Microbiocidal bicyclic heterocyclic carboxamide derivatives

Abstract

Disclosed is a compound of formula (I) wherein the substituents are as defined in claim 1, which compound can be used as a pesticidal agent, in particular a fungicide. # imgabs0 #

Description

[0001] The present invention relates to unsaturated N-bridged bicyclic heterocyclic derivatives, for example as active ingredients, which have microbicidal activity, and in particular fungicidal activity. The invention also relates to agrochemical compositions comprising at least one of these carboxamide derivatives, processes for the preparation of these compounds, and the use of these carboxamide derivatives or compositions in agriculture or horticulture for controlling or preventing infection of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, preferably fungi.

[0002] Many plant protection compounds have been developed to prevent or reduce plant diseases caused by microorganisms (e.g., fungi). For example, WO 2021 / 233861 discloses azabicyclic (thio)amides as fungicidal compounds, and WO 2021 / 249995 discloses azabicyclic substituted heterocycles as fungicides. The azabicyclic compounds disclosed therein are C-bridged.

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

[0004]

[0005] or an agrochemically acceptable salt, stereoisomer, enantiomer, and N-oxide of the compound of formula (I), wherein:

[0006] R 1 is unsubstituted or substituted with 1, 2 or 3 independently selected substituents R 11 substituted phenyl; or

[0007] 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, wherein the heteroaryl ring is unsubstituted or substituted with 1 or 2 independently selected substituents R 11 replace;

[0008] R 11 is hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, isopropyloxy, tert-butoxy, propynyloxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, or cyclopropyloxy;

[0009] L 1 Indicates a direct bond, -O-, or -OC(R L1A )(R L1B )-; where R L1A and R L1B are independently selected from hydrogen and methyl; or RL1A and R L1B together with the carbon atom to which they are attached, form a cyclopropyl group; or

[0010] L 1 Indicates -NR 10 -(CR 2 R 3 ) m -, where R 10 is selected from hydrogen or methyl; m=0 or 1, or L 1 express

[0011] wherein # marks the bond to the nitrogen atom, and the staggered lines mark the bond to the group G;

[0012] R 2 and R 3 are independently selected from hydrogen and methyl; and n is 0 or 1;

[0013] R 4 and R 5 are independently selected from hydrogen, hydroxy, fluoro, methyl, cyano, or methoxy; or

[0014] R 4 and R 5 together with the carbon atom to which they are attached, form a carbonyl, cyclopropyl, or cyclobutyl group;

[0015] G is selected from G-1, G-2, G-3, or G-4, wherein:

[0016] G-1 is phenyl or phenoxy, wherein the phenyl or phenoxy is unsubstituted or substituted with 1, 2 or 3 independently selected substituents R G1 replace;

[0017] G-2 is a 5-membered or 6-membered monocyclic heteroaryl or heteroaryl-oxy group; wherein the heteroaryl group contains 1, 2 or 3 heteroatoms each independently selected from N, O and S; and wherein the heteroaryl group is unsubstituted or substituted with 1 or 2 independently selected substituents R G2 replace;

[0018] 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; wherein the heterobicyclic ring system is saturated, partially unsaturated, or aromatic; and wherein the heterobicyclic ring system is unsubstituted or substituted with 1 or 2 independently selected substituents R G3 replace;

[0019] G-4 is a 9-membered or 10-membered carbobicyclic ring system; wherein the carbobicyclic ring system is saturated, partially unsaturated, or aromatic; and wherein the carbobicyclic ring system is unsubstituted or substituted with 1 or 2 independently selected substituents RG4 replace;

[0020] R G1 , R G2 , R G3 , and R G4 are independently hydroxy, halogen, thiol, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, isopropyloxy, tert-butoxy, propynyloxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, or cyclopropyloxy;

[0021] A is selected from A-1 to A-17:

[0022]

[0023] The ## mark and -OR 1 The % mark is the same as -C(O)-N(H)-L 1 -G's key; and

[0024] R 7 , R 8 , R 9 independently selected from hydrogen, fluorine, chlorine, bromine, iodine, 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, hydroxy, thiol, or amino.

[0025] The present invention also provides methods for preparing compounds of formula (I) and intermediate compounds useful for preparing compounds of formula (I).

[0026] Surprisingly, it has been found that the novel compounds of formula (I) have, for practical purposes, very advantageous levels of biological activity for protecting plants against diseases caused by fungi.

[0027] According to a second aspect of the present invention, there is provided an agrochemical composition comprising a fungicidally effective amount of a compound of formula (I). Such an agricultural composition may further comprise at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

[0028] According to a third aspect of the present invention, there is provided a method for controlling or preventing infection of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I), or a composition comprising this compound as an active ingredient, is applied to these plants, their parts or their loci.

[0029] 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 not comprise a method of treating the human or animal body by surgery or therapy.

[0030] According to a fifth aspect, the present invention makes it possible to obtain a plant propagation material, such as a seed, which contains a compound of formula (I) or a composition comprising such a compound, or is treated with such a compound or such a composition, or has such a compound or such a composition attached thereto.

[0031] As used herein, the term "hydroxyl" or "hydroxy" refers to an -OH group.

[0032] As used herein, the term "thiol" refers to a -SH group.

[0033] As used herein, the term "cyano" refers to a -CN group.

[0034] As used herein, amino means -NH 2 Group.

[0035] As used herein, nitro means -NO 2 Group.

[0036] As used herein, oxo refers to a =0 group (eg, as in a carbonyl (C=0) group).

[0037] As used herein, the term "halogen" or "halo" refers to fluorine (fluorine, fluoro), chlorine (chlorine, chloro), bromine (bromine, bromo) or iodine (iodine, iodo), preferably fluorine, chlorine or bromine. This also applies accordingly to halogen in combination with other meanings, such as haloalkyl.

[0038] As used herein, the term “C 1-4 "Alkyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to four carbon atoms, and attached to the remainder of the molecule by a single bond. 1-3 Alkyl should be interpreted accordingly. 1-4 Examples of alkyl groups include, but are not limited to, methyl, ethyl, isopropyl.

[0039] As used herein, the term “C 2-3 "Alkenyl" refers to a straight or branched hydrocarbon chain radical consisting solely of carbon and hydrogen atoms, containing at least one double bond which may be of (E) or (Z) configuration, having two or three carbon atoms, attached to the remainder of the molecule by a single bond. 2-3 Examples of alkenyl groups include, but are not limited to, vinyl (vinyl or ethenyl), prop-1-enyl, allyl (prop-2-enyl).

[0040] As used herein, the term “C 2-3 "Alkynyl" refers to a straight or branched hydrocarbon chain radical 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 groups include, but are not limited to, prop-1-ynyl and propargyl (prop-2-ynyl).

[0041] As used herein, the term “C 1-4 Haloalkyl", "C 2-3 Haloalkenyl", and "C 2-3 "Haloalkynyl" refers to a C as defined above substituted by one or more halogen atoms which may be the same or different. 1-4 Alkyl, C 2-3 Alkenyl, and C 2-3 Alkynyl group. 1-4 Examples of haloalkyl include, but are not limited to, fluoromethyl, fluoroethyl, difluoromethyl, trifluoromethyl, and 2,2,2-trifluoroethyl.

[0042] As used herein, the term “C 1-3 "Fluoroalkyl" refers to a C 1-3 Alkyl group. 1-3 Examples of fluoroalkyl groups include, but are not limited to, difluoromethyl and trifluoromethyl.

[0043] As used herein, the term “C 1-3 "Alkoxy" refers to a group having the formula R a O-group, where R a is C as defined above 1-3 Alkyl group. 1-3 Examples of alkoxy include, but are not limited to, methoxy, ethoxy, isopropoxy.

[0044] As used herein, the term “C 1-3 "Fluoroalkoxy" refers to a C 1-3 Alkoxy group. 1-3 Examples of fluoroalkoxy groups include, but are not limited to, trifluoromethoxy.

[0045] As used herein, the term “C 3-4 "Cycloalkyl" refers to a saturated, stable monocyclic group containing 3 or 4 carbon atoms.

[0046] As used herein, the term “C 1-3 "Alkylsulfanyl" refers to a alkylsulfanyl having the formula -SR a A group in which R a is C as defined above 1-3 Alkyl group.

[0047] As used herein, the term “C 1-3 "Alkylsulfonyl" refers to a group having the formula -S(O) 2 R a A group in which R a is C as defined above 1-3 Alkyl group.

[0048] As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic ring having 1 to 3 heteroatoms independently selected from N, O and S. Examples of heteroaryl groups include J-1 to J-43 shown in Table J below. The staggered lines in heteroaryl groups J-1 to J-43 represent the point of attachment to the rest of the compound. Preferred heteroaryl groups include pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, and thiazolyl; preferably, pyridinyl and thiazolyl.

[0049] Table J: Heteroaryl groups J-1 to J-43:

[0050]

[0051]

[0052] As used herein, the term "heterocyclyl" refers to a 3-, 4-, 5-, and 6-membered saturated monocyclic ring having 1 or 2 heteroatoms independently selected from nitrogen and oxygen. Examples of heterocyclyls include K-1 to K-26 shown in Table K below. The staggered lines in heterocyclyls K-1 to K-26 represent the point of attachment to the rest of the compound. Some of the heterocyclyls shown below contain asymmetric carbons, which means that the compounds containing them can exist in the form of chiral isomers, i.e., enantiomers or diastereomers. Preferred heterocyclyls include pyrrolidinyl, piperidinyl, piperazinyl, and tetrahydropyranyl; preferably, pyrrolidinyl, piperazinyl, and tetrahydropyranyl.

[0053] Table K: Heterocyclic groups K-1 to K-26:

[0054]

[0055]

[0056] As used herein, the term "optionally substituted" means that the referenced group is unsubstituted or substituted with a specified substituent, for example, "C 3 -C 4 Cycloalkyl is optionally substituted by 1 or 2 halogen atoms" means C 3 -C 4 Cycloalkyl, C substituted by 1 halogen atom 3 -C 4 Cycloalkyl and C substituted by 2 halogen atoms 3 -C 4 Cycloalkyl. Further, 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".

[0057] As used herein, the term "optionally in the presence of" means that a process is performed in the presence or absence of the mentioned reagent, for example "optionally performing the process in the presence of a base" means that the process can be performed with or without a base.

[0058] As used herein, staggered lines, such as in the heteroaryl groups shown in Table J and the heterocyclyl groups shown in Table K, indicate the point of connection / attachment to the rest of the compound.

[0059] As used herein, the term "control" means reducing the number of pests, eliminating pests, and / or preventing further pest damage so that damage to plants or to plant-derived products is reduced.

[0060] As used herein, the term "pest" refers to insects and molluscs present in agriculture, horticulture, forestry, storage of products of plant origin (such as fruits, grains and wood); and those pests associated with damage to man-made structures. The term pest covers all stages of the pest life cycle.

[0061] As used herein, the term "effective amount" refers to an amount of a compound or a salt thereof that provides the desired effect upon single or multiple administrations.

[0062] The effective amount is readily determined by one skilled in the art using known techniques and by observing the results obtained under similar circumstances. In determining the effective amount, many factors are considered, including, but not limited to, the type of plant or derived product to be applied; the pest to be controlled and its life cycle; the specific compound being applied; the type of application; and other relevant circumstances.

[0063] As used herein, the term "room temperature" or "RT" or "rt" refers to a temperature of about 15° C. to about 35° C. For example, rt may refer to a temperature of about 20° C. to about 30° C.

[0064] The presence of one or more possible asymmetric carbon atoms in a compound of formula (I) means that the compound can exist in the form of chiral isomers, i.e., enantiomers or diastereomers. As a result of restricted rotation around a single bond, atropisomers may also exist. Formula (I) is intended to include all those possible isomeric forms and mixtures thereof. The present invention includes all those possible isomeric forms and mixtures thereof of compounds of formula (I). Similarly, formula (I) is intended to include all possible tautomers (including lactam-lactim tautomerism and keto-enol tautomerism) (when present). The present invention includes all possible tautomeric forms of compounds of formula (I).

[0065] Compounds of formula (I) having at least one basic center can form acid addition salts, for example, 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 (such as unsubstituted or halogen-substituted C 1 -C 4 Alkanecarboxylic acids, 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 unsubstituted or halogen-substituted C 1 -C 4 The compounds of formula (I) having at least one acidic group can, for example, form salts with bases, for example mineral salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts; or with ammonia or organic amines (such as morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, for example ethylamine, diethylamine, triethylamine or dimethylpropylamine, or mono-, di- or tri-hydroxy lower alkylamines, for example monoethanolamine, diethanolamine or triethanolamine).

[0066] The compounds of formula (I) according to the invention also include hydrates which may be formed during salt formation.

[0067] In each case, the compounds of formula (I) according to the invention are in free form, oxidized form (as N-oxide), covalently hydrated form, or salt form (eg, an agronomically usable or agrochemically acceptable salt form).

[0068] N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen-containing heteroaromatic compounds. They are described, for example, by A. Albini and S. Pietra in 1991 in the book "Heterocyclic N-oxides", CRC Press, Boca Raton.

[0069] Throughout this specification, Can also be written as -(CR 2 R 3 ) n -CR 4 R 5 -and-CR 2 R 3 -CR 4 R 5 -.

[0070] The following list provides substituents A, G, L for compounds of formula (I) of the present invention. 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 of these substituents, any definition given below may be combined with any definition of any other substituent given below or elsewhere in this document.

[0071] In various embodiments of the present invention, L 1 yes

[0072] A. Direct bond, -NR 10 -CR 2 R 3 -, or -CR 2 R 3 -CR 4 R 5 -, where 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 5 together with the carbon atom to which they are attached, form a carbonyl, cyclopropyl, or cyclobutyl group; or

[0073] B.-NR 10 -CR 2 R 3 -, where R 10 is selected from hydrogen and methyl; and R 2 and R 3 are independently selected from hydrogen and methyl; or

[0074] C.-NR 10 -CR 2 R 3 -, where R 10 is selected from hydrogen and methyl; and R 2 and R 3 all hydrogen; or

[0075] D.-NR 10 -CR 2 R 3 -, where R 10 is hydrogen; and R 2 and R 3 all hydrogen; or

[0076] E.-CR 2 R 3 -CR 4 R 5 -, where 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, cyclopropyl, or cyclobutyl group; or

[0077] F.-CR 2 R 3 -CR 4 R 5 -, where R 2 and R 3 is hydrogen; R 4 and R 5 are independently selected from hydrogen and fluorine; or R 4 and R 5 together with the carbon atom to which they are attached, form a cyclopropyl group; or

[0078] G.-CR 2 R 3 -CR 4 R 5 -, where R 2 and R 3 is hydrogen; R 4and R 5 are independently selected from hydrogen and fluorine; or

[0079] H.-CH 2 -CHF- or -CH 2 -CH 2 -;or

[0080] I. Direct key.

[0081] In various embodiments of the present invention, R 1 yes:

[0082] A. unsubstituted or substituted with one, two or three independently selected substituents R 11 Substituted phenyl; for example, one or two independently selected substituents R 11 ; preferably a substituent R 11 ; where R 11 is selected from the group consisting of hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, isopropyloxy, tert-butoxy, propynyloxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy; or

[0083] B. Substituted by one or two substituents R 11 , for example, a substituent R 11 Substituted phenyl; wherein R 11 is selected from hydroxy, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or

[0084] C. phenyl substituted with one or two substituents, e.g., one substituent, independently selected from hydroxy, halogen, cyano, methyl, vinyl, ethynyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or

[0085] D. phenyl which is unsubstituted or substituted with one or two substituents independently selected from chloro, fluoro, cyano, methyl, methoxy, and cyclopropyl, for example one substituent; or

[0086] E. phenyl substituted with a single substituent selected from methyl and cyclopropyl; or

[0087] F. Cyclopropylphenyl, such as 3-cyclopropylphenyl.

[0088] In various embodiments of the present invention, R 1 It can also be:

[0089] A. A 5- or 6-membered monocyclic heteroaryl ring containing 1, 2 or 3 heteroatoms which may be the same or different and independently selected from N, O and S, wherein the heteroaryl ring is unsubstituted or substituted with 1 or 2 independently selected substituents R 11 replace; or

[0090] B. A 6-membered monocyclic heteroaryl ring containing 1, 2 or 3 nitrogen atoms, wherein the heteroaryl ring is unsubstituted or substituted with 1 or 2 independently selected substituents R 11 replace; or

[0091] C. pyridine, pyrimidine, pyridazine, or 1,2,4-triazine, wherein any of the pyridine, pyrimidine, pyridazine, or 1,2,4-triazine is unsubstituted or substituted with one or two substituents independently selected from the group consisting of hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, isopropyloxy, tert-butoxy, propynyloxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy; or

[0092] D. pyridine substituted with one or two substituents independently selected from the group consisting of hydroxy, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or

[0093] E. pyridine substituted with a single substituent selected from chloro, fluoro, cyano, methyl, methoxy, difluoromethoxy, and cyclopropyl; or

[0094] F. pyridine substituted with a single substituent selected from chloro, cyano, and methyl;

[0095] In various embodiments of the present invention, R 1 yes:

[0096] A. phenyl, pyridyl, pyrimidinyl, or pyridazinyl, each of which is unsubstituted or substituted with one or two independently selected substituents R 11 Substitution; wherein R 11 is selected from the group consisting of hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, isopropyloxy, tert-butoxy, propynyloxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy; or

[0097] B. phenyl, pyridyl, or pyrimidinyl, each unsubstituted or substituted with one or two independently selected substituents R 11Substitution; wherein R 11 is selected from hydroxy, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or

[0098] C. phenyl or pyridyl, each unsubstituted or substituted with one or two independently selected substituents R 11 Substitution; wherein R 11 is selected from hydroxy, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or

[0099] D. phenyl or pyridyl, each unsubstituted or substituted with one or two independently selected substituents R 11 Substitution; wherein R 11 is selected from chloro, fluoro, cyano, methyl, methoxy, difluoromethoxy, and cyclopropyl; or

[0100] E. phenyl or pyridyl, each unsubstituted or substituted with one or two independently selected substituents R 11 Substitution; wherein R 11 is selected from chloro, cyano, methyl and cyclopropyl; or

[0101] F. phenyl or pyridyl, each unsubstituted or substituted with one or two independently selected substituents R 11 Substitution; wherein R 11 Selected from chloro, cyano and cyclopropyl.

[0102] In various embodiments of the present invention, R 11 Selected from:

[0103] A. hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, isopropyloxy, tert-butoxy, propynyloxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy; or

[0104] B. hydroxy, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or

[0105] C. hydroxy, cyano, methyl, vinyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or

[0106] D. halogen, cyano, methyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, allyloxy, difluoromethoxy, trifluoromethoxy, and cyclopropyl; or

[0107] E. cyano, methyl, methoxy, allyloxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or

[0108] F. chloro, fluoro, cyano, methoxy, allyloxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or

[0109] G. halogen, cyano, methoxy, allyloxy, trifluoromethoxy, and cyclopropyl; or

[0110] H. chloro, fluoro, cyano, cyclopropyl and cyclobutyl; or

[0111] I. Chloro, cyano, cyclopropyl and methyl.

[0112] In embodiments of various aspects of the present invention, G is G-1: phenyl or phenoxy, wherein the phenyl or phenoxy is unsubstituted or substituted with 1, 2 or 3 independently selected substituents R G1 Replace. For example, G-1 is:

[0113] A. phenyl which is unsubstituted or substituted with one or two substituents independently selected from hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, isopropyloxy, tert-butoxy, propynyloxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, or cyclopropyloxy; or

[0114] B. phenyl which is unsubstituted or substituted with one or two substituents independently selected from the group consisting of hydroxy, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or

[0115] C. phenyl which is unsubstituted or substituted by 1, 2 or 3 substituents, for example 2 or 3 substituents, each independently selected from chlorine, fluorine, methyl, and methoxy; or

[0116] D. phenyl substituted with one or two substituents, for example one substituent, selected from chlorine and methyl; or

[0117] E. phenyl substituted with two substituents independently selected from chlorine and methyl; or

[0118] F. 2,4-disubstituted phenyl, each substituent being independently selected from chlorine and methyl; or

[0119] G. 2,4-Dichlorophenyl.

[0120] In embodiments of various aspects of the present invention, G is G-2: a 5-membered or 6-membered monocyclic heteroaryl or heteroaryl-oxy group; wherein the heteroaryl group contains 1, 2 or 3 heteroatoms each independently selected from N, O and S; and wherein the heteroaryl group is unsubstituted or substituted with 1 or 2 independently selected substituents R G2 Replace. For example, G-2 is:

[0121] A. pyridine, pyrimidine, pyridazine, or 1,2,4-triazine, wherein the pyridine, pyrimidine, pyridazine, 1,2,4-triazine is unsubstituted or substituted with one or two substituents independently selected from hydroxy, halogen, thiol, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, isopropyloxy, tert-butoxy, propynyloxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, and cyclopropyloxy; or

[0122] B. pyridine, pyrimidine, or pyridazine substituted with one or two substituents independently selected from hydroxy, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or

[0123] C. a pyrimidine or pyridazine substituted with one or two substituents independently selected from the group consisting of hydroxy, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or

[0124] D. pyridine substituted with 1, 2 or 3 substituents, for example 2 or 3 substituents, each independently selected from chlorine, fluorine, cyano, methyl, and methoxy; or

[0125] E. Pyridine substituted with one or two substituents, e.g. one substituent, selected from chlorine and methyl.

[0126] In embodiments of various aspects of the present invention, G is G-3: a 9-membered or 10-membered heterobicyclic ring system comprising 1, 2 or 3 heteroatoms each independently selected from N, O and S; wherein the heterobicyclic ring system is saturated, partially unsaturated, or aromatic; and wherein the heterobicyclic ring system is unsubstituted or substituted with 1 or 2 independently selected substituents R G3 Replace. For example, G-3 is:

[0127] A. unsubstituted or substituted with 1, 2 or 3 substituents each independently selected from chlorine, fluorine, cyano, methyl, and methoxy, for example 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, benzothiophene-2-yl, benzothiophene-3-yl, benzothiophene-5-yl, benzothiophene-6-yl; or

[0128] 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 substituted with a substituent selected from the group consisting of chlorine, fluorine, cyano, methyl, and methoxy; or

[0129] C. chroman-4-yl, isochroman-4-yl, 4H-chromen-4-yl, 2,3-dihydrobenzofuran-2-yl, or 2,3-dihydrobenzofuran-3-yl substituted with a substituent selected from the group consisting of chloro, fluoro, cyano, methyl, and methoxy; or

[0130] D. 1,3-benzodioxol-5-yl, benzothiazol-2-yl, benzothiazol-5-yl, benzothiazol-6-yl, benzoxazolyl-2-yl, benzofuran-2-yl, benzofuran-3-yl, benzothiophene-2-yl, or benzothiophene-3-yl.

[0131] In embodiments of various aspects of the present invention, G is G-4: a 9-membered or 10-membered carbobicyclic ring system; wherein the carbobicyclic ring system is saturated, partially unsaturated, or aromatic; and wherein the carbobicyclic ring system is unsubstituted or substituted with 1 or 2 independently selected substituents R G4 Replace. For example, G-4 is:

[0132] A. naphthalen-2-yl, tetralin-1-yl, tetralin-2-yl, tetralin-6-yl, indan-1-yl, indan-2-yl, or indan-5-yl, optionally substituted with 1, 2 or 3 substituents each independently selected from chloro, fluoro, cyano, methyl, and methoxy, e.g., one or two substituents; or

[0133] B. or tetralin-1-yl, tetralin-2-yl, indan-1-yl, or indan-2-yl optionally substituted with one or two substituents each independently selected from chloro, fluoro, cyano, methyl, and methoxy, such as one substituent; or

[0134] C. Tetralin-1-yl or indan-1-yl substituted with a substituent selected from the group consisting of chloro, fluoro, cyano, methyl, and methoxy.

[0135] In various embodiments of the present invention, R G1 , R G2 , R G3 , and R G4 Independently selected from:

[0136] A. hydroxy, halogen such as chlorine and fluorine, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, isopropyloxy, tert-butoxy, propynyloxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, or cyclopropyloxy; or

[0137] B. hydroxy, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or

[0138] C. hydroxy, chloro, fluoro, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl; or

[0139] D. chlorine, fluorine, cyano, methyl, and methoxy; or

[0140] E. Chlorine and methyl.

[0141] In embodiments of various aspects of the present invention, A is selected from:

[0142] 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

[0143] 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

[0144] CA-13, A-14, A-15, A-16, and A-17; or

[0145] DA-1, A-2, A-3, A-4, A-5, and A-6; or

[0146] EA-7, A-8, A-9, A-10, A-11, and A-12; or

[0147] FA-13, A-14, A-15, A-16, and A-17; or

[0148] GA-1, A-2, A-3, A-13, A-14, and A-15; or

[0149] HA-4, A-5, A-6, A-7, A-8, A-9, A-15, A-16, and A-17; or

[0150] IA-10, A-11, and A-12; or

[0151] JA-1, A-2, A-3, A-7, A-8, A-9, A-13, A-14, and A-15; or

[0152] KA-4, A-5, A-6, A-10, A-11, A-12, A-16, and A-17; or

[0153] LA-1, A-3, A-5, A-13, and A-15; or

[0154] MA-1, A-3, and A-5; or

[0155] NA-1, A-3 and A-13; or

[0156] OA-1, A-3 and A-15; or

[0157] PA-1 and A-3; or

[0158] QA-1 and A-5; or

[0159] RA-3 and A-5;

[0160] SA-3.

[0161] In embodiments of various aspects of the present invention, A is selected from A-1 to A-17, wherein R 7 , R 8 and R 9 Independently selected from:

[0162] A. Hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, allyl, propargyl, cyclopropylmethyl, cyclopropyl, 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, thiomethoxy, methoxy, ethoxy, cyano, hydroxy, mercapto, and amino; or

[0163] B. Hydrogen, fluorine, chlorine, methyl, ethyl, isopropyl, cyclopropyl, -C(=O)OCH 3 、-C(=O)N(CH 3 ) 2 , 2-(dimethylamino)-2-oxo-ethyl, 2-(methylamino)-2-oxo-ethyl, difluoromethyl, trifluoromethyl, methylsulfonyl, methoxy, and cyano; or

[0164] C. hydrogen, fluorine, chlorine, methyl, ethyl, cyclopropyl, 2-(methylamino)-2-oxo-ethyl, methylsulfonyl, methoxy, and cyano; or

[0165] D. hydrogen, fluorine, chlorine, methyl, cyclopropyl, and cyano; or

[0166] E. hydrogen, fluorine, chlorine, methyl, and cyano; or

[0167] F. hydrogen, fluorine, chlorine, and methyl; or

[0168] G. hydrogen, chlorine, and methyl; or

[0169] H. Hydrogen, chlorine, and fluorine.

[0170] In embodiments of various aspects of the present invention, A is selected from A-1 to A-17, and R 7 , R 8 and R 9 At least one of is hydrogen, and the others (when present) are selected from:

[0171] A. hydrogen, fluorine, chlorine, methyl, ethyl, cyclopropyl, 2-(methylamino)-2-oxo-ethyl, methylsulfonyl, methoxy, and cyano; or

[0172] B. hydrogen, fluorine, chlorine, methyl, cyclopropyl, and cyano; or

[0173] C. hydrogen, fluorine, chlorine, methyl, and cyano; or

[0174] D. hydrogen, fluorine, chlorine, and methyl; or

[0175] E. hydrogen, chlorine, and methyl; or

[0176] F. hydrogen, chlorine, and cyano; or

[0177] G. Hydrogen, chlorine, and fluorine; or

[0178] H. Hydrogen and chlorine.

[0179] Preferred embodiment 1 of various aspects of the present invention provides compounds having formula (IA-1), (IA-3), (IA-5), (IA-13) and (IA-15):

[0180]

[0181] or its agrochemically acceptable salts, stereoisomers, enantiomers, and N-oxides, wherein G, L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 As defined for compounds of formula (I).

[0182] Preferred embodiment 2 of various aspects of the present invention provides a compound according to preferred embodiment 1, wherein L 1 Is a direct key or -CR 2 R 3 -CR 4 R 5 -, where R 2 and R 3 are independently selected from hydrogen and methyl; and R 4 and R 5 are independently selected from hydrogen, hydroxy, fluoro, methyl, cyano, and methoxy.

[0183] Preferred embodiment 3 of various aspects of the present invention provides a compound according to preferred embodiment 1 or 2, wherein L 1 Yes-CR 2 R 3 -CR 4 R 5 -, where R 2 and R 3 is hydrogen; and R 4 and R 5 Independently selected from hydrogen, hydroxy, fluorine, methyl, cyano, and methoxy, preferably hydrogen and fluorine.

[0184] Preferred embodiment 4 of various aspects of the present invention provides a compound according to any one of preferred embodiments 1, 2 or 3, wherein L 1 Yes-CH 2 -CHF- or -CH 2 -CH 2 -(ie, R 2 and R 3 is hydrogen, and R4 or R 5 is fluorine and the other is hydrogen).

[0185] Preferred embodiment 5 of various aspects of the present invention provides a compound according to any one of preferred embodiments 1, 2, 3 or 4, wherein R 1 is phenyl, pyridyl, or pyrimidinyl, each optionally substituted by one or two substituents R independently selected from halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl 11 replace.

[0186] Preferred embodiment 6 of various aspects of the present invention provides a compound according to any one of preferred embodiments 1, 2, 3, 4, or 5, wherein R 1 is phenyl or pyridyl, each optionally substituted by one or two substituents R independently selected from chloro, fluoro, cyano, methyl, methoxy, difluoromethoxy, and cyclopropyl 11 replace.

[0187] Preferred embodiment 7 of various aspects of the present invention provides a compound according to any one of preferred embodiments 1, 2, 3, 4, 5, or 6, wherein R 1 is a substituent R optionally selected from chlorine, fluorine, cyano, methyl, methoxy, difluoromethoxy, and cyclopropyl, preferably selected from chlorine, cyano, methyl, and cyclopropyl 11 3-Substituted phenyl.

[0188] Preferred embodiment 8 of various aspects of the present invention provides a compound according to any one of preferred embodiments 1, 2, 3, 4, 5, or 6, wherein R 1 is one or two substituents R optionally independently selected from chloro, fluoro, cyano, methyl, methoxy, difluoromethoxy, and cyclopropyl 11 Substituted pyridyl, preferably pyridin-3-yl.

[0189] Preferred embodiment 9 of various aspects of the present invention provides compounds according to preferred embodiment 8, wherein R 1 is a substituent R selected from chlorine, cyano, methyl, and cyclopropyl 11 5-substituted pyridin-3-yl, preferably cyano.

[0190] Preferred embodiment 10 of various aspects of the present invention provides compounds according to any one of preferred embodiments 1, 2, 3, 4, 5, 6, 7, 8, or 9, wherein G is phenyl or phenoxy, wherein the phenyl or phenoxy is optionally substituted by 1, 2 or 3 substituents R independently selected from hydroxy, halogen, cyano, methyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, allyloxy, propargyloxy, difluoromethoxy, trifluoromethoxy, cyclopropyl, and cyclobutyl. G1 replace.

[0191] Preferred embodiment 11 of various aspects of 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 G is one or two substituents R optionally independently selected from chloro, fluoro, methyl, and methoxy G1 Substituted phenyl.

[0192] Preferred embodiment 12 of various aspects of the present 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 by two substituents independently selected from chlorine and methyl, preferably G is 2,4-dichlorophenyl.

[0193] Preferred embodiment 13 of various aspects of the present invention provides a compound according to any one of preferred embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, wherein R 7 , R 8 and R 9 independently selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, allyl, propargyl, cyclopropylmethyl, cyclopropyl, 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, thiomethoxy, methoxy, ethoxy, cyano, hydroxy, mercapto, and amino.

[0194] Preferred embodiment 14 of various aspects of the present invention provides a compound according to any one of preferred embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, wherein R 7 , R 8 and R 9 are independently selected from hydrogen, fluorine, chlorine, methyl, cyclopropyl, and cyano.

[0195] Preferred embodiment 15 of various aspects of the present invention provides a compound according to any one of preferred embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, wherein R 7 , R 8 and R 9 At least one of the is hydrogen, and the others (when present) are selected from hydrogen, fluoro, chloro, methyl, ethyl, cyclopropyl, 2-(methylamino)-2-oxo-ethyl, methylsulfonyl, methoxy, and cyano.

[0196] Preferred embodiment 16 of various aspects of the present invention provides a compound according to any one of preferred embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15, wherein R 7 , R 8 and R 9 At least one of is hydrogen, and the others (when present) are selected from hydrogen, fluorine, chlorine, methyl, and cyano; preferably, hydrogen, fluorine, chlorine, and methyl.

[0197] Preferred embodiment 17 of various aspects of the present invention provides compounds having 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.

[0198] Preferred embodiment 18 of various aspects of the present 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.

[0199] Preferred embodiment 19 of various aspects of the present invention provides a compound according to any one of preferred embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16 having formula (IA-1); wherein R 8 is selected from hydrogen, fluorine, chlorine, methyl, and cyano; preferably, hydrogen, fluorine, chlorine, and methyl; and R 9 It's hydrogen.

[0200] Preferred embodiment 20 of various aspects of the present invention provides a compound according to any one of preferred embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16 having formula (IA-3), wherein R 7 and R 8 At least one of the groups is hydrogen, and the other is selected from the group consisting of hydrogen, fluorine, chlorine, methyl, and cyano.

[0201] Preferred embodiment 21 of various aspects of the present invention provides a compound according to preferred embodiment 20, wherein R 7 is selected from hydrogen, chlorine and methyl, R 8 Selected from hydrogen, fluorine, chlorine, cyano, and methyl, at least one of R7 and R8 is hydrogen.

[0202] Preferred embodiment 22 of various aspects of the present invention provides a compound according to any one of preferred embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16 having formula (IA-5), wherein R 8 is selected from hydrogen, fluorine, chlorine, and methyl, preferably R 8 is selected from hydrogen and methyl.

[0203] Preferred embodiment 23 of various aspects of the present invention provides a compound according to any one of preferred embodiments 17, 18, 19, 20, 21, or 22, wherein R 1 is a substituent R selected from chlorine, cyano, methyl, and cyclopropyl 11 3-Substituted phenyl.

[0204] Preferred embodiment 24 of various aspects of the present invention provides a compound according to any one of preferred embodiments 17, 18, 19, 20, 21, 22, or 23, wherein L 1 Yes-CR 2 R 3 -CR 4 R 5 -, where R 2 and R 3 is hydrogen; and R 4 and R 5 are independently selected from hydrogen and fluorine.

[0205] Preferred embodiment 25 of various aspects of the present invention provides a compound according to any one of preferred embodiments 17, 18, 19, 20, 21, 22, 23, or 24, wherein G is one or two substituents R optionally independently selected from chloro, fluoro, methyl, and methoxy G1 Substituted phenyl.

[0206] Preferred embodiment 26 of various aspects of the present invention provides a compound according to any one of preferred embodiments 17, 18, 19, 20, 21, 22, 23, 24, or 25, wherein G is independently selected from chlorine, fluorine, methyl, and methoxy, preferably two substituents R selected from chlorine, fluorine, and methyl G1 2,4-Disubstituted phenyl.

[0207] 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.

[0208] In another embodiment, the compound of formula (I) according to the present invention is selected from the compounds listed in Table T1 (below).

[0209] In another embodiment of the present invention, the compound of formula (I) is selected from 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]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]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 (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-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxamide (P-1.14); 5-(3-cyclopropylphenoxy)-N-[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-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 (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) (according to Table T1 below). .

[0210] The presence of one or more possible asymmetric carbon atoms in any of the compounds according to the invention selected from the compounds of formula (I), or selected from the compounds listed in Tables A-1 to A-17 or the compounds listed in Table T1 (below) means that these compounds may exist in the form of chiral isomers, i.e., enantiomers or diastereoisomers.

[0211] Unless otherwise indicated, compounds of formula (I) can be prepared by one skilled in the art as shown in the following Schemes 1 to 29, wherein A, G, L 1 , R 1 , R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 and R 11 As defined for compounds having formula (I). Certain stereocenters are not specified for the sake of clarity and are not intended to limit the teaching of these schemes in any way.

[0212] As shown in Scheme 1, compounds of formula (I) can be obtained by reacting with a compound of formula (II) and an amine compound of formula (III), preferably in a suitable solvent (e.g., N-methylpyrrolidone, acetonitrile, dimethylacetamide, dichloromethane or tetrahydrofuran), preferably at a temperature between 25°C and 60°C, and optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine); or alternatively, an amide coupling transformation is carried out under conditions described in the literature for amide coupling (e.g., 1-propanephosphonic acid cyclic anhydride (T3P)) in a suitable solvent (e.g., acetonitrile), optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine), which amide coupling transformation is carried out by activating the carboxylic acid functional group of the compound of formula (II), which is a process that usually occurs by converting the -OH of the carboxylic acid into a good leaving group such as a chloride group, for example by using (COCl) 2 or SOCl 2 , followed by treatment with a compound of formula (III). 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.

[0213]

[0214] Solution 1

[0215] As shown in Scheme 2, compounds of formula (I) can also be prepared by reacting a nucleophilic compound of formula (IV) with an electrophilic compound of formula (V), wherein X 2 is a suitable leaving group, such as fluorine, chlorine, bromine, iodine, BF 3 K、B(OH) 2 or B (pinacol), in the presence of a base (e.g., KO-t-Bu, K 3 PO 4 , K 2 CO 3 , triethylamine, or Cs 2 CO 3) in the presence of 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, and 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. Compounds of formula (IV) are known or commercially available.

[0216]

[0217] Solution 2

[0218] As shown in Scheme 3, compounds of formula (II) can be obtained by hydrolyzing a compound of formula (VII) using an alkali metal hydroxide (e.g., NaOH, LiOH) in a suitable solvent or mixture of solvents (typically, tetrahydrofuran, methanol, water, 2-methyl-tetrahydrofuran, acetonitrile) at a temperature between 20°C and 100°C, wherein X 1 It is C 1 -C 4 - alkoxy, such as methoxy or ethoxy. For relevant examples, see WO 2008 / 133192 or J. Med. Chem. [Journal of Medicinal Chemistry] 2021, 64, 12322.

[0219] A compound having formula (VII) wherein X 1 It is C 1 -C 4 -alkoxy groups, such as methoxy or ethoxy groups, can be prepared by reacting a nucleophilic compound of formula (IV) with an electrophilic compound of formula (VI) wherein X 1 It is C 1 -C 4 - alkoxy, such as methoxy or ethoxy, and X 2 is a suitable leaving group, such as fluorine, chlorine, bromine, iodine, BF 3 K、B(OH) 2 or B (pinacol), in the presence of a base (e.g., KO-t-Bu, K 3 PO 4 , K 2 CO 3 , triethylamine, or Cs 2 CO 3) in the presence of a suitable solvent or solvent mixture (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, dimethyl sulfoxide) at a temperature between 20°C and 110°C, and 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 (IV) are known or commercially available.

[0220]

[0221] Solution 3

[0222] As shown in Scheme 4, a compound having formula (V) (wherein X 2 is a suitable leaving group, such as fluorine, chlorine, bromine, iodine, BF 3 K、B(OH) 2 or B (pinacol)) can be obtained by reacting with a compound of formula (VIII) wherein X 2 is a suitable leaving group, such as fluorine, chlorine, bromine, iodine, BF 3 K、B(OH) 2 or B (pinacol), and an amine compound of formula (III) is preferably in a suitable solvent (e.g., N-methylpyrrolidone, dimethylacetamide, dichloromethane or tetrahydrofuran), preferably at a temperature between 25°C and 60°C, and optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine); or alternatively, under conditions described in the literature for amide couplings (e.g., 1-propanephosphonic acid cyclic anhydride (T3P)), in a suitable solvent (e.g., acetonitrile), optionally in the presence of a base (e.g., triethylamine or N,N-diisopropylethylamine), the amide coupling conversion is carried out by activating the carboxylic acid function of the compound of formula (VIII), which is a process that usually occurs in the following manner: converting the -OH of the carboxylic acid into a good leaving group such as a chloride group, for example by using (COCl) 2 or SOCl 2 , followed by treatment with a compound of formula (III). 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.

[0223]

[0224] Solution 4

[0225] As shown in Scheme 5, a compound having formula (VII) wherein X 3 Is OH or C 1 -C 4 -Alkoxy groups, such as methoxy or ethoxy groups, can also be prepared by reacting a nucleophilic compound of formula (X) wherein X 3 Is OH or C 1 -C 4 - an alkoxy group, such as a methoxy group or an ethoxy group, and an electrophilic compound of formula (IX) wherein X 2 is a suitable leaving group, such as fluorine, chlorine, bromine, iodine, BF 3 K、B(OH) 2 or B (pinacol), 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., and using a metal source (e.g., Cu(OAc) 2 ), and preferably in an oxidizing agent (such as O 2 ) or a suitable palladium precatalyst (such as RockPhos Pd G3), in the presence of a base (e.g., K 3 PO 4 ) 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. [Organic Letters] 2003, 5, 1381; Tetrahedron Lett. [Tetrahedron Letters] 1998, 39, 2933; Tetrahedron Lett. [Tetrahedron Letters] 2003, 44, 3863 and Org. Lett. [Organic Letters] 2013, 15, 2876. Compounds of formula (IX) are known or commercially available.

[0226]

[0227] Solution 5

[0228] Alternatively, as shown in Scheme 6, compounds of formula (I) can also be prepared by reacting a nucleophilic compound of formula (XI) with an electrophilic compound of formula (IX), wherein X 2 is a suitable leaving group, such as fluorine, chlorine, bromine, iodine, BF 3 K、B(OH) 2or B (pinacol), in a suitable solvent (e.g., dichloromethane, 1,2-dichloromethane, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran), at a temperature between 40° C. and 80° C., and using a metal source (e.g., Cu(OAc) 2 ), optionally in the presence of an oxidizing agent (such as O 2 ) or a suitable palladium precatalyst (such as RockPhos Pd G3), in the presence of a base (e.g., K 3 PO 4 ) 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. [Organic Letters] 2003, 5, 1381; Tetrahedron Lett. [Tetrahedron Letters] 1998, 39, 2933; Tetrahedron Lett. [Tetrahedron Letters], 2003, 44, 3863 and Org. Lett. [Organic Letters] 2013, 15, 2876. Compounds of formula (IX) are known or commercially available.

[0229]

[0230] Solution 6

[0231] As shown in Scheme 7, a compound having formula (XIV) wherein X 5 is OH or halogen, which can be obtained from a compound of formula (XIII) by hydrolysis in a manner similar to that described for the conversion of a compound of formula (VII) to a compound of formula (II) in Scheme 3. A compound of formula (XIII), wherein X 3 Is OH or C 1 -C 4 - alkoxy, such as methoxy or ethoxy, and X 5 If it is OH or halogen, it can be oxidized by using a suitable oxidant (such as KMnO 4 or a cobalt(II) salt and trihydroxyisocyanuric acid (THICA)) in a suitable solvent (e.g., acetic acid) at a temperature between 25°C and 200°C, from a compound of formula (XII), wherein X 5 is OH or halogen, obtained. For relevant examples, see: Can. J. Chem. [Canadian Journal of Chemistry] 1978, 56, 1273 and WO 2021 / 160470. Compounds of formula (XII) are known or can be prepared as described in Bulletin de la Societe Chimique de France [Journal of the French Chemical Society] 1972, 8, 3198.

[0232]

[0233] Solution 7

[0234] As shown in Scheme 8, a compound having formula (VII) wherein X 1 It is C 1 -C 4 - Alkoxy groups, such as methoxy or ethoxy groups, can be oxidized using a suitable oxidizing agent (e.g., KMnO 4 or a suitable cobalt(II) salt and trihydroxyisocyanuric acid (THICA)) in a suitable solvent (e.g. acetic acid) at a temperature between 25°C and 200°C from a compound of formula (XV). For relevant examples, see: Can. J. Chem. [Canadian Journal of Chemistry] 1978, 56, 1273 and WO 2021 / 160470. Compounds of formula (XV) can be prepared as described in Bulletin de la Societe Chimique de France [Journal of the French Chemical Society] 1972, 8, 3198.

[0235] In addition, the compound of formula (XV) can be prepared by reacting a nucleophilic compound of formula (IV) with an electrophilic compound of formula (XVI) (wherein X 2 is a suitable leaving group, such as fluorine, chlorine, bromine, iodine, BF3K, B(OH)2 or B(pinacol)), in the presence of a base (e.g., KO-t-Bu, K 3 PO 4 , K 2 CO 3 , triethylamine, or Cs 2 CO 3 ) in the presence of a suitable solvent (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, dimethyl sulfoxide) at a temperature between 25°C and 100°C, and 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.

[0236]

[0237] Solution 8

[0238] As shown in Scheme 9, a compound having formula (VII) wherein X 3 Is OH or C 1 -C 4 -alkoxy groups can also be prepared by reacting a compound of formula (XVII) in an aqueous solvent mixture such as isopropanol or ethanol, optionally in a basic medium, at a temperature between 90° C. and 110° C. For related examples, see: J. Med. Chem. [Journal of Medicinal Chemistry] 2012, 55, 10118.

[0239]

[0240] Solution 9

[0241] Compounds of formula (XVII) are known or are shown in Scheme 10. These compounds can be prepared at a temperature between 50°C and 120°C, preferably between 80°C and 110°C, using a metal source such as XPhos Pd G1 (also known as: (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), 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 a mixture of solvents (such as dioxane, water, toluene, tetrahydrofuran, 2-methyl-tetrahydrofuran, xylene), from a compound having formula (XVIII) (wherein X 6 is chlorine, bromine, iodine, or trifluoromethanesulfonyl-O-). For related examples, see: J.Org.Chem. [Journal of Organic Chemistry] 2018, 83, 4922 and Org.Lett. [Organic Express] 2006, 8, 1189.

[0242]

[0243] Solution 10

[0244] As shown in Scheme 11a, a compound having formula (VII) wherein X 3 Is OH or C 1 -C 4-alkoxy, can also be prepared from a compound of formula (XVIII) wherein X is a -alkoxy, using a metal source such as XPhos Pd G1, in a pressure vessel charged with carbon monoxide, typically a stainless steel autoclave, at a pressure typically between 1 and 50 bar, more preferably between 5 and 15 bar, in the presence of an organic base such as triethylamine or diisopropylethylamine and a suitable solvent such as methanol or ethanol, at a temperature between 20°C and 130°C, preferably between 70°C and 110°C. 6 is chlorine, bromine, iodine, or trifluoromethanesulfonyl-O-, to obtain. For related examples, see: J. Med. Chem. [Journal of Medicinal Chemistry] 2014, 57, 2692 and Adv. Synth. Catal. [Advanced Synthesis Catalysis] 2006, 348, 1255.

[0245]

[0246] Scheme 11a

[0247] Alternatively, as shown in Scheme 11b, the compound of formula (II) can also be obtained by: making a compound of formula (XIX) wherein X 7 is chlorine, bromine or iodine, reacted with a lithium reagent (e.g., n-butyllithium, sec-butyllithium, tert-butyllithium or lithium diisopropylamine) at a temperature between -78°C and -30°C in an appropriate solvent (e.g., hexane, diethyl ether or tetrahydrofuran), followed by the addition of carbon dioxide. For related examples, see: J.Am.Chem.Soc. [Journal of the American Chemical Society] 2018, 140, 9140 and J.Am.Chem.Soc. [Journal of the American Chemical Society] 2021, 143, 1539.

[0248]

[0249] Option 11b

[0250] As shown in Scheme 12, a compound having the formula (XIX) (wherein X 7is 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, at temperatures between -78°C and 10°C, optionally with a base (typically lithium diisopropylamide or n-butyllithium) in a suitable solvent such as chloroform, methyltetrahydrofuran or dimethylformamide. For relevant examples, see: Tetrahedron Lett. 2003, 44, 823; J. Am. Chem. Soc. 2010, 132, 8858 and Synthesis 2005, 16, 2782.

[0251]

[0252] Solution 12

[0253] As shown in Scheme 13, compounds of formula (II) can also be prepared by reacting a compound of formula (XX) with a base (typically lithium diisopropylamine or n-butyl lithium) at a temperature between -78°C and 10°C, optionally in the presence of a catalyst (e.g., potassium tert-butoxide), in a suitable solvent (e.g., diethyl ether, cyclopentyl methyl ether, methyl tert-butyl ether or tetrahydrofuran), followed by the addition of carbon dioxide. Compounds of formula (XX) are known or commercially available. For relevant examples, see: Bioorg. Med. Chem. [Biological Organic and Medicinal Chemistry Express] 2004, 12, 5579; J. Am. Chem. Soc. [Journal of the American Chemical Society] 2010, 132, 8858 and Synthesis [Synthesis] 2005, 16, 2782.

[0254]

[0255] Solution 13

[0256] As shown in Scheme 14, a compound having the formula (XIX) (wherein X 7is chlorine, bromine or iodine) are known or can be obtained from tautomeric compounds of formula (XXI) and (XXII) by treatment with a phosphorus compound (e.g. 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.

[0257]

[0258] Solution 14

[0259] As shown in Scheme 15, compounds of formula (XXI) in equilibrium with compounds of formula (XXII) are known or can be prepared by using a compound of formula (XXIII) wherein X is preferably in a suitable solvent (e.g., 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 It is C 1 -C 4 Alkyl or C 5 -C 6 cycloalkyl, or together with the nitrogen to which they are attached form a saturated heterocyclic ring, and X 3 Is OH or C 1 -C 4 -alkoxy, and compounds of formula (XXIV) wherein X 9 are independently R as defined for compounds of formula (I): 7 , R 8 or R 9 substituted carbon atom, or nitrogen atom, and X 10 is H or a protecting group (e.g., tetrahydropyran, 2-(trimethylsilyl)ethoxymethyl or benzyl), undergoes a one-pot nucleophilic addition followed by cyclization. For related examples, see: US 2018 / 0230157; Synthesis 2006, 1, 59 and WO 2010 / 016005. Compounds of formula (XXIV) are known or commercially available.

[0260]

[0261] Solution 15

[0262] As shown in Scheme 16, a compound of formula (XXI) in equilibrium with a compound of formula (XXII) can be prepared by reacting a compound of formula (XXV) wherein X 8 It is C 1 -C 4 Alkyl or C 5 -C 6 cycloalkyl, or together with the nitrogen to which they are attached form a saturated heterocyclic ring, and X 9 are independently R as defined for compounds of formula (I): 7 , R 8 or R 9 The substituted carbon atoms, or nitrogen atoms, are intramolecularly cyclized in a suitable solvent (eg, water or ethanol) at a temperature between 20° C. and 100° C. For related examples, see: WO 2005 / 012262.

[0263]

[0264] Scheme 16

[0265] As shown in Scheme 17, a compound of formula (XXI) is in equilibrium with a compound of formula (XXII) and can be prepared by reacting a compound of formula (XXVI) wherein X 8 It is C 1 -C 4 Alkyl or C 5 -C 6 cycloalkyl, or together with the nitrogen to which they are attached form a saturated heterocyclic ring, and X 9 are independently R as defined for compounds of formula (I): 7 , R 8 or R 9 substituted carbon atom, or nitrogen atom, and X 10 is H or a protecting group (e.g., tetrahydropyran, 2-(trimethylsilyl)ethoxymethyl or benzyl), with an aminating agent (e.g., amino 4-nitrobenzoate, N-(tert-butyloxycarbonyl)-2-nitrobenzenesulfonamide, hydroxylamine-O-sulfonic acid or sodium diformamide), in a suitable solvent (e.g., dimethyl sulfoxide, dimethylformamide, dichloromethane, N-methyl-2-pyrrolidone or ethanol), at a temperature between 0°C and 110°C, more preferably between 20°C and 50°C, optionally in the presence of a base (e.g., KOH, NaOH), for amination and direct cyclization. For relevant examples, see: J. Med. Chem. 1996, 39, 582; Organometallics 2014, 33, 4035 and Chem. Eur. J. 2019, 25, 1963.

[0266]

[0267] Solution 17

[0268] As shown in Scheme 18, a compound having the formula (XXV) wherein X 8 It is C 1 -C 4 Alkyl or C 5 -C 6 cycloalkyl, or together with the nitrogen to which they are attached form a saturated heterocyclic ring, and X 9 are independently R as defined for compounds of formula (I): 7 , R 8 or R 9 Substituted carbon atoms, or nitrogen atoms, can be obtained by making a compound having the formula (XXVII) wherein X 8 It is C 1 -C 4 Alkyl or C 5 -C 6 cycloalkyl, or together with the nitrogen to which they are attached form a saturated heterocyclic ring, and X 9 are independently R as defined for compounds of formula (I): 7 , R 8 or R 9 The substituted carbon atom, or nitrogen atom, is aminated in a suitable solvent (e.g., dimethyl sulfoxide, N-methyl-2-pyrrolidone or dimethylacetamide) at a temperature between 20° C. and 120° C. For relevant examples, see: Dalton Trans. 2016, 45, 15644, J. Med. Chem. 1996, 39, 582 or Chem. Eur. J. 2019, 25, 1963.

[0269]

[0270] Scheme 18

[0271] As shown in Scheme 19, a compound having the formula (XXVI) wherein X 8 It is C 1 -C 4 Alkyl or C 5 -C 6 Cycloalkyl, or together with the nitrogen to which they are attached form a saturated heterocyclic ring, X 9 are independently R as defined for compounds of formula (I): 7 , R 8 or R 9substituted carbon atom, or nitrogen atom, and X 10 is H or a protecting group (e.g., tetrahydropyranyl, 2-(trimethylsilyl)ethoxymethyl or benzyl), can be prepared from a compound of formula (XVVIII) as follows: 9 are independently R as defined for compounds of formula (I): 7 , R 8 or R 9 substituted carbon atom, or nitrogen atom, and X 10 is H or a protecting group (e.g., tetrahydropyran, 2-(trimethylsilyl)ethoxymethyl or benzyl) obtained by reacting with a formamide equivalent, such as dimethylformamide, dimethylacetal or 1-(dimethoxymethyl)pyrrolidine neat or in a suitable solvent (e.g., toluene, dimethylformamide) at a temperature between 50° C. and 120° C. For related examples, see: WO 2021 / 2296621; WO 2008 / 149379 and Bioorg.Med.Chem.Lett. [Biological Organic and Medicinal Chemistry Express] 2022, 61, 128552.

[0272]

[0273] Solution 19

[0274] As shown in Scheme 20, a compound having the formula (XXVI) wherein X 8 It is C 1 -C 4 Alkyl or C 5 -C 6 Cycloalkyl, or together with the nitrogen to which they are attached form a saturated heterocyclic ring, X 9 are independently R as defined for compounds of formula (I): 7 , R 8 or R 9 substituted carbon atom, or nitrogen atom, and X 10 is H or a protecting group (e.g., tetrahydropyranyl, 2-(trimethylsilyl)ethoxymethyl or benzyl), can be prepared from a compound of formula (XXIX) and a compound of formula (XXX) as follows, wherein X 7 is chlorine, bromine or iodine, X 9 are independently R as defined for compounds of formula (I): 7 , R 8 or R 9 substituted carbon atom, or nitrogen atom, and X 10Is H or a protecting group (e.g., tetrahydropyran, 2-(trimethylsilyl)ethoxymethyl or benzyl) prepared using an organometallic reagent (e.g., methylmagnesium bromide, isopropylmagnesium chloride, lithium chloride, butyllithium, tert-butyllithium or phenylmagnesium chloride) at a temperature between -78°C and 15°C, more preferably between -20°C and 10°C, in a suitable solvent (e.g., tetrahydrofuran, diethyl ether, cyclopentyl methyl ether or 2-methyltetrahydrofuran). For related examples, see: WO2009 / 130193 and WO 2015 / 057205.

[0275]

[0276] Solution 20

[0277] 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 the presence or absence of oxalyl chloride or a mixture of thionyl chloride and dimethylformamide in a suitable solvent or mixture of solvents (e.g., dimethylformamide, dichloromethane or 2-methyltetrahydrofuran) at a temperature 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, chloroform, tetrahydrofuran, methyltetrahydrofuran) at a temperature between 0°C and 80°C. For related examples, see: WO 2011 / 023706 and J. Med. Chem. 2004, 47, 2405. Compounds of formula (XXXI) are known or commercially available.

[0278]

[0279] Solution 21

[0280] As shown in Scheme 22, a compound having the formula (XXIII) wherein X 3 Is OH or C 1 -C 4 -alkoxy, X 8 It is C 1 -C 4 Alkyl or C 5 -C 6 Cycloalkyl, or together with the nitrogen to which they are attached to form a saturated heterocyclic ring, can be prepared by making a compound of formula (XXXII) wherein X 3 Is OH or C 1 -C 4 -alkoxy, in the presence of C 1 -C 6-alkoxy- or C 1 -C 6 -cycloalkoxy-N,N,N',N'-tetra(C 1 -C 6 -alkyl or C 1 -C 6 The reaction is carried out neat or in a suitable solvent or solvent mixture (e.g. dimethylformamide, 2-methyltetrahydrofuran) with a cycloalkyl)methanediamine (e.g. methoxy- or tert-butyloxy-N,N,N',N'-tetramethylmethanediamine) at a temperature between 25° C. and 120° C. 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.

[0281]

[0282] Solution 22

[0283] As shown in Scheme 23a, a compound of formula (XXI) is in equilibrium with a compound of formula (XXII) and can be prepared by reacting a nucleophilic compound of formula (XXXIII) in equilibrium with a compound of formula (XXXIV) with an electrophilic compound of formula (IX), wherein X 2 is a suitable leaving group, such as fluorine, chlorine, bromine, iodine, BF 3 K、B(OH) 2 or B (pinacol), 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., and using a catalyst (e.g., Cu(OAc) 2 ), and preferably in an oxidizing agent (such as O 2 ) in the presence of; alternatively, using a suitable palladium precatalyst (such as RockPhos Pd G3), in the presence of a base (e.g., K 3 PO 4) and a suitable solvent (e.g., dimethyl ether or toluene) at a temperature between 20°C and 80°C. For related examples, see Org. Lett. 2003, 5, 1381; Tetrahedron Lett. 1998, 39, 2933; Tetrahedron Lett. 2003, 44, 3863 and Org. Lett. 2013, 15, 2876.

[0284]

[0285] Scheme 23a

[0286] Alternatively, as shown in Scheme 23b, a compound of formula (XXI) in equilibrium with a compound of formula (XXII) can be prepared from a compound of formula (XXXV) in equilibrium with a compound of formula (XXXVI), wherein X 7 is chlorine, bromine or iodine, prepared by reacting with a compound of formula (IX), optionally in the presence of a base (e.g., KO-t-Bu, K 3 PO 4 , K 2 CO 3 , triethylamine or Cs 2 CO 3 ) in the presence of a suitable solvent or solvent mixture (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, dimethyl sulfoxide) at a temperature between 50° C. and 110° C., and 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.

[0287]

[0288] Plan 23b

[0289] As shown in Scheme 24, a compound of formula (XXXV) is in equilibrium with a compound of formula (XXXVI), and can be prepared from a compound of formula (XXXVII) in equilibrium with a compound of formula (XXXVIII), wherein X can be obtained after treatment with hydrochloric acid or hydrogen bromide or in the optional presence of a transition metal (e.g., zinc, palladium) or sodium nitrite, followed by the addition of a copper salt (e.g., 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. 7 is chlorine, bromine or iodine, to obtain. For related examples, see: Mendeleev Commun. [Mendeleev Communications] 2017, 27, 285.

[0290]

[0291] Solution 24

[0292] As shown in Scheme 25, a compound of formula (XXXVII) is in equilibrium with a compound of formula (XXXVIII) and can be prepared from a compound of formula (XXXIX) after treatment with sodium or potassium nitrite, sodium hypochlorite 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 a temperature between -10°C and 30°C, wherein X 9 are independently R as defined for compounds of formula (I): 7 , R 8 or R 9 Substituted carbon atom, or nitrogen atom, X 10 is H or a protecting group (e.g., tetrahydropyran, 2-(trimethylsilyl)ethoxymethyl or benzyl) to obtain. For related 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-nitrovinyl)morpholine, 2-nitroacetaldehyde, 2-nitromalonaldehyde, 1,3-diethyl 2-nitromalonate) in a suitable solvent or a mixture of solvents (e.g., water or ethanol) at a temperature between 0°C and 60°C, optionally in the presence of a base (e.g., Na 2 CO 3 , K 2 CO 3, KOH), or alternatively optionally in the presence of a strong acid (e.g., nitric acid, hydrochloric acid). For relevant examples, see: Mendeleev Commun. [Mendeleev Communications] 2017, 27, 285; WO 2017 / 144708 or Khimiya Geterotsiklicheskikh Soedinenii [Chemistry of Heterocyclic Compounds] 1986, 5, 662. Compounds of formula (XXXIX) are known or commercially available.

[0293]

[0294] Solution 25

[0295] As shown in Scheme 26, a compound having formula (VII) wherein X 3 Is OH or C 1 -C 4 -alkoxy can be obtained by making a compound having the formula (XL) wherein X 3 Is OH or C 1 -C 4 -alkoxy, with a compound of formula (XLI), wherein X 11 is a leaving group, such as chloro, bromo, iodo, O-methylsulfonyl, O-toluenesulfonyl, and X 12 is a carbonyl or carbonyl equivalent, such as an aldehyde, acetal, acid chloride or bromide, ester or orthoester, at a temperature between 30° C. and 125° C., optionally in a microwave reactor, in a suitable solvent or mixture of solvents (e.g., dimethylformamide, dimethyl sulfoxide, toluene, ethanol, isopropanol, water), and optionally in the presence of a catalyst (e.g., hydrogen bromide or sodium carbonate). For relevant examples, see: J. Med. Chem. 2021, 64, 1197; Tetrahedron Lett. 2017, 58, 4816 and Chem. Pharm. Bull. 1992, 40, 1170. Compounds of formula (XLI) are known or commercially available.

[0296]

[0297] Scheme 26

[0298] As shown in Scheme 27, a compound having the formula (XL) wherein R 1 is as defined for compounds of formula (I), and X 3 Is OH or C 1 -C 4-alkoxy can be obtained by: making a compound having formula (XLII) (wherein OH or C 1 -C 4 - Alkoxy can be represented by X 13 and it is an alkyl or cycloalkyl group, such as methyl, ethyl or cyclohexyl) sulfone, in an aminating agent (e.g., NH 4 OH, NH 3 NH 4 OAc) and optionally in the presence of a base (e.g., triethylamine) in a suitable solvent or mixture of solvents (e.g., dimethyl sulfoxide, water, tetrahydrofuran, 1,4-dioxane, isopropanol, ethanol, methanol, dichloromethane) to perform the nucleophilic displacement. For related examples, see: Tetrahedron [Tetrahedron Express] 2009, 65, 1697; Heterocycles [Heterocycles] 1977, 8, 299 and Org. Biomol. Chem. [Organic Biomolecular Chemistry] 2015, 13, 10620.

[0299]

[0300] Scheme 27

[0301] As shown in Scheme 28, a compound having the formula (XLII) wherein R 1 is as defined for compounds of formula (I), X 3 Is OH or C 1 -C 4 -alkoxy, and X 13 is an alkyl or cycloalkyl group, such as methyl, ethyl or cyclohexyl, which can be obtained by making a compound having the formula (XLIII) wherein R 1 , X 3 and X 13 The oxidation is as defined for compounds of formula (XLII) in the presence of an oxidizing agent (e.g., 3-chloroperoxybenzoic acid, hydrogen peroxide, oxone, chlorine) in a suitable solvent or mixture of solvents (e.g., dichloromethane, acetonitrile, chloroform, water, toluene or 2-methyl-tetrahydrofuran) at a temperature between -10°C and 50°C. For relevant examples, see: Chem. Eur. J. [European Journal of Chemistry] 2021, 27, 14826; J. Org. Chem. [Journal of Organic Chemistry] 2017, 82, 2664 and J. Chem. Soc. (C) Organic [Journal of Chemical Society (C): Organic] 1967, 7, 568.

[0302]

[0303] Scheme 28

[0304] As shown in Scheme 29, a compound having the formula (XLIII) wherein R 1 is as defined for compounds of formula (I), X 3 Is OH or C 1 -C 4 -alkoxy, such as methoxy, and X 13 is an alkyl or cycloalkyl group, such as methyl, ethyl or cyclohexyl, which can be obtained by making a compound of formula (XLIV) wherein X 3 and X 13 is as defined for compounds of formula (XLIV), and X 15 is a suitable leaving group, such as a halogen, in the presence of a base (e.g., KO-t-Bu, K 3 PO 4 , K 2 CO 3 , triethylamine, or Cs 2 CO 3 ) in the presence of a suitable solvent (e.g., N-methylpyrrolidone, dimethylacetamide, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, dimethyl sulfoxide) at a temperature between 25°C and 110°C and under reflux and 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 (XLIV) are known or commercially available.

[0305]

[0306] Solution 29

[0307] As already indicated, surprisingly, it has now been found that the compounds of formula (I) according to the invention have, for practical purposes, a very advantageous level of biological activity for protecting plants against diseases caused by fungi.

[0308] Compounds with formula (I) can be used as active ingredients such as for controlling plant pests in the agricultural sector and related fields of use, or for controlling spoilage microorganisms or potentially harmful organisms to humans on non-living materials. The feature of these novel compounds is that they have excellent activity at low application rates, are well tolerated by plants and are safe for the environment. They have very useful therapeutic, preventive and systemic characteristics and can be used to protect a lot of cultivated plants. Compounds with formula (I) can be used to suppress or destroy the harmful organisms that occur on plants or plant parts (fruits, flowers, leaves, stems, tubers, roots) of different useful plant crops, while also protecting those plant parts that grow later from, for example, the infringement of phytopathogenic microorganisms.

[0309] The invention further relates to a method for controlling or preventing infestation of plants or plant propagation materials and / or harvested food crops susceptible to attack by microorganisms by treating the plants or plant propagation materials and / or harvested food crops, wherein an effective amount of a compound of formula (I) is applied to the plants, parts thereof or the locus thereof.

[0310] Compounds of formula (I) can also be used as fungicides. As used herein, the term "fungicide" means a compound that controls, modifies, or prevents fungal growth. The term "fungicidal effective amount" when used means an amount of such a compound or combination of such compounds that is capable of having an effect on fungal growth. Control or modification of the effect includes all deviations from natural development, such as killing, retardation, etc., and prevention includes barriers or other defensive structures in or on plants that prevent fungal infection.

[0311] Compounds with formula (I) can also be used as seed dressings for treating plant propagation materials (e.g., seeds, such as fruits, tubers or grains) or plant cuttings, for protection against fungal infections together with phytopathogenic fungi present in the soil. Propagation materials can be treated with a composition comprising a compound with formula (I) before planting: for example, seed dressing can be used before sowing. The active compound with formula (I) can also be applied to grains (coating) by dipping seeds in a liquid formulation or by coating them with a solid formulation. Compositions can also be applied to the planting site when planting propagation materials, for example, to the furrows of seeds during sowing. The invention also relates to such methods for treating plant propagation materials, and to plant propagation materials so treated.

[0312] In addition, the compounds of formula (I) can be used for controlling fungi in related fields, such as protection of industrial materials (including wood and wood-related industrial products), food storage, and hygiene management.

[0313] Additionally, the present invention can be used to protect non-living materials such as wood, siding and paint from fungal attack.

[0314] Compounds of formula (I) and compositions containing such compounds are, for example, effective in controlling a broad spectrum of plant diseases, such as foliar and / or soil-borne pathogens, including fungi and fungal vectors of diseases, as well as phytopathogenic bacteria and viruses, of ornamental plants, turf, vegetables, fields, cereals and fruit crops. These pathogens may include:

[0315] Oomycetes, including Phytophthora species, such as Phytophthora cactorum, Phytophthora capsici, Phytophthora cinnamomi, Phytophthora citricola, Phytophthora citrophthora, Phytophthora erythroseptica, Phytophthora fragariae, Phytophthora infestans, Phytophthora nicotianae, Phytophthora porri, and Phytophthora sojae; Pythium species, such as Pythium aphanidermatum, Pythium arrhenomanes, Pythium graminearum, Pythium truncat ... graminicola), Pythiumirregulare, and Pythium ultimum; other Peronosporales, such as Bremialactucae, Hyaloperonospora parasitica, Sclerophthoramacrospora, Sclerospora graminicola; Peronospora species, including Peronospora destructor, Peronospora farinosa f.sp. spinaciae, and Peronospora viciae f.sp.pisi); Plasmopara species, including Plasmopara halstedii and Plasmopara viticola; Pseudoperonospora species, including Pseudoperonospora cubensis and Pseudoperonospora humili; Peronosclerospora species, including Peronosclerospora maydis, Peronosclerospora philippinensis, and Peronosclerospora sorghi; Albugolese, such as Albugo candida, Albugo occidentalis, and Albugotragopogonis; and Saprolegnesales, such as Aphanomyces species, including Aphanomyces cochliodes;

[0316] Ascomycetes, including Mycosphaeriales, such as Actinothyrium graminis, Asperisporium caricae, Cercospora species, including Cercospora arachidicola, Cercospora beticola, Cercospora brassicicola, Cercospora canescens, Cercospora cf. flagellaris, Cercospora janseana, Cercospora kikuchii, Cercosporalagenariae, Cercospora sojinae, Cercospora sorghi, Cercospora zeae-maydis; Dothistroma septosporum, Fulvia fulva, Mycosphaerella species, including Mycosphaerella pomi and Mycosphaerella linicola; Neopseudocercosporella brassicae, Neopseudocercosporella capsellae, Nothopassalora personata, Nothophaeocrytopus gaeumannii, Passalora bataticola, Passalora koepkei, Pseudocercospora griseola, Pseudocercospora musaei, Pseudocercospora vitis, Pseudocercospora fijiensis. fijiensis, Ramularia species, including Ramularia beticola and Ramularia collo-cygni;Ramulariopsis gossypii, Ramulariopsis pseudoglycines, Ramulisporasorghi, Scolecostigmina palmivora, Septoria species including Septoria apiicola, Septoria glycines and Septorialycopersici; Zasmidium citri-griseum and Zymosepotriatritici; Helotiales such as Blumeriella jaapii, Botrytis species including Botrytis cinerea and Botrytis fabae; Cadophora gregata, Civorinia allii, Claireedia homoeocarpa), Diplocarpon coronariae, Diplocarpon rosae, Drepanopeziza campestris, Gloeotinia temulenta, Hymenoscyphus fraxineus, Leptotrochila medicaginis, Marssonina graminicola, species of the genus Sclerotinia, including Monilinia fructicola, Monilinia fructigena, and Monilinia laxa; Neofabraea perennans, Neofabrae avagabunda, Oculimacula yallundae, species of the genus Pezicula spp.), Pseudopeziza medicaginis, Pseudopeziza tracheiphila, and Sclerotinia species, including Pyrenopeziza brassicae;Douglas-fir leaf drop pathogen (Rhabdocline pseudotsugae), Rhacosporium species, including Rhynchosporium secalis; Sclerotinia species, including Sclerotinia minor, Sclerotinia borealis, and Sclerotinia sclerotiorum; Hypocreales, such as Acremonium strictum, Albifimbria verrucaria, Claviceps africana, Claviceps purpurea; Fusarium species, including Fusarium avenaceum, Fusarium culmorum, Fusarium fujikuroi, Fusarium graminearum, Fusarium incarnatum, Fusarium langnerii, Fusarium sclerotiorum ... langsethiae), Fusarium moniliforme, Fusarium oxysporum, Fusarium oxysporum f.sp.cubense, Fusarium poae, Fusarium proliferatum, Fusarium pseudograminearum, Fusarium subglutinans, Fusarium sulphureum, Fusarium tricinctum and Fusarium verticillioides; Glechoma species, Neocosmospora phaseoli, Neocosmospora solani, Neonectria candida, Paramyrothecium roridum, Sarocladium oryzae, Trichoderma species, including Trichoderma harzianum, Trichoderma mapseudokoningii, and Trichoderma viride;Trichothecium roseum and Ustilaginoidea virens; Gigantotrichum, such as Gaeumannomyces avenae, Gaeumannomyces graminis, Gaeumannomyces graminis tritici, Gaeumannomyces wongoonoo, Magnaporthiopsis poae, Pyricularia species, including Pyricularia grisea and Pyricularia oryzae; Gastrocoelales, such as Alternaria species, including Alternaria allii, Alternaria alternata, Alternaria arachidis, Alternaria oleracea. brassicae, Alternaria brassicicola, Alternaria dauci, Alternaria grandisi, Alternaria helianthicola, Alternaria linariae, Alternaria mali, Alternaria porri, Alternaria solani, and Alternaria tomato; Boeremia coffeee, Ascochyta species, including Ascochyta pisi and Ascochytarabiei; Bipolaris maydis, Bipolaris oryzae, Bipolaris sorokiniana, Corynespora species, Corynespora cassiicola, Curvularia species, including Curvularia australiensis, Curvularia cactivora, and Curvularia lunata;Species of the genus Didymella, including Didymella pinodella and Didymela pinodes; species of the genus Drechslera, including Drechslera glycines; Epicoccum nigrum, Exserohilum turcicum, species of the genus Helminthosporium, including Helminthosporium solani; Hendersonia creberrima, Leptosphaerulinacrassiasca, Neocamarosporium betae, Ophiosphaerella agrostidis, Ophiosphaerella herpotricha, Ophiosphaerella korrae, Ophiosphaerella narmari), Parastagonosporanodorum, Phaeosphaeria herpotrichoides, Phaeosphaeria maydis, Phoma species, Plenodomus lindquistii, Plenodomus lingam, Plenodomus species, Pseudopyrenochaeta lycopersici, Pyrenophora species, including Pyrenophorapoae, Pyrenophora teres, and Pyrenophora tritici-repentis; Remotididymella destructiva, Stagonosporatainanensis, Stagonosporopsis cucurbitacearum, Stemphylium species, including Stemphylium botryosum, Stemphylium solani, and Stemphylium vesicarium;The order Metazoales, such as Anisogramma anonmala, Apiognomonia errabunda, Cytospora platani, species of the genus Diaporthe, including Diaporthe amygdali, Diaporthe helianthin, Diaporthe neoviticola and Diaporthe phaseolorum; species of the genus Dicarpella, Discula destructiva, Gnomoniopsis fructicola, Greeneria uvicola, Juglanconis juglandina, Ophiognomonia clavigignenti-juglandacearum, Stenocarpella maydis and Tubakia dryina; Tocorrhizales, such as species of the genus Brevibacter, including Aureobasidium pullulans; Discosphaerina fulvida; Powdery mildewales, such as Blumeria graminis, Brasiliomyces malachrae, and species of the genus Erysiphe, including Erysiphe betae, Erysiphe cruciferarum, Erysiphe diffusa, Erysiphe heraclei, Erysiphe necator, and Erysiphe pisi;Golovinomyces cichoracearum, Golovinomyces orontii, Leveillula taurica, Oidiumarachidisi, Phyllactinia guttata, species of the genus Podosphaera, including Podosphaera fuliginea, Podosphaera fusca, Podosphaera leucotricha, Podosphaera macularis, Podosphaera morsuvae, Podosphaera pannosa, Podosphaera tridactyla and Podosphaera sibiricum. xanthii; Glomerales, such as Colletotrichum species, including Colletotrichum acutatum, Colletotrichum cereale, Colletotrichum chrysanthemi, Colletotrichum cliviicola, Colletotrichum coccodes, Colletotrichum fragariae, Colletotrichum gloeosporioides, Colletotrichum graminicola, Colletotrichum lentis, Colletotrichum lindemuthianum, Colletotrichum musae, Colletotrichum orbiculare, Colletotrichum siamense, and Colletotrichum truncatum;, Glomerella cingluata, Glomerella gossypii, Musicillium theobromae, Plectosphaerella cucumerina, Verticillium species including Verticillium dahlia; Venturales, such as Venturia species including Venturia carpophila, Venturia effusa, Venturia inaequalis, Venturia oleaginea, and Venturia pyrina; Xylariales, such as Eutypa lata, Microdochium albescens, Microdochium majus, Microdochium snow mold, and Microdochium spp. nivale, Microdochium paspali, Microdochium sorghi, Physalospora abdita, Seimatosporium mariae; Botryosphaeriales, such as Botryosphaeria species, including Botryosphaeria dothidea; Diplodia seriata, Dothiorella aromatica, Lasiodiplodia theobromae, Macrophoma theicola, Macrophomina phaseolina, Phyllosticta ampelicida and Phyllosticta cucurbitacearum); Eurotiales, such as Aspergillus species, including Aspergillus flavus, Aspergillus fumigatus, Aspergillus niger, and Aspergillus terreus; Penicillium species, including Penicillium digitatum, Penicillium expansum, and Penicillium italicum;Microcystales, such as Berkeleyomyces basicola, Thielaviopsis paradoxa, Ceratocystis species, including Ceratocystis fimbriata, Ceratocystis manginecans, and Ceratocystis platani; Scedosporium species, including Scedosporium apiospermum and Scedosporium prolificans; Polycoelales, such as Elsinoeampelina and Elsinoe perseae; Leptographales, such as Leptographium lundbergii, Leptographiummicrosporum, Ophiostoma novo-ulmi, Ophiostoma piceae, and Sporothrix species; Pestozoales, such as Phymatotrichopsis omnivore and Polyscytalumpustulans; Melanomycetes, such as Gibellina cerealis, Phyllachoramaydis, and Phyllachora pomigena; Cynomorales, such as Griphosphaeria corticola, Lepteutypa cupressi, and Pestalotia rhododendri; and Sophorales, such as Capnodium ramosum and Schizothyrium pomi); Scutellales, such as species of the genus Phialosporium; Cladosporales, such as species of the genus Cladosporium, including Cladosporium oxysporum; Pseudomonas, such as species of the genus Lophodermium seditiosum and Naemacyclus; Saccharomyces, such as species of the genus Cephaloascus, including Cephaloascus fragrans;Geotrichum candidum, Candida species, including Candida glabrata, Candida krusei, Candida lusitaniae, Candida parapsilosis, Candida albicans, and Candida tropicalis; Sordales, such as Chaetomium species and Monosporascus cannonballus; Sordales, such as Wongia garrettii and Wongiagriffinii; Exocystales, such as Taphrina bullata and Taphrina deformans; Onychocystales, such as Ajellomyces capsulatus, Blastomyces dermatitidis, and Blastomyces spp. dermatitidis, Coccidioides immitis; Epidermophyton species, Histoplasma species, Microsporum species, Trichophyton species, and Paracoccidioides species, including Paracoccioides brasiliensis; and others, such as Hymenulacerealis, Petersella species, and Septocyta ruborum;

[0317] Basidiomycetes, including Pucciales, such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Cronartium ribicola, Gymnosporangium juniperi-virginianae, Gymnosporangium sabinae, Puccinia species, including Hemileiavastatrix; Melampsora medusae, Melampsora lini, Phakopsora ampelopsidis, Phakopsora pachyrhizi, Phragmidium mucronatum, Puccinia species, including Puccinia spp. allii), Puccinia arachidis, Puccinia asparagi, Puccinia cacabata, Puccinia coronata, Pucciniagraminis, Puccinia helianthi, Puccinia hieracii), Puccinia hordei, Puccinia horiana, Pucciniamelanocephala, Puccinia polysora, Puccinia porri, Puccinia recondita, Puccinia sorghi), Puccinia striiformis, Puccinia striiformis f.sp.hordei, Puccinia striiformis f.sp.tritici and Puccinia triticina; Pucciniastrum coryli, Tranzschelia discolor, Uromyces species including Uromyces betae, Uromyces pisi and Uromyces viciae-fabae; Tilletiales such as Neovossia moliniae and Tilletia species including Tilletia caries and Tilletia conversationa; Ustilales such as Sporisorium reilianum and Ustilago species including Ustilago maydis, Ustilago spp. naked, Ustilago spp. segetum var. nuda), Ustilago segetum var. tritici, and Ustilago striiformis; Ustilagoales, such as Ustilago species, including Urocystis isagropyri; Agaricales, such as Marasmiellus inoderma, Agaricus species, Moniliophthora roreri, and Moniliophthora perniciosa; Cantharellales, such as Sclerotium species and Typhula species, including Typhula incarnata and Typhula ishikariensis; Angiospermatales, such as Waitea circinata and Rhizoctonia species, including Rhizoctonia cerealis, Rhizoctonia solani, and Rhizoctonia spp. solani and Rhizoctonia theobromae; Atheliales, such as Athelia rolfsii; Fugutalales, such as Corticium invisum and Laetisaria fuciformis; Ascobasidiales, such as Itersonilia perplexans; Ustilagoales, such as Entyloma calendulaef.sp.dahliae and Entylomella microspore; Exobasidiales, such as Exobasidium vexans; Pucciniales, such as Phellinus igniarius; Russularales, such as Stereum hirsutum; and Tremellales, such as Cryptococcus species, including Cryptococcus neoformans;

[0318] Zygomycetes, including Mucorales, such as Choanephora cucurbitarum, Mucor species, Rhizopus oryzae, Absidia corymbifera and Rhizomucorpusillus;

[0319] Cladomycetes, including Physoderma maydis;

[0320] along with diseases caused by other species and genera closely related to those listed above.

[0321] In addition to their fungicidal activity, the compounds of formula (I) and compositions containing such compounds may also have activity 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; and Pseudomonas species, including Pseudomonas syringae; Filopoda, such as Polymyxa betae, Polymyxa graminearum, Polymyxa spp. graminis and Spongospora subterranea; and diseases caused by Bicyclic Fungi, such as Labyrinthula zosterae,

[0322] along with diseases caused by other species and genera closely related to those listed above.

[0323] The compounds of formula (I) can be used, for example, for lawns, ornamental plants such as flowers, shrubs, broad-leaved trees or evergreen plants, such as conifers, as well as tree injection, pest management and the like.

[0324] In the context of the present invention, target crops and / or useful plants to be protected typically include perennial and annual crops, such as berry plants, for example blackberries, blueberries, cranberries, raspberries and strawberries; cereals, for example barley, maize (corn), millet, oats, rice, rye, sorghum, triticale and wheat; fiber plants, for example cotton, flax, hemp, jute and sisal; field crops, for example sugar beets and fodder beets, coffee beans, hops, mustard, rapeseed (canola), poppy, sugar cane, sunflower, tea and tobacco; fruit trees, for example apples, apricots, avocados, bananas, cherries, citrus, nectarines, peaches, pears and plums; grasses, for example Bermuda grass, bluegrass, bentgrass, centipede grass, fescue, rye, etc. Augustine grass and zoysia grass; herbs such as basil, borage, chives, cilantro, 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; palm plants such as oil palms; ornamental plants such as flowers, shrubs and trees; other trees such as cocoa, coconut, olive and rubber trees; vegetables such as asparagus, eggplant, broccoli, cabbage, carrots, cucumbers, garlic, lettuce, zucchini, melon, okra, onions, peppers, potatoes, squash, rhubarb, spinach and tomatoes; and vines such as grapes.

[0325] The term "useful plants" is to be understood as also including useful plants which have been rendered tolerant to herbicides such as bromoxynil or classes of herbicides such as, for example, HPPD inhibitors, ALS inhibitors such as primisulfuron, primisulfuron and trifloxysulfuron, EPSPS (5-enol-pyruvate-shikimate-3-phosphate-synthetase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen oxidase) inhibitors as a result of conventional breeding methods or genetic engineering. Examples of crops which have been rendered tolerant to imidazolinones such as imazamox by conventional breeding methods (mutagenesis) are Summer rapeseed (canola). Examples of crops that have been rendered tolerant to herbicides or herbicides by genetic engineering methods include glyphosate-resistant and glufosinate-resistant maize varieties, which are based on Herculex and Commercially available under the trade name ANTIQUID®.

[0326] The term "useful plants" is to be understood as also including useful plants which have been transformed by the use of recombinant DNA techniques in such a way that they are able to synthesize one or more selectively acting toxins, as are known, for example, from toxigenic bacteria, in particular those of the genus Bacillus.

[0327] Examples of such plants are: (corn variety expressing CryIA(b) toxin); YieldGard (corn variety expressing CryIIIB(b1) toxin); YieldGard (maize varieties expressing CryIA(b) and CryIIIB(b1) toxins); (corn variety expressing Cry9(c) toxin); Herculex (a corn variety expressing the CryIF(a2) toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) that confers tolerance to the herbicide glufosinate-ammonium); NuCOTN (cotton variety expressing CryIA(c) toxin); Bollgard (cotton variety expressing CryIA(c) toxin); Bollgard (cotton varieties expressing CryIA (c) and CryIIA (b) toxins); (cotton varieties expressing VIP toxin); (potato variety, expressing CryIIIA toxin); GT Advantage (GA21 glyphosate tolerance trait), CBAdvantage (Bt11 corn borer (CB) trait), RW (corn rootworm trait) and

[0328] The term "crops" is to be understood as also including crop plants which have been transformed by the use of recombinant DNA techniques in such a way that they are able to synthesize one or more selectively acting toxins, such as are known, for example, from toxigenic bacteria, in particular those of the genus Bacillus.

[0329] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus japonicus; or insecticidal proteins from Bacillus thuringiensis, such as d-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or vegetative insecticidal proteins (Vips), for example Vip1, Vip2, Vip3, or Vip3A; or insecticidal proteins of nematode-parasitic bacteria, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophila, or Xenorhabdus spp. nematophilus); toxins produced by animals, such as scorpion toxins, spider toxins, bee toxins and other insect-specific neurotoxins; toxins produced by fungi, such as streptomycin, plant lectins, such as pea lectin, barley lectin or snowdrop lectin; agglutinin; protease inhibitors, such as trypsin inhibitor, silk proteinase inhibitor, potato glycoprotein, cystatin, papain inhibitor; ribosome inactivating protein (RIP), such as ricin, corn-RIP, abrin, luffa seed toxin protein, saporin protein or bryophyllin; steroid metabolizing enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitor, HMG-COA-reductase, ion channel blockers, such as sodium channel or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

[0330] Further, in the context of the present invention, d-endotoxins (e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C) or vegetative insecticidal proteins (Vips) (e.g., Vip1, Vip2, Vip3 or Vip3A) are understood to include obviously also mixed toxins, truncated toxins and modified toxins. Mixed toxins are recombinantly produced by new combinations of different domains of those proteins (see, e.g., WO 02 / 15701). Truncated toxins, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxins are replaced. In such amino acid replacements, it is preferred that non-naturally occurring protease recognition sequences are inserted into the toxins, such as, for example, in the case of Cry3A055, the cathepsin-G-recognition sequence is inserted into the Cry3A toxin (see WO 03 / 018810).

[0331] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed in, for example, EP-A-0 374 753, WO 93 / 07278, WO 95 / 34656, EP-A-0 427 529, EP-A-451 878 and WO 03 / 052073.

[0332] Methods for preparing such transgenic plants are generally known to the person 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-A-0 367474, EP-A-0 401 979 and WO 90 / 13651.

[0333] The toxins contained in the transgenic plants render the plants tolerant to harmful insects. Such insects can be found in any insect taxonomic group, but are particularly common among beetles (Coleoptera), two-winged insects (Diptera), and moths (Lepidoptera).

[0334] Transgenic plants comprising one or more genes encoding insecticide resistance and expressing one or more toxins are known and some of them are commercially available. Examples of such plants are: (corn variety expressing Cry1Ab toxin); YieldGard (corn variety expressing Cry3Bb1 toxin); YieldGard (corn varieties expressing Cry1Ab and Cry3Bb1 toxins); (corn variety expressing Cry9C toxin); Herculex (a corn variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) that confers tolerance to the herbicide glufosinate-ammonium); NuCOTN (cotton variety expressing Cry1Ac toxin); Bollgard (cotton variety expressing Cry1Ac toxin); Bollgard (cotton varieties expressing Cry1Ac and Cry2Ab toxins); (cotton varieties expressing Vip3A and Cry1Ab toxins); (potato variety, expressing Cry3A toxin); GT Advantage (GA21 glyphosate tolerance trait), CB Advantage (Bt11 corn borer (CB) trait) and

[0335] Other examples of such genetically modified crops are:

[0336] 1. Bt11 corn, from Syngenta Seeds SAS, Chemin del'Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified maize, which is resistant to attack by European corn borer (Ostrinia nubilalis and Sesamia inermis) by transgenic expression of a truncated Cry1Ab toxin. Bt11 corn also transgenic expression of the PAT enzyme to obtain tolerance to the herbicide glufosinate ammonium.

[0337] 2. Bt176 corn, from Syngenta Seeds, 27 Hobbit Road, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. Genetically modified maize, which is resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia inermis) by transgenic expression of the Cry1Ab toxin. Bt176 corn also transgenic expression of the PAT enzyme to obtain tolerance to the herbicide glufosinate ammonium.

[0338] 3. MIR604 corn, from Syngenta Seeds, 27 Rue Hobbitt, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. Corn rendered insect resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic corn plants is described in WO 03 / 018810.

[0339] 4. MON 863 maize, from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses the Cry3Bb1 toxin and is resistant to certain coleopteran insects.

[0340] 5. IPC 531 Cotton, from Monsanto Europe AB, 270-272 Avenue Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0341] 6.1507 Maize, from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Genetically modified maize expressing the protein Cry1F for resistance to certain lepidopteran insects and the protein PAT for tolerance to the herbicide glufosinate.

[0342] 7. NK603×MON 810 maize, from Monsanto Europe 270-272 Avenue Tervuren, B-1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. It is a conventionally bred hybrid maize variety made by crossing the genetically modified varieties NK603 and MON 810. NK603×MON 810 maize transgenically expresses the protein CP4 EPSPS obtained from the Agrobacterium sp. strain CP4, making it resistant to herbicides. The plant is tolerant to glyphosate and also expresses the Cry1Ab toxin from Bacillus thuringiensis subsp. kurstakia, which confers tolerance to certain Lepidoptera, including the European corn borer.

[0343] The compounds of formula (I) can be used to control or prevent phytopathogenic diseases, especially diseases caused by phytopathogenic fungi, such as Botrytis cinerea on Rosaceae, Vitaceae, Solanaceae, Cucurbitaceae and Leguminosae; Glomerella lagenarium on Cucurbitaceae; Sclerotinia sclerotiorum on Leguminosae, Cruciferae and Asteraceae, for example soybean, rapeseed and sunflower, respectively; Alternaria solani on Solanaceae such as tomato and potato; Monographella nivalis on Poaceae; or Pyricularia teres on Poaceae such as barley.

[0344] As used herein, the term "locus" means a place where or on which plants grow, or where seeds of cultivated plants are sown, or where seeds are to be placed in the soil. It includes soil, seeds, and seedlings, together with established vegetation.

[0345] The term "plant" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, leaves and fruits.

[0346] The term "plant propagation material" should be understood as meaning the reproductive parts of a plant, such as seeds, which can be used for the propagation of a plant, and vegetative materials, such as cuttings or tubers (e.g., potatoes). For example, seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants can be mentioned. Germinated plants and young plants that will be transplanted after germination or after emergence can also be mentioned. These young plants can be treated completely or partially by dipping and protected before transplanting. Preferably, "plant propagation material" should be understood as meaning seeds.

[0347] Compounds with formula (I) can be used in unmodified form, or preferably, together with conventional adjuvants used in the field of formulations. For this purpose, they can be conveniently formulated as emulsifiable concentrates, pastes that can be coated, directly sprayable or dilutable solutions or suspensions, dilute emulsions, wettable powders, soluble powders, dusts, granules and also capsules, for example in polymeric substances, in a known manner. For the type of composition, the application method is selected according to the intended purpose and the environment at that time, such as spraying, atomizing, dusting, sowing, smearing or watering. Compositions can also contain other adjuvants, such as stabilizers, defoamers, viscosity modifiers, adhesives or tackifiers, together with fertilizers, micronutrient donors or other formulations for obtaining special effects.

[0348] Suitable carriers and adjuvants, for example, for agricultural use, can be solid or liquid and are substances useful in formulation technology, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, adhesives, or fertilizers. Such carriers are for example described in WO 97 / 33890.

[0349] Suspension concentrates are aqueous formulations in which finely divided solid particles of the active compound are suspended. Such formulations contain anti-settling agents and dispersants, and may further contain wetting agents to enhance activity, as well as defoamers and crystal growth inhibitors. When used, these concentrates are diluted in water and usually applied as a spray to the area to be treated. The amount of active ingredient can range from 0.5% to 95% of the concentrate.

[0350] Wettable powders are in the form of finely divided particles that disperse easily in water or other liquid carriers. These particles contain the active ingredient retained in a solid matrix. Typical solid matrices include Fuller's earth, kaolin, silica and other easily wetted organic or inorganic solids. Wettable powders usually contain from 5% to 95% of the active ingredient plus a small amount of a wetting agent, dispersant or emulsifier.

[0351] Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquids and may consist entirely of the active compound and a liquid or solid emulsifier, or may also contain a liquid carrier such as xylene, heavy aromatic naphtha, isophorone and other non-volatile organic solvents. When used, these concentrates are dispersed in water or other liquids and are usually applied as a spray to the area to be treated. The amount of active ingredient may range from 0.5% to 95% of the concentrate.

[0352] Granular formulations include both extrudates and coarser granules and are usually applied undiluted to the area to be treated. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite, montmorillonite, vermiculite, perlite, calcium carbonate, brick, pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, crushed corn cobs, crushed peanut shells, sugar, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesium oxide, mica, iron oxide, zinc oxide, titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth, calcium sulfate and other organic or inorganic materials that absorb or can be coated with active compounds. Granular formulations usually contain 5% to 25% active ingredients, which may include surfactants such as heavy aromatic naphtha, kerosene and other petroleum fractions, or vegetable oils; and / or adhesives such as dextrins, glues or synthetic resins.

[0353] Dusts are free-flowing mixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.

[0354] Microcapsules are typically droplets or particles of active ingredients encapsulated in an inert porous shell that allows the encapsulated material to escape into the environment at a controlled rate. The diameter of the encapsulated droplets is typically 1 to 50 microns. The encapsulated liquid typically accounts for 50% to 95% of the weight of the capsule and can also contain solvents in addition to the active compound. The encapsulated particles are usually porous particles, in which the porous membrane seals the particle pores and retains the active species in the form of a liquid inside the particle pores. The diameter of the particles typically ranges from 1 mm to 1 cm and preferably 1 mm to 2 mm. The particles are formed by extrusion, coagulation or spheroidization, or are naturally occurring. Examples of such materials are vermiculite, sintered clay, kaolin, attapulgite clay, sawdust and carbon fine particles. Shell or membrane materials include natural and synthetic rubbers, fiber materials, styrene-butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

[0355] Other useful formulations for agrochemical applications include simple solutions of the active ingredient in a solvent (such as acetone, alkylated naphthalenes, xylene and other organic solvents) in which the active ingredient is completely soluble at the desired concentration. Pressurized sprays may also be used in which the active ingredient is dispersed in finely divided form due to evaporation of a low-boiling dispersant solvent carrier.

[0356] Suitable agricultural adjuvants and carriers useful for formulating the compositions of the present invention in the above-mentioned formulation types are well known to those skilled in the art.

[0357] Liquid carriers that can be used include, for example, water, toluene, xylene, naphtha, 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 rosin acid ester, divinyl glycol butyl ether, divinyl glycol ethyl ... Alcohol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol (diproxitol), alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, α-pinene, d-limonene, vinyl glycol, vinyl glycol butyl ether, vinyl glycol methyl ether, γ-butyrolactone, Glycerin, glyceryl diacetate, glyceryl monoacetate, glyceryl triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, cumene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl caprylate, methyl oleate, vinyl chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol , polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and higher molecular weight alcohols (such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, etc.), ethylene glycol, propylene glycol, glycerol and N-methyl-2-pyrrolidone. Water is usually the carrier of choice for diluting concentrates.

[0358] Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, diatomaxeous earth, lime, calcium carbonate, bentonite, Fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour and lignin.

[0359] A wide range of surfactants may be advantageously employed in the liquid and solid compositions, especially those designed to be diluted with a carrier prior to application. These agents, when used, generally comprise from 0.1% to 15% by weight of the formulation. They may be anionic, cationic, nonionic or polymeric in nature and may be employed as emulsifiers, wetting agents, suspending agents or for other purposes. Typical surfactants include alkyl sulfates such as diethanolammonium lauryl sulfate; alkylaryl sulfonates such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products such as nonylphenol-C.18 ethoxylate; alcohol-alkylene oxide addition products such as tridecanol-C.16 ethoxylate; soaps such as sodium stearate; alkylnaphthalenesulfonates such as sodium dibutylnaphthalenesulfonate; salts of dialkyl sulfosuccinates such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitan esters such as sorbitan oleate; quaternary amines such as lauryltrimethylammonium chloride; polyethylene glycol esters of fatty acids such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and dialkyl phosphates.

[0360] Other adjuvants commonly used in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet modifiers, pigments, antioxidants, foaming agents, defoamers, opacifiers, compatibilizing agents, antifoaming agents, masking agents, neutralizing and buffering agents, corrosion inhibitors, dyes, flavor enhancers, spreading agents, penetration aids, micronutrients, emollients, lubricants, and fixatives.

[0361] In addition, further, other biocidal active ingredients or compositions can be combined with the composition of the present invention, and used in the method of the present invention and applied simultaneously or sequentially with the composition of the present invention. When applied simultaneously, these other active ingredients can be prepared or mixed in, for example, a spray tank together with the composition of the present invention. These other biocidal active ingredients can be fungicides, herbicides, insecticides, bactericides, acaricides, nematicides and / or plant growth regulators.

[0362] Pesticides referred to herein using their common names are known, for example, from “The Pesticide Manual”, 15th edition, British Crop Protection Council 2009.

[0363] In addition, the compositions of the invention may also be administered with one or more inducers of systemic acquired resistance ("SAR" inducers). SAR inducers are known and described, for example, in U.S. Pat. No. 6,919,298 and include, for example, salicylates and the commercial SAR inducer acibenzolar-S-methyl.

[0364] Compounds of formula (I) are usually used in the form of agrochemical compositions and can be applied to crop areas or crops to be treated simultaneously or sequentially with other compounds. For example, these other compounds can be fertilizers or micronutrient donors or other preparations that affect plant growth. They can also be selective herbicides or non-selective herbicides, together with insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with other carriers, surfactants or adjuvants commonly used in the formulation field to promote application.

[0365] The compounds of formula (I) can be used in the form of compositions for controlling or protecting against phytopathogenic microorganisms, which compositions comprise as active ingredients at least one compound of formula (I) or 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 above-mentioned adjuvants.

[0366] Therefore, the present invention provides a composition, preferably a fungicidal composition, comprising at least one compound of formula (I), an agriculturally acceptable carrier and optionally an adjuvant. An agriculturally acceptable carrier is, for example, a carrier suitable for agricultural use. Agricultural carriers are well known in the art. Preferably, in addition to comprising a compound of formula (I), the composition may comprise at least one or more pesticidal active compounds, such as additional fungicidal active ingredients.

[0367] The following mixtures of compounds of formula (I) with active ingredients are preferred (wherein the abbreviation "TX" means "a compound selected from the group consisting of compounds defined in Tables A-1 to A-17 and subtables thereof, or selected from the group consisting of compounds P-1.1 to P-1.19 listed in Table T1 (below)"):

[0368] A compound selected from the group 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-chlorophenylphenyl sulfone + TX, acetothion + TX, oxyaldicarb + TX, thiophos + TX, amidothioate + TX, ammonium oxalate + TX, amitraz + TX, cypermethrin + TX, arsenic trioxide + TX, azobenzene + TX, azophos + TX, benomyl + TX, benoxafos + TX, benzyl benzoate + TX, bixafen + TX, bromomethrin + TX, bromothioate +TX, bromophos +TX, bromopyralid +TX, buprofezin +TX, butanone +TX, butanone sulfone +TX, butyl pyridaben +TX, calcium polysulfide +TX, toxaphene +TX, chlormethoxam +TX, carbothion +TX, cycloimidazole +TX, mite +TX, chlorbenside +TX, chlordimeform +TX, chlordimeform hydrochloride +TX, chlorfenol +TX, chlorfenson +TX, chlorfensulfide +TX, chlorobenzilate +TX, chloromebuform +TX X, chloromethiuron + TX, chloropropylate + TX, chlorthiophos + TX, cinerin I + TX, cinerin II + TX, cinerins + TX, closantel + TX, coumaphos + TX, crotamiton + TX, crotoxyphos + TX, thiophene + TX, cyanthoate + TX, DCPM + TX, DDT + TX, demephiophos n)+TX, tanafon-O+TX, tanafon-S+TX, methyl demeton+TX, demeton-O+TX, methyl demeton-O+TX, demeton-S+TX, methyl demeton-S+TX, demeton-S-methylsulfon+TX, demeton-S+TX, dichlorvos+TX, dicliphos+TX, dimefox+TX, dimefox+TX, dinex+TX, dinex-diclexine+TX, dinocap-4+TX, dinocap-6+TX, dinitro+TX, dinopenton+TX,Dinosulfon + TX, dinoterbon + TX, dioxophos + TX, diphenyl sulfone + TX, disulfiram + TX, DNOC + TX, dofenapyn + TX, doramectin + TX, endothion + TX, eprinomectin + TX, ethoate-methyl + TX, etrimfos + TX, fenazaflor + TX, fenbutatin oxide + TX, fenothiocarb + TX, fenpyrad + TX, fenpyroximate + TX, fenpyrazamine + TX, fenson + TX, fentrifanil + TX, flubenzimine + TX, flufenuron + TX, fluenetil + TX, fluorbenside + TX, FMC 1137 + TX, fenamiform + TX, fenamiform hydrochloride + TX, formparanate + TX, γ-HCH + TX, fruit green + TX, benzyl cyprodinil + TX, hexadecyl cyclopropanecarboxylate + TX, isothiocarb + TX, jasmonate I + TX, jasmonate II + TX, iodine + TX, lindane + TX, propanil + TX, cypermethrin + TX, dithiophos + TX, methyl Sulfofen + TX, chloranil + TX, methyl bromide + TX, cypermethrin + TX, chloranil + TX, milbemycin + TX, propylamine + TX, monocrotophos + TX, chloranil + TX, moxidectin + TX, naled + TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, fluazifop + TX, nikkomycin + T X, pentaclonide + TX, pentaclonide 1:1 zinc chloride complex + TX, omethoate + TX, isothiophos + TX, sulfone + TX, pp'-DDT + TX, parathion + TX, permethrin + TX, fenthion + TX, phosalone + TX, thiophanate + TX, phosphamidon + TX, polychloroterpenes + TX, polynactins + TX, chloranil + TX, cypermethrin + TX, propoxur + TX, ethidium + TX, pyrethrin + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrin + TX, pyrimethoxam + TX, pyrimithiophos + TX, quinalphos + TX, quintiofos + TX, R-1492 + TX, glyphosate + TX, rotenone + TX,Octamethoxam + TX, clomiphene carbendazim + TX, selamectin + TX, thiophos + TX, SSI-121 + TX, sulfilam + TX, flumethrin + TX, sulfluramid + TX, sulfur + TX, fluazifop + TX, τ-fluvalinate + TX, TEPP + TX, terbutaline + TX, tetrachlorothiazide sulfone + TX, miticide + TX, thiafenox + TX, anthelmintic + TX, long-lasting anthelmintic + TX, methyl thiophos + TX, miticide + TX, thiomycin + TX, thiophos + TX, benzyl thiocarb + TX, +TX, triazophos +TX, triazuron +TX, trichloropropoxyphos +TX, triactivin +TX, aphidazole +TX, vaniliprole +TX, bethoxazin +TX, copper dioctanoate +TX, copper sulfate +TX, cybutryne +TX, dichloronaphthoquinone +TX, dichlorophen +TX, endoxan +TX, triphenyltin +TX, slaked lime +TX, sodium mancozeb +TX, quinone +TX, quinone + TX, simazine + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, fusulin + TX, piperazine + TX, thiophanate + TX, chloralose + TX, fenthion + TX, pyridine-4-amine + TX, strychnine + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 4-(quinoxaline-2-ylamino)benzenesulfonamide + TX, 8-hydroxyquinoline sulfate + TX, bronopol + TX, copper hydroxide + TX, cresol + TX, dipyrithione + TX, dodecine + TX, sodium sulfadiazine + T X, formaldehyde + TX, mercury plus fen + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel di(dimethyldithiocarbamate) + TX, trichloromethylpyridine + TX, octhionone + TX, oxolinic acid + TX, oxytetracycline + TX, potassium hydroxyquinoline sulfate + TX, thiabendazole + TX, streptomycin + TX, streptomycin sesquisulfate + TX, chloranthracene + TX, thimerosal + TX, cotton brown banded moth GV + TX, radiobacterium + TX, Amblyseius species ( spp.)+TX, celery armyworm NPV+TX, Anagrus atomus+TX, Aphelinus abdominalis+TX, Aphidius colemani+TX, Aphidoletes aphidimyza+TX, Spodoptera exigua NPV+TX, Bacillus sphaericus Neide+TX, Beauveria brongniartii+TX, Chrysoperla carnea+TX, Cryptolaemus montrouzieri+TX, Codling moth GV+TX,Dacnusa sibirica+TX, Diglyphus isaea+TX, Encarsia formosa+TX, Eretmocerus eremicus+TX, Heterorhabditis bacteriophora and H.megidis+TX, Hippodamia convergens+TX, Leptomastix dactylopii+TX, Macrolophus caliginosus+TX, Cabbage armyworm NPV+TX, Metaphycus helvolus+TX, Metarhizium anisopliae var.acridum+TX, Metarhizium anisopliae microspore variant+TX var. anisopliae)+TX, Neodiprion sertifer NPV and N. lecontei NPV+TX, species of the genus Nematode+TX, Paecilomyces fumosoroseus+TX, Phytoseiulus persimilis+TX, Steinernema bibionis+TX, Steinernema carpocapsae+TX, Steinernema glaseri+TX, Steinernema riobrave+TX, Steinernema riobravis+TX, Steinernema scapterisci+TX, species of the genus Steinernema spp.)+TX, Trichogramma species+TX, Typhlodromus occidentalis+TX, Verticillium lecanii+TX, apholate+TX, bisazir+TX, busulfan+TX, dimatif+TX, hemel+TX, hemp+TX, metepa+TX, methiotepa+TX,Methyl apholate + TX, morzid + TX, penfluron + TX, tepa + TX, thiohempa + TX, thiohempa + TX, trothamide + TX, urethaneimide + TX, (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol + TX, (E)-tridec-4-en-1-yl acetate + TX, (E)-6-methylhept-2-en-4-ol + TX, (E,Z)-tetradec-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-eicos-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)-dodec-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradec-9,12-dien-1-yl acetate + TX, 14-methyloctadec-1-ene + TX, 4 -Methylnonan-5-ol and 4-methylnonan-5-one + TX, α-polystyrene + TX, western pine beetle gathering pheromone + TX, codlelure + TX, codlemone + TX, cuelure + TX, epoxide nonadecane + TX, dodec-8-en-1-yl acetate + TX, dodec-9-en-1-yl acetate + TX, dodec-8 + TX, 10-10-dien-1-yl acetate + TX, dominicalure + TX, 4-methyloctanoic acid ethyl ester + TX, eugenol + TX, southern pine beetle gathering pheromone (frontalin) + TX, cuelure + TX Grandlure + TX, trapping ene mixture I + TX, trapping ene mixture II + TX, trapping ene mixture III + TX, trapping ene mixture IV + TX, hexalure + TX, ipsdienol + TX, ipsenol + TX, japonilure + TX, lineatin + TX, litlure + TX, looplure + TX, medlure + TX, megatomoicacid + TX, methyl eugenol + TX,muscalure + TX, 18-decane-2,13-diene-1-yl acetate + TX, 18-decane-3,13-diene-1-yl acetate + TX, orfralure + TX, oryctalure + TX, ostramone + TX, siglure + TX, sordidin + TX, sulcatol + TX, 14-decane-11-ene-1-yl acetate + TX, trimedlure + TX, Mediterranean fruit fly attractant A + TX, Mediterranean fruit fly attractant B, 1 +TX, Mediterranean fruit fly attractant B 2+TX, Mediterranean fruit fly attractant C+TX, trunc-call+TX, 2-(octylthio)ethanol+TX, butopyronoxyl+TX, butoxy(polypropylene glycol)+TX, dibutyl adipate+TX, dibutyl phthalate+TX, dibutyl succinate+TX, DEET+TX, dimethyl carbate)+TX, dimethyl phthalate+TX, ethyl hexanediol+TX, hexamide+TX, methoquin-butyl+TX, methylneodecanamide+TX, oxamate+TX, picaridin+TX, 1-dichloro-1-nitroethane+TX, 1,1-dichloro-2,2-di(4-ethylphenyl)ethane+TX, 1,2-dichloropropane and 1,3-dichloropropylene+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 dimethylcarbamate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenyl methylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidinone + TX, 2-isovaleryl indan-1,3-di 1-Hydroxy-1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, 1-nitropropene, +TX, neonicotinoids +TX, ethyl thiophanate (athidathion) +TX, methyl pyrifos +TX, Bacillus thuringiensis δ-endotoxin +TX, barium hexafluorosilicate +TX, barium polysulfide +TX, fumonisin +TX, Bayer 22 / 190 +TX, Bayer 22408 +TX, β-cyfluthrin +TX, β-cypermethrin +TX, bioethanomethrin +TX, biopermethrin +TX, bis (2-chloroethyl) ether +TX, borax +TX, bromophenazone +TX, bromo-DDT +TX, hexachlorvinphos +TX, cypermethrin +TX,Butathiofos + TX, butyl phosphine + TX, calcium arsenate + TX, calcium cyanide + TX, carbon disulfide + TX, carbon tetrachloride + TX, badan hydrochloride + TX, cevadine + TX, bornyl + TX, chlordane + TX, chlordecone + TX, chloroform + TX, chloropicrin + TX, chlornitrile oxime + TX, chlorprazophos + TX, cis-resmethrin + TX, cismethrin + TX, clocythrin (alias) + TX, copper acetoarsenite + TX, copper arsenate + TX, copper oleate + TX, coumithoate + TX, cryolite + TX, CS 708+TX, benzonitrile+TX, cypermethrin+TX, cypermethrin+TX, cypermethrin+TX, d-carbofuran+TX, DAEP+TX, dazomethane+TX, decarbofuran+TX, diamidafos+TX, isochlorphos+TX, dimethophos+TX, dicresyl+TX, cypermethrin+TX, dieldrin+TX, diethyl 5-methylpyrazol-3-yl phosphate+TX, dior+TX, tetrafluthrin+TX, demicarb+TX, pyrethrin+TX, methylchlorfenapyr+TX, difenocarb+TX, propanol+TX, pentotropol+TX, dinoseb+TX, fenpyroxene+TX, vegetable phosphorus+TX, thiopyrafos+TX, DSP+TX, ecdysterone+TX, EI 1642+TX, EMPC+TX, EPBP+TX, etaphos+TX, ethiobencarb+TX, ethyl formate+TX, ethylene dibromide+TX, ethylene dichloride+TX, ethylene oxide+TX, EXD+TX, ethiobencarb+TX, ethiobencarb+TX, fenitrothion+TX, fenoxacrim+TX, cypermethrin+TX, fenthion+TX, ethylfenthion+TX, flucofuron+TX, butylfenthion+TX, phosphonium phosphate+TX, butylcyclothion+TX, furathiocarb+TX, pyrethroid+TX, biguanide salt+TX, biguanide acetate+TX, tetramethoate Sodium thiocarbonate + TX, halfenprox + TX, HCH + TX, HEOD + TX, heptachlor + TX, cypermethrin + TX, HHDN + TX, hydrogen cyanide + TX, quinoline + TX, IPSP + TX, chlorfenapyr + TX, carbochlorin + TX, isodrin + TX, isoflavone + TX, transplanting spirit + TX, rice blast spirit + TX, oxathiophos + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, chlorpentyl + TX, methoprene + TX, lead arsenate + TX, bromophenylphos + TX, acetamiprid + TX, thiathion + TX, m-isopropyl methyl carbamate + TX,Magnesium phosphide + TX, phosphorus azide + TX, methyl aphidite + TX, aphidite + TX, mercurous chloride + TX, methyl sulfoxide + TX, metamethylenetetramine + TX, metamethylenetetramine potassium salt + TX, metamethylenetetramine sodium salt + TX, methylsulfonyl fluoride + TX, butylene phosphonate + TX, methoprolol + TX, methyl ether thiocyanate + TX, methoxychlor + TX, methyl isothiocyanate + TX, methyl chloroform + TX, dichloromethane + TX, oxadiazine + TX, anticide + TX, naphthion + TX, naphthalene + TX, NC-170 + TX, nicotine + TX, nicotine sulfate + TX, nithiazine + TX, pronicotine + TX, O-5-dichloro-4-iodophenyl O-ethylethyl phosphonothioate + TX, O,O-diethyl O-4-methyl-2-oxo-2H-benzopyran-7-yl phosphonothioate + TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphonothioate + TX, O,O,O',O'-tetrapropyl dithiodipyrophosphate + TX, oleic acid + TX, p-dichlorobenzene + TX, methyl parathion + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH 60-38+TX, fenthion+TX, parathion+TX, phosphine+TX, methyl phoxim+TX, methamidophos+TX, polychlorinated dicyclopentadiene isomers+TX, potassium arsenite+TX, potassium thiocyanate+TX, precocious element I+TX, precocious element II+TX, precocious element III+TX, amimidophos+TX, profluthrin+TX, fenthion+TX, pyraclostrobin+TX, anti-pyrethroids+TX, quassia extract (quassia) + TX, quinalphos-methyl + TX, oxathion + TX, iodophos + TX, resmethrin + TX, rotenone + TX, thiamethoxam + TX, ryanodine + TX, sabadilla + TX, octamethrin + TX, clostridium + TX, SI-0009 + TX, thiamethoxam + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium hexafluorosilicate + TX , sodium pentachlorophenol + TX, sodium selenate + TX, sodium thiocyanate + TX, sulcofuron + TX, sulcofuron-sodium + TX, sulfuryl fluoride + TX, thiopromide + TX, tar + TX, thiamethoxam + TX, TDE + TX, butylpyrimidinphos + TX, dimethoate + TX, cyclopentylthrin + TX, tetrachloroethane + TX, thiochlorvos + TX, thiophanate-sodium + TX, Cyclohexanil + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin sodium + TX, tetrabromothrin + TX, permethrin + TX, trichlormetaphos-3 + TX, cypermethrin + TX, chlorpyrifos + TX, tolprocarb + TX, chlorpyrifos + TX, chlorpyrifos + TX, chlorpyrifos + TX, chlorpyrifos + TX, chlorpyrifos + TX, veratridine + TX, XMC + TX,Zetamethrin + TX, zinc phosphide + TX, tolfenphos + TX, chlorfluanidine + TX, tetrafluanidine + TX, bis(tributyltin) oxide + TX, bromoacetamide + TX, iron phosphate + TX, niclosamide-ethanolamine + TX, tributyltin oxide + TX, pyroximate + TX, snail killer + TX, 1,2-dibromo-3-chloropropane + TX, 1,3-dichloropropylene + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6-thio-1,3,5-thiadiazole oxazine-3-yl acetic acid + TX, 6-isopentenylaminopurine + TX, anisiflupurin + TX, benclothiaz + TX, cytokinin + TX, DCIP + TX, furfural + TX, isamidophos + TX, kinetin + TX, verrucosporium mycorrhizal 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, bismuth urea + TX, brodifacoum + TX, brodifacoum + TX, brodifacoum + TX, chlordifacoum + TX, cholecalciferol + TX, chlorfenapyr + TX, clofodine + TX, clofodine + TX, clofodine + TX, clofodine + TX, clofodine + TX, clofodine + TX, clofodine + TX, calciferol + TX, fludioxaline + TX, fluoroacetamide + TX, fludioxaline Pyridine + TX, flurbiprofen hydrochloride + TX, warfarin + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, chloranil + TX, sodium fluoroacetate + TX, thallium sulfate + TX, warfarin + TX, 2-(2-butoxyethoxy)ethyl piperate + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, farnesol with nerolidol + TX, synergistic acetylene ether + TX, MGK 264+TX / piperidinol+TX, synergistic aldehyde+TX, propylisomer+TX, S421+TX, synergistic powder+TX, sesasmolin+TX, sulfoxide+TX, anthraquinone+TX, copper cyclohexaneate+TX, copper oxychloride+TX, dicyclopentadiene+TX, salen+TX, zinc cyclohexaneate+TX, zinc thiram+TX, imanin+TX, ribavirin+TX, chloroinconazide+TX, mercuric oxide+TX, thiophanate-methyl+TX, azaconazole+TX, bifenthrin+TX, oxadiazole+TX, cyproconazole+TX, difenoconazole+TX, diniconazole+TX, epoxiconazole+TX, fenbuconazole+TX, fluquinconazole+TX, flusilazole+TX, flutriafol+TX,Furoxamethylenetetracycline + TX, hexaconazole + TX, imazalil + TX, imipenem + TX, cyproconazole + TX, metconazole + TX, myclobutrazol + TX, paclobutrazol + TX, pyrifenox + TX, prochloraz + TX, propiconazole + TX, pyraconazole + TX, simeconazole + TX, tebuconazole + TX, fluconazole + TX, triadimefon + TX, triadimenol + TX, triflumizole + TX, trichlorfon + TX, pyrimidine + TX, chlorfenapyr + TX, flufenapyr + TX, bupirimate + TX, dimethirimol + T X, ethirimol + TX, dodecacyclic morpholine + TX, fenpropidin + TX, fenpropimorph + TX, spiroxamorph + TX, tridecamorph + TX, cyprodinil + TX, pyraclostrobin + TX, pyrimethanil + TX, fenpiclonil + TX, fludioxonil + TX, benalaxyl + TX, furalaxyl + TX, metalaxyl + TX, R-metalaxyl + TX, furamide + TX, oxadixyl + TX, carbendazim + TX, debacarb + TX, thiabendazole + TX, chlozolin + TX, linate + TX, dichlozoline + TX, myclozoline + TX, procymidone + TX, vinclozoline + TX, boscalid + TX, carboxin + TX, furamide + TX, flutolanil + TX, oxacarb + TX, penthiopyrad + TX, thiofuran + TX, docodine + TX, biguanide + TX, azoxystrobin + TX, etherstrobin + TX, enestroburin + TX, enestroburin +TX, fluopicolide +TX, fluoxastrobin +TX, kresoxim-methyl +TX, fenoxystrobin +TX, trifloxystrobin +TX, trifloxystrobin +TX, pyraclostrobin +TX, pyraclostrobin +TX, ferbam +TX, mancozeb +TX, maneb +TX, methanamide +TX, methyl propineb +TX, maneb +TX, captan +TX, captan +TX, pyraclostrobin +TX, thiabendazole +TX, bordeaux mixture +TX, copper oxide +TX, mancozeb +TX, quinoline copper +TX, phthalostrobin +TX, kefansan +TX, isothiocyanate +TX, chlorpyrifos +TX, tolclofos-methyl +TX, captan +TX, benzothiocyanate +TX,Blasticidin-S+TX, chloroneb+TX, thiophanate-methyl+TX, cyfluanid+TX, cymoxanil+TX, cyclobutrifluram+TX, diclocymet+TX, diclomezine+TX, dicloran+TX, diethofencarb+TX, oxadiazine+TX, flumorph+TX, dithianon+TX, ethaboxam+TX, etridiazole+TX, famoxadone+TX, fenamidone( fenamidone + TX, fenoxanil + TX, ferimzone + TX, fluazinam + TX, flumetylsulforim + TX, fluopicolide + TX, fluoxytioconazole + TX, flusulfamide + TX, flupyraclostrobin + TX, fenac + TX, fosetyl-aluminium + TX, hymexazol + TX, propineb + ​​TX, cyazofamid + TX, sulfamethoxazole (m ethasulfocarb + TX, mefenamic acid + TX, pencycuron + TX, phthalide + TX, polyoxins + TX, propamocarb + TX, pyraclostrobin + TX, proquinazid + TX, pyroquilon + TX, pyriofenone + TX, quinoxyfen + TX, pentachloronitrobenzene + TX, thiazolamide + TX, triazoxide + TX, tricyclazole + TX, triazine + TX, validamycin + TX, valerianide + TX, zoxamide + TX 、mandipropamid+TX、flubeneteram+TX、isopyrazam+TX、sedaxane+TX、benzovinflupyrazole+TX、flupyrazolehydroxylamide+TX、3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide+TX、isoflucypram+TX、isothianid+TX、dipymetitrone+TX、6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile+TX、2-(Difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile+TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide+TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine+TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine+TX, fluindapyr+TX, carboxystrobin (jia xiangjunzhi)+TX, lvbenmixianan+TX, dichlobentiazox+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-quinolinyl)oxy]phenyl]propan-2-ol+TX, oxathiapiprolin+TX, N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamic acid tert-butyl ester+TX, pyraziflumid+T X, inpyrfluxam + TX, trolprocarb + TX, chlorfluconazole + 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-piperidinyl ]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl] methanesulfonate + TX, N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamic acid but-3-ynyl ester + TX, N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, pyridachlometyl + 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-tetrazolyl-5-one+TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazolyl-5-one+TX, aminopyrifen+TX, pyraclostrobin+TX, indazolesulfazoline+TX, fluopicolide+TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl- Pent-3-enamine + TX, florylpicoxamid + TX, fenpicoxamid + TX, metaylpicoxamid + TX, isobutylethoxyquinoline + TX, ipflufenoquin + TX, quinofumelin + TX, isopropylthiopyrad + TX, ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]pyrazole-3-carboxylate + TX (can be prepared by WO 2020 / 056090), ethyl 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enyloxy]phenyl]methyl]pyrazole-3-carboxylate + TX (can be prepared by the method described in WO2020 / 056090), methyl N-[[4-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate + TX (can be prepared by the method described in WO 2020 / 097012), methyl N-[[4-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate + TX (can be prepared by the method described in WO 2020 / 097012), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide + TX (can be prepared by 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 (can be prepared by 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 (can be prepared by 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, benzathiostrobin + TX, cyanothiostrobin + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, fluopyram + TX, flufenoxadiazam + TX, fluthiazolin + TX, fluopyram + TX, pyrapropoyn e+TX, picarbutrazox+TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide+TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide+TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile+TX, metyltetraprole+TX 、2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide+TX、α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidinemethanol+TX、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 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 by the method described in WO 2020 / 193387),4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + 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-thio-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, trinexapac-ethyl + TX, syringoxystrobin + TX, zhongshengmycin + TX, thiophanate-methyl + TX, thiazole zinc + TX, amectotractin + TX, isoprodinil + TX, seboctylamine + TX; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, -ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds can be prepared from WO 2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared by the method described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl-formamidine + TX, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds can be prepared by 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-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]- 8-Fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3- Formamide + TX, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + T X, 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 made from WO 2017 / 153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline+TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline+TX, 4,4-difluoro-3,3-dimethyl -1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline+TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline+TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline+TX (these compounds can be 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 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]propanamide + TX, )-1,2,4-oxadiazol-3-yl]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]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, 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylic acid ethyl ester+TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine+TX. The compounds in this paragraph can be prepared from WO 2017 / 055473, WO 2017 / 055469,Prepared by the method described in 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 by 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 by the method described in WO 2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile+TX (this compound can be prepared by the method described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester + TX (this compound can be prepared by the method described in WO2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']bipyrrole-1,3,5,7(2H,6H)-tetraketone + 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]thiobenzamide+TX; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide+TX (this compound can be prepared by the method described in WO 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine+TX; N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine+TX (this compound can be prepared by the method described in WO 2-(Difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX (this compound can be prepared by the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone+TX,(3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX (these compounds can be prepared by the 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 by the method described in WO 2018 / 065414); 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylic acid ethyl ester + TX (this compound can be prepared by the method described in WO 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-carbonimino]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX (these compounds can be prepared by the method described in WO 2018 / 202428). 、

[0369] References in brackets after the active ingredients, e.g. [3878-19-1] refer to Chemical Abstracts Registry Numbers. The mixed compounds described above are known. In the case where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual-A World Compendium; 13th edition; Editor: CDSTomLin; The British Crop Protection Council], they are described therein by the entry number given in parentheses above for the specific compound; for example, the compound "abamectin" is described by the entry number (1). In the case where "[CCN]" is added to a specific compound above, the compound in question is included in the "Compendium of Pesticide Common Names", which can be found on the Internet [A.Wood; Compendium of Pesticide Common Names , 1995-2004]; for example, the compound "acetoprole" is described on the Internet at http: / / www.alanwood.net / pesticides / acetoprole.html.

[0370] Most of the above-mentioned active ingredients are referred to by what are called "common names" above, in individual cases using the relevant "ISO common name" or another "common name". If a name is not a "common name", the kind of name used is replaced by the name given in parentheses for the specific compound; in this case, the IUPAC name, IUPAC / Chemical Abstracts name, "Chemical Name", "Common Name", "Compound Name" or "Development Code" is used, or, if neither one of those names nor the "common name" is used, the "synonym" is used. "CAS Registry Number" means the Chemical Abstracts Registry Number.

[0371] The active ingredient mixture of a compound of formula (I) (selected from a compound as shown in Tables A-1 to A-17 and their sub-tables (below), or selected from the compounds P-1.1 to P-1.19 listed in Table T1 (below)) is preferably in a mixing ratio of from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially from 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5:1 to 1:5, particularly preferably in a ratio of 2:1 to 1:2, also preferably in a ratio of 4:1 to 2:1, especially 1:1, or 5:1 , or 5:2, or 5:3, or 5:4, 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. Those mixing ratios are by weight.

[0372] The mixtures as described above may be used in a method for controlling pests which comprises applying a composition comprising a mixture as described above to the pests or their environment, excluding methods for treating the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body.

[0373] Mixtures comprising compounds as shown in Tables A-1 to A-17 and their sub-tables (hereinafter), or compounds P-1.1 to P-1.19 listed in Table T1 (hereinafter), and one or more active ingredients as described above can be applied, for example, in a single "ready-to-use" form, in a combined spray mixture (which consists of separate formulations of the single active ingredient components) (such as a "tank mix"), and when applied in a sequential manner (i.e., one after another for a reasonably short period of time, such as a few hours or days) using these single active ingredients in combination. The order of applying the compounds as shown in Tables A-1 to A-17 and their sub-tables (hereinafter), or compounds P-1.1 to P-1.19 listed in Table T1 (hereinafter), and one or more active ingredients as described above is not critical for practicing the present invention.

[0374] The compounds of the present invention can also be used in combination with anthelmintics. Such anthelmintics include compounds selected from macrolide compounds, such as ivermectin, avermectin, abamectin, emamectin, eprinomectin, doramectin, selamectin, moxidectin, nemaketin and milbemycin derivatives, as described in EP-357460, EP-444964 and EP-594291. Other anthelmintics include semisynthetic and biosynthetic avermectin / milbemycin derivatives, such as those described in US-5015630, WO-9415944 and WO-9522552. Other anthelmintics include benzimidazoles, such as albendazole, cambendazole, fenbendazole, flubendazole, mebendazole, oxfendazole, oxbendazole, parbendazole and other members of this category. Additional anthelmintics include imidazothiazoles and tetrahydropyrimidines, such as tetramisole, levamisole, pyrantel pamoate, octadalafil or morantel. Additional anthelmintics include flukeicides (such as triclabendazole and clorsulon) and tapewormicides (such as praziquantel and ethacistel).

[0375] The compounds of the present invention may be used in combination with derivatives and analogs of the paraherquamide / marcfortine class of anthelmintics and antiparasitic oxazolines such as those disclosed in US-5478855, US-4639771 and DE-19520936.

[0376] The compounds of the invention can be used in combination with derivatives and analogs of the general class of dioxomorpholine antiparasitic agents as described in WO 96 / 15121 and also 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.

[0377] The compounds of the present invention can be used in combination with other ectoparasiticides; for example, fipronil; pyrethroids; organophosphates; insect growth regulators such as chlorfenuron; ecdysone agonists such as tebufenozide; neonicotinoids such as imidacloprid, etc.

[0378] The compounds of the present invention may be used in combination with terpene alkaloids, such as those described in International Patent Application Publication Nos. WO 95 / 19363 or WO 04 / 72086, in particular the compounds disclosed therein.

[0379] Other examples of such biologically active compounds that can be used in combination with the compounds of the present invention include, but are not limited to, the following:

[0380] Organophosphates: acephate, methyl pyraclofos, ethyl azinphos-methyl, methyl azinphos-methyl, bromophos, ethyl bromophos, cadusin, chlorethoxyphos, chlorpyrifos, chlorfenapyr, chlormethylphos, demeton, demeton-S-methyl, demeton-S-methyl sulfone, chlormethimide, diazinon, dichlorvos, dicrotophos, dimethoate, ethion, ethion, ethion, oxamethoxam, fenamiphos, fenitrothion, fenthion, fenthion, fenthion, pyrifos, fenfothion, anchovy, thiamethoxam, heptenophos, chlorazophos, isothiophos, isoxazophos, ma Lanthion, cypermethrin, methamidophos, methidathion, methyl parathion, mefenphos, monocrotophos, dibromophos, omethoate, methyl oxo-demeton, paraoxon, parathion, methyl parathion, fenthion, phosalone, thiocyanate, phosphamidon, phosphamidon, phosphamidon, phosphamidon, phosphamidon, phosphamidon, phosphamidon, phosphamidon, phosphamidon, phosphamidon, phosphamidon, phosphamidon, pyrimidinephos, pyrimidinephos-methyl, bromophos, propanphos, proetamphos, pyraclofos, pyridazinephos, quinalphos, thiopromide, thimeton, terbufos, butyl pyrimidinephos, stirophos, thimeton, triazophos, trichlorfon, and cypermethrin.

[0381] Carbamates: aldicarb, 2-sec-butylphenyl methyl carbamate, benfuracarb, carbaryl, chlorpyrifos, carbofuran, butylthiocarb, diflubenzuron, ethiofencarb, fenoxycarb, fenthiocarb, furathiocarb, HCN-801, isoprocarb, indoxacarb, methiocarb, methomyl, 5-methyl-m-isopropylphenylbutynyl (methyl) carbamate, cypermethrin, pirimicarb, propoxur, thiodicarb, long-lasting carb, triazolam, UC-51717.

[0382] Pyrethroids: flumethrin, allethrin, cis-cypermethrin, 5-benzyl-3-furylmethyl (E)-(1R)-cis-2,2-dimethyl-3-(2-oxothiolane-3-ylidenemethyl) cyclopropanecarboxylate, bifenthrin, β-cyfluthrin, flucythrin, a-cypermethrin, β-cypermethrin, bio-allethrin, bio-allethrin ((S)-cyclopentyl isomer), bio-resmethrin, bifenthrin, NCI-85193, cypermethrin, chlorfluthrin Permethrin, cypermethrin, cypermethrin, deltamethrin, cypermethrin, cypermethrin, esfenvalerate, ether cypermethrin, fenfluthrin, cypermethrin, flucythrin, fluvalinate (D isomer), imiprothrin, cyfluthrin, λ-cyfluthrin, permethrin, phenothrin, prallethrin, pyrethrin (natural product), resmethrin, tetramethrin, transfluthrin, θ-cypermethrin, flutomethrin, t-flutomethrin, tefluthrin, tralomethrin, ζ-cypermethrin.

[0383] Arthropod growth regulators: a) Chitin synthesis inhibitors: benzoyl ureas: chlorfenapyr, diflubenzuron, fluazifop, flufenoxuron, flufenoxuron, hexaflumuron, chlorfenuron, isoflurane, diflubenzuron, dimethoate, thiophanate-methyl, benzathine, hexathiazolin, etoxazole, chlorfentazine; b) Ecdysone antagonists: chlorfenapyr, methoxyfenapyr, fenpyroximate; c) Juvenile hormone analogs: pyriproxyfen, methoprene (including S-methoprene), fenoxycarb; d) Lipid biosynthesis inhibitor: spirodiclofen.

[0384] Other antiparasitic drugs: acequinoxaline, amitraz, AKD-1022, ANS-118, azadirachtin, Bacillus thuringiensis, sulfamethoxazole, bifenazate, binacarb, bromocriptine, BTG-504, BTG-505, toxaphene, cartap, ethyl cypermethrin, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, chlorfenapyr, clothianidin, cypermethrin, diacloden, cypermethrin, DBI-3204, diclofenac, dihydroxy methyl dihydroxypyrrolidine, dimethoate, dimethoate, endosulfan, ethiprole, fenpyroxen, flumite, MTI-800, fenpyroximate, pyrimidine, flumethrin, bromothrin, flumethoate, trifluroxyfen, halofenprox, hydrazone, IKI-220, sodium silicate, NC-196, neem guard), nidinorterfuran, nitenpyram, SD-35651, WL-108477, pyridalyl, propargite, protrifenbute, pymetrozine, pyridabenzane, pyrimidine, NC-1111, R-195, RH-0345, RH-2485, RYI-210, S-1283, S-1833, SI-8601, flutoxin, silomadine, spinosad, tebufenpyrad, trichloroacetic acid sulfone, tetracycline, thiacloprid, thiamethoxam, tolfenpyrad, triacetin, triacylglycerol, synergistic acetyl ether, vertalec, YI-5301.

[0385] Biological agents: Bacillus thuringiensis ssp aizawai, Bacillus thuringiensis ssp kurstaki, Bacillus thuringiensis delta endotoxin, baculovirus, insect pathogenic bacteria, viruses and fungi.

[0386] Bactericides: chlortetracycline, oxytetracycline, streptomycin.

[0387] Other biologics: enrofloxacin, febantel, pentoxacillin, meloxicam, cephalexin, kanamycin, pimobendan, clenbuterol, omeprazole, tiamulin, benazepril, pyriprole, cefquinome, florfenicol, buserelin, cefuroxime, tolamectin, ceftiofur, carprofen, mefluazione, praziquantel, triclabendazole.

[0388] The compositions according to the invention may also contain other solid or liquid adjuvants, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soybean oil), defoamers (for example silicone oils), preservatives, viscosity regulators, adhesives and / or tackifiers, fertilizers or other active ingredients for obtaining specific effects, such as bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0389] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries, for example by grinding, screening and / or compressing the solid active ingredient; and in the presence of at least one auxiliary, for example by intimately mixing the active ingredient with one or more auxiliary agents and / or grinding the active ingredient with one or more auxiliary agents. These methods for preparing the compositions and the use of compound (I) for preparing these compositions are also the subject matter of the present invention.

[0390] Another aspect of the invention relates to the use of a compound of formula (I), or preferably an 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 mixed with other fungicides or insecticides as described above for controlling or preventing plants, such as useful plants (such as crop plants), their propagation materials (such as seeds), harvested crops (such as harvested food crops), or non-living materials from infestation by insects or phytopathogenic microorganisms, preferably fungal organisms.

[0391] Another aspect of the invention relates to a method for controlling or preventing infestation of plants, for example useful plants (such as crop plants), their propagation materials (such as seeds), harvested crops (such as harvested food crops), or non-living materials by insects or phytopathogenic or spoilage microorganisms or organisms potentially harmful to humans (especially fungal organisms), which method comprises applying a compound of formula (I) or preferably a single compound as defined above as an active ingredient to these plants, parts of these plants or their locus, their propagation materials, or any part of these non-living materials.

[0392] Control or prevention means the reduction of infestation by phytopathogenic or spoilage microorganisms or organisms potentially harmful to humans, especially fungal organisms, to such a level that an improvement is demonstrated.

[0393] The preferred method for controlling or preventing crop plants from being infected by plant pathogenic microorganisms (especially fungal organisms) or insects is foliar application, which includes applying a compound with formula (I) or an agrochemical composition containing at least one of the compounds. The frequency of application and the application ratio will depend on the risk of infection by the corresponding pathogen or insect. However, the compound with formula (I) can also penetrate the plant through the soil through the root (systemic effect) by soaking the plant with a liquid formulation or by applying the compound in solid form, for example, in a granular form to the soil (soil application). In rice crops, such granules can be applied to the paddy field of irrigation. The compound with formula (I) can also be applied to seeds (coating) in the following manner: the seeds or tubers are impregnated with a liquid formulation of a fungicide, or they are coated with a solid formulation.

[0394] Formulations (e.g. compositions containing a compound of formula (I) and, if desired, solid or liquid adjuvants or monomers for encapsulating the compound of formula (I)) can be prepared in a known manner, typically by intimately mixing and / or grinding the compound with extenders (e.g. solvents, solid carriers and optionally surface-active compounds (surfactants)).

[0395] Advantageous application rates are generally from 5 g to 2 kg of active ingredient (ai) / hectare (ha), preferably from 10 g to 1 kg ai / ha, most preferably from 20 g to 600 g ai / ha. When used as a seed drench, a suitable dosage is from 10 mg to 1 g of active substance / kg seed.

[0396] When the combination of the invention is used to treat seed, a ratio of 0.001 to 50 g of compound of formula (I) per kg of seed, preferably from 0.01 to 10 g per kg of seed, is generally sufficient.

[0397] Suitably, the composition according to the invention comprising a compound of formula (I) is administered prophylactically (meaning before development of the disease) or therapeutically (meaning after development of the disease).

[0398] The composition of the present invention can be used in any conventional form, for example in the form of a twin pack, a dry powder for seed treatment (DS), an emulsion for seed treatment (ES), a flowable concentrate for seed treatment (FS), a solution for seed treatment (LS), a water-dispersible powder for seed treatment (WS), a capsule suspension for seed treatment (CF), a gel for seed treatment (GF), an emulsion concentrate (EC), a suspension concentrate (SC), a suspoemulsion (SE), a capsule suspension (CS), a water-dispersible granule (WG), an emulsifiable granule (EG), an oil-in-water emulsion (EO), an oil-in-water emulsion (EW), a microemulsion (ME), a dispersible oil suspension (OD), an oil suspension (OF), an oil-soluble liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (SU), an ultra-low volume liquid (UL), a master batch (TK), a dispersible concentrate (DC), a wettable powder (WP) or any technically feasible formulation in combination with an agriculturally acceptable adjuvant.

[0399] Such compositions can be produced in a conventional manner, for example by mixing the active ingredient with appropriate formulation inerts (diluents, solvents, fillers and optionally other formulation ingredients, such as surfactants, biocides, antifreeze agents, adhesives, thickeners and compounds providing auxiliary effects). Conventional sustained-release formulations intended for long-term sustained efficacy can also be used. In particular, formulations to be applied in a 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 agents and dispersants) and other compounds providing auxiliary effects, such as condensation products of formaldehyde with naphthalene sulfonates, alkyl aryl sulfonates, lignin sulfonates, fatty alkyl sulfates and ethoxylated alkylphenols and ethoxylated fatty alcohols.

[0400] The seed dressing formulation is applied to the seed in a manner known per se using the combination of the invention and the diluent in the form of a suitable seed dressing formulation, for example an aqueous suspension or dry powder with good adhesion to the seed. Such seed dressing formulations are known in the art. The seed dressing formulation may contain a single active ingredient or a combination of active ingredients in encapsulated form, for example as a sustained-release capsule or microcapsule.

[0401] Typically, these formulations include by weight from 0.01% to 90% of active agent, from 0 to 20% of agriculturally acceptable surfactant and 10% to 99.99% of solid or liquid formulation inert agent and one or more adjuvants, the active agent is composed of at least a compound of formula (I) optionally together with other active agents (particularly microbicides or preservatives, etc.). The concentrated form of the composition typically contains by weight between about 2% and 80%, preferably between about 5% and 70% of the active agent. The application form of the formulation can, for example, contain by weight from 0.01% to 20%, preferably by weight from 0.01% to 5% of the active agent. However, commercial products will preferably be formulated as concentrates, and end users will typically use diluted formulations.

[0402] While it is preferred that commercial products be formulated as concentrates, the end user will generally employ a diluted formulation.

[0403] The compounds according to 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 show preferred compounds of formula (Ia).

[0404]

[0405] Table A : A compound having formula (Ia), wherein R 1 , R 7 , R 8 and R 9 Defined in Tables A-1 to A-17, and NH-L 1 -G is defined in Table Z below.

[0406] Table Z

[0407]

[0408]

[0409] Table A-1 : A compound having formula (Ia-A-1), wherein R 1 , R 7 , R 8 and R 9 As defined in Tables A-1a to A-1j, and NH-L 1 -G is as defined in Table Z above:

[0410]

[0411] Table A-1a: This subtable provides 23 compounds A-1a.01 to A-1a.23 of formula (Ia-A-1), wherein R1 is 3-cyclopropyl-2-fluorophenyl, R 8 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0412] Table A-1b: This subtable provides 23 compounds A-1b.01 to A-1b.23 having formula (Ia-A-1), wherein R 1 is 3-(trifluoromethyl)phenyl, R 8 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0413] Table A-1c: This subtable provides 23 compounds A-1c.01 to A-1c.23 having formula (Ia-A-1), wherein R 1 is 3-ethynylphenyl, R 8 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0414] Table A-1d: This subtable provides 23 compounds A-1d.01 to A-1d.23 having formula (Ia-A-1), wherein R 1 is 3-chlorophenyl, R 8 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0415] Table A-1e: This subtable provides 23 compounds A-1e.01 to A-1e.23 having formula (Ia-A-1), wherein R 1 is 5-cyanopyridin-3-yl, R 8 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0416] Table A-1f: This subtable provides 23 compounds A-1f.01 to A-1f.23 having formula (Ia-A-1), wherein R 1 is 3-cyclopropylphenyl, R 8 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0417] Table A-1g:This subtable provides 23 compounds A-1g.01 to A-1g.23 having formula (Ia-A-1), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 8 is methyl and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0418] Table A-1h: This subtable provides 23 compounds A-1h.01 to A-1h.23 having formula (Ia-A-1), wherein R 1 is 3-(trifluoromethyl)phenyl, R 8 is chlorine and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0419] Table A-1i: This subtable provides 23 compounds A-1i.01 to A-1i.23 having formula (Ia-A-1), wherein R 1 is 5-cyanopyridin-3-yl, R 8 is hydrogen and R 9 is chlorine, and the substituent NH-L 1 -G is as defined in Table Z above.

[0420] Table A-1j: This subtable provides 23 compounds A-1j.01 to A-1j.23 having formula (Ia-A-1), wherein R 1 is 3-cyclopropylphenyl, R 8 is methyl and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0421] Table A-2 : A compound having formula (Ia-A-2), wherein R 1 , R 7 , R 8 and R 9 are defined in Tables A-2a to A-2k, and NH-L1-G is as defined in Table Z above:

[0422]

[0423] Table A-2a: This subtable provides 23 compounds A-2a.01 to A-2a.23 of formula (Ia-A-2), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 7 and R 9 is hydrogen, and the substituent NH-L1 -G is as defined in Table Z above.

[0424] For example, compound A-2a.01 is:

[0425]

[0426] Table A-2b: This subtable provides 23 compounds A-2b.01 to A-2b.23 of formula (Ia-A-2), wherein R 1 is 3-(trifluoromethyl)phenyl, R 7 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0427] Table A-2c: This subtable provides 23 compounds A-2c.01 to A-2c.23 having formula (Ia-A-2), wherein R 1 is 3-ethynylphenyl, R 7 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0428] Table A-2d: This subtable provides 23 compounds A-2d.01 to A-2d.23 having formula (Ia-A-2), wherein R 1 is 3-chlorophenyl, R 7 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0429] Table A-2e: This subtable provides 23 compounds A-2e.01 to A-2e.23 having formula (Ia-A-2), wherein R 1 is 5-cyanopyridin-3-yl, R 7 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0430] Table A-2f: This subtable provides 23 compounds A-2f.01 to A-2f.23 having formula (Ia-A-2), wherein R 1 is 5-(cyclopropyl)pyridin-3-yl, R 7 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0431] Table A-2g:This subtable provides 23 compounds A-2g.01 to A-2g.23 having formula (Ia-A-2), wherein R 1 is 3-cyclopropylphenyl, R 7 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0432] Table A-2h: This subtable provides 23 compounds A-2h.01 to A-2h.23 having formula (Ia-A-2), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 7 is hydrogen, R 9 is methyl, and the substituent NH-L 1 -G is as defined in Table Z above.

[0433] Table A-2i: This subtable provides 23 compounds A-2i.01 to A-2i.23 of formula (Ia-A-2), wherein R 1 is 3-(trifluoromethyl)phenyl, R 7 is hydrogen, R 9 is methyl, and the substituent NH-L 1 -G is as defined in Table Z above.

[0434] Table A-2j: This subtable provides 23 compounds A-2j.01 to A-2j.23 having formula (Ia-A-2), wherein R 1 is 5-cyanopyridin-3-yl, R 7 is hydrogen, R 9 is methyl, and the substituent NH-L 1 -G is as defined in Table Z above.

[0435] Table A-2k: This subtable provides 23 compounds A-2k.01 to A-2k.23 of formula (Ia-A-2), wherein R 1 is 3-cyclopropylphenyl, R 7 is hydrogen, R 9 is methyl, and the substituent NH-L 1 -G is as defined in Table Z above.

[0436] Table A-3 : A compound having formula (Ia-A-3), wherein 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:

[0437]

[0438] Table A-3a: This subtable provides 23 compounds A-3a.01 to A-3a.23 of formula (Ia-A-3), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 7 and R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0439] Table A-3b: This subtable provides 23 compounds A-3b.01 to A-3b.23 of formula (Ia-A-3), wherein R 1 is 3-(trifluoromethyl)phenyl, R 7 and R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0440] Table A-3c: This subtable provides 23 compounds A-3c.01 to A-3c.23 having formula (Ia-A-3), wherein R 1 is 3-ethynylphenyl, R 7 and R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0441] Table A-3d: This subtable provides 23 compounds A-3d.01 to A-3d.23 having formula (Ia-A-3), wherein R 1 is 3-chlorophenyl, R 7 and R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0442] Table A-3e: This subtable provides 23 compounds A-3e.01 to A-3e.23 having formula (Ia-A-3), wherein R 1 is 5-cyanopyridin-3-yl, R 7 and R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0443] Table A-3f: This subtable provides 23 compounds A-3f.01 to A-3f.23 having formula (Ia-A-3), wherein R 1 is 5-(cyclopropyl)pyridin-3-yl, R7 and R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0444] Table A-3g: This subtable provides 23 compounds A-3g.01 to A-3g.23 having formula (Ia-A-3), wherein R 1 is 3-cyclopropylphenyl, R 7 and R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0445] Table A-3h: This subtable provides 23 compounds A-3h.01 to A-3h.23 having formula (Ia-A-3), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 7 is methyl and R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0446] Table A-3i: This subtable provides 23 compounds A-3i.01 to A-3i.23 having formula (Ia-A-3), wherein R 1 is 3-(trifluoromethyl)phenyl, R 7 is chlorine and R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0447] For example, compound A-3i-15 is:

[0448]

[0449] Table A-3j: This subtable provides 23 compounds A-3j.01 to A-3j.23 having formula (Ia-A-3), wherein R 1 is 5-cyanopyridin-3-yl, R 7 is hydrogen and R 8 is chlorine, and the substituent NH-L 1 -G is as defined in Table Z above.

[0450] Table A-3k: This subtable provides 23 compounds A-3k.01 to A-3k.23 having formula (Ia-A-3), wherein R 1 is 3-cyclopropylphenyl, R 7 is hydrogen and R 8 is fluorine, and the substituent NH-L 1-G is as defined in Table Z above.

[0451] Table A-4 : A compound having formula (Ia-A-4), wherein R 1 , R 7 , R 8 and R 9 As defined in Tables A-4a to A-4d, and NH-L 1 -G is as defined in Table Z above:

[0452]

[0453] Table A-4a: This subtable provides 23 compounds A-4a.01 to A-4a.23 of formula (Ia-A-4), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0454] Table A-4b: This subtable provides 23 compounds A-4b.01 to A-4b.23 of formula (Ia-A-4), wherein R 1 is 3-(trifluoromethyl)phenyl, R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0455] Table A-4c: This subtable provides 23 compounds A-4c.01 to A-4c.23 having formula (Ia-A-4), wherein R 1 is 5-cyanopyridin-3-yl, R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0456] Table A-4d: This subtable provides 23 compounds A-4d.01 to A-4d.23 having formula (Ia-A-4), wherein R 1 is 3-cyclopropylphenyl, R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0457] Table A-5 : A compound having formula (Ia-A-5), wherein R 1 , R 7 , R 8 and R 9 As defined in Tables A-5a to A-5d, and NH-L 1 -G is as defined in Table Z above:

[0458]

[0459] Table A-5a: This subtable provides 23 compounds A-5a.01 to A-5a.23 having formula (Ia-A-5), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0460] Table A-5b: This subtable provides 23 compounds A-5b.01 to A-5b.23 having formula (Ia-A-5), wherein R 1 is 3-(trifluoromethyl)phenyl, R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0461] Table A-5c: This subtable provides 23 compounds A-5c.01 to A-5c.23 having formula (Ia-A-5), wherein R 1 is 5-(cyclopropyl)pyridin-3-yl, R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0462] Table A-5d: This subtable provides 23 compounds A-5d.01 to A-5d.23 having formula (Ia-A-5), wherein R 1 is 3-cyclopropylphenyl, R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0463] Table A-6 : A compound having formula (Ia-A-6), wherein R 1 , R 7 , R 8 and R 9 As defined in Tables A-6a to A-6c, and NH-L 1 -G is as defined in Table Z above:

[0464]

[0465] Table A-6a: This subtable provides 23 compounds A-6a.01 to A-6a.23 of formula (Ia-A-6), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 7 is hydrogen, and the substituent NH-L1 -G is as defined in Table Z above.

[0466] Table A-6b: This subtable provides 23 compounds A-6b.01 to A-6b.23 having formula (Ia-A-6), wherein R 1 is 3-(trifluoromethyl)phenyl, R 7 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0467] Table A-6c: This subtable provides 23 compounds A-6c.01 to A-6c.23 having formula (Ia-A-6), wherein R 1 is 3-cyclopropylphenyl, R 7 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0468] For example, compound A-6c.02 is:

[0469]

[0470] Table A-7 : A compound having formula (Ia-A-7), wherein R 1 , R 7 , R 8 and R 9 As defined in Tables A-7a to A-7f, and NH-L 1 -G is as defined in Table Z above:

[0471]

[0472] Table A-7a: This subtable provides 23 compounds A-7a.01 to A-7a.23 of formula (Ia-A-7), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 8 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0473] Table A-7b: This subtable provides 23 compounds A-7b.01 to A-7b.23 having formula (Ia-A-7), wherein R 1 is 3-(trifluoromethyl)phenyl, R 8 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0474] Table A-7c:This subtable provides 23 compounds A-7c.01 to A-7c.23 having formula (Ia-A-7), wherein R 1 is 3-cyclopropylphenyl, R 8 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0475] Table A-7d: This subtable provides 23 compounds A-7d.01 to A-7d.23 having formula (Ia-A-7), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 8 is chlorine and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0476] For example, compound A-7d.03 is:

[0477]

[0478] Table A-7e: This subtable provides 23 compounds A-7e.01 to A-7e.23 having formula (Ia-A-7), wherein R 1 is 3-(trifluoromethyl)phenyl, R 8 is hydrogen and R 9 is chlorine, and the substituent NH-L 1 -G is as defined in Table Z above.

[0479] Table A-7f: This subtable provides 23 compounds A-7f.01 to A-7f.23 having formula (Ia-A-7), wherein R 1 is 3-cyclopropylphenyl, R 8 is methyl and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0480] Table A-8 : A compound having formula (Ia-A-8), wherein R 1 , R 7 , R 8 and R 9 As defined in Tables A-8a to A-8h, and NH-L 1 -G is as defined in Table Z above:

[0481] like

[0482]

[0483] Table A-8a:This subtable provides 23 compounds A-8a.01 to A-8a.23 of formula (Ia-A-8), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 7 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0484] Table A-8b: This subtable provides 23 compounds A-8b.01 to A-8b.23 of formula (Ia-A-8), wherein R 1 is 3-(trifluoromethyl)phenyl, R 7 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0485] Table A-8c: This subtable provides 23 compounds A-8c.01 to A-8c.23 having formula (Ia-A-8), wherein R 1 is 5-cyanopyridin-3-yl, R 7 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0486] Table A-8d: This subtable provides 23 compounds A-8d.01 to A-8d.23 having formula (Ia-A-8), wherein R 1 is 5-(cyclopropyl)pyridin-3-yl, R 7 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0487] Table A-8e: This subtable provides 23 compounds A-8e.01 to A-8e.23 having formula (Ia-A-8), wherein R 1 is 3-cyclopropylphenyl, R 7 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0488] Table A-8f: This subtable provides 23 compounds A-8f.01 to A-8f.23 having formula (Ia-A-8), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 7 is hydrogen, R 9 is methyl, and the substituent NH-L 1 -G is as defined in Table Z above.

[0489] Table A-8g: This subtable provides 23 compounds A-8g.01 to A-8g.23 having formula (Ia-A-8), wherein R 1 is 3-(trifluoromethyl)phenyl, R 7 is hydrogen, R 9 is methyl, and the substituent NH-L 1 -G is as defined in Table Z above.

[0490] Table A-8h: This subtable provides 23 compounds A-8h.01 to A-8h.23 having formula (Ia-A-8), wherein R 1 is 3-cyclopropylphenyl, R 7 is hydrogen, R 9 is methyl, and the substituent NH-L 1 -G is as defined in Table Z above.

[0491] For example, compound A-8h.22 is:

[0492]

[0493] Table A-9 : A compound having formula (Ia-A-9), wherein R 1 , R 7 , R 8 and R 9 As defined in Tables A-9a to A-9h, and NH-L 1 -G is as defined in Table Z above:

[0494]

[0495] Table A-9a: This subtable provides 23 compounds A-9a.01 to A-9a.23 having formula (Ia-A-9), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 7 and R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0496] Table A-9b: This subtable provides 23 compounds A-9b.01 to A-9b.23 having formula (Ia-A-9), wherein R 1 is 3-(trifluoromethyl)phenyl, R 7 and R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0497] Table A-9c: This subtable provides 23 compounds A-9c.01 to A-9c.23 having formula (Ia-A-9), wherein R 1 is 5-cyanopyridin-3-yl, R 7 and R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0498] For example, compound A-9c.19 is:

[0499]

[0500] Table A-9d: This subtable provides 23 compounds A-9d.01 to A-9d.23 having formula (Ia-A-9), wherein R 1 is 3-cyclopropylphenyl, R 7 and R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0501] Table A-9e: This subtable provides 23 compounds A-9e.01 to A-9e.23 having formula (Ia-A-9), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 7 is chlorine and R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0502] Table A-9f: This subtable provides 23 compounds A-9f.01 to A-9f.23 having formula (Ia-A-9), wherein R 1 is 3-(trifluoromethyl)phenyl, R 7 is hydrogen and R 8 is chlorine, and the substituent NH-L 1 -G is as defined in Table Z above.

[0503] Table A-9g: This subtable provides 23 compounds A-9g.01 to A-9g.23 having formula (Ia-A-9), wherein R 1 is 5-cyanopyridin-3-yl, R 7 is hydrogen and R 8 is fluorine, and the substituent NH-L 1 -G is as defined in Table Z above.

[0504] Table A-9h: This subtable provides 23 compounds A-9h.01 to A-9h.23 having formula (Ia-A-9), wherein R1 is 3-cyclopropylphenyl, R 7 is hydrogen and R 8 is methyl, and the substituent NH-L 1 -G is as defined in Table Z above.

[0505] Table A-10 : A compound having formula (Ia-A-10), wherein R 1 , R 7 , R 8 and R 9 As defined in Tables A-10a to A-10c, and NH-L 1 -G is as defined in Table Z above:

[0506]

[0507] Table A-10a: This subtable provides 23 compounds A-10a.01 to A-10a.23 having formula (Ia-A-10), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0508] Table A-10b: This subtable provides 23 compounds A-10b.01 to A-10b.23 having formula (Ia-A-10), wherein R 1 is 3-(trifluoromethyl)phenyl, R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0509] For example, compound A-10b.21 is:

[0510]

[0511] Table A-10c: This subtable provides 23 compounds A-10c.01 to A-10c.23 having formula (Ia-A-10), wherein R 1 is 3-cyclopropylphenyl, R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0512] Table A-11 : A compound having formula (Ia-A-11-1), wherein R 1 , R 7 , R 8 and R 9 As defined in Tables A-11a to A-11c, and NH-L1 -G is as defined in Table Z above:

[0513]

[0514] Table A-11a: This subtable provides 23 compounds A-11a.01 to A-11a.23 having formula (Ia-A-11), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 7 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0515] Table A-11b: This subtable provides 23 compounds A-11b.01 to A-11b.23 having formula (Ia-A-11), wherein R 1 is 3-(trifluoromethoxy)phenyl, R 7 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0516] Table A-11c: This subtable provides 23 compounds A-11c.01 to A-11c.23 having formula (Ia-A-11), wherein R 1 is 3-cyclopropylphenyl, R 7 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0517] Table A-12 : A compound having formula (Ia-A-12), wherein R 1 , R 7 , R 8 and R 9 Defined in Tables A-12a to A-12c, and NH-L 1 -G is as defined in Table Z above:

[0518]

[0519] Table A-12a: This subtable provides 23 compounds A-12a.01 to A-12a.23 of formula (Ia-A-12), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0520] Table A-12b: This subtable provides 23 compounds A-12b.01 to A-12b.23 having formula (Ia-A-12), wherein R 1is 3-(trifluoromethyl)phenyl, R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0521] Table A-12c: This subtable provides 23 compounds A-12c.01 to A-12c.23 having formula (Ia-A-12), wherein R 1 is 3-cyclopropylphenyl, R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0522] Table A-13 : A compound having formula (Ia-A-13), wherein R 1 , R 7 , R 8 and R 9 Defined in Table A-13a, and NH-L 1 -G is as defined in Table Z above:

[0523]

[0524] Table A-13a: This subtable provides 23 compounds A-13a.01 to A-13a.23 of formula (Ia-A-13), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 8 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0525] Table A-14 : A compound having formula (Ia-A-14), wherein R 1 , R 7 , R 8 and R 9 As defined in Tables A-14a to A-14f, and NH-L 1 -G is as defined in Table Z above:

[0526]

[0527] Table A-14a: This subtable provides 23 compounds A-14a.01 to A-14a.23 of formula (Ia-A-14), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 7 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0528] Table A-14b: This subtable provides 23 compounds A-14b.01 to A-14b.23 having formula (Ia-A-14), wherein R 1 is 3-(trifluoromethyl)phenyl, R 7 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0529] Table A-14c: This subtable provides 23 compounds A-14c.01 to A-14c.23 having formula (Ia-A-14), wherein R 1 is 5-cyanopyridin-3-yl, R 7 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0530] Table A-14d: This subtable provides 23 compounds A-14d.01 to A-14d.23 having formula (Ia-A-14), wherein R 1 is 3-cyclopropylphenyl, R 7 and R 9 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0531] Table A-14e: This subtable provides 23 compounds A-14e.01 to A-14e.23 having formula (Ia-A-14), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 7 is hydrogen, R 9 is methyl, and the substituent NH-L 1 -G is as defined in Table Z above.

[0532] Table A-14f: This subtable provides 23 compounds A-14f.01 to A-14f.23 having formula (Ia-A-14), wherein R 1 is 3-(trifluoromethyl)phenyl, R 7 is hydrogen, R 9 is methyl, and the substituent NH-L 1 -G is as defined in Table Z above.

[0533] Table A-15 : A compound having formula (Ia-A-15), wherein R 1 , R 7 , R 8 and R 9 As defined in Tables A-15a to A-15f, and NH-L1 -G is as defined in Table Z above:

[0534]

[0535] Table A-15a: This subtable provides 23 compounds A-15a.01 to A-15a.23 having formula (Ia-A-15), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 7 and R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0536] Table A-15b: This subtable provides 23 compounds A-15b.01 to A-15b.23 having formula (Ia-A-15), wherein R 1 is 3-(trifluoromethyl)phenyl, R 7 and R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0537] Table A-15c: This subtable provides 23 compounds A-15c.01 to A-15c.23 having formula (Ia-A-15), wherein R 1 is 5-cyanopyridin-3-yl, R 7 and R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0538] Table A-15d: This subtable provides 23 compounds A-15d.01 to A-15d.23 having formula (Ia-A-15), wherein R 1 is 5-(cyclopropyl)pyridin-3-yl, R 7 and R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0539] Table A-15e: This subtable provides 23 compounds A-15e.01 to A-15e.23 having formula (Ia-A-15), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 7 is chlorine and R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0540] Table A-15f:This subtable provides 23 compounds A-15f.01 to A-15f.23 having formula (Ia-A-15), wherein R 1 is 3-cyclopropylphenyl, R 7 is methyl and R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0541] Table A-16 : A compound having formula (Ia-A-16), wherein R 1 , R 7 , R 8 and R 9 As defined in Tables A-16a to A-16e, and NH-L 1 -G is as defined in Table Z above:

[0542]

[0543] Table A-16a: This subtable provides 23 compounds A-16a.01 to A-16a.23 of formula (Ia-A-16), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 7 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0544] Table A-16b: This subtable provides 23 compounds A-16b.01 to A-16b.23 having formula (Ia-A-16), wherein R 1 is 3-(trifluoromethyl)phenyl, R 7 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0545] Table A-16c: This subtable provides 23 compounds A-16c.01 to A-16c.23 having formula (Ia-A-16), wherein R 1 is 5-cyanopyridin-3-yl, R 7 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0546] Table A-16d: This subtable provides 23 compounds A-16d.01 to A-16d.23 having formula (Ia-A-16), wherein R 1 is 5-(cyclopropyl)pyridin-3-yl, R 7 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0547] Table A-16e: This subtable provides 23 compounds A-16e.01 to A-16e.23 having formula (Ia-A-16), wherein R 1 is 3-cyclopropylphenyl, R 7 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0548] Table A-17 : A compound having formula (Ia-A-17), wherein R 1 , R 7 , R 8 and R 9 As defined in Tables A-17a to A-17c, and NH-L 1 -G is as defined in Table Z above:

[0549]

[0550] Table A-17a: This subtable provides 23 compounds A-17a.01 to A-17a.23 of formula (Ia-A-17), wherein R 1 is 3-cyclopropyl-2-fluorophenyl, R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0551] Table A-17b: This subtable provides 23 compounds A-17b.01 to A-17b.23 having formula (Ia-A-17), wherein R 1 is 3-(trifluoromethyl)phenyl, R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0552] Table A-17c: This subtable provides 23 compounds A-17c.01 to A-17c.23 having formula (Ia-A-17), wherein R 1 is 3-cyclopropylphenyl, R 8 is hydrogen, and the substituent NH-L 1 -G is as defined in Table Z above.

[0553] It also makes available certain intermediate compounds of formula (II), (V), (VI) and (XVIII), some of which are novel. For example:

[0554] - a compound of formula (II) wherein R 1 and A is as defined in any of Tables A-1 to A-17 and their subtables:

[0555]

[0556] And more particularly, compounds having formula (II-A-1i) to (II-A-17i), as shown in Table II below, wherein R 1 , R 7 , R 8 and R 9 As defined in any of Tables A-1 to A-17 and their respective subtables:

[0557] Table II

[0558]

[0559] A compound of formula (V) wherein X 2 is a suitable leaving group, such as fluorine, chlorine, bromine, iodine, BF 3 K、B(OH) 2 or B (pinacol), and wherein A is as defined in any one of Tables A-1 to A-17 and their respective subtables, and NH-L 1 -G is defined in Table Z:

[0560]

[0561] And more particularly, compounds having formula (VA-1i) to (VA-17i), as shown in Table V below, wherein X 2 is a suitable leaving group, such as fluorine, chlorine, bromine, iodine, BF 3 K、B(OH) 2 or B(pinacol), and wherein R 7 , R 8 and R 9 As defined in any of Tables A-1 to A-17 and their respective subtables, and NH-L 1 -G is defined in Table Z:

[0562] Table V

[0563]

[0564] A compound of formula (VI) wherein X 1 It is C 1 -C 4 -alkoxy and X 2 is a suitable leaving group, such as fluorine, chlorine, bromine, iodine, BF 3 K、B(OH) 2 or B (pinacol), and wherein A is as defined in any one of Tables A-1 to A-17 and their respective subtables:

[0565]

[0566] And more particularly, compounds having formula (VI-A-1i) to (VI-A-17i), as shown in Table VI below, wherein X 1 It is C 1 -C 4 - alkoxy, such as methoxy or ethoxy, and X 2 is a suitable leaving group, such as fluorine, chlorine, bromine, iodine, BF 3 K、B(OH) 2 or B(pinacol), and wherein R 7 , R 8 and R 9 As defined in any of Tables A-1 to A-17 and their respective subtables:

[0567] Table VI

[0568]

[0569] A compound having formula (XVIII) wherein X 6 is chloro, bromo, iodo, trifluoromethanesulfonyl-O-, and wherein R 1 and A is as defined in any of Tables A-1 to A-17 and their subtables:

[0570]

[0571] And more particularly, compounds having formula (XVIII-A-1i) to (XVIII-A-17i), as shown in Table XVIII below, wherein X 6 is chloro, bromo, iodo, trifluoromethanesulfonyl-O-, and wherein R 1 , R 7 , R 8 and R 9 As defined in any of Tables A-1 to A-17 and their respective subtables:

[0572] Table XVIII

[0573]

[0574] In a further aspect, the present invention thus makes available compounds of the formulae (II), (V), (VI) and (XVIII), in which in each case, if applicable, R 1 , R 2 , R 3 , R 4 , R 5 , L 1 , G and A, including R7 , R 8 and R 9 , as defined in the first aspect for formula (I); and X 2 is a suitable leaving group, such as fluorine, chlorine, bromine, iodine, BF 3 K、B(OH) 2 , or B (pinacol); X 3 Is OH or C 1 -C 4 -alkoxy; and X 6 is chlorine, bromine, iodine, trifluoromethanesulfonyl-O-. In addition, the corresponding embodiments shown for formula (I) are also applicable to compounds having formula (II), (V), (VI), and (XVIII).

[0575] Examples

[0576] The following examples are provided to illustrate the invention and are not meant to limit the invention in any way.

[0577] The compounds of the invention may be distinguished from known compounds by a greater efficacy at low application rates, which can be demonstrated by a person skilled in the art using the experimental procedures outlined in the examples, using lower application rates (if necessary), for example, 60 ppm, 20 ppm or 2 ppm.

[0578] Compounds of formula (I) may have any number of benefits, including, among others, favorable levels of biological activity for protecting plants from diseases caused by fungi or superior properties for use as agrochemical active ingredients (e.g., higher biological activity, favorable activity spectrum, increased safety (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).

[0579] 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 spectrometry and a description of the apparatus and methods follows.

[0580] Recorded on a Bruker 400 MHz mass spectrometer 1 H NMR and 19 F NMR measurements, chemical shifts relative to TMS ( 1 H) and CFCl 3 ( 19 F) Standards are given in ppm. Spectra were measured in deuterated solvents as indicated. The compounds were characterized using any of the following LCMS methods. The characteristic LCMS values ​​obtained for each compound are the retention time ("Rt", recorded in minutes) and the measured molecular ion (M+H)+ or (MH) - .

[0581] Method A:

[0582] Spectra were recorded on a mass spectrometer (6410 triple quadrupole mass spectrometer) from Agilent Technologies equipped with an electrospray source (positive and negative polarity switching, capillary voltage (kV) 4.00, scan type MS2 scan, fragmentor voltage (V) 100.00, gas temperature (°C): 350, gas flow (L / min): 11, nebulizer gas (psi): 45, mass range: 110 Da 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

[0583] Gradient conditions:

[0584] Solvent A: Water containing 0.1% formic acid: Acetonitrile: 95:5 v / v

[0585] Solvent B: 0.1% formic acid in acetonitrile

[0586] Time (min) A (%) B (%) Flow rate (ml / min)

[0587]

[0588] If desired, enantiomerically pure final compounds can be obtained, where appropriate, from racemic materials via standard physical separation techniques (eg, reverse phase chiral chromatography) or by stereoselective synthetic techniques (eg, by using chiral starting materials).

[0589] Method B:

[0590] Spectra were recorded on a mass spectrometer from Agilent Technologies (6410 triple quadrupole mass spectrometer) equipped with an electrospray source (positive and negative polarity switching, capillary voltage (kV) 7.00, scan type MS2 scan, fragmentor voltage (V) 120.00, gas temperature (°C): 350, gas flow (L / min): 11, nebulizer gas (psi): 40, mass range: 110 Da 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

[0591] Gradient conditions:

[0592] Solvent A: Water containing 0.1% formic acid: Acetonitrile: 95:5 v / v

[0593] Solvent B: 0.1% formic acid in acetonitrile

[0594] Time (min) A (%) B (%) Flow rate (ml / min)

[0595]

[0596]

[0597] If desired, enantiomerically pure final compounds can be obtained, where appropriate, from racemic materials via standard physical separation techniques (eg, reverse phase chiral chromatography) or by stereoselective synthetic techniques (eg, by using chiral starting materials).

[0598] Method C:

[0599] Spectra were recorded on a mass spectrometer from Waters (Acquity QDA mass spectrometer) equipped with an electrospray source (positive and negative polarity switching, capillary voltage (kV) 0.8, cone voltage (V) 25.00, full scan, source temperature (°C): 120, desolvation gas flow (L / Hr): 1000, desolvation temperature (°C): 600, cone gas flow (L / Hr): 50, mass range: 110 Da to 850 Da) and HPLC: DAD wavelength range: 230 to 400 nm, column Acquity UPLC HSS T3C18, column length: 30 mm, column inner diameter: 2.1 mm, particle size: 1.8 μm, column oven temperature: 40°C.

[0600] Gradient conditions:

[0601] Solvent A: Water containing 0.1% formic acid: acetonitrile: 95:5 v / v

[0602] Solvent B: acetonitrile containing 0.05% formic acid

[0603] Time (min) A (%) B (%) Flow rate (ml / min)

[0604]

[0605] If desired, enantiomerically pure final compounds can be obtained, where appropriate, from racemic materials via standard physical separation techniques (eg, reverse phase chiral chromatography) or by stereoselective synthetic techniques (eg, by using chiral starting materials).

[0606] Method D:

[0607] Spectra were recorded on a mass spectrometer from Waters (Acquity SDQ mass spectrometer) equipped with an electrospray source (positive and negative polarity switching, capillary voltage (kV) 3.0, full scan, cone voltage (V) 41.0, source temperature (°C): 150, desolvation temperature: 500°C, cone gas flow (L / Hr): 50, mass range: 110 Da to 800 Da) and HPLC "H" grade: DAD wavelength range: 210 to 400 nm, column Acquity UPLC HSS T3C18, column length: 30 mm, column inner diameter: 2.1 mm, particle size: 1.8 μm, column oven temperature: 40°C

[0608] Gradient conditions:

[0609] Solvent A: Water containing 0.1% formic acid: acetonitrile: 95:5 v / v

[0610] Solvent B: acetonitrile containing 0.05% formic acid

[0611] Time (min) A (%) B (%) Flow rate (ml / min)

[0612]

[0613] Method E:

[0614] Spectra were recorded on a mass spectrometer (QDa) from Waters (polarity: positive and negative, 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 Da to 850 Da).

[0615] Chiral column (analytical) SFC: Waters Acquity UPC 2 / QDa PDA Detector Waters AcquityUPC 2 , column: Daicel SFC AY, 3μm, 0.3cm x 10cm, 40°C, Mobile phase: A: CO2, B: IPA, No gradient: 25% B, ABPR: 1800psi, Flow rate: 2.0ml / min, Detection: 240nm, Sample concentration: 1mg / mL in MeOH / ACN, Injection: 2μL

[0616] Preparation Examples

[0617] The following examples are used to illustrate the present invention.

[0618]

[0619] The active ingredient is mixed thoroughly with the adjuvant and the mixture is ground thoroughly in a suitable grinder to provide a wettable powder which can be diluted with water to give a suspension of the desired concentration.

[0620]

[0621] The active ingredient is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable grinder to provide a dust that can be used directly for seed treatment.

[0622] Emulsifiable concentrates

[0623] Active ingredient [compound of formula (i)] 10％ Octylphenol polyglycol ether (4-5 mol ethylene oxide) 3％ Calcium dodecylbenzenesulfonate 3％ Castor oil polyglycol ether (35 mol ethylene oxide) 4％ Cyclohexanone 30％ Xylene mixture 50％

[0624] Emulsions of any desired dilution which can be used in plant protection can be obtained from these concentrates by dilution with water.

[0625]

[0626] Ready-to-use dusts are obtained by mixing the active ingredient with a carrier and grinding the mixture in a suitable grinder. Such dusts can also be used for dry seed dressing of seeds.

[0627] Extruded granules

[0628] Active ingredient [compound of formula (i)] 15％ Sodium lignin sulfonate 2％ Carboxymethyl cellulose 1％ Kaolin 82％

[0629] The active ingredient is mixed with the auxiliary agents and ground, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

[0630] Coated granules

[0631] Active ingredient [compound of formula (i)] 8％ Polyethylene glycol (molecular weight 200) 3％ Kaolin 89％

[0632] The finely ground active ingredient is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

[0633] Suspension concentrates

[0634]

[0635]

[0636] The finely ground active ingredient is intimately mixed with the adjuvant to give a suspension concentrate from which suspension concentrates of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants together with plant propagation materials can be treated and protected against infection by microorganisms by spraying, pouring or immersion.

[0637] Flowable concentrate for seed treatment

[0638]

[0639] The finely ground active ingredient is intimately mixed with the adjuvant to give a suspension concentrate from which suspension concentrates of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants together with plant propagation materials can be treated and protected against infection by microorganisms by spraying, pouring or immersion.

[0640] Extended-release capsule suspension

[0641] 28 parts of the combination of compounds of formula (I) are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polyvinyl-polyphenyl isocyanate 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 reached. To this emulsion is added a mixture of 2.8 parts of 1,6-hexanediamine in 5.3 parts of water. The mixture is stirred until the polymerization reaction is complete.

[0642] The obtained capsule suspension is stabilized by adding 0.25 parts of thickener and 3 parts of dispersant. The capsule suspension formulation contains 28% of active ingredient. The diameter of the medium capsule is 8-15 microns.

[0643] The resulting formulation is applied to the seeds as an aqueous suspension in an apparatus suitable for this purpose.

[0644] List of abbreviations:

[0645] Abbreviations used in synthetic schemes and preparative examples

[0646] ACN Acetonitrile

[0647] Boc tert-Butyloxycarbonyl

[0648] DBU 1,8-diazabicyclo[5.4.0]undec-7-ene

[0649] DCM Dichloromethane

[0650] DDQ 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone

[0651] DMSO Dimethyl sulfoxide

[0652] DMSO-d 6 Deuterated dimethyl sulfoxide

[0653] DPEN Diphenylethylenediamine

[0654] Et 3 N-Triethylamine

[0655] EtOAc Ethyl acetate

[0656] hr / hrs hours

[0657] MeCN Acetonitrile

[0658] MeOH Ethanol

[0659] Ms methanesulfonyl (methylsulfonyl)

[0660] n-Bu n-butyl

[0661] NHC N-Heterocyclic Carbene

[0662] NPhth 1-Phthalimide

[0663] OMs mesylate group

[0664] OTf triflate group

[0665] OTs Tosylate group

[0666] PdCl 2 dppf 1,1'-Bis(diphenylphosphino)ferrocene]palladium(II) dichloride

[0667] TBME tert-butyl methyl ether

[0668] TEA Triethylamine

[0669] TEMPO (2,2,6,6-tetramethylpiperidin-1-yl) oxygen nitrogen free radical

[0670] Tf Trifluoromethanesulfonyl (Trifluoromethanesulfonyl)

[0671] TFA Trifluoroacetic acid

[0672] THF Tetrahydrofuran

[0673] Ts p-Toluenesulfonyl (tosyl)

[0674] X-Phos 2-Dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl

[0675] aq. water-based

[0676] ℃ Celsius

[0677] equiv. Equivalent

[0678] h hour

[0679] LC / MS or Liquid Chromatography Mass Spectrometry

[0680] LC-MS

[0681] M Moore

[0682] MHz Megahertz

[0683] min

[0684] mp or MP melting point

[0685] NMR Nuclear Magnetic Resonance

[0686] ppm parts per million

[0687] RT or rt Room temperature

[0688] Rt retention time

[0689] RBF Round Bottom Flask

[0690] Preparation Example

[0691] The following examples further illustrate (but do not limit) the present invention. One skilled in the art will quickly recognize from these procedures appropriate variations on reactants as well as on reaction conditions and techniques.

[0692] Unless otherwise stated, 1 H NMR spectra were recorded at 400 MHz and 19 FNMR spectra were recorded at 377 MHz and chemical shifts are reported in ppm. The following abbreviations are used: s = singlet; br s = broad; d = doublet; br d = broad doublet; dd = double of doublets; dt = double of triplets; t = triplet, tt = triplet of triplets, q = quartet, quin = quintet, sept = septet; m = multiplet.

[0693] Throughout this specification, 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 apparatus and method is:

[0694] If desired, enantiomerically pure final compounds can be obtained, where appropriate, from racemic materials via standard physical separation techniques (eg, reverse phase chiral chromatography) or by stereoselective synthetic techniques (eg, by using chiral starting materials).

[0695] Example P1: This example illustrates the reaction of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl] Preparation of imidazo[1,2-a]pyrimidine-5-carboxamide (Compound 1.1 of Table T1)

[0696] (Compound P-1.1 of Table T1)

[0697] a) Preparation of Ethyl 2-(3-cyclopropylphenoxy)acetate

[0698] In a single-necked round-bottom flask, cesium carbonate (5.82g, 17.8mmol) is added to a solution of 3-cyclopropylphenol (2.0g, 14.9mmol) in acetonitrile (22mL). Ethyl 2-bromoacetate (2.98g, 17.8mmol) is added thereto and the resulting reaction mixture is stirred at room temperature for 4hr. The reaction process is monitored by LCMS. The reaction mixture is then diluted with water and extracted with EtOAc. The organic layer is washed with salt water, dried over sodium sulfate and concentrated under reduced pressure. The gained crude residue is purified by silica gel chromatography (cyclohexane / EtOAc), to obtain ethyl 2-(3-cyclopropylphenoxy) acetate.

[0699] LCMS (method B): retention time 1.48 min, 221 (M+H)

[0700] b) Preparation of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate

[0701] In a sealed glass reactor, a solution of ethyl 2-(3-cyclopropylphenoxy) acetate (1.5 g, 6.8 mmol) and 1-tert-butoxy-N, N, N', N'-tetramethyl-methylenediamine (9.2 g, 48.0 mmol) was heated to 90 ° C for 2 hr. The reaction process 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 obtain a crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to obtain ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate.

[0702] LCMS (method B): retention time 1.52 min, 276 (M+H)

[0703] c) Preparation of 6-(3-cyclopropylphenoxy)-8H-imidazo[1,2-a]pyrimidin-5-one

[0704] In a round-bottom flask, a mixture of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate (1.0 g, 3.63 mmol), 2H-imidazole-2-amine (0.30 g, 3.63 mmol) and sodium acetate (0.30 g, 3.63 mmol) in acetic acid (10 mL) was stirred at 110 ° C for 4 hr. The reaction process was monitored by LCMS. The reaction mixture was then concentrated under reduced pressure and then co-distilled twice with toluene under reduced pressure to obtain a crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to obtain 6-(3-cyclopropylphenoxy)-8H-imidazo[1,2-a]pyrimidine-5-one as a brown solid.

[0705] LCMS (method B): retention time 1.24 min, 268 (M+H)

[0706] d) Preparation of 5-chloro-6-(3-cyclopropylphenoxy)imidazo[1,2-a]pyrimidine

[0707] In a round-bottom flask, 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 oxychloride (V) (10.6 mL, 113 mmol) was stirred at 90 ° C for 12 hr. The reaction progress was monitored by LCMS. After 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 obtain a crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to obtain 5-chloro-6-(3-cyclopropylphenoxy)imidazo[1,2-a]pyrimidine.

[0708] LCMS (method B): retention time 1.42 min, 286 (M+H)

[0709] e) Preparation of methyl 6-(3-cyclopropylphenoxy)imidazo[1,2-a]pyrimidine-5-carboxylate The autoclave 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)Cl 2 CH 2 Cl 2To the mixture of 4-nitropropene (0.057g, 0.07mmol) and methanol (20mL). The reactor is flushed with carbon monoxide gas three times and 10 bar of carbon monoxide is loaded. The reaction mixture is heated to 80 ° C for 1.5hr. The reaction process is monitored by LCMS. The reaction mixture is then diluted with water and extracted with EtOAc. The organic layer is washed with brine, dried over sodium sulfate and concentrated under reduced pressure to obtain a crude residue. The obtained crude residue is purified by silica gel chromatography (cyclohexane / EtOAc) to obtain methyl 6- (3- cyclopropylphenoxy) imidazo [1,2-a] pyrimidine -5- carboxylate as a yellow solid.

[0710] LCMS (method B): retention time 1.36 min, 310 (M+H)

[0711] f) Preparation of lithium 6-(3-cyclopropylphenoxy)imidazo[1,2-a]pyrimidine-5-carboxylate

[0712] 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 hr. The progress of the reaction was monitored by TLC and LCMS. The reaction mixture was then concentrated at 30 ° C under reduced pressure and then co-distilled twice with toluene to obtain 6-(3-cyclopropylphenoxy)imidazo[1,2-a]pyrimidine-5-carboxylic acid lithium, which was used as is in the next step.

[0713] LCMS (method B): retention time 0.45 min, 296 (M+H)

[0714] g) 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]imidazo[1,2-a]pyrimidine- Preparation of 5-formamide (Compound P-1.1, Table T1)

[0715] At 0 ° C, 2-(2,4-dichlorophenyl)-2-fluoro-ethylamine (0.067g, 0.32mmol), 1-propanephosphonic anhydride solution (T3P, 50% in EtOAc, 0.48mL, 0.81mmol) and triethylamine (0.08mL, 0.59mmol) were added to 6-(3-cyclopropylphenoxy)imidazo[1,2-a]pyrimidine-5-carboxylic acid lithium (0.10g, 0.27mmol) in EtOAc (1.35mL). The reaction mixture was stirred at room temperature for 2hr. The reaction progress was monitored by TLC and LCMS. After 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 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]imidazo[1,2-a]pyrimidine-5-carboxamide as a yellow solid.

[0716] 1 H NMR (400 MHz, CDCl 3 )δppm 8.79(d,J=1.38Hz,1H),8.36(s,1H),7.95(d,J=1.38Hz,2H),7.36-7.38(m,1H),7.29-7.34(m,1

[0717] H),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).

[0718] LCMS (method B): retention time 1.55 min, 485 (M+H)

[0719] Example P2: This example illustrates the Preparation of [1,2,4]triazolo[1,5-a]pyrimidine-7-carboxamide (Compound P-1.2 of Table T1)

[0720] (Compound P-1.2 of Table T1)

[0721] Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate was prepared as described in Example 1, steps a) and b).

[0722] a) Preparation of 6-(3-cyclopropylphenoxy)-4H-[1,2,4]triazolo[1,5-a]pyrimidin-7-one

[0723] In a round-bottom flask equipped with a nitrogen balloon, ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate (3g, 10.35mmol) and 4H-1,2,4-triazole-3-amine (0.96g, 10.35mmol) were dissolved in acetic acid (30mL). Sodium acetate (0.86g, 10.35mmol) was added thereto and stirred at 90 °C for 18hr under nitrogen. The progress was monitored by TLC and LCMS analysis. After the starting material was completely consumed, the reaction mixture was cooled to room temperature, diluted with ice-cold water, and extracted with EtOAc. The combined organic layer was 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.

[0724] 1 H NMR(400MHz,DMSO-d6)δppm 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)

[0725] LCMS (method B): retention time 1.21 min, 269 (M+H)

[0726] b) Preparation of 7-chloro-6-(3-cyclopropylphenoxy)-[1,2,4]triazolo[1,5-a]pyrimidine

[0727] In a round-bottom flask equipped with a nitrogen balloon and a 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). N,N-dimethylaniline (1.77 g, 13.88 mmol) was added thereto and the resulting reaction mixture was stirred at 85 ° C for 12 hr. The reaction progress was monitored by TLC and LCMS analysis. After completion, the reaction mixture was cooled to room temperature and immediately added to crushed ice and extracted with EtOAc. The combined organic layers were dried over sodium sulfate and concentrated in vacuo to obtain a crude residue, which was then purified by silica gel chromatography (0-20% EtOAc in cyclohexane) to obtain 7-chloro-6-(3-cyclopropylphenoxy)-[1,2,4]triazolo[1,5-a]pyrimidine as a light yellow solid.

[0728] 1 H NMR (400 MHz, CDCl3 )δppm 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).

[0729] LCMS (method B): retention time 1.43 min, 287 (M+H)

[0730] c) Preparation of methyl 6-(3-cyclopropylphenoxy)-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxylate

[0731] The autoclave 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)Cl 2 CH 2 Cl 2 To the 4-nitro-2-nitropropene (0.58g, 0.70mmol) and methanol (30mL). The reactor is flushed with carbon monoxide gas three times and 10 bar of carbon monoxide is loaded. The reaction mixture is heated to 80 ° C for 1.5hr. The reaction process is monitored by LCMS. After completion, the reaction mixture is cooled to room temperature and filtered through diatomaceous earth. The filtrate is then evaporated under reduced pressure. The crude compound is purified by silica gel chromatography (0-20% EtOAc in cyclohexane) to obtain methyl 6- (3- cyclopropylphenoxy) -[1,2,4] triazolo [1,5-a] pyrimidine -7- carboxylate in a light yellow viscous substance.

[0732] 1 H NMR (400 MHz, CDCl 3 )δppm 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).

[0733] LCMS (method B): retention time 1.4 min, 311 (M+H)

[0734] d) Preparation of 6-(3-cyclopropylphenoxy)-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxylic acidTo 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 reaction progress was monitored by TLC and LCMS. After the reaction was completed, 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 obtain 2-(3-cyclopropylphenoxy)imidazo[1,5-b]pyridazine-3-carboxylic acid as a beige solid.

[0735] LCMS (method B): retention time 1.12 min, 297 (M+H)

[0736] e) 6-(3-Cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-[1,2,4]triazolo[1, 5-a] Preparation of pyrimidine-7-carboxamide (Compound P-1.2, Table T)

[0737] 2-(2,4-dichlorophenyl)-2-fluoro-ethylamine (0.23 g, 1.1 mmol) was added 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), 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 hr. The reaction progress was monitored by TLC and LCMS. After 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-fluoro-ethyl]-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxamide as a white solid.

[0738] 1 H NMR (400 MHz, CDCl 3)δppm 8.99(br s,1H),8.74(s,1H),8.58(s,1H),7.46(brd,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).

[0739] LCMS (method C): retention time 1.22 min, 486.2 (M+H)

[0740] Example P3: This example illustrates the reaction of 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl] Preparation of pyrazolo[1,5-a]pyrimidine-7-carboxamide (Compound P-1.3 in Table T1)

[0741] (Compound P-1.3 of Table T1)

[0742] Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate was prepared as described in Example 1, steps a) and b).

[0743] a) Preparation of 6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidin-7-one

[0744] In a single-necked round-bottom flask, a mixture of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate (1.0 g, 3.63 mmol), 3H-pyrazole-3-amine (0.30 g, 3.63 mmol) and sodium acetate (0.30 g, 3.63 mmol) in acetic acid (2 mL) was stirred at 90 ° C for 24 hr. The reaction process was monitored by LCMS. The reaction mixture was then concentrated under reduced pressure, and a crude residue was obtained after two consecutive co-distillations with toluene under reduced pressure. The resulting residue was finally purified by silica gel chromatography (cyclohexane / EtOAc) to obtain 6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidine-7-one as a brown solid.

[0745] LCMS (method B): retention time 1.24 min, 268 (M+H)

[0746] b) Preparation of 7-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine

[0747] In a round-bottom flask, at 0 ° C, 6- (3-cyclopropylphenoxy) -4H- pyrazolo [1,5-a] pyrimidine -7-one (0.33 g, 1.23 mmol) and phosphorus oxychloride (V) (8.76 mL, 93.83 mmol) were added N, N- dimethylaniline (0.64 g, 5.06 mmol). The reaction mixture was heated at 90 ° C for 12 hr. 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. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to obtain 7-chloro-6- (3-cyclopropylphenoxy) pyrazolo [1,5-a] pyrimidine.

[0748] LCMS (method B): retention time 2.53 min, 286 (M+H)

[0749] c) Preparation of methyl 6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate The autoclave 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)Cl 2 CH 2 Cl 2 To the mixture of 4-nitropropene (0.057g, 0.07mmol) and methanol (20mL). The reactor was flushed with carbon monoxide gas three times and 10 bar of carbon monoxide was loaded. The reaction mixture was heated to 80 ° C for 1.5hr. The reaction process 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 obtained crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to obtain methyl 6- (3- cyclopropylphenoxy) pyrazolo [1,5-a] pyrimidine -7- carboxylate as a yellow solid.

[0750] LCMS (method D): retention time 1.10 min, 310 (M+H)

[0751] d) Preparation of lithium 6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate

[0752] 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 hr. The reaction progress was monitored by TLC and LCMS. After the reaction was completed, the reaction mixture was concentrated in vacuo to obtain 6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate lithium as an off-white solid, which was used directly in the next step.

[0753] LCMS (method B): retention time 1.37 min, 296 (M+H)

[0754] e) 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]pyrazolo[1,5-a]pyrimidine- Preparation of 7-carboxamide (Compound P-1.3, Table T1)

[0755] At 0 ° C, 2-(2,4-dichlorophenyl)-2-fluoro-ethylamine (0.016 g, 0.08 mmol) was added to 6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylic acid lithium (0.02 g, 0.06 mmol) in EtOAc (2 mL), followed by 1-propanephosphonic anhydride solution (T3P, 50% in EtOAc, 0.12 g, 0.19 mmol) and triethylamine (0.015 g, 0.14 mmol). The reaction mixture was stirred at room temperature for 24 hr. The reaction progress was monitored by TLC and LCMS. After 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 (cyclohexane / EtOAc) to give 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide.

[0756] 1 H NMR (400 MHz, CDCl 3 )δppm 9.64(br s,1H),8.43(s,1H),8.19(d,J=2.50Hz,1H),7.48(d,J=8.38Hz,1H),7.36-7.43(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),3.80-3.82(m,1H),1.85-1.89(m,1H),0.96-0.98(m,2H),0.67-0.72(m,2H).

[0757] LCMS (method C): retention time 1.29 min, 485 (M+H)

[0758] Example P4: This example illustrates the reaction of 7-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl] Preparation of imidazo[1,2-b]pyridazine-8-carboxamide (Compound P-1.4 in Table T1)

[0759] (Compound P-1.4 of Table T1)

[0760] a) Preparation of 2-[(2-bromoimidazol-1-yl)methoxy]ethyl-trimethyl-silane

[0761] At 0 ° C, sodium hydride (60% by mass, 0.65 g, 16 mmol) was added to a solution of 2-bromo-1H-imidazoles (2.0 g, 14 mmol) in tetrahydrofuran (5 mL). 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 hr. The reaction process was monitored by TLC and LCMS. After 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 obtain 2-[(2-bromoimidazole-1-yl)methoxy]ethyl-trimethyl-silane as a light yellow liquid.

[0762] 1 H NMR (400 MHz, CDCl 3 )δppm 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)

[0763] b) 2-(3-Cyclopropylphenoxy)-1-[1-(2-trimethylsilylethoxymethyl)imidazol-2-yl]ethylene Preparation of ketone

[0764] In a double-necked round-bottom flask, 2-[(2-bromoimidazole-1-yl)methoxy]ethyl-trimethyl-silane (2.35g, 8.50mmol) was dissolved in tetrahydrofuran (42mL) and cooled to 0°C. Isopropylmagnesium chloride lithium chloride complex solution (1.3mol / L in THF, 6.5mL, 8.50mmol) was added dropwise thereto and stirred for 30 minutes. Afterwards, 2-(3-cyclopropylphenoxy)-N-methoxy-N-methyl-acetamide (1.0g, 4.25mmol) was added as a solution in tetrahydrofuran (2mL). The reaction mixture was stirred at room temperature for 1 hour. The reaction progress was monitored by TLC and LCMS. After completion, the reaction mixture was quenched with saturated ammonium chloride solution and diluted with water. The desired organic material was extracted with EtOAc, 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)-1-[1-(2-trimethylsilylethoxymethyl)imidazol-2-yl]eneketone as a light yellow liquid.

[0765] LCMS (method B): retention time 1.69 min, 373 (M+H)

[0766] 2-(3-Cyclopropylphenoxy)-N-methoxy-N-methyl-acetamide used in step b) was prepared as follows:

[0767] i. Preparation of 2-(3-cyclopropylphenoxy)acetic acid

[0768] Lithium hydroxide (0.83 g, 19.40 mmol) is 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 is allowed to proceed at room temperature for 1 hour. The reaction progress is monitored by TLC and LCMS. After completion, the reaction mixture is diluted with water and washed with ethyl acetate. The water layer is then acidified with 2N HCl and extracted with EtOAc. The combined organic layers are dried over sodium sulfate and concentrated in vacuo to obtain 2-(3-cyclopropylphenoxy)acetic acid as a beige solid.

[0769] 1 H NMR (400 MHz, CDCl 3 )δppm 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).

[0770] LCMS (method B): retention time 1.24 min, 190.8 (MH)

[0771] ii. Preparation of 2-(3-cyclopropylphenoxy)-N-methoxy-N-methyl-acetamide

[0772] Methoxy (methyl) ammonium chloride (0.97 g, 9.93 mmol) was added to 2- (3- cyclopropylphenoxy) acetic acid (1.34 g, 6.62 mmol) in EtOAc (26.8 mL), 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 hr. The reaction progress was monitored by TLC and LCMS. After 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 (10%-30% EtOAc in cyclohexane) to obtain 2- (3- cyclopropylphenoxy) -N-methoxy-N-methyl-acetamide as a viscous substance.

[0773] 1 H NMR (400 MHz, CDCl 3 )δppm 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).

[0774] LCMS (method B): retention time 1.32 min, 236 (M+H)

[0775] c) Preparation of 2-(3-cyclopropylphenoxy)-1-(1H-imidazol-2-yl)ethylene ketone

[0776] In a round-bottom flask, 2-(3-cyclopropylphenoxy)-1-[1-(2-trimethylsilylethoxymethyl)imidazol-2-yl]ethanone (0.25g, 0.47mmol) was dissolved in methanol (2mL) and hydrochloric acid (1.4mL, 5.63mmol) was added thereto. The reaction mixture was stirred at 80°C for 3hr. The reaction process was monitored by TLC and LCMS. After 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 layer was dried under reduced pressure to obtain 2-(3-cyclopropylphenoxy)-1-(1H-imidazole-2-yl) ketene. The resulting crude residue was used as it is in the next step.

[0777] LCMS (method C): retention time 1.03 min, 243 (M+H)

[0778] d) Preparation of 2-(3-cyclopropylphenoxy)-3-(dimethylamino)-1-(1H-imidazol-2-yl)prop-2-en-1-one Preparation

[0779] In a sealed glass reactor, 2-(3-cyclopropylphenoxy)-1-(1H-imidazole-2-yl)ethanone (0.60g, 2.0mmol) and 1-tert-butoxy-N,N,N',N'-tetramethyl-methanediamine (5.0g, 20.0mmol) were heated to 90°C for 2hr. 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 obtain 2-(3-cyclopropylphenoxy)-3-(dimethylamino)-1-(1H-imidazole-2-yl)prop-2-ene-1-one.

[0780] LCMS (method B): retention time 1.05 min, 298 (M+H)

[0781] e) Preparation of 7-(3-cyclopropylphenoxy)-5H-imidazo[1,2-b]pyridazin-8-one

[0782] In a round-bottom flask, 2-(3-cyclopropylphenoxy)-3-(dimethylamino)-1-(1H-imidazole-2-yl)prop-2-ene-1-one (0.03g, 0.10mmol) is dissolved in N-methyl-2-pyrrolidone (1mL). Then potassium tert-butoxide (0.012g, 0.10mmol) is added as a suspension in N-methyl-2-pyrrolidone (0.5mL). The resulting reaction mixture is stirred at room temperature for 30 minutes. Afterwards, a solution of amino 4-nitrobenzoate (0.022g, 0.12mmol) in N-methyl-2-pyrrolidone (1mL) is added, and the reaction mixture is stirred at room temperature for 18hr. The reaction process is monitored by LCMS. The reaction mixture is then diluted with water and extracted with EtOAc. The organic layer is washed with salt water, 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. The mixture was used as is in the next step.

[0783] LCMS (Method B): retention time 0.28 min, 313 (M+H) and retention time 1.9 min, 268 (M+H)

[0784] f) Preparation of 8-chloro-7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine

[0785] A mixture of 1-(1-aminoimidazole-2-yl)-2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-ene-1-one and 7-(3-cyclopropylphenoxy)-5H-imidazo[1,2-b]pyridazine-8-one (0.4 g), N,N-dimethylaniline (0.7 mL, 5 mmol) and phosphorus oxychloride (V) (8 mL, 90 mmol) was stirred at 90 ° C for 12 hr. 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 obtain a crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to obtain 8-chloro-7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine as a brown viscous substance.

[0786] LCMS (method B): retention time 1.47 min, 286 (M+H)

[0787] g) Preparation of methyl 7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine-8-carboxylate

[0788] 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)Cl 2 CH 2 Cl 2 To the mixture of 7- (3- cyclopropylphenoxy) imidazo[1,2-b]pyridazine-8-carboxylate was added 4- nitropropene (0.093 g, 0.11 mmol) and methanol (20 mL). The reactor was flushed with carbon monoxide gas three times and 10 bar of carbon monoxide was loaded. The reaction mixture was heated to 80 ° C for 1.5 hr. The reaction process 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 obtained crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to obtain methyl 7- (3- cyclopropylphenoxy) imidazo[1,2-b]pyridazine-8-carboxylate as a yellow solid.

[0789] LCMS (method B): retention time 2.03 min, 310 (M+H)

[0790] h) Preparation of lithium 7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine-8-carboxylate

[0791] 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 hr. The reaction progress was monitored by TLC and LCMS. After the reaction was completed, the reaction mixture was concentrated at 30 ° C under reduced pressure, and then co-distilled twice with toluene continuously to obtain 7-(3-cyclopropylphenoxy)imidazo[1,2-b]pyridazine-8-carboxylic acid lithium, which was used as is in the next step.

[0792] LCMS (method B): retention time 0.51 min, 296 (M+H)

[0793] i) 7-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]imidazo[1,2-b]pyridazine- Preparation of 8-formamide (Compound P-1.4, Table T1)

[0794] At 0 ° C, 2- (2,4-dichlorophenyl) -2- fluoro-ethylamine (0.041g, 0.19mmol) was added to 7- (3-cyclopropylphenoxy) imidazo [1,2-b] pyridazine -8- lithium carboxylate (0.0.5g, 0.16mmol) in EtOAc (0.83mL), followed by 1-propanephosphonic anhydride solution (T3P, 50% in EtOAc, 0.3mL, 0.50mmol) and triethylamine (0.05mL, 0.36mmol). The reaction mixture was then stirred at room temperature for 2hr. The reaction progress was monitored by TLC and LCMS. After 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 give 7-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]imidazo[1,2-b]pyridazine-8-carboxamide as a white solid.

[0795] 1 H NMR (400 MHz, CDCl 3)δppm 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,1 H),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,1H),3.72-3.84(m,1H),1.85-1.92(m,1H),0.84-1.01(m,2H),0.68-0.72(m,2H)

[0796] LCMS (method B): retention time 1.48 min, 485 (M+H)

[0797] Example P5: This example illustrates the 4] Preparation of triazolo[1,5-a]pyrimidine-7-carboxamide (Compound P-1.5 in Table T1)

[0798] (Compound P-1.5 of Table T1)

[0799] 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).

[0800] a) Preparation of 6-(3-cyclopropylphenoxy)-[1,2,4]triazolo[1,5-a]pyrimidine-7-carbonyl chloride

[0801] Under argon atmosphere, oxalyl chloride (0.03 mL, 0.34 mmol) was added dropwise 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). A drop of dry N,N-dimethylformamide was then added to the reaction mixture. Gas release was observed. The reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was concentrated in vacuo under nitrogen, and the brown residue of the obtained 6-(3-cyclopropylphenoxy)-[1,2,4]triazolo[1,5-a]pyrimidine-7-carbonyl chloride was used immediately in the next step.

[0802] b) 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]-[1,2,4]triazolo[1,5-a]pyrimidine Preparation of pyridine-7-carboxamide (Compound P-1.5, Table T1)

[0803] To a mixture of 2-(2,4-dichlorophenyl)ethylamine (0.04g, 0.21mmol) and pyridine (0.04mL, 0.53mmol) in acetonitrile (0.85mL), a solution of 6-(3-cyclopropylphenoxy)-[1,2,4]triazolo[1,5-a]pyrimidine-7-carbonyl chloride (0.07g, 0.21mmol) in acetonitrile (0.85mL) was slowly added. The reaction mixture was stirred at room temperature for 12hr overnight. The reaction process was monitored by TLC and LCMS. After completion, the reaction mixture was diluted with water, extracted with EtOAc, and the organic layer was washed with salt water, dried over sodium sulfate and concentrated under reduced pressure. The resulting crude residue was purified by reverse phase chromatography (0-70% acetonitrile in water) to afford 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxamide as a white solid.

[0804] 1 H NMR (400 MHz, CDCl 3 )δppm 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).

[0805] LCMS (method C): retention time 1.24 min, 468.3 (M+H)

[0806] Example P6: This example illustrates the Preparation of [1,2-a]pyrimidine-5-carboxamide (Compound P-1.6, Table T1)

[0807] (Compound P-1.6 of Table T1)

[0808] a) Preparation of 5-bromo-N-[2-(2,4-dichlorophenyl)ethyl]-2-methylsulfanyl-pyrimidine-4-carboxamide

[0809] At 0 ° C, 2-(2,4-dichlorophenyl)ethylamine (1.67 g, 8.83 mmol) was added to 5-bromo-2-methylsulfanyl-pyrimidine-4-carboxylic acid (2.0 g, 8.02 mmol) in EtOAc (20 mL), followed by 1-propanephosphonic anhydride solution (T3P, 50% in EtOAc, 14.3 mL, 24.0 mmol) and triethylamine (2.25 mL, 16.0 mmol). The reaction mixture was stirred at room temperature for 2 hr. The reaction progress was monitored by TLC and LCMS. After 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.

[0810] LCMS (method C): retention time 1.18 min, 419.8 (M+H)

[0811] b) 5-(3-Cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]-2-methylsulfanyl-pyrimidine-4-carboxylic acid Preparation of amides

[0812] 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 added and dissolved in dimethyl sulfoxide. The reaction mixture was purged with argon for 15 minutes. Potassium phosphate (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 was flushed with argon. The round-bottom flask was kept on a preheating 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 layer was washed with water (20 mL) and then with 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 / EtOAc) to give 5-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]-2-methylsulfanyl-pyrimidine-4-carboxamide.

[0813] LCMS (method D): retention time 1.29 min, 474 (M+H)

[0814] c) 5-(3-Cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]-2-methylsulfonyl-pyrimidine-4-carboxylic acid Preparation of amides

[0815] In a round-bottom flask, 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 at 0 ° C. To this solution was added 3-chloroperoxybenzoic acid (1.82 g, 6.32 mmol) in batches. The resulting reaction mixture was stirred at room temperature for 4 hr. The reaction progress was monitored by TLC and LCMS. After the reaction was completed, the reaction mixture was quenched by sodium thiosulfate solution (monitoring the amount of peroxide by starch test paper), and the reaction mixture was 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.

[0816] LCMS (method C): retention time 1.18 min, 507 (M+H)

[0817] d) Preparation of 2-amino-5-(3-cyclopropylphenoxy)-N-[2-(2,4-i-chlorophenyl)ethyl]pyrimidine-4-carboxamide Preparation

[0818] 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) were loaded into a premixed pressure reactor. Ammonia (0.5 mol / L, 10 mL) in 1,4-dioxane was added thereto, and the reaction was heated at 90 ° C for 5 hr. The reaction progress was monitored by LCMS. After the reaction was completed, the reaction mixture was concentrated under reduced pressure, diluted with water and extracted twice with EtOAc. The combined 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 obtain 2-amino-5-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]pyrimidine-4-carboxamide.

[0819] LCMS (method C): retention time 1.22 min, 443.3 (M+H)

[0820] e) 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)ethyl]imidazo[1,2-a]pyrimidine-5-carboxylate Preparation of amines (compound P-1.6, Table T1)

[0821] 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) were loaded into a microwave container. The reaction was irradiated at 98 ° C for 12 hr. The reaction progress was monitored by LCMS. After completion, the reaction mixture was concentrated under reduced pressure, diluted with water and extracted twice with EtOAc. The combined 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 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.

[0822] 1 H NMR (400 MHz, CDCl 3 )δppm 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),3.78-3.86(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).

[0823] LCMS (method D): retention time 1.15 min, 467.0 (M+H)

[0824] Example P7: This example illustrates the Preparation of 2-methyl-imidazo[1,2-a]pyrimidine-5-carboxamide (Compound P-1.7, Table T1)

[0825] (Compound P-1.7 of Table T1)

[0826] Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate was prepared as described in Example 1, steps a) and b).

[0827] a) Preparation of 6-(3-cyclopropylphenoxy)-2-methyl-8H-imidazo[1,2-a]pyrimidin-5-one

[0828] In a single-necked round-bottom flask, a mixture of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate (2.00 g, 6.90 mmol), 5-methyl-1H-imidazole-2-amine hydrochloride (0.92 g, 6.90 mmol) and sodium acetate (0.57 g, 6.90 mmol) in acetic acid (20 mL) was stirred at 100 ° C for 18 hr. The reaction process was monitored by LCMS. After the reaction was completed, 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 obtain a crude residue, which was purified by silica gel chromatography (cyclohexane / EtOAc) to obtain 6-(3-cyclopropylphenoxy)-2-methyl-8H-imidazo[1,2-a]pyrimidine-5-one as a white solid.

[0829] LCMS (method B): retention time 1.31 min, 282 (M+H)

[0830] b) Preparation of 5-chloro-6-(3-cyclopropylphenoxy)-2-methyl-imidazo[1,2-a]pyrimidine

[0831] In a single-necked round-bottom flask, under stirring at 0°C, 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 oxychloride (V) (25 mL). The mixture was allowed to reach room temperature and then stirred at 70°C for 5 hr. The reaction progress was monitored by LCMS. After the reaction was completed, the reaction mixture was concentrated in a vacuum 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 a saline solution, dried over sodium sulfate and concentrated under reduced pressure to obtain a crude residue. The resulting crude residue was purified by silica gel chromatography (0-20% EtOAc in cyclohexane) to obtain 5-chloro-6-(3-cyclopropylphenoxy)-2-methyl-imidazo[1,2-a]pyrimidine as a light yellow viscous substance.

[0832] LCMS (method C): retention time 1.12 min, 300 (M+H)

[0833] c) Preparation of methyl 6-(3-cyclopropylphenoxy)-2-methyl-imidazo[1,2-a]pyrimidine-5-carboxylate

[0834] An autoclave 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), Pd(dppf)Cl 2 CH 2 Cl 2In 40% ethyl acetate (0.33g, 0.40mmol). The container was flushed with carbon monoxide gas three times and loaded with 10 bar of carbon monoxide. The reaction mixture was heated to 80 ° C for 3hr. The reaction process was monitored by LCMS. After the reaction was completed, 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 obtain a crude residue. The obtained crude residue was purified by silica gel chromatography (0-30% EtOAc in cyclohexane) to obtain methyl 6- (3- cyclopropylphenoxy) -2- methyl-imidazo [1,2-a] pyrimidine -5- carboxylate in a yellow viscous substance.

[0835] LCMS (method D): retention time 1.09 min, 324 (M+H)

[0836] d) 6-(3-Cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2-methyl-imidazo[1, 2-a] Preparation of pyrimidine-5-carboxamide (Compound P-1.7, Table T1)

[0837] 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-ethylamine (0.06 g, 0.30 mmol) were loaded into a 10 mL microwave vial, and the vial was sealed and irradiated with microwaves for 2 hr at 100 ° C. The reaction progress was monitored by TLC and LCMS. After 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 combi flash chromatography (using 0-70% acetonitrile in water as eluent) to give 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2-methyl-imidazo[1,2-a]pyrimidine-5-carboxamide as a yellow solid.

[0838] 1 H NMR (400MHz, chloroform-d) δppm 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).

[0839] LCMS (method C): retention time 1.22 min, 499 (M+H)

[0840] Example P8: This example illustrates the Preparation of [1,5-a]pyrazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.8, Table T1)

[0841] (Compound P-1.8 of Table T1)

[0842] Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate was prepared as described in Example 1.

[0843] a) Preparation of 2-bromo-6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidin-7-one

[0844] In a single-necked 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 heated to 120 ° C for about 4 hr. 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.

[0845] LCMS (method A): retention time 0.87 min, 348 (M+3H)

[0846] b) Preparation of 6-(3-cyclopropylphenoxy)-7-oxo-4H-pyrazolo[1,5-a]pyrimidine-2-carbonitrile

[0847] In a 30 mL vial, zinc cyanide (0.43 g, 3.65 mmol), Pd2(dba) 3 (1.57g, 1.66mmol), Pd(dppf)Cl 24-(3-cyclopropylphenoxy)-7-oxo-4H-pyrazolo[1,5-a]pyrimidine-2-carbonitrile was added. The mixture was purged with argon. The vial was sealed and the reaction mixture was stirred for 2 hr under heating at 120 ° C. The reaction progress was monitored by LCMS. The reaction mixture was then quenched with water, filtered through a celite pad, and diluted with EtOAc. The organic layer was washed with water (5x40 mL). C18 120g chromatography (water / 20%-70% acetonitrile) was performed to obtain 6-(3-cyclopropylphenoxy)-7-oxo-4H-pyrazolo[1,5-a]pyrimidine-2-carbonitrile.

[0848] LCMS (method A): retention time 0.85 min, 293 (M+H)

[0849] c) Preparation of 7-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-2-carbonitrile

[0850] Under stirring, 6-(3-cyclopropylphenoxy)-7-oxo-4H-pyrazolo[1,5-a]pyrimidine-2-carbonitrile (0.32 g, 1.1 mmol) and POCl 3 The mixture was stirred at 90 ° C for 20 hrs. The reaction mixture was concentrated to dryness under vacuum, then diluted in EtOAc, washed three times with water, washed 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 used in the next step without further purification.

[0851] LCMS (method A): retention time 1.13 min, 311 (M+H)

[0852] d) Preparation of methyl 2-cyano-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate

[0853] 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), Pd(dppf)Cl 2 CH 2 Cl 2The reaction mixture was stirred for 2 hours at 4 ℃ for 1 h.Then the mixture was stirred for 2 hours at 4 ℃ for 3 hours.(0.19g, 0.23mmol).The reactor was flushed with nitrogen gas, then flushed twice with carbon monoxide gas, and then 10 bar of carbon monoxide was loaded.The reaction mixture was heated to 80 ° C for 2 hours.The reaction process was monitored by LCMS.After the reaction was completed, 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 obtain a crude residue.The obtained crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to obtain methyl 2-cyano-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate.

[0854] LCMS (method A): retention time 1.08 min, 335 (M+H)

[0855] e) Preparation of Lithium 2-Cyano-6-(3-Cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate

[0856] 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 the reaction was completed, the reaction mixture was concentrated at 30 ° C under reduced pressure and then co-distilled twice with toluene. The crude 2-cyano-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylic acid lithium salt was used as is in the next step.

[0857] LCMS (method A): retention time 0.75 min, 321 (M+H)

[0858] f) 2-Cyano-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]pyrazolo[1,5- a] Preparation of pyrimidine-7-carboxamide (Compound P-1.8, Table T1)

[0859] A solution of 2-cyano-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylic acid lithium salt (0.20 g, 0.613 mmol), (1-cyano-2-ethoxy-2-oxoethylideneaminooxy)dimethylamino-morpholino-carbonium hexafluorophosphate (0.32 g, 0.74 mmol) in EtOAc (6 mL) was stirred at room temperature. Diisopropylethylamine (0.32 mL, 1.84 mmol) was added, followed by 2-(2,4-dichlorophenyl)-2-fluoroethane-1-amine (0.14 g, 0.67 mmol). The reaction progress was monitored by LCMS and TLC. After the reaction was completed, the reaction mixture was diluted with water. It was then extracted twice with EtOAc. The combined organic layer was washed once with brine, dried over anhydrous sodium sulfate, filtered and concentrated at 60 ° C under reduced pressure. The crude residue was purified by chromatography (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-fluoro-ethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide.

[0860] 1 H NMR (400 MHz, CDCl 3 )δppm 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,1H ),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)

[0861] LCMS (method A): retention time 1.19 min, 510 (M+H)

[0862] Example P9: This example illustrates the reaction of 3-chloro-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro- Preparation of ethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.9, Table T1)

[0863] (Compound P-1.9 of Table T1)

[0864] Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate was prepared as described in Example 1.

[0865] a) Preparation of 3-chloro-6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidin-7-one

[0866] In a single-necked round-bottom flask, a mixture of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate (1.50 g, 5.20 mmol), 4-chloro-1H-pyrazole-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 hr. The reaction process was monitored by LCMS. After completion, the reaction mixture was diluted with ice-cold water and stirred for 15 minutes. The solid obtained was filtered through a Buchner funnel and dried under vacuum to obtain 3-chloro-6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidine-7-one as a brown solid.

[0867] LCMS (method B): retention time 1.34 min, 302 (M+H)

[0868] b) Preparation of 3,7-dichloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine

[0869] In a single-necked 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 oxychloride (V) (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 at 0 ° C by a syringe, and the resulting reaction mixture was stirred at room temperature, then stirred at 85 ° C for 16 hr. The reaction progress was monitored by LCMS. After completion, the reaction mixture was cooled to room temperature, concentrated in vacuo to a minimum volume and quenched by adding it to crushed ice, and the desired organic material was extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate and concentrated under reduced pressure to obtain a crude residue. The resulting 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 sticky substance.

[0870] LCMS (method B): retention time 1.73 min, 320 (M+H)

[0871] c) Preparation of methyl 3-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate

[0872] The 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), Pd(dppf)Cl 2 CH 2 Cl 2 In 40% ethyl acetate (0.32g, 0.39mmol). The reactor was flushed with carbon monoxide gas three times and 10 bar of carbon monoxide was loaded. The reaction mixture was heated to 80 ° C for 3 hours. The reaction process was monitored by LCMS. After 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 obtain a crude residue. The obtained crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to obtain methyl 3-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate in a yellow viscous substance.

[0873] LCMS (method B): retention time 1.67 min, 344 (M+H)

[0874] d) 3-Chloro-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]pyrazolo[1,5-a] Preparation of pyrimidine-7-carboxamide (Compound P-1.9, Table T1)

[0875] Methyl 3-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate (110mg, 0.32mmol) and 2-(2,4-dichlorophenyl)-2-fluoro-ethylamine (133mg, 0.64mmol) were loaded into a 10mL microwave vial. The vial was then sealed and irradiated with microwaves for 2hr under stirring at 90°C. The reaction process was monitored by TLC and LCMS. After completion, the reaction mixture was diluted with water and extracted with EtOAc. The obtained organic layer was washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The obtained crude residue was purified by silica gel chromatography (cyclohexane / EtOAc as eluent) to obtain 3-chloro-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide as an off-white solid.

[0876] 1 H NMR (400 MHz, CDCl 3)δppm 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)

[0877] 19 F NMR (377 MHz, CDCl 3 )δppm 188.27(s,1F)

[0878] LCMS (method C): retention time 1.25 min, 517 (MH)

[0879] The analytical sample rac-3-chloro-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide was analyzed by chiral phase column chromatography.

[0880] Method: SFC: Waters Acquity UPC 2 / QDa PDA Detector Waters Acquity UPC 2 , column: Daicel SFC AY, 3μm, 0.3cm x10cm, 40°C, mobile phase: A: CO2, B: IPA, isogradient: 25% B, ABPR: 1800psi, flow rate: 2.0ml / min, detection: 240nm, sample concentration: 1mg / mL in MeOH / ACN, injection: 2μl.

[0881] 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 (retention time 5.59 min). The preparative sample was obtained by preparative chiral column:

[0882] Preparation method: Sepiatec Prep SFC 100; Column: Daicel AY, 5□m, 2.0cm x 25cm

[0883] Mobile phase: A:CO 2 , B: EtOH, isogradient: 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

[0884] The first eluting peak (retention time about 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 two samples measured on the above analytical column was >98%.

[0885] Example P10: This example illustrates the Preparation of 2-fluoro-pyrazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.10, Table T1)

[0886] (Compound P-1.10 of Table T1)

[0887] Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate was prepared as described in Example 1.

[0888] a) Preparation of 6-(3-cyclopropylphenoxy)-2-fluoro-4H-pyrazolo[1,5-a]pyrimidin-7-one

[0889] In a single-necked 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-pyrazole-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 hr. The reaction process was monitored by LCMS. After completion, the reaction mixture was cooled to room temperature and diluted with ice-cold water. The resulting solid compound was then precipitated, filtered on a Buchner funnel, washed with cold water and dried to obtain 6-(3-cyclopropylphenoxy)-2-fluoro-4H-pyrazolo[1,5-a]pyrimidine-7-one as an off-white solid.

[0890] LCMS (method B): retention time 1.32 min, 284 (MH)

[0891] b) Preparation of 7-chloro-6-(3-cyclopropylphenoxy)-2-fluoro-pyrazolo[1,5-a]pyrimidine

[0892] In a single-necked round-bottom flask, at 0 ° C, pyridine (1.71 mL, 21.0 mmol) was added to a mixture of 6- (3- cyclopropylphenoxy) -2- fluoro-4H-pyrazolo [1,5-a] pyrimidine -7-one (1.5 g, 5.25 mmol) and phosphorus oxychloride (V) (37.3 mL, 399 mmol). The reaction mixture was stirred at 85 ° C for 12 hr. The reaction process was monitored by LCMS. After completion, the reaction mixture was concentrated to a minimum volume, then diluted with ice water and extracted with EtOAc. The obtained organic layer was washed with brine, dried over sodium sulfate and concentrated under reduced pressure to obtain a crude residue. The obtained crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to obtain 7- chloro-6- (3- cyclopropylphenoxy) -2- fluoro-pyrazolo [1,5-a] pyrimidine as a light yellow solid.

[0893] LCMS (method B): retention time 1.70 min, 304 (M+H)

[0894] c) Preparation of methyl 6-(3-cyclopropylphenoxy)-2-fluoro-pyrazolo[1,5-a]pyrimidine-7-carboxylate

[0895] 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), Pd(dppf)Cl 2 CH 2 Cl 2 In 40mL 40mL 40mL ethanol (0.47g, 0.57mmol). The reactor is flushed with carbon monoxide gas three times and 10 bar of carbon monoxide is loaded. The reaction mixture is heated to 80 ° C for 3 hours. The reaction process is monitored by LCMS. After completion, the reaction mixture is diluted with water and extracted with EtOAc. The organic layer is washed with brine, dried over sodium sulfate and concentrated under reduced pressure to obtain a crude residue. The obtained crude residue is purified by silica gel chromatography (cyclohexane / EtOAc) to obtain methyl 6- (3- cyclopropylphenoxy) -2- fluoro- pyrazolo [1,5-a] pyrimidine -7- carboxylate in a yellow viscous substance.

[0896] LCMS (method B): retention time 1.65 min, 328 (M+H)

[0897] d) 6-(3-Cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2-fluoro-pyrazolo[1,5- a] Preparation of pyrimidine-7-carboxamide (Compound P-1.10, Table T1)

[0898] Methyl 3-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate (100mg, 0.30mmol) and 2-(2,4-dichlorophenyl)-2-fluoro-ethylamine (127mg, 0.61mmol) were loaded into a 10mL microwave vial. The vial was then sealed and irradiated with microwaves for 2hr under stirring at 90°C. The reaction process was monitored by TLC and LCMS. After completion, the reaction mixture was diluted with water and extracted with EtOAc. The obtained organic layer was washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The obtained crude residue was purified by silica gel chromatography (cyclohexane / EtOAc as eluent) to obtain 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2-fluoro-pyrazolo[1,5-a]pyrimidine-7-carboxamide as a white solid.

[0899] 1 H NMR (400 MHz, CDCl 3 )δppm 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)

[0900] 19 F NMR (377 MHz, CDCl 3 )δppm 117.63(s,1F),-188.54(s,1F)

[0901] LCMS (method C): retention time 1.29 min, 503 (M+H)

[0902] Example P11: This example illustrates the Preparation of 3-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.11, Table T1)

[0903] (Compound P-1.11 of Table T1)

[0904] Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate was prepared as described in Example 1.

[0905] a) Preparation of 6-(3-cyclopropylphenoxy)-3-methyl-4H-pyrazolo[1,5-a]pyrimidin-7-one

[0906] In a single-necked round-bottom flask, a mixture of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate (0.30 g, 1.09 mmol), 4-methyl-1H-pyrazole-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 hr. The reaction progress was monitored by LCMS. After completion, the reaction mixture was cooled to room temperature and diluted with ice-cold water. The solid obtained was filtered and vacuum dried to obtain 6-(3-cyclopropylphenoxy)-3-methyl-4H-pyrazolo[1,5-a]pyrimidine-7-one as a brown solid.

[0907] LCMS (method B): retention time 1.28 min, 282 (M+H) +

[0908] b) Preparation of 7-chloro-6-(3-cyclopropylphenoxy)-3-methyl-pyrazolo[1,5-a]pyrimidine

[0909] In a single-necked round-bottom flask, a mixture of 6-(3-cyclopropylphenoxy)-2-methyl-4H-pyrazolo[1,5-a]pyrimidin-7-one (170mg, 0.60mmol) and phosphorus oxychloride (V) (4.3mL, 45.9mmol) was cooled to 0°C, and pyridine (19.7 μL, 2.41mmol) was added dropwise by a syringe at 0°C. The resulting reaction mixture was stirred at 80°C for 2hr. The reaction progress was monitored by LCMS. After completion, the reaction mixture was concentrated under reduced pressure, 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 obtain a crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to obtain 7-chloro-6-(3-cyclopropylphenoxy)-3-methyl-pyrazolo[1,5-a]pyrimidine as a light yellow viscous substance.

[0910] LCMS (method B): retention time 1.79 min, 300 (M+H)

[0911] c) Preparation of methyl 6-(3-cyclopropylphenoxy)-3-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxylate

[0912] 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), Pd(dppf)Cl 2 CH 2 Cl 2In 40% ethyl acetate (20% ethyl acetate) 4-nitropropene (2-nitropropene ...

[0913] LCMS (method B): retention time 1.63 min, 324 (M+H)

[0914] d) 6-(3-Cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-3-methyl-pyrazolo[1, 5-a] Preparation of pyrimidine-7-carboxamide (Compound P-1.11, Table T1)

[0915] 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-ethylamine (45.0 mg, 0.22 mmol) were loaded into a 10 mL microwave vial. The vial was then sealed and irradiated with microwaves for 2 hr under stirring at 100 ° C. The reaction progress was monitored by TLC and LCMS. After 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 (cyclohexane / EtOAc as eluent) to obtain 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-3-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxamide.

[0916] 1 H NMR (400 MHz, CDCl 3 )δppm 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)

[0917] 19F NMR (377 MHz, CDCl 3 )δppm 187.91(s,1F)

[0918] LCMS (method B): retention time 1.80 min, 499 (M+H)

[0919] Example P12: This example illustrates the Preparation of ethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.12, Table T1)

[0920] (Compound P-1.12 of Table T1)

[0921] Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate was prepared as described in Example 1, steps a) and b).

[0922] a) Preparation of 2-chloro-6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidin-7-one

[0923] In a single-necked round-bottom flask, a mixture of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate (0.50 g, 2.00 mmol), 5-chloro-3H-pyrazole-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 hr. The reaction progress was monitored by LCMS. After the reaction was completed, the reaction mixture was concentrated under reduced pressure and water was added. The solid obtained was filtered and dried to obtain 2-chloro-6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidine-7-one as a brown solid.

[0924] LCMS (method B): retention time 1.38 min, 302 (M+H)

[0925] b) Preparation of 2,7-dichloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine

[0926] In a single-necked round-bottom flask, a mixture of 2-chloro-6-(3-cyclopropylphenoxy)-4H-pyrazolo[1,5-a]pyrimidine-7-one (0.20 g, 0.66 mmol), pyridine (0.2 mL, 2.65 mmol) in phosphorus oxychloride (V) (5.0 mL, 50.3 mmol) was stirred at 90 ° C for 4 hr. The reaction process was monitored by LCMS. After the reaction was completed, the reaction mixture was diluted with ice water and extracted with EtOAc. The obtained organic layer was washed with brine, dried over sodium sulfate and concentrated under reduced pressure to obtain a crude residue. The obtained crude residue was purified by silica gel chromatography (cyclohexane / ethyl acetate) to obtain 2,7-dichloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine as a yellow solid.

[0927] LCMS (method B): retention time 1.77 min, 320 (M+H)

[0928] c) Preparation of methyl 2-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate

[0929] An autoclave 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), Pd(dppf)Cl 2 CH 2 Cl 2 The reactor was stirred for 2 hours at room temperature for 1 hour.The reactor was stirred for 2 hours at room temperature for 3 hours.(0.051g, 0.06mmol).The reactor was flushed with carbon monoxide gas three times and 10 bar of carbon monoxide was loaded.The reaction mixture was heated to 80 ° C for 2 hours.The reaction process was monitored by LCMS.After the reaction was completed, the reaction mixture was diluted with water and extracted with EtOAc.The obtained organic layer was washed with brine, dried over sodium sulfate and concentrated under reduced pressure to obtain a crude residue.The obtained crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to obtain methyl 2-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate as a yellow viscous substance.

[0930] LCMS (method B): retention time 2.92 min, 344 (M+H)

[0931] d) 2-Chloro-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]pyrazolo[1,5- a] Preparation of pyrimidine-7-carboxamide (Compound P-1.12, Table T1)

[0932] In a microwave vial, a mixture of methyl 2-chloro-6-(3-cyclopropylphenoxy)pyrazolo[1,5-a]pyrimidine-7-carboxylate (0.06g, 0.14mmol) and 2-(2,4-dichlorophenyl)-2-fluoro-ethylamine (0.029g, 0.14mmol) was stirred at 80 ° C for 2hr. The reaction process was monitored by TLC and LCMS. After completion, the reaction mixture was diluted with water and extracted with EtOAc. The obtained organic layer was washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The obtained crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to obtain 2-chloro-6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]pyrazolo[1,5-a]pyrimidine-7-carboxamide as a brown solid.

[0933] 1 H NMR (400 MHz, CDCl 3)δppm 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).

[0934] LCMS (method B): retention time 1.88 min, 519 (M+H)

[0935] Example P13: This example illustrates the Preparation of 2-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.13, Table T1)

[0936] (Compound P-1.13 of Table T1)

[0937] Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate was prepared as described in Example 1, steps a) and b).

[0938] a) Preparation of 6-(3-cyclopropylphenoxy)-2-methyl-4H-pyrazolo[1,5-a]pyrimidin-7-one

[0939] In a single-necked round-bottom flask, a mixture of ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate (2.20 g, 7.59 mmol), 5-methyl-1H-pyrazole-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 hr. The reaction process was monitored by LCMS. After the reaction was completed, the reaction mixture was concentrated under reduced pressure and co-distilled twice with toluene under reduced pressure to obtain a crude residue. The obtained crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to obtain 6-(3-cyclopropylphenoxy)-2-methyl-4H-pyrazolo[1,5-a]pyrimidine-7-one as a brown solid.

[0940] LCMS (method B): retention time 1.28 min, 282 (M+H)

[0941] b) Preparation of 7-chloro-6-(3-cyclopropylphenoxy)-2-methyl-pyrazolo[1,5-a]pyrimidine

[0942] In a single-necked 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 oxychloride (V) (9.46 g, 60.5 mmol) was cooled to 0 ° C, and pyridine (0.25 g, 3.18 mmol) was added dropwise by a syringe at 0 ° C. The resulting reaction mixture was stirred at 70 ° C for 5 hr. The reaction progress was monitored by LCMS. After the reaction was completed, 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 obtain a crude residue. The resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to obtain 7-chloro-6-(3-cyclopropylphenoxy)-2-methyl-pyrazolo[1,5-a]pyrimidine as a light yellow viscous substance.

[0943] LCMS (method D): retention time 1.14 min, 300 (M+H)

[0944] c) Preparation of methyl 6-(3-cyclopropylphenoxy)-2-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxylate

[0945] 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), Pd(dppf)Cl 2 CH 2 Cl 2 In 40% ethyl acetate (0.13g, 0.15mmol), 1% ethyl acetate (0.13g, 0.15mmol) was added into the reactor. (0.13g, 0.15mmol). The reactor was flushed with carbon monoxide gas three times and 10 bar of carbon monoxide was loaded. The reaction mixture was heated to 80 ° C for 3hr. The reaction process was monitored by LCMS. After the reaction was completed, the reaction mixture was diluted with water and extracted with EtOAc. The obtained organic layer was washed with brine, dried over sodium sulfate and concentrated under reduced pressure to obtain a crude residue. The obtained crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to obtain methyl 6- (3- cyclopropylphenoxy) -2- methyl -pyrazolo [1,5-a] pyrimidine -7- carboxylate in a light yellow viscous substance.

[0946] LCMS (method C): retention time 1.18 min, 324 (M+H)

[0947] d) 6-(3-Cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2-methyl-pyrazolo[1, 5-a] Preparation of pyrimidine-7-carboxamide (Compound P-1.13, Table T1)

[0948] Methyl 6-(3-cyclopropylphenoxy)-2-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxylate (70.0mg, 0.22mmol) and 2-(2,4-dichlorophenyl)-2-fluoro-ethylamine (90.0mg, 0.43mmol) were loaded into a 10mL microwave vial, and the vial was sealed and irradiated with microwaves for 4hr under stirring at 100°C. The reaction process was monitored by TLC and LCMS. After completion, the reaction mixture was diluted with water and extracted with EtOAc. The obtained organic layer was washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The obtained crude residue was purified by silica gel chromatography (cyclohexane / EtOAc as eluent) to obtain 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2-methyl-pyrazolo[1,5-a]pyrimidine-7-carboxamide as an off-white solid.

[0949] 1 H NMR (400 MHz, CDCl 3 )δppm 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).

[0950] LCMS (method C): retention time 1.30 min, 499 (M+H)

[0951] Example P14: This example illustrates the Preparation of 2-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxamide (compound P-1.14, Table T1)

[0952] (Compound P-1.14 of Table T1)

[0953] Note: Ethyl 2-(3-cyclopropylphenoxy)-3-(dimethylamino)prop-2-enoate was prepared as described in Example 1, steps a) and b).

[0954] a) Preparation of 6-(3-cyclopropylphenoxy)-2-methyl-4H-[1,2,4]triazolo[1,5-a]pyrimidin-7-one

[0955] In a single-necked 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-triazole-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 hr. The reaction progress was monitored by LCMS. After the reaction was completed, the reaction mixture was diluted with ice-cold water and stirred for 15 min. The solid obtained was filtered through a Buchner funnel and dried under vacuum to obtain 6-(3-cyclopropylphenoxy)-2-methyl-4H-[1,2,4]triazolo[1,5-a]pyrimidine-7-one as a white solid.

[0956] LCMS (method B): retention time 1.20 min, 283 (M+H)

[0957] b) Preparation of 7-chloro-6-(3-cyclopropylphenoxy)-2-methyl-[1,2,4]triazolo[1,5-a]pyrimidine

[0958] In a single-necked round-bottom flask, a mixture of 6-(3-cyclopropylphenoxy)-2-methyl-4H-[1,2,4]triazolo[1,5-a]pyrimidine-7-one (1.70 g, 6.02 mmol), N,N-dimethylaniline (3.15 g, 24.7 mmol) and phosphorus oxychloride (V) (42.8 mL, 458 mmol) was stirred at 90 ° C for 12 hr. The reaction progress was monitored by LCMS. After the reaction was completed, the reaction mixture was diluted with ice water and extracted with EtOAc. The obtained organic layer was washed with brine, dried over sodium sulfate and concentrated under reduced pressure to obtain a crude residue. The obtained crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to obtain 7-chloro-6-(3-cyclopropylphenoxy)-2-methyl-[1,2,4]triazolo[1,5-a]pyrimidine] as a yellow solid.

[0959] LCMS (method B): retention time 1.54 min, 301 (M+H)

[0960] c) Preparation of methyl 6-(3-cyclopropylphenoxy)-2-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxylate Preparation

[0961] 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)Cl in methanol (20 mL). 2 CH 2 Cl 2The reactor was stirred for 2 hours at room temperature for 1 hour. (0.36g, 0.44mmol). The reactor was flushed with carbon monoxide gas three times and 10 bar of carbon monoxide was loaded. The reaction mixture was heated to 80 ° C for 2 hours. The reaction process was monitored by LCMS. After the reaction was completed, the reaction mixture was diluted with water and extracted with EtOAc. The obtained organic layer was washed with brine, dried over sodium sulfate and concentrated under reduced pressure to obtain a crude residue. The obtained crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to obtain methyl 6- (3- cyclopropylphenoxy) -2- methyl - [1,2,4] triazolo [1,5-a] pyrimidine -7- carboxylate in a yellow viscous substance.

[0962] LCMS (method B): retention time 1.42 min, 325 (M+H)

[0963] d) 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2-methyl-[1,2,4]triazine Preparation of oxazolo[1,5-a]pyrimidine-7-carboxamide (Compound P-1.14, Table T1)

[0964] In a microwave vial, a mixture of methyl 6-(3-cyclopropylphenoxy)-2-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxylate (0.10g, 0.30mmol) and 2-(2,4-dichlorophenyl)-2-fluoro-ethylamine (0.12g, 0.61mmol) was stirred at 80 ° C for 2hr. The reaction progress was monitored by TLC and LCMS. After completion, the reaction mixture was diluted with water and extracted with EtOAc. The obtained organic layer was washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The obtained crude residue was purified by reverse phase chromatography (acetonitrile / water) to 6-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl]-2-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-carboxamide as an off-white solid.

[0965] 1 H NMR (400 MHz, CDCl 3 )δppm 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)

[0966] LCMS (method C): retention time 1.22 min, 500 (M+H)

[0967] Example P15: This example illustrates the reaction of 5-(3-cyclopropylphenoxy)-N-[2-(2,4-dichlorophenyl)-2-fluoro-ethyl] Preparation of pyrazolo[1,5-b]pyridazine-4-carboxamide (Compound P-1.15 in Table T1)

[0968] (Compound P-1.15 of Table T1).

[0969] a) Preparation of 2-[(3-iodopyrazol-1-yl)methoxy]ethyl-trimethyl-silane

[0970] At 0 ° C, sodium hydride (1.24 g, 30.9 mmol, 60% by mass) was added to a solution of 3-iodo-1H-pyrazole (5.0 g, 25.8 mmol) in tetrahydrofuran (50 mL). The reaction mixture was stirred for 15 min, 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 hr. The reaction process was monitored by TLC and LCMS. After 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 obtain 2-[(3-iodopyrazole-1-yl)methoxy]ethyl-trimethyl-silane as a sticky substance.

[0971] LCMS (method B): retention time 1.59 min, 325 (M+H)

[0972] b) 2-(3-cyclopropylphenoxy)-1-[1-(2-trimethylsilylethoxymethyl)pyrazol-3-yl]ethanone Preparation

[0973] In a double-necked round-bottom flask, 2-[(3-iodopyrazole-1-yl)methoxy]ethyl-trimethyl-silane (0.55g, 1.70mmol) was dissolved in tetrahydrofuran (3.4mL) and cooled to 0°C. Isopropylmagnesium chloride lithium chloride complex solution (1.3mol / L in THF, 1.3mL, 1.70mmol) was added dropwise thereto and stirred for 30 minutes. After 30 minutes, 2-(3-cyclopropylphenoxy)-N-methoxy-N-methyl-acetamide (prepared in three steps, respectively) (0.20g, 0.85mmol) was added as a solution in tetrahydrofuran. The reaction mixture was stirred at room temperature for 2hr. The reaction process was monitored by TLC and LCMS. After completion, the reaction mixture was poured into ice-cold water and 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 resulting crude residue was purified by silica gel chromatography (cyclohexane / EtOAc) to give 2-(3-cyclopropylphenoxy)-1-[1-(2-trimethylsilylethoxymethyl)pyrazol-3-yl]ethanone as a yellow sticky substance.

[0974] LCMS (method B): retention time 1.69 min, 373 (M+H)

[0975] c) Preparation of 2-(3-cyclopropylphenoxy)-N-methoxy-N-methyl-acetamide

[0976] i. Preparation of Ethyl 2-(3-cyclopropylphenoxy)acetate

[0977] In a single-necked round-bottom flask, 3-cyclopropylphenol (2.0g, 14.9mmol) is dissolved in acetonitrile (22mL), and cesium carbonate (5.82g, 17.8mmol) is added thereto. Ethyl 2-bromoacetate (2.98g, 17.8mmol) is added thereto and the resulting reaction mixture is stirred at room temperature for 4hr. The reaction process is monitored by LCMS. After the completion of the reaction, the reaction mixture is diluted with water and extracted with EtOAc. The organic layer is washed with salt water, dried over sodium sulfate and concentrated under reduced pressure, to obtain crude residue. The gained crude residue is purified by silica gel chromatography (cyclohexane / EtOAc), to obtain ethyl 2-(3-cyclopropylphenoxy) acetate.

[0978] LCMS (method B): retention time 1.48 min, 221 (M+H)

[0979] ii. Preparation of 2-(3-cyclopropylphenoxy)acetic acid

[0980] 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 hr. The reaction process was monitored by TLC and LCMS. After the reaction was completed, the reaction mixture was diluted with water and washed with EtOAc. The water 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 obtain 2-(3-cyclopropylphenoxy)acetic acid as a beige solid.

[0981] LCMS (method B): retention time 1.28 min, 193 (M+H)

[0982] iii. Preparation of 2-(3-cyclopropylphenoxy)-N-methoxy-N-methyl-acetamide

[0983] Methoxy (methyl) ammonium chloride (0.97 g, 9.93 mmol) was added to 2- (3- cyclopropylphenoxy) acetic acid (1.34 g, 6.62 mmol) in EtOAc (26.8 mL), 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 hr. The reaction progress was monitored by TLC and LCMS. After 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 obtain 2- (3- cyclopropylphenoxy) -N- methoxy -N- methyl - acetamide as a viscous substance.

[0984] LCMS (method B): retention time 1.32 min, 236 (M+H)

[0985] d) Preparation of 2-(3-cyclopropylphenoxy)-1-(1H-pyrazol-3-yl)ethanone

[0986] In a round-bottom flask, 2-(3-cyclopropylphenoxy)-1-[1-(2-trimethylsilylethoxymethyl)pyrazole-3-yl]ethanone (1.00g, 2.70mmol) was dissolved in methanol (11mL) and 4M hydrochloric acid (8.10mL, 32mmol) in dioxane was added thereto. The reaction mixture was stirred at 80°C for 2hr. The reaction progress was monitored by TLC and LCMS. After the reaction was completed, the reaction mixture was concentrated under reduced pressure, neutralized with saturated sodium bicarbonate and extracted with EtOAc. The combined organic layer was dried under reduced pressure to obtain 2-(3-cyclopropylphenoxy)-1-(1H-pyrazole-3-...

Claims

1. A compound having formula (I) or a stereoisomer, enantiomer, salt, or N-oxide of the compound of formula (I), wherein: R 1 is unsubstituted or substituted with 1, 2 or 3 independently selected substituents R 11 substituted phenyl; 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, wherein the heteroaryl ring is unsubstituted or substituted with 1 or 2 independently selected substituents R 11 replace; R 11 is hydroxy, halogen, mercapto, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, isopropyloxy, tert-butoxy, propynyloxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, or cyclopropyloxy; L 1 Indicates a direct bond, -O-, or -OC(R L1A )(R L1B )-; where 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 group; or L 1 Indicates -NR 10 -(CR 2 R 3 ) m -, where R 10 is selected from hydrogen or methyl; and m is 0 or 1; or L 1 express wherein # marks the bond to the nitrogen atom, and the staggered lines mark the bond to the group G; R 2 and R 3 are 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; or R 4 and R 5 together with the carbon atom to which they are attached, form a carbonyl, cyclopropyl, or cyclobutyl group; G is selected from G-1, G-2, G-3, or G-4, wherein: G-1 is phenyl or phenoxy, wherein the phenyl or phenoxy is unsubstituted or substituted with 1, 2 or 3 independently selected substituents R G1 replace; G-2 is a 5-membered or 6-membered monocyclic heteroaryl or heteroaryl-oxy group; wherein the heteroaryl group contains 1, 2 or 3 heteroatoms each independently selected from N, O and S; and wherein the heteroaryl group is unsubstituted or substituted with 1 or 2 independently selected substituents R G2 replace; 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; wherein the heterobicyclic ring system is saturated, partially unsaturated, or aromatic; and wherein the heterobicyclic ring system is unsubstituted or substituted with 1 or 2 independently selected substituents R G3 replace; G-4 is a 9-membered or 10-membered carbobicyclic ring system; wherein the carbobicyclic ring system is saturated, partially unsaturated, or aromatic; and wherein the carbobicyclic ring system is unsubstituted or substituted with 1 or 2 independently selected substituents R G4 replace; R G1 , R G2 , R G3 , and R G4 are independently hydroxy, halogen, thiol, amino, cyano, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, propyloxy, isopropyloxy, tert-butoxy, propynyloxy, methylsulfanyl, methylsulfonyl, difluoromethoxy, trifluoromethoxy, cyclopropyl, cyclobutyl, or cyclopropyloxy; A is selected from A-1 to A-17: The ## mark and -OR 1 The % mark is the same as -C(O)-N(H)-L 1 -G's key; and R 7 , R 8 , R 9 Independently selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, isopropyl, allyl, propargyl, cyclopropylmethyl, cyclopentyl, cyclohexyl, -C(=O)OCH3, -C(=O)N(CH3)2, 2-(dimethylamino)-2-oxo-ethyl, 2-(methylamino)-2-oxo-ethyl, difluoromethyl, trifluoromethyl, methylsulfonyl, methylsulfanyl, methoxy, ethoxy, cyano, hydroxyl, thiol, or amino.

2. The compound according to claim 1, wherein A is selected from A-1, A-3, A-5, A-13 and A-15, and wherein R 7 , R 8 and R 9 are independently selected from hydrogen, fluorine, chlorine, methyl, cyclopropyl, or cyano.

3. The compound according to claim 1 or claim 2, wherein L 1 Is a direct key, -NR 10 -CR 2 R 3 -, or -CR 2 R 3 -CR 4 R 5 -,in: 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 are independently selected from hydrogen, hydroxy, fluoro, methyl, cyano, or methoxy.

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

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

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

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

8. An agrochemical composition comprising a fungicidally effective amount of the compound according to any one of claims 1 to 7.

9. The composition according to claim 8, further comprising at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

10. A method for controlling or preventing infection of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound according to any one of claims 1 to 7, or a composition comprising this compound as an active ingredient, is applied to the plants, parts thereof or the locus thereof.

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

12. A plant propagation material, such as a seed, comprising the compound according to any one of claims 1 to 7 or a composition comprising the compound as an active ingredient, or being treated with the compound or the composition, or having the compound or the composition adhered thereto.

13. A compound having formula (II), (V), (VI), and (XVIII) in A.R 1 , L 1 and G are as defined in claim 1, 2, 3, 4, 5, 6 or 7 for a compound of formula (I), and wherein: X 1 is C1-C4-alkoxy; X 2 is a suitable leaving group, such as fluorine, chlorine, bromine, iodine, BF3K, B(OH)2, or B(pinacol); and X 6 It is chloro, bromo, iodo, or trifluoromethanesulfonyl-O-.

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