Pyrazole compound, and preparation method therefor and use thereof

Abstract

Provided are a pyrazole compound, and a preparation method therefor and the use thereof. The pyrazole compound has a structure represented by formula I, and exhibits a significant effect on controlling diseases in agriculture and forestry, particularly a good control effect on cucumber powdery mildew, cucumber downy mildew, soybean rust and rice blast, thus having wide application prospects.

Description

A pyrazole compound, its preparation method and application Technical Field

[0001] This application belongs to the field of agricultural fungicides, and relates to a pyrazole compound, its preparation method and application. Background Technology

[0002] Plant diseases severely impact plant growth, leading to reduced yields in crops, ornamental plants, pastures, and forestry, resulting in economic losses. With the long-term and extensive use of existing fungicides, pathogens can develop resistance to these commercial fungicides. Therefore, there is a continuous need to invent new and improved fungicidal compounds that are more effective, lower in cost, less toxic, more environmentally safer, and / or have different modes of action.

[0003] Some pyrazole compounds and their applications have been reported in the prior art.

[0004] For example, patent document P1 (WO2018051252) discloses pyrazole compounds represented by general formula (A), wherein Q is selected from Q-1 and HET is selected from substituted pyrazole groups represented by Het1, and discloses the acaricidal and aphidic activities of the pyrazole compounds in the patent.

[0005]

[0006] Patent document P2 (WO2019081477) discloses pyrazole compounds represented by general formula (B), and discloses the herbicidal activity of the pyrazole compounds in the patent.

[0007]

[0008] In this field, the development of more efficient fungicides to meet the needs of agriculture and forestry remains a desirable goal. Summary of the Invention

[0009] In view of the problems existing in the prior art, the purpose of this application is to provide a pyrazole compound, its preparation method and application.

[0010] To achieve this objective, the present application adopts the following technical solution (hereinafter referred to as technical solution 1A):

[0011] ;

[0012] in,

[0013] Q 1 and Q 2 Each is independently selected from hydrogen, halogen, cyano, C1-C 12 Alkyl, C1-C 12The alkyl or 5- to 7-membered aryl ring group is a ring system selected from carbon atoms and 0 to 3 heteroatoms, wherein the heteroatoms are independently selected from a maximum of 1 S atom, a maximum of 1 O atom, or a maximum of 3 N atoms, and each ring system may optionally be divided by a maximum of 5 identical or different R atoms. 6 Replace, Q 1 and Q 2 At least one of them is an aryl group;

[0014] R 1 R 2 and R 3 Each is independently selected from hydrogen, halogen, cyano, C1-C 12 Alkyl, C1-C 12 Haloalkyl, C1-C 12 Alkoxy, C1-C 12 Halogenated alkoxy groups, C3-C 12 cycloalkyl or at least one R 6 Substituted aryl group;

[0015] R 2 and R 3 They can form ternary to hexa-membered saturated cyclic groups together with the carbon atoms in the I-frame they are connected to.

[0016] R 4 Selected from hydrogen, halogen, cyano, nitro, C1-C 12 Alkyl, C1-C 12 Alkoxy, C1-C 12 Haloalkyl, C1-C 12 Halogenated alkoxy groups, C1-C 12 Alkoxycarbonyl or C1-C 12 Alkylaminocarbonyl, and the above alkyl, haloalkyl, haloalkoxy, alkoxycarbonyl, and alkylaminocarbonyl groups can be further reacted with R 6 replace;

[0017] R 5 Selected from halogens, C1-C 12 Alkyl, C3-C 12 Cycloalkyl, C3-C8 cycloalkyl, C1-C 12 Alkyl, C1-C 12 Alkoxy, C1-C 12 Alkoxy C1-C 12 Alkyl, C1-C 12 Haloalkyl, C1-C 12 Halogenated alkoxy groups, C1-C 12 Alkylamine, N,N-di(C1-C) 12 Alkyl)amino, C1-C 12 Alkylthio, C1-C12 Haloalkylthio groups, C1-C 12 alkyl sulfinyl, C1-C 12 Halogenated alkyl sulfinyl group, C1-C 12 Alkyl sulfonyl, C1-C 12 Haloalkylsulfonyl, aryl C1-C 12 Alkyl or aryl, and the above alkyl, cycloalkyl, cycloalkylalkyl, alkoxy, alkoxyalkyl, haloalkyl, haloalkoxy, alkylamino, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, arylalkyl or aryl can be further R 6 replace;

[0018] R 6 Selected from hydrogen, halogen, cyano, amino, hydroxyl, nitro, mercapto, C1-C 12 Alkyl, C1-C 12 Alkoxy, C1-C 12 Alkylthio, C1-C 12 Alkylamino, C1-C 12 Haloalkyl, C1-C 12 Halogenated alkoxy groups, C1-C 12 Halogenated alkylamino, N,N-di(C1-C) 12 Alkyl)amino, C3-C 12 cycloalkyl, C3-C 12 Cycloalkyloxy, C3-C 12 cycloalkylthio, C3-C 12 Cycloalkylamino, C2-C 12 alkenyloxy group, C2-C 12 alkynyloxy group, tri(C1-C) 12 Alkyl)silyl, C1-C 12 alkyl sulfinyl, C1-C 12 Alkyl sulfonyl, C3-C8 cycloalkyl C1-C 12 Alkoxy, C1-C 12 Alkyl carbonyl, C1-C 12 Alkyl carbonyloxy group, C1-C 12 Alkyl carbonyl amino, C1-C 12 Halogenated alkyl carbonyl amino, C1-C 12 Alkylsulfonylamino, C1-C 12 Haloalkylsulfonylamino, N,N-di(C1-C 12 alkyl)aminosulfonate group, N,N-di(C1-C 12Alkyl)aminosulfonyl, heterocyclic oxy, heterocyclic acylamino, piperidinyl, morpholinyl, tetrahydropyrrolyl, pyrazolyl, pyrroleyl, oxadiazolyl, phenyl or benzyl, and the above groups may also be replaced by one or more halogens, cyano, nitro, C1-C 12 Alkyl, C2-C 12 alkenyl, C2-C 12 alkynyl group, C1-C 12 Alkoxy, C1-C 12 Alkylamino or C1-C 12 Further substitution by any combination of alkylthio groups; T is selected from oxygen or sulfur atoms; n represents an integer from 1 to 5.

[0019] In this application, as a preferred technical solution (hereinafter referred to as technical solution 1B), in formula I,

[0020] Q 1 Selected from Ar1 to Ar 33：

[0021] ;

[0022] Q 2 Selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, C1-C 12 Alkyl or C1-C 12 Halogenated alkyl groups;

[0023] R 1 R 2 R 3 R 4 R 5 R 6 The definitions of T and n are the same as those in the above technical solution 1A; m represents an integer from 0 to 5.

[0024] In this application, Ar1 to Ar 33 The "#" in the formula indicates the position connected to pyrazole I.

[0025] In this application, as a preferred technical solution (hereinafter referred to as technical solution 1C), in formula I,

[0026] Q 1 Selected from hydrogen, fluorine, chlorine, bromine, iodine or C1-C 12 alkyl;

[0027] Q 2 Selected from Ar1 to Ar 33 Ar1 to Ar 33 The definition of Q in the above technical solution 1B is the same as that in the above technical solution. 1 Selected from Ar1 to Ar 33 Same definition;

[0028] R1 R 2 R 3 R 4 R 5 R 6 The definitions of T and n are the same as those in the above technical solution 1A; m represents an integer from 0 to 5.

[0029] In this application, as a further preferred technical solution (hereinafter referred to as technical solution 1D), in formula I,

[0030] Q 1 Selected from Ar1, Ar2, Ar3, Ar4, Ar5, Ar6, Ar 14 Ar 15 Ar 23 Ar 24 Or Ar 33 Here, Ar1, Ar2, Ar3, Ar4, Ar5, Ar6, and Ar 14 Ar 15 Ar 23 Ar 24 Or Ar 33 The definition is the same as that in technical solution 1B above; Q 2 Selected from hydrogen, fluorine, chlorine, bromine, or iodine; R 1 R 2 R 3 R 4 R 5 R 6 The definitions of T and n are the same as those in the above technical solution 1A; m represents an integer from 0 to 5.

[0031] In this application, as a further preferred technical solution (hereinafter referred to as technical solution 1E), in formula I,

[0032] Q 1 Selected from hydrogen; Q 2 Ar1 is selected, and the definition of Ar1 is the same as that in the above technical solution 1B;

[0033] R 1 R 2 R 3 R 4 R 5 R 6 The definitions of T and n are the same as those in the above technical solution 1A; m represents an integer from 0 to 5.

[0034] In this application, as a further preferred technical solution (hereinafter referred to as technical solution 1F), in formula I,

[0035] Q 1 Selected from Ar1 to Ar33 Ar1 to Ar 33 The definition of Q in the above technical solution 1B is the same. 1 Selected from Ar1 to Ar 33 Same definition; Q 2 Selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, C1-C 12 Alkyl or C1-C 12 Halogenated alkyl; R 1 Selected from hydrogen or C1-C 12 Alkyl; R 2 and R 3 Each is independently selected from hydrogen, fluorine, C1-C6 alkyl, or C3-C6 cycloalkyl, R 2 and R 3 They can form ternary to hexacyclic saturated cyclic groups together with the carbon atoms in the I-frame they are attached to; R 4 Selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, or C1-C3 alkyl; R 5 Selected from C1-C3 alkyl groups; R 6 Selected from hydrogen, halogen, cyano, amino, hydroxyl, nitro, mercapto, C1-C6 alkyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkylamino, C1-C8 haloalkyl, C1-C6 haloalkoxy, C1-C6 haloalkylamino, N,N-di(C1-C6 alkyl)amino, C3-C6 cycloalkyl, C3-C6 cycloalkyloxy, C3-C6 cycloalkylthio, C3-C6 cycloalkylamino, C2-C6 alkenyloxy, C2-C6 alkynyloxy, tris(C1-C6 alkyl)silyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C3-C6 cycloalkylC1-C3 alkoxy, C1-C6 alkylcarbonyl, C1-C6 alkylcarbonyl The group may be further substituted by any combination of one or more of the following groups: oxy, C1-C6 alkylcarbonylamino, C1-C6 haloalkylcarbonylamino, C1-C6 alkylsulfonylamino, C1-C6 haloalkylsulfonylamino, N,N-di(C1-C6 alkyl)aminosulfonate, N,N-di(C1-C6 alkyl)aminosulfonyl, heterocyclic acylamino, oxetane-3-oxy, morpholino, or phenyl, and may be further substituted by one or more combinations of fluorine, chlorine, bromine, iodine, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkoxy, C1-C6 alkylamino, or C1-C6 alkylthio; m represents an integer from 0 to 5; n represents an integer from 1 to 5; T is selected from oxygen or sulfur atoms.

[0036] In this application, as a further preferred technical solution (hereinafter referred to as technical solution 1G), in formula I,

[0037] Q 1 Selected from hydrogen, fluorine, chlorine, bromine, iodine or C1-C12 alkyl;

[0038] Q 2 Selected from Ar1 to Ar 33 Ar1 to Ar 33 The definition of Q in the above technical solution 1B is the same. 1 Selected from Ar1 to Ar 33 Same definition;

[0039] R 1 R 2 R 3 R 4 R 5 R 6 The definitions of m, n and T are the same as those in the above technical solution 1F.

[0040] As a further preferred technical solution of this application (hereinafter referred to as technical solution 1H), in formula I,

[0041] Q 1 Selected from Ar1, Ar2, Ar3, Ar4, Ar5, Ar6, Ar 14 Ar 15 Ar 23 Ar 24 Or Ar 33 Here, Ar1, Ar2, Ar3, Ar4, Ar5, Ar6, and Ar 14 Ar 15 Ar 23 Ar 24 Or Ar 33 Same as the definition in technical solution 1B above; Q 2 Selected from hydrogen, fluorine, chlorine, bromine, or iodine; R 1 Selected from hydrogen or methyl; R 2 and R 3 Each is independently selected from hydrogen, fluorine, methyl, ethyl, propyl, butyl, or R. 2 and R 3 Together with the carbon atoms in their linked I-framework, they form cyclopropane; R 4 Selected from hydrogen, fluorine, chlorine, bromine, iodine, or cyano; R 5 Selected from methyl; R 6Selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, amino, hydroxyl, nitro, mercapto, methyl, ethyl, isopropyl, tert-butyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl, neopentyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, 3-methyl-2-butoxy, neopentoxy, n-hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl-3-pentoxy, 3,3-dimethyl-2-butoxy, n-heptoxy, 2-heptoxy, 3-heptoxy, 4-heptoxy, n-octoxy, cyanomethyloxy, allyloxy 3,3-Dichloroallyloxy, propargyloxy, trimethylsilyl, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, tert-butylthio, n-pentylthio, 2-pentylthio, 3-pentylthio, 3-methyl-2-butylthio, neopentylthio, n-hexylthio, 2-hexylthio, 3-hexylthio, 2-methyl-3-pentylthio, 3,3-dimethyl-2-butylthio, n-heptylthio, 2-heptylthio, 3-heptylthio, 4-heptylthio, n-octylthio, methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, tert-butylamino, n-pentylamino, 2-pentyl Amine, 3-pentylamino, neopentylamino, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, 2,2,2-trifluoroethylamino, N,N-dimethylamino, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclopropylthio, methylsulfinyl, methylsulfonyl, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylthio, difluoromethylsulfinyl, difluoromethylsulfonyl, 2,2,2-trifluoroethylthio, 2,2,2-trifluoroethylsulfinyl Acyl, 2,2-difluoroethylthio, 2,2-difluoroethylsulfinyl, methoxymethylthio, methoxymethylsulfinyl, cyanomethylthio, phenylthio, cyclopropylmethoxy, methylcarbonyl, ethylcarbonyl, isopropylcarbonyl, methylcarbonyloxy, ethylcarbonyloxy, isopropylcarbonyloxy, methylcarbonylamine, ethylcarbonylamine, isopropylcarbonylamine, trifluoromethylcarbonylamine, methylsulfonylamine, trifluoromethylsulfonylamine, N,N-dimethylaminosulfonate, oxetane-3-oxy, morpholinyl, or phenyl; m represents an integer from 0 to 5; n represents an integer from 1 to 5; T is selected from oxygen or sulfur atoms.

[0042] As a further preferred technical solution of this application (hereinafter referred to as technical solution 1J), in formula I, Q 1 Selected from hydrogen; Q 2 Selected from Ar1, the definition of Ar1 is the same as that in the above technical solution 1B; R 1 R 2 R3 R 4 R 5 R 6 The definitions of m, n and T are the same as those in the above technical solution 1H.

[0043] As a further preferred technical solution of this application (hereinafter referred to as technical solution 1K), in formula I, Q 1 Selected from Ar1, Ar2, Ar3, Ar 14 Ar 23 Ar1, Ar2, Ar3, Ar 14 Ar 23 The definition is the same as that in technical solution 1B above; Q 2 Selected from hydrogen; R 1 Selected from hydrogen; R 2 and R 3 Each is independently selected from hydrogen, fluorine, or methyl; R 4 Selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, or methyl; R 5 Selected from methyl; R 6 Selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, n-hexyloxy, cyanomethyloxy, 3,3-dichloroallyloxy, trimethylsilyl, isopropylamino, N,N-dimethylamino, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, cyclohexyl, methylthio, ethylthio, isopropylthio, methylsulfinyl Methylsulfonyl, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylthio, difluoromethylsulfinyl, difluoromethylsulfonyl, 2,2,2-trifluoroethylthio, 2,2,2-trifluoroethylsulfinyl, 2,2-difluoroethylthio, 2,2-difluoroethylsulfinyl, methoxymethylthio, methoxymethylsulfinyl, cyanomethylthio, phenylthio, methylcarbonyl, oxetane-3-oxy, morpholinyl, or phenyl; n is 1; m represents an integer from 0 to 5; T is selected from oxygen atoms.

[0044] As a further preferred technical solution of this application, the pyrazole compound is any one of the compounds having general formula I shown in Table 1 below:

[0045]

[0046] Table 1

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075] illustrate:

[0076] In Table 1 above and in this application, the "#" in the substituents indicates the position where it is connected to the pyrazole in Formula I. In Table 1 above and in the compound structures of this application, the "#" indicates the position where it is connected to the pyrazole in Formula I. "Regardless of the tilt angle, it indicates that the substituent connected to the molecular skeleton is a racemic mixture."

[0077] Most preferably, the pyrazole compound described in this application is any one of the following compounds:

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085] .

[0086] The alkyl group referred to in this application is either straight-chain or branched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, or n-hexyl groups. A haloalkyl group is a group in which an alkyl group is substituted by one or more halogen atoms. An alkoxy group is a group with an oxygen atom attached to the alkyl terminus, such as methoxy, ethoxy, n-propoxy, isopropoxy, or tert-butoxy groups. A haloalkoxy group is a group in which an alkoxy group is substituted by one or more halogen atoms. The halogen is F, Cl, Br, or I.

[0087] The term "C1-C" is used in this application. 12 "Alkyl" refers to a straight-chain or branched alkyl group having 1 to 12 carbon atoms, and includes, without limitation, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, and n-hexyl. The term "C1-C" is also used. 12 "Alkoxy" refers to a straight-chain or branched alkoxy group having 1 to 12 carbon atoms, and includes, without limitation, methoxy, ethoxy, n-propoxy, isopropoxy, and tert-butoxy. The term "C1-C..." 12"Halogenated alkyl" refers to a straight-chain or branched alkyl group having 1 to 12 carbon atoms substituted with halogen atoms, and includes, without limitation, trifluoromethyl, difluoromethyl, 1,1,1-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, etc. The term "C3-C8 cycloalkyl" as used in this application refers to a cyclic alkyl group having 3 to 8 carbon atoms on the ring, and includes, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. The term "C3-C8 halogenated cycloalkyl" as used in this application refers to a cyclic alkyl group having 3 to 8 carbon atoms substituted with halogen atoms on the ring, and includes, without limitation, 1-chlorocyclopropyl, 1-fluorocyclopropyl, perfluorocyclopropyl, 1-chlorocyclobutyl, 1-chlorocyclopentyl, etc.

[0088] In this application, the C1-C preceding the specific group 12 C3-C8, etc., indicate the number of carbon atoms in a group, for example, C1-C8. 12 C3-C8 indicates a group with 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, and C3-C8 indicates a group with 3, 4, 5, 6, 7 or 8 carbon atoms, and so on.

[0089] In this application, "#" in the radical represents the connection position of the radical.

[0090] On the other hand, this application provides a method for preparing the pyrazole compounds as described above, wherein the preparation method is as follows:

[0091] The reaction of the compound shown in Formula II with the compound shown in Formula III yields the pyrazole compound shown in Formula I, as shown in the following reaction formula:

[0092] ;

[0093] Among them, R 1 R 2 R 3 R 4 R 5 Q 1 Q 2 The limitations of T are as described above and will not be repeated here.

[0094] Preferably, the molar ratio of the compound shown in Formula II to the compound shown in Formula III is 0.5-2:1, for example 0.5:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 1.8:1 or 2:1.

[0095] Preferably, the solvent for the reaction is any one or a combination of at least two of the following: dichloromethane, chloroform, ethyl acetate, toluene, acetonitrile, tetrahydrofuran, dioxane, ethanol, methanol, N,N-dimethylformamide, or dimethyl sulfoxide.

[0096] Preferably, the reaction temperature is greater than or equal to room temperature and less than or equal to the boiling point of the reaction solvent, such as 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 60°C, 70°C, 75°C, 80°C, 85°C, 90°C, etc., or the reaction is carried out at the boiling point of the solvent, i.e., under reflux.

[0097] Preferably, the reaction time is 0.5-48 hours, for example 0.5 hours, 1 hour, 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 23 hours, 25 hours, 28 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 44 hours or 48 hours.

[0098] The compound shown in Formula III was prepared by reacting the compound of Formula IV in the presence of a base to obtain the compound shown in Formula III, as shown in the following reaction formula:

[0099] ;

[0100] Where R 1 R 2 R 3 Q 1 Q 2 The limitations of T are as described above and will not be repeated here; among them, R 6 It is a C1-C4 alkyl group.

[0101] Preferably, in the preparation of the compound shown in Formula III, the reaction is carried out in the presence of a basic substance, which is an organic base and / or an inorganic base.

[0102] The organic base is any one or a combination of at least two of the following: triethylamine, pyridine, and diisopropylethylamine.

[0103] The inorganic acid is any one or a combination of at least two of lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium carbonate, and cesium carbonate.

[0104] Preferably, in the preparation of the compound shown in Formula III, the reaction can be carried out in a suitable solvent, wherein the solvent is any one or a combination of at least two of the following: water, dichloromethane, chloroform, ethyl acetate, toluene, acetonitrile, tetrahydrofuran, 1,4-dioxane, methanol, ethanol, isopropanol, n-butanol, water, N,N-dimethylformamide, or dimethyl sulfoxide.

[0105] Preferably, in the preparation of the compound represented by Formula III, the reaction temperature is greater than or equal to 0°C and less than or equal to the boiling point of the reaction solvent.

[0106] Preferably, in the preparation of the compound shown in Formula III, the reaction time is 0.5-48 hours.

[0107] The compound shown in Formula IV was prepared by the following method: the compound shown in Formula V was reacted with a basic substance to give the compound shown in Formula IV, as shown in the following reaction:

[0108] ;

[0109] Where R 1 R 2 R 3 R 6 The limitations of Q1, Q2, and T are as described above and will not be repeated here.

[0110] Preferably, in the preparation of the compound shown in Formula IV, the reaction is carried out in the presence of a basic substance, which is an organic base and / or an inorganic base.

[0111] The organic base is any one or a combination of at least two of the following: triethylamine, pyridine, and diisopropylethylamine.

[0112] The inorganic acid is any one or a combination of at least two of potassium carbonate and cesium carbonate.

[0113] Preferably, in the preparation of the compound shown in Formula IV, the solvent for the reaction is any one or a combination of at least two of the following: dichloromethane, chloroform, ethyl acetate, toluene, acetonitrile, tetrahydrofuran, dioxane, ethanol, methanol, N,N-dimethylformamide, saturated aqueous ammonium chloride solution, acetic acid, hydrochloric acid, water, or dimethyl sulfoxide.

[0114] Preferably, in the preparation of the compound shown in Formula IV, the reaction temperature is greater than or equal to 0°C and less than or equal to the boiling point of the reaction solvent.

[0115] Preferably, in the preparation of the compound shown in Formula IV, the reaction time is 0.5-48 hours.

[0116] The compound shown in Formula II was prepared by reacting Formula VI in the presence of a halogenating agent to give the compound shown in Formula II, as shown in the following reaction:

[0117] ;

[0118] Where R 4 R 5 The limitations are as described above and will not be repeated here.

[0119] Preferably, in the preparation of the compound shown in Formula II, the reaction is carried out in the presence of a halogenated substance, wherein the halogenating agent is chlorosuccinamide, bromosuccinamide, or iodosuccinamide.

[0120] Preferably, in the preparation of the compound represented by Formula II, the solvent for the reaction is any one or a combination of at least two of the following: dichloromethane, chloroform, acetone, toluene, acetonitrile, tetrahydrofuran, dioxane, methanol, ethanol, N,N-dimethylformamide, dimethyl sulfoxide, or hexamethylphosphoric triamine.

[0121] Preferably, in the preparation of the compound shown in Formula II, the reaction temperature is greater than or equal to 0°C and less than or equal to the boiling point of the reaction solvent, such as 0°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 60°C, 70°C, 75°C, 80°C, 85°C, 90°C, etc., or the reaction is carried out at the boiling point of the solvent, i.e., under reflux.

[0122] Preferably, in the preparation of the compound shown in Formula II, the reaction time is 0.5-48 hours.

[0123] In this application, some of the raw materials used are commercially available reagents, and some compounds can be synthesized with reference to literature, such as European Journal of Medicinal Chemistry (2019), 181, 111577; Archiv der Pharmazie (Weinheim, Germany) (2023), 356(11), 2300309.

[0124] On the other hand, this application provides the application of pyrazole compounds as described above in the prevention and control of plant diseases.

[0125] The pyrazole compounds described in this application have unexpectedly high fungicidal activity and excellent control effect on plant diseases.

[0126] In this application, the plant diseases include diseases of the classes Oomycetes, Ascomycetes, Basidiomycetes, or Deuteromycetes.

[0127] Preferably, the plant diseases include, but are not limited to: wheat rust, wheat powdery mildew, wheat scab, wheat root rot, wheat sheath blight, wheat take-all, wheat glume blight, cucumber downy mildew, cucumber powdery mildew, melon powdery mildew, bitter melon powdery mildew, cucumber anthracnose, cucumber wilt, cucumber gray mold, grape downy mildew, tomato early blight, tomato late blight, rice sheath blight, rice blast, watermelon vine blight, peanut scab, peanut black spot, citrus scab, pepper root rot, cotton verticillium wilt, cotton wilt, rapeseed black stem rot, rapeseed sclerotinia rot, pear scab, ginseng rust rot, corn rust, corn curvature blight, corn large leaf spot, mango stem rot, apple ring rot, apple rot fungus, banana leaf spot, soybean rust, or potato late blight.

[0128] Preferably, the plant diseases include wheat rust, wheat powdery mildew, wheat scab, cucumber powdery mildew, cucumber downy mildew, or soybean rust.

[0129] On the other hand, this application provides a fungicide composition comprising an active ingredient and a pesticide-acceptable carrier, wherein the active ingredient is a pyrazole compound as described above.

[0130] The bactericide composition described in this application can be used in agriculture, forestry, sanitation and other fields.

[0131] Preferably, in the bactericide composition, the weight percentage of the active ingredient is 1-99%, for example 1%, 3%, 5%, 8%, 10%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99%.

[0132] Preferably, the pesticide-acceptable carrier includes a surfactant.

[0133] In this application, the surfactant is an ionic surfactant or a nonionic surfactant.

[0134] The surfactants include emulsifiers, dispersants, or wetting agents. Emulsifiers can be polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty amines, and commercially available emulsifiers (such as Agricultural Emulsion 2201B, Agricultural Emulsion 0203B, Agricultural Emulsion 100#, Agricultural Emulsion 500#, Agricultural Emulsion 600#, Agricultural Emulsion 600-2#, Agricultural Emulsion 1601, Agricultural Emulsion 2201, Agricultural Emulsion NP-10, Agricultural Emulsion NP-15, Agricultural Emulsion 507#, Agricultural Emulsion OX-635, Agricultural Emulsion OX-622, Agricultural Emulsion OX-653, Agricultural Emulsion OX-667, and Ningru 36#). Dispersants include sodium lignosulfonate, dispersing agents, calcium lignosulfonate, and methylnaphthalenesulfonic acid formaldehyde condensate, etc. Wetting agents include sodium lauryl sulfate, sodium dodecylbenzenesulfonate, and sodium alkylnaphthalenesulfonate, etc.

[0135] Preferably, the pesticide-acceptable carrier includes a solid carrier and / or a liquid carrier.

[0136] Preferably, the solid carrier comprises natural or synthetic clays and silicates, such as natural silica and diatomaceous earth; magnesium silicates, such as talc; magnesium aluminum silicates, such as kaolinite, montmorillonite, and mica; white carbon black, calcium carbonate, and light calcium carbonate; calcium sulfate; limestone; sodium sulfate; and amine salts such as ammonium sulfate and hexamethylethylenediamine. The liquid carrier comprises water and organic solvents, which can also be used as auxiliaries or antifreeze additives when water is used as a solvent or diluent. Suitable organic solvents include aromatic hydrocarbons such as benzene, xylene, and toluene; chlorinated hydrocarbons such as chlorobenzene, vinyl chloride, chloroform, and dichloromethane; aliphatic hydrocarbons such as petroleum fractions, cyclohexane, and light mineral oils; alcohols such as isopropanol, butanol, ethylene glycol, glycerol, and cyclohexanol; their ethers and esters; and ketones such as acetone, cyclohexanone, dimethylformamide, and N-methylpyrrolidone.

[0137] In the formulation of bactericide compositions, the active components can be mixed with liquid and / or solid carriers, and surfactants (such as emulsifiers, dispersants, stabilizers, and wetting agents) can be added. Other additives (such as binders, defoamers, and oxidants) can also be added.

[0138] On the other hand, this application provides a method for preventing and controlling plant diseases, the method being: applying an effective dose of the fungicide composition as described above to the plant disease to be controlled or its growing medium.

[0139] Preferably, the effective dose is 10-1000 g per hectare, more preferably 20-500 g per hectare.

[0140] The compositions of this application can be applied to the disease or its growth medium in formulation form. Compound I of general formula is dissolved or dispersed in a carrier or formulated as an active ingredient for easier dispersion when used as a fungicide. For example, these chemical formulations can be formulated into various liquids, emulsifiable concentrates, suspensions, aqueous suspensions, microemulsions, emulsions, water-in-oil emulsions, powders, wettable powders, soluble powders, granules, water-dispersible granules, or capsules.

[0141] For certain applications, such as in agriculture, one or more other fungicides, insecticides, herbicides, plant growth regulators, or fertilizers may be added to the bactericidal composition of this application, thereby producing additional advantages and effects.

[0142] Compared with the prior art, this application has the following advantages:

[0143] The pyrazole compounds of this application, having the structure shown in Formula I, exhibit significant effects in controlling agricultural and forestry diseases, particularly effective against cucumber powdery mildew, cucumber downy mildew, soybean rust, and wheat scab. At a concentration of 10 ppm, the control efficacy against cucumber powdery mildew is ≥90%, and at 100 ppm, the control efficacy against cucumber downy mildew is ≥90%. At a concentration of 10 ppm, the control efficacy against soybean rust is ≥90%. At a concentration of 100 ppm, the inhibition rate of wheat scab spore germination is ≥90%. Furthermore, the preparation method is simple, efficient, and easy to scale up, showing broad application prospects. Detailed Implementation

[0144] The technical solution of this application will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of this application and should not be considered as specific limitations thereof. Unless otherwise specified in the embodiments and this application: when characterizing the compounds using 1H NMR spectroscopy, the corresponding samples are dissolved in deuterated dimethyl sulfoxide (DMSO-d6), and 1H NMR data are obtained using a 400 MHz NMR spectrometer. The chemical shift unit is ppm (i.e., (ppm); The eluent for column chromatography purification was prepared according to the volume ratio of PE (abbreviated as PE): ethyl acetate (abbreviated as EA).

[0145] Synthesis Examples

[0146] Example 1: Preparation of Compound 1

[0147]

[0148] Step 1: Synthesis of ethyl 2-(4-phenyl-1H-pyrazol-1-yl)acetate:

[0149] 4-Phenyl-1H-pyrazole (5.0 g, 34.7 mmol), ethyl bromoacetate (11.6 g, 69.4 mmol), and cesium carbonate (22.6 g, 69.4 mmol) were added to 30 mL of DMF and reacted at room temperature for 4 hours. The reaction mixture was poured into a mixture of 50 mL of water and 100 mL of ethyl acetate, and extracted by separation. The organic layer was collected, washed with saturated sodium chloride water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue did not require purification, yielding 7.0 g of yellow oil in 88% yield, which was directly used for the next step.

[0150] Step 2: Synthesis of 2-(4-phenyl-1H-pyrazol-1-yl)acetic acid:

[0151] Ethyl 2-(4-phenyl-1H-pyrazol-1-yl)acetate (7.0 g, 30.4 mmol) was dissolved in 35 mL of ethanol, and 10 mL of 4M sodium hydroxide aqueous solution (40 mmol) was added. The reaction was carried out at room temperature, and after 2 hours the reaction was completed. 60 mL of 1M hydrochloric acid aqueous solution was added dropwise, and a solid precipitated. The solid was filtered and dried in an oven at 60-70°C to give 5.5 g of white solid, with a yield of 89.5%.

[0152] Step 3: Synthesis of N-(4-chloro-3-methylisothiazo-5-yl)-2-(4-phenyl-1H-pyrazol-1-yl)acetamide:

[0153] 2-(4-phenyl-1H-pyrazol-1-yl)acetic acid (200 mg, 0.99 mmol), 3-methylisothiazolyl-5-amine hydrochloride (149 mg, 0.99 mmol), N,N,N',N'-tetramethylchloromethamine hexafluorophosphate (416 mg, 1.48 mmol), and N-methylmorpholine (300 mg, 2.97 mmol) were added to 5 mL of acetonitrile and reacted at room temperature for 8 hours until the reaction was complete. The reaction mixture was poured into a mixture of 50 mL of water and 100 mL of ethyl acetate, and extracted by separation. The organic layer was collected, washed with saturated sodium chloride water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography (eluent:PE:EA = 2:1) to give 200 mg of yellow oily compound 1, with a yield of 67.8%.

[0154] Compound 1 1 H NMR, : 12.26 (s, 1H), 8.24 (d, 1H), 7.96 (d, 1H), 7.65 – 7.53 (m, 2H), 7.37 (dd, 2H), 7.26 – 7.13 (m, 1H), 6.80 (s, 1H), 5.20 (s, 2H), 2.33 (s, 3H).

[0155] Example 2: Preparation of Compound 95

[0156]

[0157] Step 1: Synthesis of (E)-1-(4-chlorophenyl)-3-(dimethylamino)-2-propen-1-one:

[0158] 4-Chloroacetophenone (5.0 g, 32.3 mmol) and N,N-dimethylformamide dimethyl acetal (19.3 g, 161.7 mmol) were added to 50 mL of DMF and refluxed. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and 100 mL of water and 150 mL of ethyl acetate were added. The mixture was extracted by separation, and the organic layer was washed with saturated sodium chloride water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue did not require purification, and 6.0 g of pale yellow solid was obtained, with a yield of 88.5%.

[0159] Step 2: Synthesis of 3-(4-chlorophenyl)-1H pyrazole:

[0160] (E)-1-(4-chlorophenyl)-3-(dimethylamino)-2-propen-1-one (5.0 g, 23.9 mmol) was added to 30 mL of anhydrous ethanol, followed by the addition of 85% hydrazine hydrate (7.0 g, 119.2 mmol). The mixture was refluxed and reacted. After 8 hours, the reaction solution was cooled to room temperature, and 50 mL of water was added dropwise to precipitate the solid. The mixture was stirred and beaten for 4 hours, and then filtered to obtain 3.5 g of yellow solid, with a yield of 82.2%.

[0161] Step 3: Synthesis of ethyl 2-(3-(4-chlorophenyl)-1H-pyrazole-1-yl)acetate:

[0162] 3-(4-chlorophenyl)-1H-pyrazole (3.0 g, 16.8 mmol), ethyl bromoacetate (5.6 g, 33.6 mmol), and cesium carbonate (10.9 g, 33.6 mmol) were added to 30 mL of DMF and reacted at room temperature for 4 hours. The reaction mixture was poured into a mixture of 50 mL of water and 100 mL of ethyl acetate, and the mixture was extracted separately. The organic layer was collected, washed with saturated sodium chloride water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue did not require purification, yielding 4.0 g of pale yellow oil in 90% yield, which was directly used for the next step.

[0163] Step 4: Synthesis of 2-(3-(4-chlorophenyl)-1H-pyrazol-1-yl)acetic acid:

[0164] Ethyl 2-(3-(4-chlorophenyl)-1H-pyrazol-1-yl)acetate (4.0 g, 15.0 mmol) was dissolved in 20 mL of ethanol, and 5 mL of 4M sodium hydroxide aqueous solution (20 mmol) was added. The reaction was carried out at room temperature, and after 2 hours the reaction was completed. 40 mL of 1M hydrochloric acid aqueous solution was added dropwise, and a solid precipitated. The solid was filtered and dried in an oven at 60-70°C to give 3.0 g of white solid, with a yield of 83.9%.

[0165] Step 5: Synthesis of N-(4-chloro-3-methylisothiazo-5-yl)-2-(3-(4-chlorophenyl)-1H-pyrazol-1-yl)acetamide:

[0166] 2-(3-(4-chlorophenyl)-1H-pyrazol-1-yl)acetic acid (200 mg, 0.85 mmol), 4-chloro-3-methylisothiazolyl-5-amine (125 mg, 0.85 mmol), N,N,N',N'-tetramethylchloroformamidine hexafluorophosphate (356 mg, 1.27 mmol) and N-methylmorpholine (256 mg, 2.54 mmol) were added to 5 mL of acetonitrile and reacted at room temperature for 8 hours until the reaction was complete. 10 mL of water was added dropwise to precipitate the solid, which was filtered and dried in an oven at 60-70°C to give 250 mg of a yellow solid compound 95, with a yield of 80%.

[0167] Compound 95 1 H NMR : 12.04 (s, 1H), 7.90 – 7.78 (m, 3H), 7.46 (dd, 2H), 6.82 (d, 1H), 5.38 (s, 2H), 2.35 (s, 3H).

[0168] Example 3: Preparation of Compound 271

[0169]

[0170] Step 1: Synthesis of 4-isopropoxyacetophenone:

[0171] 4-Hydroxyacetophenone (5.0 g, 36.7 mmol) and potassium carbonate (10.1 g, 73.5 mmol) were added to 40 mL of acetonitrile, followed by the addition of isopropane iodoformide (12.5 g, 73.5 mmol). The mixture was refluxed, and the reaction was monitored by TLC. After the reaction was completed, the reaction solution was cooled to room temperature, and 100 mL of water and 100 mL of ethyl acetate were added. The mixture was extracted by separation, and the organic layer was washed with saturated sodium chloride water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give 6 g of pale yellow solid, with a yield of 91.7%. The solid was directly used for the next step without further purification.

[0172] Step 2: Synthesis of (E)-1-(4-isopropoxyphenyl)-3-(dimethylamino)-2-propen-1-one:

[0173] 4-Isopropoxy-acetophenone (5.0 g, 28.1 mmol) and N,N-dimethylformamide dimethyl acetal (16.7 g, 140.3 mmol) were added to 50 mL of DMF and refluxed. After the reaction was completed by TLC monitoring, the reaction solution was cooled to room temperature, and 100 mL of water and 150 mL of ethyl acetate were added. The mixture was extracted by separation, and the organic layer was washed with saturated sodium chloride water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue did not require purification to give 6.0 g of pale yellow oil, with a yield of 91.6%.

[0174] Step 3: Synthesis of 3-(4-isopropoxyphenyl)-1H pyrazole:

[0175] (E)-1-(4-isopropoxyphenyl)-3-(dimethylamino)-2-propen-1-one (5.0 g, 21.4 mmol) was added to 30 mL of anhydrous ethanol, followed by the addition of 85% hydrazine hydrate (5.0 g, 85.7 mmol). The mixture was refluxed and reacted. After 8 hours, the reaction solution was cooled to room temperature, and 50 mL of water was added dropwise to precipitate the solid. The mixture was stirred and beaten for 4 hours, and then filtered to obtain 4 g of yellow solid, with a yield of 92.3%.

[0176] Step 4: Synthesis of ethyl 2-(3-(4-isopropoxyphenyl)-1H-pyrazol-1-yl)ethyl acetate:

[0177] 3-(4-isopropoxyphenyl)-1H-pyrazole (3.0 g, 14.8 mmol), ethyl bromoacetate (5.0 g, 29.7 mmol), and cesium carbonate (9.7 g, 29.7 mmol) were added to 30 mL of DMF and reacted at room temperature for 4 hours. The reaction mixture was poured into a mixture of 50 mL of water and 100 mL of ethyl acetate, and extracted by separation. The organic layer was collected, washed with saturated sodium chloride water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography (eluent:PE:EA = 5:1) to give 3.5 g of a pale yellow oily compound, with a yield of 81.8%.

[0178] Step 5: Synthesis of 2-(3-(4-isopropoxyphenyl)-1H-pyrazol-1-yl)acetic acid:

[0179] Ethyl 2-(3-(4-isopropoxyphenyl)-1H-pyrazol-1-yl)acetate (2.5 g, 8.7 mmol) was dissolved in 15 mL of ethanol, and 4 M sodium hydroxide aqueous solution (4 mL, 16 mmol) was added. The reaction was carried out at room temperature, and after 2 hours the reaction was completed. 30 mL of 1 M hydrochloric acid aqueous solution was added dropwise, and a solid precipitated. The solid was filtered and dried in an oven at 60-70°C to give 1.8 g of white solid, with a yield of 79.7%.

[0180] Step 6: Synthesis of N-(4-chloro-3-methylisothiazo-5-yl)-2-(3-(4-isopropoxyphenyl)-1H-pyrazole-1-yl)acetamide:

[0181] 2-(3-(4-isopropoxyphenyl)-1H-pyrazol-1-yl)acetic acid (200 mg, 0.77 mmol), 4-chloro-3-methylisothiazolyl-5-amine (114 mg, 0.77 mmol), N,N,N',N'-tetramethylchloromethamine hexafluorophosphate (323 mg, 1.15 mmol), and N-methylmorpholine (233 mg, 2.31 mmol) were added to 5 mL of acetonitrile and reacted at room temperature for 8 hours until the reaction was complete. The reaction mixture was poured into a mixture of 20 mL of water and 40 mL of ethyl acetate, and extracted by separation. The organic layer was collected, washed with saturated sodium chloride water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography (eluent:PE:EA = 4:1) to give 180 mg of pale yellow solid compound 271, yield 59.9%.

[0182] Compound 271 1 H NMR : 11.98 (s, 1H), 7.81 (d, 1H), 7.69 (d, 2H), 6.93 (d, 2H), 6.67 (d, 1H), 5.34 (s, 2H), 4.63 (m, 1H), 2.35 (s, 3H), 1.27 (d, 6H).

[0183] Example 4: Preparation of compound 391

[0184]

[0185] Step 1: Synthesis of 3-(4-isopropylthiophenyl)-1H pyrazole:

[0186] 3-Iodopyrazole (3.0 g, 15.5 mmol), 4-isopropylthiophenylboronic acid (3.6 g, 18.6 mmol), and potassium phosphate (6.6 g, 40.0 mmol) were added to a mixture of 15 mL of 1,4-dioxane and 3 mL of water. The catalyst dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium(II) (300 mg, 0.04 mmol) was added. The reaction was carried out under nitrogen protection and refluxed. After 8 hours, the reaction mixture was cooled to room temperature and poured into a mixture of 50 mL of water and 100 mL of ethyl acetate. The mixture was extracted separately, and the organic layer was washed with saturated sodium chloride water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography (eluent:PE:EA = 5:1) to give 2.5 g of a pale yellow oily compound, with a yield of 74.0%.

[0187] Step 2: Synthesis of ethyl 2-(3-(4-isopropylthiophenyl)-1H-pyrazol-1-yl)ethyl acetate:

[0188] 3-(4-isopropylthiophenyl)-1H-pyrazole (2.0 g, 9.2 mmol), ethyl bromoacetate (3.1 g, 18.4 mmol), and cesium carbonate (6.0 g, 18.4 mmol) were added to 20 mL of DMF and reacted at room temperature for 4 hours. The reaction mixture was poured into a mixture of 50 mL of water and 100 mL of ethyl acetate, and extracted separately. The organic layer was collected, washed with saturated sodium chloride water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography (eluent:PE:EA = 5:1) to give 2.1 g of a pale yellow oily compound, with a yield of 75.3%.

[0189] Step 3: Synthesis of 2-(3-(4-isopropylthiophenyl)-1H-pyrazol-1-yl)acetic acid:

[0190] Ethyl 2-(3-(4-isopropylthiophenyl)-1H-pyrazol-1-yl)acetate (2.0 g, 6.6 mmol) was dissolved in 15 mL of ethanol, and 3 mL of 4M sodium hydroxide aqueous solution (12 mmol) was added. The reaction was carried out at room temperature, and after 2 hours the reaction was completed. 30 mL of 1M hydrochloric acid aqueous solution was added dropwise, and a solid precipitated. The solid was filtered and dried in an oven at 60-70°C to give 1.4 g of white solid, with a yield of 77.1%.

[0191] Step 4: Synthesis of N-(4-bromo-3-methylisothiazo-5-yl)-2-(3-(4-isopropylthiophenyl)-1H-pyrazol-1-yl)acetamide:

[0192] 2-(3-(4-isopropylthiophenyl)-1H-pyrazol-1-yl)acetic acid (200 mg, 0.72 mmol), 4-bromo-3-methylisothiazolyl-5-amine (140 mg, 0.72 mmol), N,N,N',N'-tetramethylchloromethamine hexafluorophosphate (305 mg, 1.09 mmol), and N-methylmorpholine (220 mg, 2.17 mmol) were added to 5 mL of acetonitrile and reacted at room temperature for 8 hours until the reaction was complete. The reaction mixture was poured into a mixture of 20 mL of water and 40 mL of ethyl acetate, and extracted by separation. The organic layer was collected, washed with saturated sodium chloride water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography (eluent:PE:EA = 4:1) to give 220 mg of pale yellow solid compound 391, with a yield of 67.3%.

[0193] Compound 391 1 H NMR : 11.78 (s, 1H), 7.86 (d, 1H), 7.75 (m, 2H), 7.41 – 7.36 (m, 2H), 6.78 (d, 1H), 5.39 (s, 2H), 3.50 (m, 1H), 2.38 (s, 3H), 1.25 (d, 6H).

[0194] Example 5: Preparation of compound 163

[0195]

[0196] Step 1: Synthesis of methyl (R)2-(3-(4-bromophenyl)-1H-pyrazole-1-yl)propionate:

[0197] 3-(4-bromophenyl)-1H-pyrazole (2.0 g, 8.97 mmol), methyl (S)-2-chloropropionate (1.3 g, 10.8 mmol), and cesium carbonate (5.8 g, 17.9 mmol) were added to 15 mL of DMF and reacted at room temperature for 4 hours. The reaction mixture was poured into a mixture of 50 mL of water and 100 mL of ethyl acetate, and extracted separately. The organic layer was collected, washed with saturated sodium chloride water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography (eluent:PE:EA = 5:1) to give 1.8 g of a pale yellow oily compound, with a yield of 64.9%.

[0198] Step 2: Synthesis of (R)2-(3-(4-bromophenyl)-1H-pyrazol-1-yl)propionic acid:

[0199] Methyl (R)2-(3-(4-bromophenyl)-1H-pyrazol-1-yl)propionate (1.8 g, 5.8 mmol) was dissolved in 15 mL of ethanol, and 4 M sodium hydroxide aqueous solution (4 mL, 16 mmol) was added. The reaction was carried out at room temperature, and the reaction was completed after 2 hours. 30 mL of 1 M hydrochloric acid aqueous solution was added dropwise, and a solid precipitated. The solid was filtered and dried in an oven at 60-70°C to give 1.5 g of white solid, with a yield of 87.3%.

[0200] Step 4: Synthesis of (R)-2-(3-(4-bromophenyl)-1H-pyrazol-1-yl)-N-(4-chloro-3-methylisothiazolyl-5-yl)propionamide:

[0201] (R)2-(3-(4-bromophenyl)-1H-pyrazol-1-yl)propionic acid (200 mg, 0.68 mmol), 4-chloro-3-methylisothiazolyl-5-amine (101 mg, 0.68 mmol), N,N,N',N'-tetramethylchloromethamine hexafluorophosphate (285 mg, 1.02 mmol), and N-methylmorpholine (206 mg, 2.03 mmol) were added to 5 mL of acetonitrile and reacted at room temperature for 8 hours until the reaction was complete. The reaction mixture was poured into a mixture of 20 mL of water and 40 mL of ethyl acetate, and extracted by separation. The organic layer was collected, washed with saturated sodium chloride water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography (eluent:PE:EA = 4:1) to give 138 mg of yellow solid compound 163, yield 47.8%.

[0202] Compound 163 1 H NMR : 11.98 (s, 1H), 8.01 (d, 1H), 7.79 – 7.71 (m, 2H), 7.66 – 7.54 (m, 2H), 6.84 (d, 1H), 5.68 (q, 1H), 2.34 (s, 3H), 1.78 (d, 3H).

[0203] Example 6: Preparation of compound 359

[0204]

[0205] Synthesis of N-(4-bromo-3-methylisothiazo-5-yl)-2-(3-(4-methylthiophenyl)-1H-pyrazol-1-yl)acetamide

[0206] 2-(3-(4-methylthiophenyl)-1H-pyrazol-1-yl)acetic acid (200 mg, 0.81 mmol), 4-bromo-3-methylisothiazolyl-5-amine (156 mg, 0.81 mmol), N,N,N',N'-tetramethylchloromethamine hexafluorophosphate (399 mg, 1.21 mmol), and N-methylmorpholine (244 mg, 2.42 mmol) were added to 5 mL of acetonitrile and reacted at room temperature for 8 hours until the reaction was complete. The reaction mixture was poured into a mixture of 20 mL of water and 40 mL of ethyl acetate, and extracted by separation. The organic layer was collected, washed with saturated sodium chloride water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography (eluent:PE:EA = 4:1) to give 180 mg of pale yellow solid compound 359, yield 52.8%.

[0207] Compound 359 1 H NMR : 11.79 (s, 1H), 7.85 (d, 1H), 7.78 – 7.69 (m, 2H), 7.35 – 7.25 (m, 2H), 6.76 (d, 1H), 5.38 (s, 2H), 2.49 (s, 3H), 2.38 (s, 3H).

[0208] Example 7: Preparation of Compound 454

[0209]

[0210] Synthesis of N-(4-bromo-3-methylisothiazolyl-5-yl)-2-(3-(4-((N,N-dimethylsulfonyl)oxy)phenyl)-1H-pyrazole-1-yl)acetamide:

[0211] 2-(3-(4-((N,N-dimethylsulfanyl)oxy)phenyl)-1H-pyrazol-1-yl)acetic acid (200 mg, 0.61 mmol), 4-bromo-3-methylisothiazolyl-5-amine (119 mg, 0.61 mmol), N,N,N',N'-tetramethylchloroformamidine hexafluorophosphate (259 mg, 0.92 mmol), and N-methylmorpholine (187 mg, 1.84 mmol) were added to 10 mL of acetonitrile and reacted at room temperature for 8 hours until complete. The reaction mixture was poured into a mixture of 20 mL of water and 40 mL of ethyl acetate, and extracted by separation. The organic layer was collected, washed with saturated sodium chloride water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography (eluent:PE:EA = 4:1) to give 190 mg of yellow solid compound 454, yield 61.8%.

[0212] Compound 454 1 H NMR : 11.80 (s, 1H), 7.90 – 7.85 (m, 3H), 7.39 – 7.33 (m, 2H), 6.82 (d, 1H), 5.40 (s, 2H), 2.91 (s, 6H), 2.38 (s, 3H).

[0213] Example 8: Preparation of Compound 584

[0214]

[0215] Synthesis of compound N-(4-bromo-3-methylisothiazo-5-yl)-2-(1'-methyl-1H,1'H-[3,3'-bipyrazole]-1-yl)acetamide:

[0216] 2-(1'-methyl-1H,1'H-[3,3'-bipyrazole]-1-yl)acetic acid (200 mg, 0.97 mmol), 4-bromo-3-methylisothiazolyl-5-amine (187 mg, 0.97 mmol), N,N,N',N'-tetramethylchloromethamine hexafluorophosphate (408 mg, 1.45 mmol), and N-methylmorpholine (294 mg, 2.91 mmol) were added to 10 mL of acetonitrile and reacted at room temperature for 8 hours until the reaction was complete. The reaction mixture was poured into a mixture of 20 mL of water and 40 mL of ethyl acetate, and extracted by separation. The organic layer was collected, washed with saturated sodium chloride water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography (eluent:PE:EA = 4:1) to give 167 mg of pale yellow solid compound 584, with a yield of 45.2%.

[0217] Compound 584 1 H NMR : 11.76 (s, 1H), 7.99 (s, 1H), 7.78 (d, 1H), 7.70 (s, 1H), 6.47 (d, 1H), 5.33 (s, 2H), 3.86 (s, 3H), 2.39 (s, 3H).

[0218] Example 9: Preparation of Compound 288

[0219]

[0220] Synthesis of N-(4-chloro-3-methylisothiazo-5-yl)-2-(3-(4-isopropoxyphenyl)-1H-pyrazol-1-yl)ethylthioamide:

[0221] N-(4-chloro-3-methylisothiazolin-5-yl)-2-(3-(4-isopropoxyphenyl)-1H-pyrazol-1-yl)amide (300 mg, 0.77 mmol) and Lawson's reagent (620 mg, 1.53 mmol) were added to 150 mL of toluene and refluxed for 8 hours until the reaction was complete. The reaction mixture was poured into a mixture of 20 mL of water and 40 mL of ethyl acetate, and extracted separately. The organic layer was collected, washed with saturated sodium chloride water, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography (eluent:PE:EA = 4:1) to give 200 mg of yellow solid compound 288, yield 64.0%.

[0222] Compound 288 1 H NMR : 12.87 (s, 1H), 7.86 (d, 1H), 7.75 – 7.67 (m, 2H), 6.98 – 6.90 (m, 2H), 6.69 (d, 1H), 5.61 (s, 2H), 4.63 (m, 1H), 2.40 (s, 3H), 1.27 (d, 6H).

[0223] Example 10: Preparation of compound 383

[0224]

[0225] Step 1: Synthesis of 3-(4-((trifluoromethyl)thio)phenyl)-1H-pyrazole:

[0226] 1-Bromo-4-(trifluoromethylthio)benzene (5 g, 19.5 mmol) was dissolved in a mixture of 1,4-dioxane (25 mL) and water (10 mL), along with 1-H-pyrazole-3-boronate pinacol ester (4.5 g, 23.2 mmol), potassium phosphate (8.3 g, 38.9 mmol), and dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine(II) (1.3 g, 1.9 mmol). The reaction mixture was purged three times with nitrogen. The reaction mixture was heated to 100 °C and reacted for 5 hours. After the reaction was complete, the solution was diluted with 25 mL of water and extracted with ethyl acetate. The combined organic layers were washed with brine. The organic layers were dried and concentrated. The concentrate was purified by silica gel column chromatography, eluting with petroleum ether:ethyl acetate at ratios of 50:1 to 10:1, to give 4 g of a pale yellow solid product, yield: 84%.

[0227] Step 2: Synthesis of ethyl-2-(3-(4-((trifluoromethyl)thio)phenyl)-1H-pyrazol-1-yl)acetate:

[0228] 3-(4-((trifluoromethyl)thio)phenyl)-1H-pyrazole (3 g, 12.3 mmol) and cesium carbonate (8.0 g, 24.6 mmol) were added to 30 mL of DMF. Ethyl bromoacetate (4.1 g, 24.6 mmol) was added dropwise to the solvent under ice bath conditions. The reaction was carried out at room temperature for 10 minutes. The reaction mixture was poured into a mixture of 37 mL of 1 M hydrochloric acid aqueous solution and 40 mL of ethyl acetate. The mixture was extracted separately, and the organic layer was washed with saturated sodium chloride water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give 3 g of pale yellow solid. The crude product was used directly in the next step.

[0229] Step 3: Synthesis of 2-(3-(4-((trifluoromethyl)thio)phenyl)-1H-pyrazol-1-yl)acetic acid:

[0230] Crude ethyl-2-(3-(4-((trifluoromethyl)thio)phenyl)-1H-pyrazol-1-yl)acetate (3 g) was dissolved in 30 mL of ethanol, and 6 mL of 4M sodium hydroxide aqueous solution (24 mmol) was added. The reaction was carried out at room temperature, and after 4 hours the reaction was completed. 30 mL of 1M hydrochloric acid aqueous solution was added dropwise, and a solid precipitated. The solid was filtered and dried in an oven at 60-70°C to give 2 g of off-white solid. The two-step yield was 54%.

[0231] Step 4: Synthesis of N-(4-chloro-3-methylisothiazo-5-yl)-2-(3-(4-((trifluoromethyl)thio)phenyl)-1H-pyrazole-1-yl)acetamide:

[0232] 2-(3-(4-((trifluoromethyl)thio)phenyl)-1H-pyrazol-1-yl)acetic acid (300 mg, 1.0 mmol), 4-chloro-3-methylisothiazolyl-5-amine (145 mg, 1.0 mmol), N,N,N',N'-tetramethylchloroformamidine hexafluorophosphate (420 mg, 1.5 mmol), and N-methylmorpholine (300 mg, 3 mmol) were added to 15 mL of acetonitrile and reacted at room temperature for 4 hours until the reaction was complete. 15 mL of water was added to the reaction solution to precipitate the solid. The solid was filtered and dried in an oven at 60-70°C to give 350 mg of a white solid compound 383, with a yield of 92%.

[0233] Compound 383 1 H NMR 8.02-7.79 (m, 3H), 7.77-7.68 (m, 2H), 6.90 (d, 1H), 5.41 (s, 2H), 2.34 (s, 3H).

[0234] Example 11: Preparation of Compound 655

[0235]

[0236] Step 1: Synthesis of 3-(4-(methylthio)phenyl)-5-(trifluoromethyl)-1H-pyrazole:

[0237] 4-(methylthio)benzaldehyde (2 g, 13.1 mmol), 2-bromo-3,3,3-trifluoropropene (4.6 g, 26.2 mmol), 4-methylbenzenesulfonylhydrazine (2.9 g, 15.8 mmol), and DBU (6.0 g, 39.3 mmol) were dissolved in toluene (25 mL). The reaction mixture was heated to 65 °C and reacted for 6 hours. After the reaction was complete, 50 mL of aqueous phase was added, and the aqueous phase was extracted with 50 mL of ethyl acetate. The combined organic layers were washed with brine. The organic layers were dried and concentrated. The concentrate was purified by silica gel column chromatography, eluting with petroleum ether:ethyl acetate = 50:1 to 10:1, to give 2.3 g of white solid product, yield: 64%.

[0238] Step 2: Synthesis of ethyl 2-(3-(4-(methylthio)phenyl)-5-(trifluoromethyl)-1H-pyrazole-1-yl)acetate:

[0239] 3-(4-(methylthio)phenyl)-5-(trifluoromethyl)-1H-pyrazole (1 g, 3.9 mmol) and cesium carbonate (2.5 g, 7.8 mmol) were added to 10 mL of DMF. Ethyl bromoacetate (1.3 g, 7.8 mmol) was added dropwise to the solvent under ice bath conditions. The reaction mixture was reacted at room temperature for 10 min. The reaction mixture was poured into a mixture of 20 mL of 1 M hydrochloric acid aqueous solution and 40 mL of ethyl acetate. The mixture was extracted separately, and the organic layer was washed with saturated sodium chloride water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography and eluted with petroleum ether:ethyl acetate at ratios of 60:1 to 10:1 to give 0.5 g of white solid, yield: 38%.

[0240] Step 3: Synthesis of 2-(3-(4-(methylthio)phenyl)-5-(trifluoromethyl)-1H-pyrazol-1-yl)acetic acid:

[0241] Ethyl 2-(3-(4-(methylthio)phenyl)-5-(trifluoromethyl)-1H-pyrazol-1-yl)acetate (0.5 g, 1.5 mmol) was dissolved in 5 mL of ethanol, and 1 mL of 4M sodium hydroxide aqueous solution (4 mmol) was added. The reaction was carried out at room temperature for 4 hours. After the reaction was completed, 5 mL of 1M hydrochloric acid aqueous solution was added dropwise, and a solid precipitated. The solid was filtered and dried in an oven at 60-70°C to give 300 mg of white solid, with a yield of 65%.

[0242] Step 4: Synthesis of N-(4-bromo-3-methylisothiazo-5-yl)-2-(3-(4-(methylthio)phenyl)-5-(trifluoromethyl)-1H-pyrazole-1-yl)acetamide:

[0243] 2-(3-(4-(methylthio)phenyl)-5-(trifluoromethyl)-1H-pyrazol-1-yl)acetic acid (200 mg, 0.6 mmol), 4-bromo-3-methylisothiazolyl-5-amine (122 mg, 0.6 mmol), N,N,N',N'-tetramethylchloromethamine hexafluorophosphate (250 mg, 0.9 mmol), and N-methylmorpholine (190 mg, 1.8 mmol) were added to 10 mL of acetonitrile and reacted at room temperature for 4 hours until the reaction was complete. 10 mL of water was added to the reaction solution to precipitate the solid. The solid was filtered and dried in an oven at 60-70°C to obtain 150 mg of a yellow solid, with a yield of 48%.

[0244] Compound 655 1 H NMR : 11.88 (s, 1H), 7.90 – 7.76 (m, 2H), 7.53 (s, 1H), 7.38 – 7.28 (m, 2H), 5.58 (s, 2H), 2.51 (s, 3H), 2.38 (s, 3H).

[0245] In addition to the compounds described above, the compounds in Table 1 can be prepared by similar methods as described in Synthesis Examples 1-11. Table 2 below provides NMR data for some of the compounds synthesized according to Synthesis Examples 1-11 (the solvent marked with * in the upper right corner of the compound number is CDCl3).

[0246] Table 2

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264] Other compounds of general formula I in this application can be synthesized by referring to the above method.

[0265] Formulation Example 1

[0266] In this embodiment, a bactericide formulation was prepared from the obtained pyrazole compound, and a 30% concentration suspension of compound 94 was prepared according to the mass ratio shown in Table 3.

[0267]

[0268] The preparation method is as follows: Compound 94 and other components are thoroughly mixed to obtain a 30% suspension. The suspension is then diluted with water to obtain a diluted solution of the desired concentration.

[0269] Bioactivity testing examples

[0270] The compounds obtained above were tested against various pathogens. Unless otherwise specified in the embodiments and in this application: the sample preparation method is to weigh 10 mg of the original drug of the sample to be tested, dissolve it in 1 mL of DMF to prepare a 10000 ppm stock solution, and dilute the stock solution with 0.05% Tween-80 water to the required concentration for activity testing.

[0271] Test Example 1: Fungicidal Activity of Compounds Against Soybean Rust

[0272] In this embodiment, the efficacy of the prepared pyrazole compounds in controlling soybean rust (Phakopsora pachyrhizi) was determined using the following method:

[0273] The screening method employed a live pot assay, where the sample of the compound to be tested was dissolved in a small amount of solvent (the solvent type, such as acetone, methanol, DMF, etc., selected based on its solubility in the sample, with a solvent-to-spray volume ratio equal to or less than 0.05), diluted with water containing 0.1% Tween 80, to prepare a test solution of the desired concentration. Two-leaf stage soybeans were cultivated in a greenhouse as the experimental host plant for soybean rust (Phakopsora pachyrhizi). The compound of this application was applied as a foliar spray at the designed concentration. A blank control was sprayed with water, with three replicates. Inoculation with pathogens was performed 24 hours after treatment. After inoculation, the plants were placed in an artificial climate chamber for humidified cultivation (temperature: 25°C daytime, 20°C nighttime, relative humidity: 95-99%). After 24 hours of cultivation, the experimental materials were transferred to the greenhouse. The disease control efficacy of the compound was evaluated after the control group had fully developed disease (usually one week). The results of the survey were based on "A Manual of Assessment Keys for Plant Diseases" compiled by the American Society for Plant Diseases, using a scale of 100 to 0, with "100" representing no disease and "0" representing the most severe disease severity.

[0274] Compounds 115, 231, 232, 261, 262, 266, 267, 288, 397, 446, 450, 456, 474, 475, and 592 showed a control efficacy of >90% against soybean rust at a concentration of 400 ppm.

[0275] Test Example 2: Fungicidal Activity of Compounds Against Cucumber Powdery Mildew

[0276] In this embodiment, the efficacy of the prepared pyrazole compounds in controlling cucumber powdery mildew (Erysiphe cichoracearum) was determined using the following method:

[0277] The screening method employed a live pot assay, where the sample of the compound to be tested was dissolved in a small amount of solvent (the solvent type, such as acetone, methanol, DMF, etc., selected based on its solubility in the sample, with the volume ratio of solvent to spray volume equal to or less than 0.05), and then diluted with water containing 0.1% Tween 80 to prepare the test solution at the required concentration. Two-leaf stage cucumber seedlings cultivated in a greenhouse were used as the experimental host plants for cucumber powdery mildew (Erysiphe cichoracearum). The compound of this application was applied as a foliar spray at the designed concentration. A blank control was also applied by spraying with water. The treatment was repeated three times, and the pathogen was inoculated 24 hours after treatment. After inoculation, the plants were placed in an artificial climate chamber for humidified cultivation (temperature: 25°C during the day, 20°C at night, relative humidity: 95-99%). After 24 hours of cultivation, the experimental materials were transferred to the greenhouse. The disease control effect of the compound was evaluated after the control group had fully developed disease (usually one week). The survey results were represented by a scale of 100 to 0, with "100" representing no disease and "0" representing the most severe level of disease.

[0278] Compounds 65, 116, 117, 138, 157, 160, 161, 163, 164, 201, 202, 210, 211, 222, 223, 251, 252, 253, 259, 261, 262, 264, 266, 267, 268, 269, 271, 272, 273, 288, 301, 302, 303, 306, 307, 308, 318, 319, 320, 322, 323 The following drugs, at a concentration of 25 ppm, showed a control efficacy of >80% against cucumber powdery mildew.

[0279] Test Example 3: Fungicidal activity of compound against cucumber downy mildew

[0280] In this embodiment, the efficacy of the prepared pyrazole compounds against cucumber downy mildew (Pseudoperonospora cubensis) was determined using the following method:

[0281] The screening method employed a live pot assay, whereby the sample of the compound to be tested was dissolved in a small amount of solvent (the type of solvent, such as acetone, methanol, DMF, etc., selected based on its solubility in the sample, with the volume ratio of solvent to spray volume equal to or less than 0.05), and then diluted with water containing 0.1% Tween 80 to prepare the test solution at the required concentration. Two-leaf stage cucumber seedlings cultivated in a greenhouse were used as the experimental host plants for cucumber downy mildew (Pseudoperonospora cubensis). The compound of this application was applied as a foliar spray at the designed concentration. A blank control was also applied by spraying with water, with three replicates. Inoculation with pathogens was performed 24 hours after treatment. After inoculation, the plants were placed in an artificial climate chamber for humidified cultivation (temperature: 25°C during the day, 20°C at night, relative humidity: 95-99%). After 24 hours of cultivation, the experimental materials were transferred to the greenhouse. The disease control effect of the compound was evaluated after the control group had fully developed disease (usually one week). The results were based on "A Manual of Assessment Keys for Plant Diseases" compiled by the American Plant Pathology Society, using a scale of 100 to 0, with "100" representing no disease and "0" representing the most severe disease severity.

[0282] Compounds 82, 83, 94, 95, 97, 117, 132, 133, 137, 138, 139, 159, 160, 161, 163, 164, 165, 167, 168, 169, 184, 185, 210, 211, 252, 253, 254, 358, 359, 360, 379, 380, 381, 383, 384, 387, 390, 391, 392, 398, 402, 403, 405, 406, 407, 4 The following drugs, at a concentration of 25 ppm, showed a control efficacy of >80% against cucumber downy mildew.

[0283] Test Example 4: Fungicide activity of compound against rice blast disease

[0284] In this embodiment, the efficacy of the prepared pyrazole compounds against rice blast (Pyricularia oryzae) was determined using the following method:

[0285] The screening method employed a live pot assay, where the sample of the compound to be tested was dissolved in a small amount of solvent (the solvent could be acetone, methanol, DMF, etc., selected based on its solubility in the sample, with the volume ratio of solvent to spray volume equal to or less than 0.05), diluted with water containing 0.1% Tween 80, and prepared into a test solution of the desired concentration. Four-leaf-one-heart stage rice seedlings cultivated in a greenhouse were used as the experimental host plants for rice blast (Pyricularia oryzae). The compound of this application was applied as a foliar spray at the designed concentration. A blank control was also applied by spraying with water. The treatment was repeated three times, and the pathogen was inoculated 24 hours after treatment. After inoculation, the seedlings were transferred to a humidified chamber (relative humidity above 95%, maintaining dew on the leaves, temperature 25°C–26°C) and cultured in the dark for 24 hours. Then, they were cultured under light (light intensity approximately 2000 lx) in a humidified chamber at 25°C–26°C and 85%–90% relative humidity. After the control group has fully developed disease (usually within one week), the efficacy of the compound for disease control is evaluated. Results are based on the "A Manual of Assessment Keys for Plant Diseases" published by the American Plant Pathology Society, using a scale of 100 to 0, with "100" representing no disease and "0" representing the most severe disease severity.

[0286] Compounds 261, 262, 266, 268, 271, 272, 273, 395, 396, 460, and 610 showed a control effect of >80% against rice blast at a concentration of 400 ppm.

[0287] This application illustrates the pyrazole compounds, their preparation methods, and applications through the above embodiments. However, this application is not limited to the above embodiments, meaning that this application does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this application, equivalent substitutions of raw materials for the products, additions of auxiliary components, and selection of specific methods all fall within the protection and disclosure scope of this application.

Claims

1. A pyrazole compound having the structure shown in Formula I: ； in, Q 1 and Q 2 Each is independently selected from hydrogen, halogen, cyano, C1-C 12 Alkyl, C1-C 12 The alkyl or 5- to 7-membered aryl ring group is a ring system selected from carbon atoms and 0 to 3 heteroatoms, wherein the heteroatoms are independently selected from a maximum of 1 S atom, a maximum of 1 O atom, or a maximum of 3 N atoms, and each ring system may optionally be divided by a maximum of 5 identical or different R atoms. 6 Replace, Q 1 and Q 2 At least one of them is an aryl group; R 1 R 2 and R 3 Each is independently selected from hydrogen, halogen, cyano, C1-C 12 Alkyl, C1-C 12 Haloalkyl, C1-C 12 Alkoxy, C1-C 12 Halogenated alkoxy groups, C3-C 12 cycloalkyl or at least one R 6 Substituted aryl group; R 2 and R 3 They can form ternary to hexa-membered saturated cyclic groups together with the carbon atoms in the I-frame they are connected to. R 4 Selected from hydrogen, halogen, cyano, nitro, C1-C 12 Alkyl, C1-C 12 Alkoxy, C1-C 12 Haloalkyl, C1-C 12 Halogenated alkoxy groups, C1-C 12 Alkoxycarbonyl or C1-C 12 Alkylaminocarbonyl, and the above alkyl, haloalkyl, haloalkoxy, alkoxycarbonyl, and alkylaminocarbonyl groups can be further reacted with R 6 replace; R 5 Selected from halogens, C1-C 12 Alkyl, C3-C 12 Cycloalkyl, C3-C8 cycloalkyl, C1-C 12 Alkyl, C1-C 12 Alkoxy, C1-C 12 Alkoxy C1-C 12 Alkyl, C1-C 12 Haloalkyl, C1-C 12 Halogenated alkoxy groups, C1-C 12 Alkylamine, N,N-di(C1-C) 12 Alkyl)amino, C1-C 12 Alkylthio, C1-C 12 Haloalkylthio groups, C1-C 12 alkyl sulfinyl, C1-C 12 Halogenated alkyl sulfinyl group, C1-C 12 Alkyl sulfonyl, C1-C 12 Haloalkylsulfonyl, aryl C1-C 12 Alkyl or aryl, and the above alkyl, cycloalkyl, cycloalkylalkyl, alkoxy, alkoxyalkyl, haloalkyl, haloalkoxy, alkylamino, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, arylalkyl or aryl can be further R 6 replace; R 6 Selected from hydrogen, halogen, cyano, amino, hydroxyl, nitro, mercapto, C1-C 12 Alkyl, C1-C 12 Alkoxy, C1-C 12 Alkylthio, C1-C 12 Alkylamino, C1-C 12 Haloalkyl, C1-C 12 Halogenated alkoxy groups, C1-C 12 Halogenated alkylamino, N,N-di(C1-C) 12 Alkyl)amino, C3-C 12 cycloalkyl, C3-C 12 Cycloalkyloxy, C3-C 12 cycloalkylthio, C3-C 12 Cycloalkylamino, C2-C 12 alkenyloxy group, C2-C 12 alkynyloxy group, tri(C1-C) 12 Alkyl)silyl, C1-C 12 alkyl sulfinyl, C1-C 12 Alkyl sulfonyl, C3-C8 cycloalkyl C1-C 12 Alkoxy, C1-C 12 Alkyl carbonyl, C1-C 12 Alkyl carbonyloxy group, C1-C 12 Alkyl carbonyl amino, C1-C 12 Halogenated alkyl carbonyl amino, C1-C 12 Alkylsulfonylamino, C1-C 12 Haloalkylsulfonylamino, N,N-di(C1-C 12 alkyl)aminosulfonate group, N,N-di(C1-C 12 Alkyl)aminosulfonyl, heterocyclic oxy, heterocyclic acylamino, piperidinyl, morpholinyl, tetrahydropyrrolyl, pyrazolyl, pyrroleyl, oxadiazolyl, phenyl or benzyl, and the above groups may also be replaced by one or more halogens, cyano, nitro, C1-C 12 Alkyl, C2-C 12 alkenyl, C2-C 12 alkynyl group, C1-C 12 Alkoxy, C1-C 12 Alkylamino or C1-C 12 Further substitution by any combination of alkylthio groups; T is selected from oxygen or sulfur atoms; n represents an integer from 1 to 5.

2. The pyrazole compound according to claim 1, wherein: Q 1 Selected from Ar1 to Ar 33 : ； Q 2 Selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, C1-C 12 Alkyl or C1-C 12 Halogenated alkyl groups; m represents an integer between 0 and 5; "#" indicates the position connected to formula I pyrazole; Preferably, Q 1 Selected from Ar1, Ar2, Ar3, Ar4, Ar5, Ar6, Ar 14 Ar 15 Ar 23 Ar 24 Or Ar 33 Q 2 It is selected from hydrogen, fluorine, chlorine, bromine or iodine.

3. The pyrazole compound according to claim 1 or 2, wherein: Q 1 Selected from hydrogen, fluorine, chlorine, bromine, iodine or C1-C 12 alkyl; Q 2 Selected from Ar1 to Ar 33 , Ar1 to Ar 33 The definitions are the same as those in claim 2; Preferably, Q 1 Selected from hydrogen; Q 2 Selected from Ar1.

4. The pyrazole compound according to any one of claims 1-3, wherein: R 1 Selected from hydrogen or C1-C 12 alkyl; R 2 and R 3 Each is independently selected from hydrogen, fluorine, C1-C6 alkyl, or C3-C6 cycloalkyl, R 2 and R 3 They can form ternary to hexa-membered saturated cyclic groups together with the carbon atoms in the I-frame they are connected to. R 4 Selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, or C1-C3 alkyl; R 5 Selected from C1-C3 alkyl groups; R 6 Selected from hydrogen, halogen, cyano, amino, hydroxyl, nitro, mercapto, C1-C6 alkyl, C1-C8 alkoxy, C1-C8 alkylthio, C1-C8 alkylamino, C1-C8 haloalkyl, C1-C6 haloalkoxy, C1-C6 haloalkylamino, N,N-di(C1-C6 alkyl)amino, C3-C6 cycloalkyl, C3-C6 cycloalkyloxy, C3-C6 cycloalkylthio, C3-C6 cycloalkylamino, C2-C6 alkenyloxy, C2-C6 alkynyloxy, tris(C1-C6 alkyl)silyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C3-C6 cycloalkylC1-C3 alkoxy, C1- C6 alkyl carbonyl, C1-C6 alkyl carbonyloxy, C1-C6 alkyl carbonyl amino, C1-C6 haloalkyl carbonyl amino, C1-C6 alkyl sulfonyl amino, C1-C6 haloalkyl sulfonyl amino, N,N-di(C1-C6 alkyl)aminosulfonate, N,N-di(C1-C6 alkyl)aminosulfonyl, heterocyclic acyl amino, oxetane-3-oxy, morpholino, or phenyl, and the above groups may be further substituted by any combination of one or more fluorine, chlorine, bromine, iodine, cyano, nitro, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkoxy, C1-C6 alkylamino, or C1-C6 alkylthio. m represents an integer between 0 and 5; n represents an integer from 1 to 5; Preferably, R 1 Selected from hydrogen or methyl; R 2 and R 3 Each is independently selected from hydrogen, fluorine, methyl, ethyl, propyl, butyl, or R. 2 and R 3 Together with the carbon atoms in their linked I-framework, they form cyclopropane; R 4 Selected from hydrogen, fluorine, chlorine, bromine, iodine, or cyano; R 5 Selected from methyl; R 6 Selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, amino, hydroxyl, nitro, mercapto, methyl, ethyl, isopropyl, tert-butyl, isobutyl, n-pentyl, 2-pentyl, 3-pentyl, neopentyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, 3-methyl-2-butoxy, neopentoxy, n-hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl-3-pentoxy, 3,3-dimethyl-2-butoxy, n-heptoxy, 2-heptoxy, 3-heptoxy, 4-heptoxy, n-octoxy, cyanomethyl Oxygen group, allyloxy group, 3,3-dichloroallyloxy group, propyryloxy group, trimethylsilyl group, methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, tert-butylthio group, n-pentylthio group, 2-pentylthio group, 3-pentylthio group, 3-methyl-2-butylthio group, neopentylthio group, n-hexylthio group, 2-hexylthio group, 3-hexylthio group, 2-methyl-3-pentylthio group, 3,3-dimethyl-2-butylthio group, n-heptylthio group, 2-heptylthio group, 3-heptylthio group, 4-heptylthio group, n-octylthio group, methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butylamino group, isobutylamino group, tert-butylamino group, tert-butylamino group, n-pentylthio group Butylamino, n-pentylamino, 2-pentylamino, 3-pentylamino, neopentylamino, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, 2,2,2-trifluoroethylamino, N,N-dimethylamino, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclopropylthio, methylsulfinyl, methylsulfonyl, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylthio, difluoromethylsulfinyl, difluoromethylsulfonyl, 2, 2,2-Trifluoroethylthio, 2,2,2-Trifluoroethylsulfinyl, 2,2-Difluoroethylthio, 2,2-Difluoroethylsulfinyl, methoxymethylthio, methoxymethylsulfinyl, cyanomethylthio, phenylthio, cyclopropylmethoxy, methylcarbonyl, ethylcarbonyl, isopropylcarbonyl, methylcarbonyloxy, ethylcarbonyloxy, isopropylcarbonyloxy, methylcarbonylamine, ethylcarbonylamine, isopropylcarbonylamine, trifluoromethylcarbonylamine, methylsulfonylamine, trifluoromethylsulfonylamine, N,N-dimethylaminosulfonate, oxetane-3-oxy, morpholino, or phenyl; m represents an integer between 0 and 5; n represents an integer from 1 to 5.

5. The pyrazole compound according to any one of claims 1-4, wherein, Q 1 Selected from Ar1, Ar2, Ar3, Ar 14 Ar 23 Q 2 Selected from hydrogen; R 1 Selected from hydrogen; R 2 and R 3 Each is independently selected from hydrogen, fluorine, or methyl; R 4 Selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, or methyl; R 5 Selected from methyl; R 6 Selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, n-hexyloxy, cyanomethyloxy, 3,3-dichloroallyloxy, trimethylsilyl, isopropylamino, N,N-dimethylamino, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, cyclohexyl, methylthio, ethylthio, isopropyl... Propylthio, methylsulfinyl, methylsulfonyl, trifluoromethylthio, trifluoromethylsulfinyl, trifluoromethylsulfonyl, difluoromethylthio, difluoromethylsulfinyl, difluoromethylsulfonyl, 2,2,2-trifluoroethylthio, 2,2,2-trifluoroethylsulfinyl, 2,2-difluoroethylthio, 2,2-difluoroethylsulfinyl, methoxymethylthio, methoxymethylsulfinyl, cyanomethylthio, phenylthio, methyl carbonyl, oxetane-3-oxy, morpholino, or phenyl; n is 1; m represents an integer from 0 to 5; Preferably, the pyrazole compound is any one of the following compounds:

6. The application of pyrazole compounds according to any one of claims 1-5 in the prevention and control of plant diseases.

7. A fungicide composition comprising an active ingredient and a pesticide-acceptable carrier, said active ingredient being a pyrazole compound as described in any one of claims 1-5.

8. The bactericide composition according to claim 7, wherein, The weight percentage of active ingredients is 1-99%.

9. A method for controlling plant diseases, comprising: Apply an effective dose of any one of the pyrazole compounds as described in claims 1-5 or the fungicide composition as described in claim 7 or 8 to the plant disease that needs to be controlled or to the medium in which it grows.

10. The method for controlling plant diseases according to claim 9, wherein, The effective dosage is 10-1000 g per hectare, preferably 20-500 g per hectare.

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