7.35-7.44(m,1H),7.28-7. 29(m,1H),7.20-7.24(m,1H),6.84-6.86(d,J=7.75Hz,1H),6.79(s,1H), 6.73-6.77(m,2H),5.90-6.05(m,1H),4.08-4.25(m,1H),3.77-3.93(m,1 H),1.87(tt,J=8.44,5.00Hz,1H),0.97-0.99(m,2H),0.63-0.75(m,2H). LCMS (Method B): Retention time 1.88 min, 519(M+H)

[0476] Example P13: This example illustrates the preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]-2-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.13, Table T1). [ka] (Compound P-1.13 in Table T1)

[0477] Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate was prepared as described in Example 1, steps a) and b).

[0478] a) Preparation of 6-(3-cyclopropylphenoxy)-2-methyl-4H-pyrazolo[1,5-a]pyrimidin-7-one In a single-neck round-bottom flask, a mixture of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate (2.20 g, 7.59 mmol), 5-methyl-1H-pyrazol-3-amine (0.73 g, 7.59 mmol), and sodium acetate (0.30 g, 3.63 mmol) in acetic acid (22.0 mL) was stirred at 100 °C for 16 h. The reaction progress was monitored by LCMS. After completion of the reaction, the reaction mixture was concentrated under reduced pressure and co-evaporated twice with toluene under reduced pressure to give a crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give 6-(3-cyclopropylphenoxy)-2-methyl-4H-pyrazolo[1,5-a]pyrimidin-7-one as a brown solid. LCMS (Method B): Retention time 1.28 min, 282 (M+H)

[0479] b) Preparation of 7-chloro-6-(3-cyclopropylphenoxy)-2-methyl-pyrazolo[1,5-a]pyrimidine In a single-neck round-bottom flask, a mixture of 6-(3-cyclopropylphenoxy)-2-methyl-4H-pyrazolo[1,5-a]pyrimidin-7-one (0.32 g, 0.79 mmol) and phosphorus(V) oxychloride (9.46 g, 60.5 mmol) was cooled to 0 °C, and pyridine (0.25 g, 3.18 mmol) was added dropwise via syringe at 0 °C. The resulting reaction mixture was stirred at 70 °C for 5 h. The reaction progress was monitored by LCMS. After completion of the reaction, the reaction mixture was diluted with ice water and extracted with EtOAc. The resulting organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give 7-chloro-6-(3-cyclopropylphenoxy)-2-methyl-pyrazolo[1,5-a]pyrimidine as a pale yellow gum. LCMS (Method D): Retention time 1.14 min, 300 (M+H)

[0480] c) Preparation of methyl 6-(3-cyclopropylphenoxy)-2-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxylate An autoclave vessel was charged with 7-chloro-6-(3-cyclopropylphenoxy)-2-methyl-pyrazolo[1,5-a]pyrimidine (0.19 g, 0.63 mmol), triethylamine (0.18 mL, 1.27 mmol), and Pd(dppf)Cl2CH2Cl2 (0.13 g, 0.15 mmol) in methanol (19 mL). The reactor was flushed with carbon monoxide gas three times and then charged with 10 bar of carbon monoxide. The reaction mixture was heated to 80 °C for 3 h. The progress of the reaction was monitored by LCMS. After completion of the reaction, the reaction mixture was diluted with water and extracted with EtOAc. The resulting organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The crude residue obtained was purified by silica gel chromatography (cyclohexane / EtOAc) to give methyl 6-(3-cyclopropylphenoxy)-2-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxylate as a pale yellow gum. LCMS (Method C): Retention time 1.18 min, 324(M+H)

[0481] d) Preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]-2-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.13, Table T1 A 10 mL microwave vial was charged with methyl 6-(3-cyclopropylphenoxy)-2-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxylate (70.0 mg, 0.22 mmol) and 2-(2,4-dichlorophenyl)-2-fluoro-ethanamine (90.0 mg, 0.43 mmol), the vial was sealed, and microwaved at 100 °C for 4 h with stirring. The reaction progress was monitored by TLC and LCMS. Upon completion, the reaction mixture was diluted with water and extracted with EtOAc. The resulting 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 / EtOAc as eluent) to give 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]-2-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxamide as an off-white solid. 1 H NMR(400MHz,CDCl3)δ ppm 9.87(br s,1H),8.37(s,1H),7.49(d,J=8.50Hz,1H),7.37-7.42(m,1H),7.25-7.27(m,1H ),7.20(t,J=7.94Hz,1H),6.81(d,J=7.75Hz,1H),6.68-6.75(m,2H),6.64(s,1H ),5.93-6.04(dd,J=7.00,3.25Hz,1H),4.13-4.26(m,1H),3.76-3.88(m,1H),2. 56(s,3H),1.86(tt,J=8.44,5.00Hz,1H),0.87-1.01(m,2H),0.66-0.71(m,2H). LCMS (Method C): Retention time 1.30 min, 499(M+H)

[0482] Example P14: This example illustrates the preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]-2-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.14, Table T1). [ka] (Compound P-1.14 in Table T1)

[0483] Note: Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate was prepared as described in Example 1, steps a) and b).

[0484] a) Preparation of 6-(3-cyclopropylphenoxy)-2-methyl-4H-[1,2,4]triazolo[1,5-a]pyrimidin-7-one In a single-neck round-bottom flask, a mixture of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate (1.04 g, 3.59 mmol), 5-methyl-4H-1,2,4-triazol-3-amine (0.35 g, 3.59 mmol), and sodium acetate (0.30 g, 3.59 mmol) in acetic acid (10 mL) was stirred at 120 °C for 12 h. The reaction progress was monitored by LCMS. After completion of the reaction, the reaction mixture was diluted with ice-cold water and stirred for 15 min. The resulting solid was filtered through a Buchner funnel and dried under vacuum to give 6-(3-cyclopropylphenoxy)-2-methyl-4H-[1,2,4]triazolo[1,5-a]pyrimidin-7-one as a white solid. LCMS (Method B): Retention time 1.20 min, 283(M+H)

[0485] b) Preparation of 7-chloro-6-(3-cyclopropylphenoxy)-2-methyl-[1,2,4]triazolo[1,5-a]pyrimidine In a single-neck round-bottom flask, a mixture of 6-(3-cyclopropylphenoxy)-2-methyl-4H-[1,2,4]triazolo[1,5-a]pyrimidin-7-one (1.70 g, 6.02 mmol), N,N-dimethylaniline (3.15 g, 24.7 mmol), and phosphorus(V) oxychloride (42.8 mL, 458 mmol) was stirred at 90 °C for 12 h. The reaction progress was monitored by LCMS. After completion of the reaction, the reaction mixture was diluted with ice water and extracted with EtOAc. The resulting organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give 7-chloro-6-(3-cyclopropylphenoxy)-2-methyl-[1,2,4]triazolo[1,5-a]pyrimidine as a yellow solid. LCMS (Method B): Retention time 1.54 min, 301(M+H)

[0486] c) Preparation of methyl 6-(3-cyclopropylphenoxy)-2-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxylate An autoclave vessel was charged with 7-chloro-6-(3-cyclopropylphenoxy)-2-methyl-[1,2,4]triazolo[1,5-a]pyrimidine (0.53 g, 1.76 mmol), triethylamine (0.50 mL, 3.52 mmol), and Pd(dppf)Cl2CH2Cl2 (0.36 g, 0.44 mmol) in methanol (20 mL). The reactor was flushed with carbon monoxide gas three times and then charged with 10 bar of carbon monoxide. The reaction mixture was heated to 80 °C for 2 h. The progress of the reaction was monitored by LCMS. After completion of the reaction, the reaction mixture was diluted with water and extracted with EtOAc. The resulting organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The crude residue obtained was purified by silica gel chromatography (cyclohexane / EtOAc) to give methyl 6-(3-cyclopropylphenoxy)-2-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxylate as a yellow gum. LCMS (Method B): Retention time 1.42 min, 325(M+H)

[0487] d) Preparation of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]-2-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.14, Table T1) In a microwave vial, a mixture of methyl 6-(3-cyclopropylphenoxy)-2-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxylate (0.10 g, 0.30 mmol) and 2-(2,4-dichlorophenyl)-2-fluoroethanamine (0.12 g, 0.61 mmol) was stirred at 80 °C for 2 hours. The reaction progress was monitored by TLC and LCMS. Upon completion, the reaction mixture was diluted with water and extracted with EtOAc. The resulting organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude residue was purified by reverse phase chromatography (acetonitrile / water) to give 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]-2-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxamide as an off-white solid. 1 H NMR(400MHz,CDCl3)δ ppm 9.12-9.0(m,1H),8.69(s,1H),7.46(br d,J=8.19Hz,1H),7.40(s,1H),7.22-7.25(m,2H),6.88(d,J=7.58Hz,1H),6.72-6.80(m,2H),6.04-5.92(m,1H) ),4.13-4.26(m,1H),3.77-3.91(m,1H),2.70(s,3H),1.80-1.90(m,1H),0.94-1.03(m,2H),0.67-0.73(m,2H) LCMS (Method C): Retention time 1.22 min, 500 (M+H)

[0488] Example P15: This example illustrates the preparation of 5-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]pyrazolo[1,5-b]pyridazine-4-carboxamide (compound P-1.15 of Table T1). [ka] (Compound P-1.15 in Table T1).

[0489] a) Preparation of 2-[(3-iodopyrazol-1-yl)methoxy]ethyl-trimethyl-silane To a solution of 3-iodo-1H-pyrazole (5.0 g, 25.8 mmol) in tetrahydrofuran (50 mL) was added sodium hydride (1.24 g, 30.9 mmol, 60% by weight) at 0° C. The reaction mixture was stirred for 15 minutes, and then 2-(trimethylsilyl)ethoxymethyl chloride (5.28 mL, 28.4 mmol) was added thereto at 0° C. The resulting reaction mixture was stirred at room temperature for 12 hours. The progress of the reaction was monitored by TLC and LCMS. Upon completion, the reaction mixture was diluted with water and extracted with EtOAc. 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 / EtOAc) to afford 2-[(3-iodopyrazol-1-yl)methoxy]ethyl-trimethyl-silane as a gum. LCMS (Method B): Retention time 1.59 min, 325(M+H)

[0490] b) Preparation of 2-(3-cyclopropylphenoxy)-1-[1-(2-trimethylsilylethoxymethyl)pyrazol-3-yl]ethanone In a two-necked round-bottom flask, 2-[(3-iodopyrazol-1-yl)methoxy]ethyl-trimethyl-silane (0.55 g, 1.70 mmol) was dissolved in tetrahydrofuran (3.4 mL) and cooled to 0 °C. A solution of isopropylmagnesium chloride lithium chloride complex (1.3 mol / L in THF, 1.3 mL, 1.70 mmol) was added dropwise and stirred for 30 minutes. After 30 minutes, 2-(3-cyclopropylphenoxy)-N-methoxy-N-methyl-acetamide (prepared separately in three steps) (0.20 g, 0.85 mmol) was added as a tetrahydrofuran solution. The reaction mixture was stirred at room temperature for 2 hours. The progress of the reaction was monitored by TLC and LCMS. Upon completion, the reaction mixture was poured into ice-cold water, acidified with 2N hydrochloric acid, and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The crude residue obtained was purified by silica gel chromatography (cyclohexane / EtOAc) to give 2-(3-cyclopropylphenoxy)-1-[1-(2-trimethylsilylethoxymethyl)pyrazol-3-yl]ethanone as a yellow gum. LCMS (Method B): Retention time 1.69 min, 373(M+H)

[0491] c) Preparation of 2-(3-cyclopropylphenoxy)-N-methoxy-N-methyl-acetamide i. Preparation of ethyl 2-(3-cyclopropylphenoxy)acetate In a single-neck round-bottom flask, 3-cyclopropylphenol (2.0 g, 14.9 mmol) was dissolved in acetonitrile (22 mL) and cesium carbonate (5.82 g, 17.8 mmol) was added. Ethyl 2-bromoacetate (2.98 g, 17.8 mmol) was added, and the resulting reaction mixture was stirred at room temperature for 4 hours. The reaction progress was monitored by LCMS. After completion of the reaction, the reaction mixture was diluted with water and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give ethyl 2-(3-cyclopropylphenoxy)acetate. LCMS (Method B): Retention time 1.48 min, 221(M+H)

[0492] ii. Preparation of 2-(3-cyclopropylphenoxy)acetic acid To a solution of ethyl 2-(3-cyclopropylphenoxy)acetate (0.5 g, 2.27 mmol) in tetrahydrofuran (5.7 mL) and water (2.7 mL) was added lithium hydroxide (0.22 g, 9.08 mmol). The reaction mixture was stirred at room temperature for 2 hours. The progress of the reaction was monitored by TLC and LCMS. After completion of the reaction, the reaction mixture was diluted with water and washed with EtOAc. The aqueous layer was then acidified with 1N HCl and extracted with EtOAc. The combined organic layers were dried over sodium sulfate and concentrated in vacuo to give 2-(3-cyclopropylphenoxy)acetic acid as a beige solid. LCMS (Method B): Retention time 1.28 min, 193(M+H)

[0493] iii. Preparation of 2-(3-cyclopropylphenoxy)-N-methoxy-N-methyl-acetamide To 2-(3-cyclopropylphenoxy)acetic acid (1.34 g, 6.62 mmol) in EtOAc (26.8 mL) was added methoxy(methyl)ammonium chloride (0.97 g, 9.93 mmol), followed by 1-propanephosphonic anhydride solution (T3P, 50% in EtOAc, 4.64 g, 7.29 mmol) and N,N-diisopropylethylamine (3.5 mL, 19.9 mmol). The reaction mixture was stirred at room temperature for 12 h. The reaction progress was monitored by TLC and LCMS. Upon completion, the reaction mixture was diluted with water and extracted with EtOAc. The organic layer was then washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The resulting crude residue was purified by silica gel chromatography (10–30% EtOAc in cyclohexane) to give 2-(3-cyclopropylphenoxy)-N-methoxy-N-methyl-acetamide as a gum. LCMS (Method B): Retention time 1.32 min, 236 (M+H)

[0494] d) Preparation of 2-(3-cyclopropylphenoxy)-1-(1H-pyrazol-3-yl)ethanone In a round-bottom flask, 2-(3-cyclopropylphenoxy)-1-[1-(2-trimethylsilylethoxymethyl)pyrazol-3-yl]ethanone (1.00 g, 2.70 mmol) was dissolved in methanol (11 mL) and 4 M hydrochloric acid in dioxane (8.10 mL, 32 mmol) was added. The reaction mixture was stirred at 80° C. for 2 hours. The progress of the reaction was monitored by TLC and LCMS. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, neutralized with saturated sodium bicarbonate, and extracted with EtOAc. The combined organic layers were dried under reduced pressure to give 2-(3-cyclopropylphenoxy)-1-(1H-pyrazol-3-yl)ethanone. The crude residue obtained was used directly in the next step. LCMS (Method B): Retention time 1.35 min, 241(MH)

[0495] e) Preparation of 2-(3-cyclopropylphenoxy)-3-(dimethylamino)-1-(1H-pyrazol-3-yl)prop-2-en-1-one A solution of 2-(3-cyclopropylphenoxy)-1-(1H-pyrazol-3-yl)ethanone (0.80 g, 3.30 mmol) and 1-tert-butoxy-N,N,N',N'-tetramethyl-methanediamine (7.58 mL, 33.0 mmol) was heated to 90 °C for 6 h in a sealed glass reactor. The reaction progress was monitored by LCMS. After completion of the reaction, the reaction mixture was diluted with water and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give 2-(3-cyclopropylphenoxy)-3-(dimethylamino)-1-(1H-pyrazol-3-yl)prop-2-en-1-one as an off-white solid. LCMS (Method B): Retention time 1.30 min, 298 (M+H)

[0496] f) Preparation of 5-(3-cyclopropylphenoxy)-7H-pyrazolo[1,5-b]pyridazin-4-one In a round-bottom flask, 2-(3-cyclopropylphenoxy)-3-(dimethylamino)-1-(1H-pyrazol-3-yl)prop-2-en-1-one (0.06 g, 2.01 mmol) was dissolved in N-methyl-2-pyrrolidone (6 mL), and potassium tert-butoxide (0.24 g, 2.12 mmol) was added as a solution in N-methyl-2-pyrrolidone (2.0 mL). The resulting reaction mixture was stirred at room temperature for 30 minutes. A solution of amino 4-nitrobenzoic acid (0.44 g, 2.42 mmol) in N-methyl-2-pyrrolidone (2 mL) was added to the mixture, and the reaction mixture was stirred at room temperature overnight. The progress of the reaction was monitored by LCMS. After completion of the reaction, the reaction mixture was diluted with water and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give a mixture of 2-(3-cyclopropylphenoxy)-3-(dimethylamino)-1-(1H-pyrazol-3-yl)prop-2-en-1-one and 5-(3-cyclopropylphenoxy)-7H-pyrazolo[1,5-b]pyridazin-4-one, which was used directly in the next step. LCMS (Method C): Retention time 2.76 min, 298 (M+H) and Retention time 2.95 min, 268 (M+H)

[0497] g) Preparation of 4-chloro-5-(3-cyclopropylphenoxy)pyrazolo[1,5-b]pyridazine In a round-bottom flask, 5-(3-cyclopropylphenoxy)-7H-pyrazolo[1,5-b]pyridazin-4-one (0.37 g, 1.38 mmol), pyridine (0.45 mL, 5.53 mmol), and phosphorus(V) oxychloride (9.8 mL, 105 mmol) were stirred at 90 °C for 12 hours. The reaction progress was monitored by LCMS. After completion of the reaction, the reaction mixture was concentrated. The crude reaction mixture was diluted with ice water, basified with saturated sodium bicarbonate, and extracted with EtOAc. The resulting organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give 4-chloro-5-(3-cyclopropylphenoxy)pyrazolo[1,5-b]pyridazine as a brown gum. LCMS (Method B): Retention time 1.57 min, 286 (M+H)

[0498] h) Preparation of methyl 5-(3-cyclopropylphenoxy)pyrazolo[1,5-b]pyridazine-4-carboxylate An autoclave vessel was charged with 4-chloro-5-(3-cyclopropylphenoxy)pyrazolo[1,5-b]pyridazine (45.0 mg, 0.16 mmol), triethylamine (0.04 mL, 0.31 mmol), and Pd(dppf)Cl2CH2Cl2 (0.10 g, 0.13 mmol) in methanol (20 mL). The reactor was flushed with carbon monoxide gas three times and then charged with 10 bar of carbon monoxide. The reaction mixture was heated to 90 °C for 6 h. The reaction progress was monitored by LCMS. After completion of the reaction, the reaction mixture was diluted with water and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure to give a crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give methyl 5-(3-cyclopropylphenoxy)pyrazolo[1,5-b]pyridazine-4-carboxylate as a yellow gum. LCMS (Method B): Retention time 1.48 min, 310 (M+H)

[0499] i) Preparation of Lithium; 5-(3-cyclopropylphenoxy)pyrazolo[1,5-b]pyridazine-4-carboxylate To a solution of methyl 5-(3-cyclopropylphenoxy)pyrazolo[1,5-b]pyridazine-4-carboxylate (0.03 g, 0.10 mmol) in tetrahydrofuran (1 mL) and water (0.06 mL) was added lithium hydroxide monohydrate (12.4 mg, 0.30 mmol). The reaction mixture was stirred at room temperature for 5 hours. The progress of the reaction was monitored by TLC and LCMS. After completion of the reaction, the reaction mixture was concentrated under reduced pressure at 30 °C and subsequently co-distilled twice with toluene to give lithium 5-(3-cyclopropylphenoxy)pyrazolo[1,5-b]pyridazine-4-carboxylate, which was used directly in the next step. LCMS (Method B): Retention time 1.34 min, 296(M+H)

[0500] j) Preparation of 5-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]pyrazolo[1,5-b]pyridazine-4-carboxamide (compound P-1.15, Table T1) To lithium 5-(3-cyclopropylphenoxy)pyrazolo[1,5-b]pyridazine-4-carboxylate (0.04 g, 0.13 mmol) in EtOAc (0.66 mL) was added 2-(2,4-dichlorophenyl)-2-fluoroethanamine (33.0 mg, 0.16 mmol), followed by the addition of 1-propanephosphonic anhydride solution (T3P, 50% in EtOAc, 0.23 mL, 0.40 mmol) and triethylamine (0.04 mL, 0.30 mmol) at 0 °C. The reaction mixture was stirred at room temperature for 12 hours. The progress of the reaction was monitored by TLC and LCMS. Upon completion, the reaction mixture was diluted with water and extracted with EtOAc. The resulting organic layer was washed with brine, dried over sodium sulfate, and concentrated under reduced pressure. The crude residue obtained was purified by silica gel chromatography (cyclohexane / EtOAc) to give 5-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoroethyl]pyrazolo[1,5-b]pyridazine-4-carboxamide as a yellow gum. 1 H NMR(400MHz,CDCl3)δ ppm 8.10(d,J=2.38Hz,1H),7.98(s,1H),7.73(br s,1H),7.31-7.39(m,2H),7.29(d,J=2.63Hz,2H),7.10(dd,J=8.38,2.00Hz,1H),7.08(d,J=7.75Hz,1H),6.86(ddd,J=8.13,2.5 0,0.88Hz,1H),6.76-6.81(m,1H),5.89-6.02(m,1H),3.86-4.16(m,2H),1.89-1.97(m,1H),0.98-1.13(m,2H),0.69-0.78(m,2H) LCMS (Method B): Retention time 1.64 min, 485(M+H)

[0501] Further examples of synthetic compounds of formula (I) are shown in Table T1.

[0502] [Table 21-1] [Table 21-2] [Table 21-3] [Table 21-4]

[0503] Biological Examples and Test Methods The following examples serve to illustrate the present invention.The compounds of the present invention can be distinguished from known compounds due to their greater effectiveness at low application doses, which can be verified by those skilled in the art using the experimental procedures outlined in the examples, using lower application doses as needed, for example, 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

[0504] Compounds of formula (I) may have any number of benefits, including, inter alia, advantageous levels of biological activity for protecting plants from diseases caused by fungi or superior properties for use as pesticide active ingredients (e.g., greater biological activity, advantageous spectrum of activity, increased safety profile (including improved crop tolerance), improved physicochemical properties or increased biodegradability).

[0505] General description of the test method Leaf discs or segments of various plant species are excised from plants grown in a greenhouse. The excised leaf discs or segments are placed on water agar in multiwell plates (24-well format). The leaf discs are sprayed with the test solution either before inoculation (preventive) or after inoculation (curative). The test compound is prepared as a DMSO solution (maximum 10 mg / mL) diluted to the appropriate concentration with 0.025% Tween 20 immediately before spraying. The inoculated leaf discs or segments are incubated under specified conditions (temperature, relative humidity, light, etc.) according to the respective test system. A single assessment of disease level is made 3 to 14 days after inoculation, depending on the pathogen system. The percent disease control relative to the untreated check leaf discs or segments is then calculated.

[0506] Freshly prepared fungal mycelium segments or conidial suspensions from fungal liquid cultures or cryogenic storage are mixed directly into nutrient broth. A DMSO solution of the test compound (up to 10 mg / mL) is diluted 50-fold with 0.025% Tween 20, and 10 μL of this solution is pipetted into a microtiter plate (96-well format). The nutrient broth containing the fungal spores / mycelium segments is then added to obtain the final concentration of test compound. The test plate is incubated in the dark at 24 °C and 96% relative humidity. Inhibition of fungal growth is determined photometrically after 2–7 days, depending on the pathogenic system, and the percent antifungal activity relative to untreated controls is calculated.

[0507] Example B-1: Alternaria solani / Tomato / Leaf disc (leaf blight) Tomato leaf discs (cv. sprouts) are placed on agar in multiwell plates (24-well format) and sprayed with formulated test compounds diluted in water. The discs are inoculated with a fungal spore suspension two days after application. The inoculated discs are incubated in a climate cabinet at 23°C / 21°C (day / night) and 80% rh under 12 / 12 h light / dark light conditions. Compound activity is assessed as % disease control when an appropriate level of disease damage appears on untreated check disc leaf discs (5-7 days after application) compared to untreated.

[0508] The following compounds provided at least 80% control of Alternaria solani at 200 ppm when compared to untreated controls under the same conditions that showed widespread disease development: P-1.13.

[0509] Example B-2: Botryotinia fuckeliana Botrytis cinerea / liquid culture (gray mold) Fungal conidia from cryogenic storage are mixed directly into nutrient broth (Vogels broth). A (DMSO) solution of the test compound is placed in a microtiter plate (96-well format), followed by the addition of the nutrient broth containing the fungal spores. The test plate is incubated at 24°C, and growth inhibition is determined photometrically 3-4 days after application.

[0510] The following compounds provided at least 80% control of Botryotinia fuckeliana at 20 ppm when compared to untreated controls, which showed widespread disease development under the same conditions: P-1.1, P-1.2, P-1.3, P-1.5, P-1.7, P-1.8, P-1.9, P-1.10, P-1.11, P-1.12, P-1.13, P-1.14, P-1.15, P-1.16, P-1.18, P-1.19, and P-1.20.

[0511] Example B-3: Glomerella lagenarium (Colletotrichum lagenarium) / Liquid Culture (Anthrax) Fungal conidia from cryogenic storage are mixed directly into nutrient broth (PDB potato dextrose broth). A (DMSO) solution of the test compound is placed in a microtiter plate (96-well format), followed by the addition of the nutrient broth containing the fungal spores. The test plate is incubated at 24 °C, and growth inhibition is measured photometrically 3-4 days after application.

[0512] The following compounds provided at least 80% control of Glomerella lagenarium at 20 ppm when compared to untreated controls, which showed extensive disease development under the same conditions: P-1.1, P-1.2, P-1.3, P-1.6, P-1.7, P-1.8, P-1.10, P-1.11, P-1.12, P-1.13, P-1.14, P-1.15, P-1.16, and P-1.20.

[0513] Example B-4: Blumeria graminis f.sp. tritici, Erysiphe graminis f.sp. tritici / wheat / leaf disc prevention (wheat powdery mildew) Wheat leaf segments (cv. Kanzler) were placed on agar in multiwell plates (24-well format) and sprayed with formulated test compounds diluted in water. Leaf discs were inoculated by shaking powdery mildew-infected plants on the test plates one day after application. The inoculated leaf discs were incubated in a climate chamber at 20°C and 60% rh under a 24-hour dark followed by 12-hour light / 12-hour dark cycl...

Claims

1. Formula (I) 【Chemical 1】 (In the formula, R 1 is unsubstituted or contains one, two, or three independently selected substituents R 11 or R 1 is a 5- or 6-membered monocyclic heteroaryl ring containing 1, 2, or 3 heteroatoms each independently selected from N, O, and S, said heteroaryl ring being unsubstituted or containing 1 or 2 independently selected substituents R 11 is replaced by R 11 is hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, iso-propyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, iso-propyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl or cyclopropyloxy, L 1 is a direct bond, —O— or —O—C(R L1A ) (R L1B )-, R L1A and R L1B are independently selected from hydrogen or methyl, or R L1A and R L1B together with the carbon atom to which they are attached form a cyclopropyl, or L 1 is -NR 10 - (CR 2 R 3 ) m represents -, and R 10 is selected from hydrogen or methyl, and m is 0 or 1; or L 1 teeth, 【Chemistry 2】 where # indicates the bond to the nitrogen atom and the zigzag line indicates the bond to the group G, R 2 and R 3 is independently selected from hydrogen or methyl, and n is 0 or 1; R 4 and R 5 are independently selected from hydrogen, hydroxy, fluoro, methyl, cyano or methoxy; R 4 and R 5 together with the carbon atom to which they are attached form a carbonyl group, a cyclopropyl group, or a cyclobutyl group, G is selected from G-1, G-2, G-3, or G-4; G-1 is phenyl or phenoxy, said phenyl or phenoxy being unsubstituted or containing one, two or three independently selected substituents R G1 is replaced by G-2 is a 5- or 6-membered monocyclic heteroaryl or heteroaryl-oxy, wherein the heteroaryl contains 1, 2, or 3 heteroatoms each independently selected from N, O, and S, and the heteroaryl is unsubstituted or contains 1 or 2 independently selected substituents R G2 is replaced by G-3 is a 9- or 10-membered heterobicyclic ring system containing 1, 2, or 3 heteroatoms each independently selected from N, O, and S, said heterobicyclic ring system being saturated, partially unsaturated, or aromatic, said heterobicyclic ring system being unsubstituted or containing 1 or 2 independently selected substituents R G3 is replaced by G-4 is a 9- or 10-membered carbobicyclic ring system, said carbobicyclic ring system being saturated, partially unsaturated or aromatic, said carbobicyclic ring system being unsubstituted or containing one or two independently selected substituents R G4 is replaced by R G1 , R G2 , R G3 and R G4 are independently hydroxyl, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, iso-propyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, iso-propyloxy, tert-butoxy, propynoxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, or cyclopropyloxy; A is A-1 to A-17: 【Table 1】 is selected from ## is -O-R 1 and % indicates the bond to —C(O)—N(H)—L 1 -G, and R 7 , R 8 , R 9 is hydrogen, fluoro, chloro, bromo, iodo, methyl, ethyl, propyl, isopropyl, allyl, propargyl, cyclopropylmethyl, cyclopentyl, cyclohexyl, -C(=O)OCH 3 , -C(=O)N(CH 3 ) 2 , 2-(dimethylamino)-2-oxo-ethyl, 2-(methylamino)-2-oxo-ethyl, difluoromethyl, trifluoromethyl, methylsulfonyl, methylsulfanyl, methoxy, ethoxy, cyano, hydroxyl, mercapto, or amino). or a stereoisomer, enantiomer, salt or N-oxide of the compound of formula (I).

2. A is selected from A-1, A-3, A-5, A-13 and A-15; R 7 , R 8 and R 9 2. The compound of claim 1, wherein is independently selected from hydrogen, fluoro, chloro, methyl, cyclopropyl, or cyano.

3. L 1 is a direct bond, -NR 10 -CR 2 R 3 -or-CR 2 R 3 -CR 4 R 5 - and R 10 is selected from hydrogen or methyl; R 2 and R 3 are independently selected from hydrogen or methyl, and R 4 and R 5 3. The compound of claim 1 or 2, wherein is independently selected from hydrogen, hydroxy, fluoro, methyl, cyano, or methoxy.

4. R 1 A compound according to any one of claims 1 to 3, wherein is phenyl substituted with a single substituent selected from methyl or cyclopropyl.

5. R 1 A compound according to any one of claims 1 to 3, wherein is pyridine substituted with a single substituent selected from chloro, cyano or methyl.

6. 6. The compound of any one of claims 1 to 5, wherein G is phenyl or phenoxy, unsubstituted or substituted with one or two substituents independently selected from chloro or methyl.

7. The compound of any one of claims 1 to 5, wherein G is pyridine substituted with one or two substituents independently selected from chloro or methyl.

8. A pesticide composition comprising a fungicidally effective amount of a compound according to any one of claims 1 to 7.

9. 10. The composition of claim 8, further comprising at least one additional active ingredient and / or an agriculturally acceptable diluent or carrier.

10. 10. A method for controlling or preventing infestation of useful plants by phytopathogenic microorganisms, which comprises applying a fungicidally effective amount of a compound according to any one of claims 1 to 7 or a composition comprising said compound as an active ingredient to said plant, a part thereof or its habitat.

11. Use of a compound according to any one of claims 1 to 7 as a fungicide.

12. 8. Plant propagation material such as seeds comprising, treated with or having attached thereto a compound according to any one of claims 1 to 7 or a composition comprising said compound as an active ingredient.

13. Formulas (II), (V), (VI) and (XVIII) 【Chemistry 3】 (In the formula, A, R 1 , L 1 and G are as defined for compounds of formula (I) according to any one of claims 1 to 7, X 1 is C 1 ~C 4 -alkoxy, X 2 is fluoro, chloro, bromo, iodo, BF 3 K, B(OH) 2 or B (pinacol), and X 6 is chloro, bromo, iodo or trifluoromethanesulfonyl-O— Compound.

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