Pyrimidine amine benzoate compounds, methods of making and uses thereof

Abstract

The present application discloses pyrimidine amide benzoic acid ester compounds shown in formula (I) and isomers or salts thereof, their preparation method and use. In the formula, R, R', R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , W, X, n have the definitions given in the specification. The compounds of formula (I) of the present application have insecticidal / mite, fungicidal biological activity, especially high activity against diseases.

Description

Technical Field

[0001] This invention belongs to the field of insecticides / miticides and fungicides, specifically relating to a novel benzoic acid ester compound containing pyrimidine amine and its isomers or salts thereof, their preparation methods and uses. Background Technology

[0002] Pyrimidine amine compounds have broad-spectrum activity and have been widely reported in the literature. For example, pyrimidine amine pyrazole ether compound 33-19 (D1) reported in CN201610326565.8 and pyrimidine amine pyridine ether compound I-B3-1 (D2) reported in CN202010492284.6 both have high activity against powdery mildew and rust. The activity of D1 and D2 against wheat powdery mildew and corn rust is comparable to or even better than that of commercial fungicides fluazinam (D3), tebuconazole (D4), and fluazinam (D5).

[0003]

[0004] Benzoate esters containing pyrimidine amines are rarely reported, as are fatty carboxylic acid esters containing pyrimidine amines, and aromatic heterocyclic carboxylic acid esters containing pyrimidine amines have not been reported. Table 1 of EP0323757 discloses 108 N-alkylpyrimidine amine compounds, including two pyrimidine amine benzoate esters: 76 (D6) and 83 (D7), and 11 fatty carboxylic acid esters containing pyrimidine amines: 72 (D8), 74 (D9), 75 (D10), 73 (D11), 77 (D12), 78 (D13), 81 (D14), 82 (D15), 84 (D16), 79 (D17), and 80 (D18). However, only Example 26 of EP0323757 reported grade 4 activity against diamondback moth at 300 ppm: compounds 74 (D9) and 79 (D17) showed grade 5 activity, and compound 80 (D18) showed grade 5 activity; Example 29 reported grade 4 activity against adult female two-spotted spider mites at 300 ppm: compounds 73 (D11), 76 (D6), and 84 (D16) showed grade 4 activity, and compounds 72 (D8), 75 (D10), and 79 (D17) showed grade 5 activity; Example 33 reported grade 5 activity against rice blast at 300 ppm: compound 77 (D12). The data disclosed in EP0323757 indicate that the insecticidal / acaricidal and fungicidal bioactivity of the two pyrimidine amine benzoate compounds D6 and D7 and the eleven pyrimidine amine fatty carboxylic acid ester compounds D8–D18 is not outstanding.

[0005]

[0006] In order to obtain a novel active molecule that can be used to control pests / mites and harmful bacteria in agriculture or other fields, the inventors conducted in-depth research on compounds containing pyrimidine amines and discovered that novel pyrimidine amine benzoate compounds that have not been reported in the literature have better biological activity than the above-mentioned compounds and are more convenient and economical to synthesize. Summary of the Invention

[0007] This invention provides pyrimidine amine benzoate compounds of formula (I) and their isomers or salts of compounds of formula (I) that have biological activity against pests / mites and harmful pathogens:

[0008] in:

[0009] R is selected from H, halogen, cyano, nitro, amino, hydroxy, mercapto, carboxyl, methyl, haloethyl, C3-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, and C3-C6 heterocyclic. The hydrogen atoms in R may be partially or completely substituted by substituents selected from the following same or different groups: halogen, cyano, nitro, amino, hydroxy, mercapto, carboxyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 alkylamino, and C1-C6 alkylcarbonyl.

[0010] W is selected from H, halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, and C3-C6 heterocyclic. The hydrogen atoms in W may be partially or completely substituted by the same or different substituents selected from the following: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 alkylamine, C1-C6 alkylcarbonyl, and C1-C6 alkoxycarbonyl.

[0011] X is selected from halogens;

[0012] R 1 R 2 R 3 R 4 R 5It is the same or different, selected from hydrogen, halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 heterocyclic, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylsilyl, C1-C6 alkylamine, C1-C6 dialkylamine, C1-C6 alkylcarbonyl, C1-C6 alkylcarbonyloxy, C1-C6 alkoxycarbonyloxy, C1-C6 alkoxycarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthiocarbonyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyloxy, C1-C6 alkylsulfinyloxy, C1-C6 alkylsulfonyloxy, phenyl, phenoxy, phenylthio, heteroaryl, heteroaryloxy, heteroarylthio, R 1 R 2 R 3 R 4 R 5 The hydrogen atom can be partially or completely substituted by the same or different substituents selected from the following: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylamine, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, R 1 R 2 R 3 R 4 R 5 It can also form five-, six-, seven-, or eight-membered rings containing C, N, O, or S with the connected benzene ring;

[0013] R'、R 6 R 7 R 8 R 9 R 10 R 11 They are the same or different, selected from H, halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 heterocyclic, phenyl, phenoxy, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthiocarbonyl, C1-C6 alkylaminecarbonyl, R', R 6 R 7 R 8 R 9 R 10 R 11The hydrogen atom can be partially or completely substituted by a substituent selected from the following same or different substituents: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 alkylamine, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, R 6 R 7 R 8 R 9 R 10 R 11 The C atoms connected to it can form C3-C6 rings or C3-C6 heterocycles;

[0014] n is an integer of 0, 1, 2, or 3. When n is 2 or 3, R 10 Or R 11 Are they the same or different?

[0015] Salts of Formula (I): Salts of compounds of Formula (I) with organic or inorganic acids; organic acids refer to carboxylic acids or sulfonic acids, selected from C1-C6. 18 Alkyl carboxylic acids, C2-C 18 Alkyl dicarboxylic acid, C4-C 18 Alkane tricarboxylic acid, C5-C 18 Alkanetetracarboxylic acid, C3-C 18 Encarboxylic acids, C4-C 18 olefinic acid, C3-C 18 Alkynic acid, C4-C 18 Alkyne dicarboxylic acid, benzoic acid, phthalic acid, C1-C 18 Alkanesulfonic acid, C3-C 18 Enyl sulfonic acid, C3-C 18 In acetylsulonic acids, the hydrogen atoms can be partially or completely substituted by the same or different substituents from the following: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C. 18 Alkyl, C1-C 18 Alkoxy, C1-C 18 Alkylthio, C1-C 18 Alkylamine group, C1-C 18 Alkyl carbonyl, C1-C 18 Alkoxycarbonyl; the inorganic acid is selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, or carbonic acid;

[0016] In the definition given in equation (I) above, the terms used, whether alone or in compound words, represent the following substituents:

[0017] Halogens: refer to fluorine, chlorine, bromine, and iodine;

[0018] Alkyl: refers to straight-chain or branched alkyl groups;

[0019] Cycloalkyl: refers to saturated or unsaturated cycloalkyl groups;

[0020] Alkenyl; refers to a straight-chain or branched alkyl group, and may have one or more double bonds at any position;

[0021] Alkynyl group; refers to a straight-chain or branched alkyl group, and may have one or more triple bonds at any position;

[0022] Halogenation: refers to the replacement of some or all of the hydrogen atoms with halogen atoms.

[0023] The preferred compounds of this invention are compounds of formula (I) and their isomers or salts of compounds of formula (I), wherein:

[0024] R is selected from methyl, propyl, isopropyl, cyclopropyl, and C1-C3 haloalkyl;

[0025] W is selected from H, halogen, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 heterocyclic, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylamine, and C1-C6 dialkylamine. The hydrogen atoms in W may be partially or completely substituted by substituents selected from the following same or different substituents: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylamine, C1-C6 alkylcarbonyl, and C1-C6 alkoxycarbonyl.

[0026] X is selected from halogens;

[0027] R 1 R 2 R 3 R 4 R 5 It is the same or different, selected from hydrogen, halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 heterocyclic, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylsilyl, C1-C6 alkylamine, C1-C6 dialkylamine, C1-C6 alkylcarbonyl, C1-C6 alkylcarbonyloxy, C1-C6 alkoxycarbonyloxy, C1-C6 alkoxycarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthiocarbonyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyloxy, C1-C6 alkylsulfinyloxy, C1-C6 alkylsulfonyloxy, phenyl, phenoxy, phenylthio, heteroaryl, heteroaryloxy, heteroarylthio, R 1 R 2 R 3 R 4 R 5The hydrogen atom can be partially or completely substituted by the same or different substituents selected from the following: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylamine, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, R 1 R 2 R 3 R 4 R 5 It can also form five-, six-, seven-, or eight-membered rings containing C, N, O, or S with the connected benzene ring;

[0028] R' represents H; R 6 R 7 R 8 R 9 R 10 R 11 They are the same or different, selected from H, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl; n is 0 or 1.

[0029] The preferred compounds of this invention are compounds of formula (I) and their isomers or salts of compounds of formula (I), wherein:

[0030] R is selected from methyl, fluoromethyl, and fluoroethyl;

[0031] W is selected from H, halogen, C1-C3 alkyl, cyclopropyl, C1-C3 alkoxy, C1-C3 alkylthio, C1-C3 alkylamine, and C1-C3 dialkylamine.

[0032] X is selected from halogens;

[0033] R 1 R 2 R 3 R 4 R 5It is the same or different, selected from hydrogen, halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 heterocyclic, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylsilyl, C1-C6 alkylamine, C1-C6 dialkylamine, C1-C6 alkylcarbonyl, C1-C6 alkylcarbonyloxy, C1-C6 alkoxycarbonyloxy, C1-C6 alkoxycarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthiocarbonyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyloxy, C1-C6 alkylsulfinyloxy, C1-C6 alkylsulfonyloxy, phenyl, phenoxy, phenylthio, heteroaryl, heteroaryloxy, heteroarylthio, R 1 R 2 R 3 R 4 R 5 The hydrogen atom can be partially or completely substituted by the same or different substituents selected from the following: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylamine, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, R 1 R 2 R 3 R 4 R 5 It can also form five-, six-, seven-, or eight-membered rings containing C, N, O, or S with the connected benzene ring;

[0034] R' represents H; R 6 R 7 R 8 R 9 R 10 R 11 They may be the same or different, and are selected from hydrogen, C1-C3 alkyl, and cyclopropyl;

[0035] n is 0 or 1.

[0036] The present invention further preferably uses compounds of formula (I) and their isomers or salts of formula (I), wherein:

[0037] R is selected from methyl, fluoromethyl, and fluoroethyl;

[0038] W is selected from H, halogen, and methyl;

[0039] X is selected from halogens;

[0040] R 1 R 2 R 3R 4 R 5 It is the same or different, selected from hydrogen, halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 heterocyclic, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylsilyl, C1-C6 alkylamine, C1-C6 dialkylamine, C1-C6 alkylcarbonyl, C1-C6 alkylcarbonyloxy, C1-C6 alkoxycarbonyloxy, C1-C6 alkoxycarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthiocarbonyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyloxy, C1-C6 alkylsulfinyloxy, C1-C6 alkylsulfonyloxy, phenyl, phenoxy, phenylthio, heteroaryl, heteroaryloxy, heteroarylthio, R 1 R 2 R 3 R 4 R 5 The hydrogen atom can be partially or completely substituted by the same or different substituents selected from the following: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylamine, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, R 1 R 2 R 3 R 4 R 5 It can also form five-, six-, seven-, or eight-membered rings containing C, N, O, or S with the connected benzene ring;

[0041] R' is H; R 6 R 7 R 8 R 9 R 10 R 11 They are the same or different, selected from hydrogen, methyl, ethyl; n is 0 or 1.

[0042] The present invention particularly prefers compounds of the formulas IA, IB, IC, ID, IE, IF, IG, IH, II, IJ, IK, IL, IM, IN, IO, IP, IQ, IR, IS, IT, and their isomers or salts.

[0043]

[0044]

[0045] in:

[0046] R is selected from H, halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, and C3-C6 heterocyclic. The hydrogen atom in R may be partially or completely substituted by the same or different substituents selected from the following: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 alkylamine, and C1-C6 alkylcarbonyl.

[0047] W is selected from H, halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, and C3-C6 heterocyclic. The hydrogen atoms in W may be partially or completely substituted by the same or different substituents selected from the following: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 alkylamine, C1-C6 alkylcarbonyl, and C1-C6 alkoxycarbonyl.

[0048] X is selected from halogens;

[0049] R 1 R 2 R 3 R 4 R 5 It is the same or different, selected from hydrogen, halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 heterocyclic, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylsilyl, C1-C6 alkylamine, C1-C6 dialkylamine, C1-C6 alkylcarbonyl, C1-C6 alkylcarbonyloxy, C1-C6 alkoxycarbonyloxy, C1-C6 alkoxycarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthiocarbonyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyloxy, C1-C6 alkylsulfinyloxy, C1-C6 alkylsulfonyloxy, phenyl, phenoxy, phenylthio, heteroaryl, heteroaryloxy, heteroarylthio, R 1 R 2 R 3 R 4 R 5The hydrogen atom can be partially or completely substituted by the same or different substituents selected from the following: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylamine, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, R 1 R 2 R 3 R 4 R 5 It can also form five-, six-, seven-, or eight-membered rings containing C, N, O, or S with the connected benzene ring;

[0050] Salts of Formula (I): Salts of compounds of Formula (I) with organic or inorganic acids; the organic acids are selected from formic acid, acetic acid, propionic acid, butyric acid, cyclopentanoic acid, oxalic acid, adipic acid, benzoic acid, phthalic acid, lauric acid, maleic acid, fumaric acid, sorbic acid, malic acid, citric acid, tartaric acid, coconut oil acid, methanesulfonic acid, ethanesulfonic acid, and benzenesulfonic acid. The hydrogen atoms in the organic acid may be partially or completely substituted by the following same or different substituents: halogen, amino group, hydroxyl group, mercapto group, C1-C... 12 Alkyl, C1-C 12 Haloalkyl, C1-C 12 Alkoxy, C1-C 12 Halogenated alkoxy group; inorganic acid selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or carbonic acid.

[0051] The compounds of this invention can exist in various isomer forms. For example, in the compound of formula (I), the double bond is connected to different substituents to form Z and E geometric isomers, including Z isomers, E isomers, or mixtures thereof in any proportion; in the compound of formula (I), the carbon atom is connected to four different substituents to form R and S stereoisomers, including R isomers, S isomers, or mixtures thereof in any proportion; in the compound of formula (I), cycloalkyl or heterocycloalkyl groups are connected to two or more substituents on different carbons to form cis and trans isomers, including cis isomers, trans isomers, or mixtures thereof in any proportion.

[0052] This invention also relates to a composition containing a bioactive amount of a compound of formula (I) and at least one other ingredient selected from surfactants and diluents for the control of pests / mites and harmful pathogens. The composition contains a bioactive amount of a compound of formula (I) and an effective amount of at least one other bioactive compound or preparation. The weight percentage of the compound of formula (I) in the composition is 0.5-99%.

[0053] This invention also relates to a method for controlling pests / mites and harmful pathogens, comprising contacting a bioavailable amount of a compound of formula (I) with the pests / mites, harmful pathogens, or their environment. It also relates to a method for controlling pests / mites and harmful pathogens by contacting the pests / mites, harmful pathogens, or their environment with a bioavailable amount of a compound of formula (I) or a mixture containing a compound of formula (I) and at least one other compound or preparation of bioavailable amount.

[0054] The compounds of formula (I) of this invention have broad-spectrum activity: they can be used to control harmful bacteria and pests / mites; moreover, some compounds have high biological activity against harmful bacteria, so that good results can be obtained at very low doses.

[0055] The preferred composition of the present invention is a composition containing the above-mentioned preferred compound. The preferred method is a method using the preferred compound.

[0056] Table 1 lists the R values ​​in equation (I). 1 R 2 R 3 R 4 R 5 Some specific substituents, but not limited to these substituents.

[0057] In Table 1, Equation (I) contains R 1 R 2 R 3 R 4 R 5 Selected specific substituents

[0058]

[0059]

[0060]

[0061]

[0062] This invention can be further illustrated by the compounds of formula (I) listed in Table 2-22 and the salts listed in Table 23, but is not limited thereto. The molecular ion peaks of the compounds of this invention can be observed in GC-MS (EI) and LC-MS (APCI). The synthesized compounds were identified by MS. Table 24 lists the NMR data of some compounds of formula (I). The melting points given in this invention are uncorrected. When the compounds of formula (I) of this invention are viscous liquids or viscous solids, some compounds will solidify after standing.

[0063] Table 2

[0064]

[0065]

[0066] Table 3

[0067]

[0068] Table 4

[0069]

[0070] Table 5

[0071]

[0072]

[0073] Table 6

[0074]

[0075] Table 7

[0076]

[0077] Table 8

[0078]

[0079] Table 9

[0080]

[0081]

[0082] Table 10

[0083]

[0084] Table 11

[0085]

[0086] Table 12

[0087]

[0088] Table 13

[0089]

[0090] Table 14

[0091]

[0092] Table 15

[0093]

[0094] Table 16

[0095]

[0096]

[0097] Table 17

[0098]

[0099] Table 18

[0100]

[0101] Table 19

[0102]

[0103] Table 20

[0104]

[0105]

[0106] Table 21

[0107]

[0108] Table 22

[0109]

[0110] Table 23 Partial Formula (I) Compound Salts

[0111]

[0112] NMR data for some compounds in formula (I) in Table 24

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119] Compound (I) of the present invention can be obtained by reaction 1 shown below; (II) in reaction 1 can be obtained by reaction 2; salts of the compounds of the present invention can be obtained by reaction 3; (III) and (IV) in reaction 1, and (V) and (VI) in reaction 2 can be synthesized by purchasing or referring to relevant literature; L in the reaction formula represents the leaving group chlorine or bromine, and acid in reaction 3 is an organic acid or an inorganic acid. Other substituents are as specified above unless otherwise specified.

[0120] Reaction 1:

[0121]

[0122] Reaction 2:

[0123]

[0124] Reaction 3:

[0125]

[0126] Preparation of compound (I) (Reaction 1-1): In a suitable solvent such as dichloromethane, dichloroethane, toluene, xylene, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, pyridine, tetrahydrofuran, methanol, ethanol, isopropanol, acetone, butanone, methyl isobutyl ketone, acetonitrile, ethyl acetate, or dioxane, at -10°C to reflux temperature, in the presence of a suitable dehydrating agent and a suitable base, compound (II) reacts with compound (III) to obtain compound (I). The suitable dehydrating agent is selected from... The suitable base is selected from dicyclohexylcarbodiimide, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, 2-(7-azabenzotriazole)-N,N,N',N'-tetramethylurea hexafluorophosphate or benzotriazole-1-yl-oxytripyrrolylphosphine hexafluorophosphate, and the suitable base is selected from alkali metal hydrides such as sodium hydride, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, alkali metal carbonates such as sodium carbonate or potassium carbonate, alkali metal alkoxides such as sodium methoxide or sodium ethoxide, organic amines such as pyridine, methylpyridine, triethylamine or diisopropylethylamine.

[0127] Preparation of compound (I) (reaction formulas 1-2): In a suitable solvent, such as dichloromethane, dichloroethane, toluene, xylene, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, pyridine, tetrahydrofuran, methanol, ethanol, isopropanol, acetone, butanone, methyl isobutyl ketone, acetonitrile, ethyl acetate, or dioxane, at -10°C to reflux temperature, in the absence of a base or in the presence of a suitable base, compound (II) reacts with compound (IV) to obtain compound (I). The suitable base is selected from alkali metal hydrides such as sodium hydride, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, alkali metal carbonates such as sodium carbonate or potassium carbonate, alkali metal alkoxides such as sodium methoxide or sodium ethoxide, and organic amines such as pyridine, methylpyridine, triethylamine, or diisopropylethylamine.

[0128] Preparation of compound (II) (Reaction 2): In a suitable solvent such as dichloromethane, dichloroethane, toluene, xylene, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, pyridine, tetrahydrofuran, methanol, ethanol, isopropanol, acetone, butanone, methyl isobutyl ketone, acetonitrile, ethyl acetate, or dioxane, at -10°C to reflux temperature, in the absence of a base or in the presence of a suitable base, compound (V) reacts with compound (VI) to obtain compound (II). The suitable base is selected from alkali metal hydrides such as sodium hydride, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, alkali metal carbonates such as sodium carbonate or potassium carbonate, alkali metal alkoxides such as sodium methoxide or sodium ethoxide, and organic amines such as pyridine, methylpyridine, triethylamine, or diisopropylethylamine.

[0129] Preparation of salt of compound (I) (reaction formula 3): In one or two suitable solvents, at 0°C to reflux temperature, compound (I) reacts with acid to obtain salt of compound (I). The suitable solvent is selected from dichloromethane, dichloroethane, trichloromethane, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, N,N-dimethylformamide, tetrahydrofuran, ethyl acetate, methanol, ethanol, isopropanol or dioxane.

[0130] The specific synthesis method is described in more detail in the examples below.

[0131] The compound of formula (I) of this invention exhibits broad-spectrum biological activity at dosages of 3.75–2250 g active ingredient per hectare. It can be used to control harmful pathogens and diseases, as well as harmful insects and mites, exhibiting particularly excellent activity in the control of agricultural, horticultural, floricultural, and sanitary pests / mites and harmful pathogens. The harmful organisms include, but are not limited to, the following:

[0132] Harmful pathogens include species from the genera *Phytophthora*, *Powdery mildew*, *Fusarium*, *Aureobasidium*, *Sclerotinia*, *Rhizoctonia*, *Botrytis*, *Pyrrosia*, and *Fusarium*. Examples include rice blast (*Pyricularia oryzae*); stripe rust (*Puccinia striiformis*) and leaf rust (*Puccinia recondita*); powdery mildew on barley and wheat (*Erysiphe graminis*), cucumber powdery mildew (*Sphaerothecafuligenea*), apple powdery mildew (*Podosphaera leucotrichar*), and grape powdery mildew (*Podosphaera leucotrichar*); and wheat sheath blight and glume blight (*Septoria nodorum*). Diseases on cereals include diseases caused by *Helicobacter*, *Pseudocercosporella*, *Pseudocercosporella herpotrichoides*, and wheat take-all (*Gaeumannomyces graminis*). Peanut brown spot (Cercospora arachidicola) and peanut black spot (Cercosporidium personata); apple ring rot fungus (Botryosphaeria berengrianaf. sppiricola) and apple rot fungus (Cytospora sp.); diseases of *Cercospora* on sugar beets, soybeans, and rice. Gray mold (Botrytis cinerea) on tomatoes, cucumbers, and grapes. *Hymenospora* diseases on vegetables such as cucumbers. Anthracnose on cucumbers, apple black spot, cucumber downy mildew, grape downy mildew, blight on potatoes and tomatoes, *Thanatephorus cucumeris* on rice and other ruthecidae on other hosts such as wheat and barley, and other *Rhizoctonia* fungi on vegetables; sclerotinia sclerotiorum on rapeseed; scab (Gibberellazeae) on wheat; *Phytophythora capsici* on peppers.

[0133] Harmful insects: Lepidoptera pests such as armyworm, beet armyworm, diamondback moth, beet armyworm, cabbage white caterpillar; Orthoptera such as cockroach; Thysanoptera such as cotton thrips, rice thrips, melon thrips; Homoptera such as leafhoppers, planthoppers, aphids; Hymenoptera such as sawfly larvae; Diptera such as Aedes mosquito, Culex mosquito, flies; Acari mites such as citrus spider mite, cotton spider mite, two-spotted spider mite, etc.

[0134] When used alone, the compounds of formula (I) of this invention are effective in controlling pests / mites and harmful pathogens, and they can also be used in conjunction with other biochemicals such as insecticides, acaricides, nematicides, and fungicides.

[0135] Agricultural formulations using compounds of formula (I) of the present invention as active ingredients, as well as compositions of compounds of formula (I) of the present invention, can be formulated into any desired dosage form, such as dry compressed granules, free-flowing mixtures, granules, wettable powders, water-dispersible granules, emulsifiable concentrates, powders, powdered concentrates, microemulsions, suspensions, emulsifiable concentrates, water-in-oil emulsions, soluble liquids, aqueous solutions, and dispersible liquids. Suitable adjuvants include carrier diluents and other adjuvants such as spreading agents, emulsifiers, wetting agents, dispersants, binders, and disintegrants. These formulations contain compounds of the present invention mixed with inert, pharmacologically acceptable solid or liquid diluents.

[0136] The present invention will be further described below with reference to embodiments, but it is not intended to limit the present invention.

[0137] Example 1 This example illustrates the preparation method of compound (S)-33.

[0138]

[0139] 6-(difluoromethyl)pyrimidin-4-ol was reacted at 5-10°C with stirring. A 30% methanol solution of sodium methoxide (0.45 mol) was added dropwise to a solution of formamidine acetate (0.33 mol) and methanol (150 mL). After the addition was complete, stirring was continued for 0.5-1.0 h. Ethyl 4,4-difluoro-3-oxobutyrate (0.30 mol) was then added dropwise, and the mixture was allowed to naturally warm to room temperature for 8-12 h. The pH of the reaction solution was adjusted to 4-5 with concentrated sulfuric acid, refluxed for 1-2 h, and methanol was removed under reduced pressure. Ethyl acetate was added, insoluble matter was filtered off, and the solution was concentrated to obtain the title compound, which was used in the next reaction step.

[0140] N-chlorosuccinimide (0.31 mol) was added in portions to a solution of 6-(difluoromethyl)pyrimidin-4-ol and acetonitrile (350 mL) under stirring at 50-60 °C. The mixture was kept at this temperature for 3-5 h until the reaction was complete. The reaction solution was concentrated under reduced pressure to obtain a solid. The solid was washed with a small amount of water, filtered, and the title compound was obtained for the next step of the reaction.

[0141] 4,5-Dichloro-6-(difluoromethyl)pyrimidine was added in portions to toluene (350 mL) under stirring at 0-5 °C. After stirring for 10-15 min, phosphorus oxychloride (0.75 mol) was added dropwise. The mixture was heated to reflux for 3-6 h until complete. After removing phosphorus oxychloride, the reactants were poured into ice water. The mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to obtain the crude product, which was purified by column chromatography (petroleum ether / ethyl acetate = 80 / 1) to give 14.29 g of the title compound.

[0142] (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propanol was added dropwise to a solution of 4,5-dichloro-6-(difluoromethyl)pyrimidine (20 mmol) and potassium carbonate (25 mmol) in 30 mL of tetrahydrofuran (30 mL) under stirring at room temperature. After stirring for 15-30 min, the mixture was heated to reflux until complete. The reactants were cooled and poured into ice water, extracted with ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to give 4.00 g of the title compound.

[0143] (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 2,6-dichlorobenzoate was reacted with triethylamine (3.0 mmol) and 2,6-dichlorobenzoyl chloride (2.5 mmol) dropwise to a solution of (S)-2-((5-chloro-6-difluoromethylpyrimidin-4-yl)amino)propanol (2.5 mmol) in dichloromethane (10 mL) under stirring at 0–5 °C. After stirring for 15–30 min, the mixture was allowed to warm naturally to room temperature for 6–10 h until complete. The reactants were then poured into ice water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the solvent was removed to obtain the crude product. The crude product was subjected to column chromatography with ethyl acetate and petroleum ether to give 0.56 g of the title compound.

[0144] (RS)-33 and (R)-33 can be prepared by replacing (S)-2-aminopropanol with (RS)-2-aminopropanol and (R)-2-aminopropanol, respectively.

[0145] Example 2 This example illustrates the preparation method of compound (S)-243.

[0146]

[0147] (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 1-naphthoate was added sequentially to a solution of (S)-2-((5-chloro-6-difluoromethylpyrimidin-4-yl)amino)propanol (5.0 mmol) in dichloromethane (10 mL) under stirring at 0–5 °C. Then, catalytic amounts of 4-dimethylaminopyridine and 1-naphthoic acid (5.2 mmol) were added. After stirring for 15–30 min, the mixture was allowed to naturally warm to room temperature for 6–10 h until complete. The reactants were poured into ice water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the solvent was removed to obtain the crude product. The crude product was subjected to column chromatography with ethyl acetate and petroleum ether to give 1.05 g of the title compound.

[0148] Example 3 This example illustrates the preparation method of compound (S)-1171.

[0149]

[0150] Ethyl 2-chloro-3-oxo-4,4-difluorobutyrate was reacted by adding sulfonyl chloride (0.33 mol) dropwise to a solution of ethyl difluoroacetoacetate (0.30 mol) and dichloromethane (100 mL) at -5°C with stirring. After the addition was complete, the mixture was allowed to naturally warm to room temperature until the reaction was complete. The reaction solution was poured into ice water, and the organic layer was separated. The aqueous layer was extracted with dichloromethane, and the combined organic phases were dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain the title compound, which was used in the next reaction.

[0151] 5-Chloro-6-(difluoromethyl)-2-methylpyrimidin-4-ol was reacted at 5-10 °C with stirring. A 30% methanol solution of sodium methoxide (0.45 mol) was added dropwise to acetamiprid hydrochloride (0.33 mol) and methanol (150 mL). After stirring for 0.5-1.0 h, ethyl 2-chloro-3-oxo-4,4-difluorobutyrate was added dropwise. The mixture was allowed to naturally warm to room temperature and reacted for 10-12 h. The pH of the reaction solution was adjusted to 4-5 with concentrated sulfuric acid, refluxed for 1-2 h, and methanol was removed under reduced pressure. Ethyl acetate was added, and insoluble matter was filtered off. The filtrate was concentrated to obtain the solid title compound, which was used in the next reaction step.

[0152] 4,5-Dichloro-6-(difluoromethyl)-2-methylpyrimidine was added in portions to toluene (350 mL) under stirring at 0-5 °C. After stirring for 10-15 min, phosphorus oxychloride (0.75 mol) was added dropwise. The mixture was refluxed for 3-6 h until complete. After removing phosphorus oxychloride, the reactants were poured into ice water. The mixture was extracted with ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to obtain the crude product, which was purified by column chromatography (petroleum ether / ethyl acetate = 80 / 1) to give 11.92 g of the title compound.

[0153] (S)-2-((5-chloro-6-(difluoromethyl)-2-methylpyrimidin-4-yl)amino)propanol was added dropwise to a solution of 4,5-dichloro-6-(difluoromethyl)-2-methylpyrimidin (20 mmol) and potassium carbonate (25 mmol) in tetrahydrofuran (25 mL) under stirring at room temperature. The mixture was stirred for 15-30 min and then heated to reflux until complete. After cooling, the reactants were poured into ice water, extracted with ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to give 3.86 g of the title compound.

[0154] (S)-2-((5-chloro-6-(difluoromethyl)-2-methylpyrimidin-4-yl)amino)propyl 2-(trifluoromethyl)benzoate was added dropwise to (S)-2-((5-chloro-6-(difluoromethyl)-2-methylpyrimidin-4-yl)amino)propanol (5 mmol) and dichloromethane (10 mL) with stirring. After stirring for 15-30 min, the mixture was allowed to naturally warm to room temperature for 6-12 h until complete. The reactants were poured into ice water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the crude product, after solvent removal under reduced pressure, was subjected to column chromatography with ethyl acetate and petroleum ether to give 1.32 g of the title compound.

[0155] Example 4 This example illustrates the preparation method of compound 32033.

[0156]

[0157] 2-((5-chloro-6-difluoromethylpyrimidin-4-yl)amino)ethanol was added dropwise to a solution of 4,5-dichloro-6-(difluoromethyl)pyrimidine (20 mmol) and potassium carbonate (25 mmol) in tetrahydrofuran (25 mL) at room temperature with stirring. The mixture was stirred for 15-30 min and then refluxed until complete. After cooling, the reactants were poured into ice water, extracted with ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to give 3.45 g of the title compound.

[0158] 2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)ethyl 2,6-dichlorobenzoate was added dropwise to a solution of 2-((5-chloro-6-difluoromethylpyrimidin-4-yl)amino)ethanol (5 mmol) in dichloromethane (10 mL) under stirring at 0–5 °C. Triethylamine (6 mmol) and 2,6-dichlorobenzoyl chloride (6 mmol) were added dropwise sequentially. After stirring for 15–30 min, the mixture was allowed to naturally warm to room temperature for 6–12 h until complete. The reactants were poured into ice water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the solvent was removed to obtain the crude product. The crude product was subjected to column chromatography with ethyl acetate and petroleum ether to give 1.19 g of the title compound.

[0159] Example 5 This example illustrates the preparation method of compound 48006.

[0160]

[0161] 2-((5-chloro-6-difluoromethylpyrimidin-4-yl)(methyl)amino)ethanol was added dropwise to a solution of 4,5-dichloro-6-difluoromethylpyrimidin-4-yl)(methyl)amino)ethanol in tetrahydrofuran (25 mL) at room temperature with stirring. The mixture was stirred for 15-30 min and then heated to reflux until complete. After cooling, the reactants were poured into ice water, extracted with ethyl acetate, and the organic layer was dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to give 3.85 g of the title compound.

[0162] 2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)(methyl)amino)ethyl 2-(trifluoromethyl)benzoate was added sequentially to a solution of 2-((5-chloro-6-difluoromethylpyrimidin-4-yl)(methyl)amino)ethanol (5.0 mmol) in dichloromethane (10 mL) under stirring at 0–5 °C. The reaction mixture was then stirred for 15–30 min, and the mixture was allowed to naturally warm to room temperature for 6–16 h until complete. The reactants were poured into ice water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, and the solvent was removed to obtain the crude product. The crude product was subjected to column chromatography with ethyl acetate and petroleum ether to give 0.82 g of the title compound.

[0163] Example 6 This example illustrates the preparation method of compound (S)-1171 hydrochloride.

[0164] (S)-2-((5-chloro-6-(difluoromethyl)-2-methylpyrimidin-4-yl)amino)propyl 2-(trifluoromethyl)benzoate hydrochloride was reacted with stirring at 15-25 °C by slowly passing hydrogen chloride gas (2.5 mmol) through a solution of (S)-1171 (2.0 mmol) and ethyl acetate (10 mL). Stirring continued until salt formation was complete. The solution was concentrated under reduced pressure, a small amount of dichloromethane was added, the mixture was stirred, filtered, and the solid was washed with dichloromethane to give the title compound.

[0165] The yields in the examples have not been optimized. Other compounds of the present invention can be prepared by referring to the above examples and related literature.

[0166] Example 7 This example illustrates a method for preparing a 10% floating oil of compound (S)-1171.

[0167] Weigh an appropriate amount (10% by weight) of compound (S)-1171 of formula (I), an appropriate amount of cosolvent (such as ethyl acetate), an appropriate amount of pesticide adjuvant and solvent (such as toluene), and put them into a reaction vessel. First, add a certain amount of solvent (such as toluene) and defoamer and stir for 10-30 minutes. Then add an appropriate amount of stabilizer, synergist, penetrant and other components and continue stirring for 10-30 minutes. Adjust the pH and then add the effective amount of solvent into the vessel. After stirring evenly, a 10% emulsifiable concentrate of compound (S)-1171 of the present invention is obtained.

[0168] The insecticidal / miticidal and fungicidal activities of the compounds of this invention were evaluated. The activities were classified into four levels: A, B, C, and D. Level A was 100% ≥ 90% activity; Level B was 90% > 70% activity; Level C was 70% > 50% activity; and Level D was 50% > 0% activity. The results show that the compounds of this invention possess excellent biological activity, some of which are shown below.

[0169] Example 8: Insecticidal activity against aphids (Aphis fabae)

[0170] Spraying method: The test compound was dissolved in a suitable solvent such as N,N-dimethylformamide (DMF), and then diluted to the required concentration with water containing 0.2% Tween 80 emulsifier. A blank control was set up without the test compound. Each treatment was repeated three times. Broad bean seedlings infested with 3-day-old broad bean nymphs were uprooted, with 30-100 nymphs per plant, and placed in a beaker containing water. The beaker mouth was sealed with parafilm, and a plastic gasket was attached. The plant was sprayed using an electric sprayer, with a spray volume of 2 mL per plant. After the plants dried, they were covered with a lantern and placed in a recovery room for incubation. Mortality was assessed after 48 hours. Based on the blank control, the mortality rate was calculated, and the average value was taken. The results show that the compound of this invention has good activity against aphids. Some results are shown below.

[0171] 200 mg / L. The activity of some compounds of this invention and D6 and D8 against aphids is shown in Table 25.

[0172] At concentrations of 100 mg / L, 25 mg / L, and 6.25 mg / L, the compounds of this invention still exhibit good activity against aphids.

[0173] Table 26 lists the aphid activity of some compounds at 25 mg / L;

[0174] At 6.25 mg / L, (S)-107 and (S)-179 still maintain 100% activity against aphids.

[0175] Table 25. Activity (%) of some compounds against aphids under 200 mg / L conditions.

[0176]

[0177] Table 26. Activity (%) of some compounds against aphids at 25 mg / L.

[0178] No. (S)-10 (S)-26 (S)-33 (S)-37 (S)-56 (S)-107 (S)-171 (RS)-171 Activity 94.96 86.21 98.76 87.73 100 100 100 100 No. (S)-179 (S)-180 (S)-191 (S)-220 (S)-1006 (RS)-14171 32033 32171 Activity 100 100 98.08 83.21 90.78 90.54 97.50 77.79

[0179] Example 9: Evaluation of acaricidal activity against cotton red spider mite (Tetranychus urticae)

[0180] Spray method: The test compound was dissolved in a suitable solvent such as DMF, and then diluted to the required concentration with water containing 0.2% Tween 80 emulsifier. A blank control was set up without the test compound. Each treatment was repeated three times. Broad bean seedlings infested with the test mites were cut, 100-200 mites per plant, and placed in a beaker containing water. The beaker opening was sealed with parafilm and secured with a plastic gasket. A motorized sprayer was used to spray the seedlings, with a spray volume of 2 mL per plant. After the plants dried, they were covered with a kerosene lamp and placed in a recovery room for incubation. Mortality was assessed after 72 hours. Based on the blank control, the mortality rate was calculated, and the average value was taken. Partial results are shown below.

[0181] 200 mg / L. The activity of some compounds of this invention and D6 and D8 against cotton red spider mites is shown in Table 27.

[0182] At concentrations of 100 mg / L and 25 mg / L, the compounds of this invention still exhibit good activity against cotton spider mites. For example, at 25 mg / L, (S)-56 still exhibits 100% activity against cotton spider mites.

[0183] Table 27. Activity (%) of some compounds against cotton red spider mites under 200 mg / L conditions.

[0184] No. (S)-8 (S)-19 (S)-20 (S)-33 (S)-55 (S)-56 (S)-57 (S)-59 (S)-72 (S)-78 Activity 95.69 100 100 70.00 76.38 100 100 100 77.03 84.14 No. (S)-104 (RS)-171 (S)-173 (S)-220 (S)-225 (R)-14171 48006 D6 D8 Activity 79.86 88.89 100 100 100 100 79.78 47.28 49.00

[0185] Example 10: Evaluation of bioactivity against armyworm (Mythimna separata)

[0186] Potter spray method: The test compound is dissolved in a suitable solvent such as DMF, and then diluted to the required concentration with water containing 0.2% Tween 80 emulsifier. A blank control is set up without the test compound. Fresh, tender corn leaves are cut into pieces of roughly the same size and placed in a petri dish (Ф90mm) lined with filter paper. Ten third-instar armyworm larvae are then introduced into the dish, and the dish is placed under a Potter spray tower for quantitative spraying. The spray volume is 1mL, and each concentration is repeated three times. After treatment, the dish is covered and placed in a recovery room for incubation. Regular observation is performed, and mortality is investigated after 72 hours. Based on the blank control, the mortality rate is calculated, and the average value is taken.

[0187] 200 mg / L. Some compounds of this invention and the activities of D6 and D8 against armyworms are shown in Table 28.

[0188] At 100 mg / L, (S)-3, (S)-10, (S)-21, and (S)-107 showed 100% activity against armyworm; at 50 mg / L, (S)-10 and (S)-21 showed 100% activity against armyworm; and at 25 mg / L, (S)-10 showed 100% activity against armyworm.

[0189] Table 28. Activity (%) of some compounds against armyworms under 200 mg / L conditions.

[0190] No. (S)-3 (S)-8 (S)-10 (S)-19 (S)-21 (S)-33 (S)-37 (S)-59 (S)-72 Activity 100 100 100 100 100 95.00 90.00 75.00 100 No. (S)-98 (S)-107 (S)-113 (RS)-171 (S)-173 (S)-220 (S)-48003 D6 D8 Activity 100 100 100 70.00 100 100 100 0 0

[0191] Example 11: Fungicide activity against wheat powdery mildew (Erysiphegraminis)

[0192] Pot method: The test compound was dissolved in a suitable solvent such as DMF, and then diluted to the required concentration with sterile water containing 0.2% Tween 80 emulsifier. Pots with stems approximately 15cm in diameter were used, and 20 plump, healthy wheat seeds were sown in each pot. The seedlings were allowed to develop two leaves and a bud before being used for the experiment. Prepared wheat seedlings were sprayed with a certain concentration of the agent, and inoculated with pathogens one day later. Each treatment was repeated three times. A blank control (containing no test compound) and a commercial control (flusilazole (D3)) were used. The plants were incubated at a suitable temperature and humidity until the blank control developed symptoms. The lesion area was then assessed, and the control efficacy was calculated. The average value of the results was taken. Some results are shown below.

[0193] 50mg / L, (S)-8, (S)-11, (S)-17, (S)-37, (S)-41, (S)-43, (S)-55, (S)-56, (S) )-57, (S)-58, (S)-59, (S)-65, (S)-72, (S)-78, (S)-83, (S)-90, (S)-98, (S)- 102, (S)-104, (S)-107, (S)-113, (S)-133, (S)-151, (S)-171, (RS)-171, (S)- 173, (S)-178, (S)-179, (S)-180, (S)-191, (S)-192, (S)-220, (S)-225, (S)-3 06, (S)-315, (S)-421, (S)-1008, (S)-1056, (S)-1171, (S)-5171, (RS)-14171, and 48007 have Grade A control efficacy against wheat powdery mildew. (S)-1, (S)-7, (S)-16, (S)-26, (S)-33, (S)-35, and (S)-38 have similar efficacy. (S)-47, (S)-82, (S)-145, (S)-242, (S)-243, (S)-248, (S)-266, (S)-328, (S)-1006, (S)-5421, 32171, and 48006 have Class B protection effectiveness; under the same conditions, D3 has Class A protection effectiveness, D8 has Class B protection effectiveness, and D6 has Class C protection effectiveness.

[0194] 10 mg / L, (S)-8, (S)-17, (S)-55, (S)-56, (S)-58, (S)-65, (S)-78, (S)-90, (S)-104, (S)-107, (S)-151, (S)-171, (S)-178, (S)-179, (S)-191, (S)-192, (S)-220, (S)-421, and (S)-306 have Grade A control efficacy against wheat powdery mildew, while (S)-1, (S)-11, (S)-16, (S)-26, (S)-37, (S)-41, (S)-43, and (S)- 47, (S)-57, (S)-59, (S)-72, (S)-82, (S)-83, (S)-98, (S)-102, (S)-113, (S)-133, (RS)-171, (S)-173, (S)-180, (S)-225, (S)-235, (S)-315, (S)-328, (S)-1006, (S)-1008, (S)-1056, (S)-1171, (S)-5171, (RS)-14171, 48006, and 48007 have Class B protection effectiveness; under the same conditions, D3 has Class B protection effectiveness.

[0195] Further screening results showed that the compounds of this invention have good activity against wheat powdery mildew, and some results are as follows:

[0196] (S)-8, (S)-17, (S)-55, (S)-56, (S)-58, (S)-65, (S)-72, (S)-78, (S)-90, (S)-102, (S)-107 , (S)-171, (RS)-171, (S)-178, (S)-191, (S)-192, (S)-220, (S)-306, (S)-421, (S)-5171: ED 50 ≤0.50mg / L,

[0197] (S)-37, (S)-41, (S)-98, (S)-104, (S)-113, (S)-173, (S)-179: 0.50 <ED 50 ≤1.00mg / L,

[0198] (S)-16, (S)-59, (S)-83, (S)-266, (S)-315, (S)-1008: 1.00 <ED 50 <2.00 mg / L;

[0199] D1: ED 50 =0.80 mg / L, D3:ED 50 =1.07 mg / L, D5:ED 50 <0.50mg / L.

[0200] Example 12: Fungicide activity against corn rust (Puccinia polysora)

[0201] Pot method: The compound is dissolved in a suitable solvent such as DMF, and then diluted to the required concentration with sterile water containing 0.2% Tween 80 emulsifier. A blank control without the test compound is set up, and tebuconazole (D4) is used as a commercial control. Each treatment is replicated 4 times. Diseased corn leaves are cut off, and spores are washed off with a 0.05% Tween 80 or other suitable surfactant aqueous solution. The spores are filtered through 2-4 layers of gauze to prepare 1×10⁻⁶ spores. 5 A suspension of spores / mL was prepared; the test compound solution was sprayed on corn when it reached the 2-leaf, 1-heart stage. One day later, the spore suspension was sprayed for inoculation. After inoculation, the corn was transferred to a humidifier (relative humidity above 95%, temperature 20-22℃, light intensity 5000-10000 Lux under low light conditions) for 15-24 hours. When the disease rate of the blank control reached more than 50%, the disease incidence of each treatment was investigated, the control efficacy was calculated, and the average value was taken. Some results are as follows:

[0202] 50mg / L, (S)-17, (S)-33, (S)-37, (S)-47, (S)-55, (S)-56, (S)-57, (S)-58, (S)-59, (S) -65, (S)-72, (S)-78, (S)-82, (S)-83, (S)-90, (S)-98, (S)-102, (S)-104, (S)-107, (S) -113, (S)-133, (S)-145, (S)-171, (RS)-171, (S)-173, (S)-178, (S)-179, (S)-180, (S) -192, (S)-220, (S)-225, (S)-235, (S)-242, (S)-306, (S)-315, (S)-328, (S)-421, (S)- 1006, (S)-1008, (S)-1056, (S)-1171, (S)-5171, (S)-10171, (R)-14171, (S)-14171, (RS)-14171, 32033, 32171, (S)-48005, and 48007 have Grade A control efficacy against corn rust. (S)-1, (S)-7, (S)-8, and (S)-10... (S)-11, (S)-20, (S)-21, (S)-35, (S)-38, (S)-41, (S)-151, (S)-191, (S)-243, (S)-5421, (S)-14031, 48006, and (RS)-48008 have Class B protection efficacy; under the same conditions, D4 has Class A protection efficacy against corn rust, D8 has Class B protection efficacy, and D6 has Class C protection efficacy.

[0203] 10mg / L, (S)-33, (S)-37, (S)-55, (S)-56, (S)-57, (S)-58, (S)-65, (S) -72, (S)-78, (S)-83, (S)-90, (S)-98, (S)-104, (S)-107, (S)-113, (S) -133, (S)-171, (RS)-171, (S)-173, (S)-192, (S)-225, (S)-235, (S)-3 06. (S)-315, (S)-328, (S)-421, (S)-1056, (S)-1171, (R)-14171, 48007 It has Grade A control efficacy against corn rust, while (S)-7, (S)-17, (S)-47, (S)-59, (S)-82, (S)-102, (S)-145, (S)-151, (S)-178, (S)-179, (S)-180, (S)-220, (S)-242, (S)-243, (S)-1006, (S)-1008, (S)-5171, (S)-10171, (S)-14171, (RS)-14171, 32033, 32171, and 48006 have Grade B control efficacy. Under the same conditions, D4 has Grade B control efficacy against corn rust, D8 has Grade C control efficacy, and D6 has Grade D control efficacy.

[0204] Further screening results showed that the compounds of this invention have good activity against corn rust, and some results are as follows:

[0205] (S)-33, (S)-37, (S)-56, (S)-57, (S)-58, (S)-72, (S)-90, (S)-98, (S)-107, (S) )-113, (S)-171, (RS)-171, (S)-173, (S)-306, (S)-421, (S)-1056, (S)-1171: ED 50 ≤0.15mg / L,

[0206] (S)-55, (S)-65, (S)-78, (S)-102, (S)-192, (S)-315, (S)-328: 0.15 <ED 50 ≤0.25mg / L,

[0207] (S)-83, (S)-104, (S)-133, (S)-220, (S)-225, (S)-5171, (S)-10171: 0.25 <ED 50 ≤0.55mg / L,

[0208] (S)-17, (S)-145, (S)-151, (S)-179, (S)-235, (S)-242, (S)-1008, (RS)-14171, 32033, 32171, 48007: 0.55 <ED 50 ≤1.55mg / L;

[0209] D1: ED 50 =0.70 mg / L, D2:ED 50 =0.40 mg / L, D4:ED 50 =1.12 mg / L, D5:ED 50 =0.26mg / L.

[0210] Example 13: Fungicide activity against Gibberella zeae (wheat scab)

[0211] Methods: The test compound was dissolved in a suitable solvent such as DMF, and then diluted to the required concentration with sterile water containing 0.2% Tween 80 emulsifier. A blank without the test compound was set as a control. Each treatment was repeated 4 times. 3 mL of the drug solution was pipetted into 27 mL of potato agar medium (PDA) cooled to 45 °C and thoroughly mixed before being poured into a petri dish. After cooling, a 6 mm diameter mycelial block was taken from the edge of a 7-day-old bacterial colony using an inoculation needle and transferred to the center of the petri dish with the mycelial side facing down. After treatment, the petri dish was placed in a 28 °C constant temperature biochemical incubator for cultivation. The mycelial growth diameter was measured after 4 days. EXCEL statistical software was used for analysis and the mycelial growth inhibition rate was calculated. The activity relative to the blank control was expressed as a percentage, and the average value was taken.

[0212] Following the same method used for detecting Fusarium head blight in wheat, the fungicidal activities of *Phytophthora capsici* (the causal agent of pepper blight), *Alternaria alternata* (the causal agent of tobacco star rot), and *Botrytis cinerea* (the causal agent of gray mold in cucumber) were determined. Some results are shown below:

[0213] 50mg / L, (S)-7, (S)-10, (S)-11, (S)-17, (S)-33, (S)-47, (S)-55, (S)-56, (S) -65, (S)-90, (S)-104, (S)-107, (S)-133, (R)-171, (S)-173, (S)-179, (S)-19 1. (S)-220, (S)-225, (S)-306, (S)-421, (S)-1056, (S)-1171, (S)-5171, (S)-5421, (S)-10171, (S)-48001, and (S)-48005 exhibit Class C activity against Fusarium graminearum, the causal agent of wheat blight; under the same conditions, D6 and D8 exhibit Class D activity.

[0214] At 50 mg / L, (S)-8, (S)-11, (S)-17, (S)-19, (S)-56, (S)-58, (S)-65, (S)-78, (S)-104, (S)-171, (S)-173, (S)-225, (S)-5421, (R)-14171, (S)-48001, 48006, and 48007 exhibited Class C activity against Phytophthora capsici; under the same conditions, D6 and D8 exhibited Class D activity.

[0215] At 50 mg / L, (S)-178 exhibits grade B activity against *Acer buergerianum*, and the following active ingredients are listed: (S)-7, (S)-8, (S)-27, (S)-33, (S)-35, (S)-38, (S)-41, (S)-43, (S)-55, (S)-56, (S)-57, (S)-58, (S)-65, (S)-72, (S)-78, (S)-83, (S)-90, (S)-104, (S)-133, (S)-145, (S)-151, (S)-171, (RS)-171, (S)-178, (S)-179, and (S)-225. (S)-242, (S)-243, (S)-248, (S)-306, (S)-315, (S)-328, (S)-421, (S)-1006, (S)-1008, (S)-1056, (S)-1171, (S)-5171, (S)-5421, (S)-10171, (S)-14031, (R)-14171, (S)-14171, (RS)-14171, (S)-48001, (S)-48005, and 48006 exhibit Class C activity; under the same conditions, D6 exhibits Class C activity, and D8 exhibits Class D activity.

[0216] At 50 mg / L, (S)-48003 exhibited Grade A activity against gray mold of cucumber, (S)-133 and (S)-48001 exhibited Grade B activity, and (S)-3, (S)-8, (S)-10, (S)-16, (S)-21, (S)-33, (S)-35, (S)-37, (S)-56, (S)-59, (S)-248, (S)-306, (S)-315, (S)-328, and (S)-5421 exhibited Grade C activity; under the same conditions, D6 and D8 exhibited Grade D activity.

Claims

1. A pyrimidine amine benzoate compound, characterized in that... The structures of pyrimidine amine benzoate compounds are shown in general formula (I). in: R is selected from H, halogen, cyano, nitro, amino, hydroxy, mercapto, carboxyl, methyl, haloethyl, C3-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, and C3-C6 heterocyclic. The hydrogen atoms in R may be partially or completely substituted by substituents selected from the following same or different groups: halogen, cyano, nitro, amino, hydroxy, mercapto, carboxyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 alkylamino, and C1-C6 alkylcarbonyl. W is selected from H, halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, and C3-C6 heterocyclic. The hydrogen atoms in W may be partially or completely substituted by the same or different substituents selected from the following: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 alkylamine, C1-C6 alkylcarbonyl, and C1-C6 alkoxycarbonyl. X is selected from halogens; R 1 R 2 R 3 R 4 R 5 It is the same or different, selected from hydrogen, halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 heterocyclic, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylsilyl, C1-C6 alkylamine, C1-C6 dialkylamine, C1-C6 alkylcarbonyl, C1-C6 alkylcarbonyloxy, C1-C6 alkoxycarbonyloxy, C1-C6 alkoxycarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthiocarbonyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyloxy, C1-C6 alkylsulfinyloxy, C1-C6 alkylsulfonyloxy, phenyl, phenoxy, phenylthio, heteroaryl, heteroaryloxy, heteroarylthio, R 1 R 2 R 3 R 4 R 5 The hydrogen atom can be partially or completely substituted by the same or different substituents selected from the following: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylamine, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, R 1 R 2 R 3 R 4 R 5 It can also form five-, six-, seven-, or eight-membered rings containing C, N, O, or S with the connected benzene ring; R'、R 6 R 7 R 8 R 9 R 10 R 11 They are the same or different, selected from H, halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 heterocyclic, phenyl, phenoxy, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthiocarbonyl, C1-C6 alkylaminecarbonyl, R', R 6 R 7 R 8 R 9 R 10 R 11 The hydrogen atom can be partially or completely substituted by a substituent selected from the following same or different substituents: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 alkylamine, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, R 6 R 7 R 8 R 9 R 10 R 11 The C atoms connected to it can form C3-C6 rings or C3-C6 heterocycles; n is an integer of 0, 1, 2, or 3. When n is 2 or 3, R 10 Or R 11 Are they the same or different? Salts of Formula (I): Salts of compounds of Formula (I) with organic or inorganic acids; organic acids refer to carboxylic acids or sulfonic acids, selected from C1-C6. 18 Alkyl carboxylic acids, C2-C 18 Alkyl dicarboxylic acid, C4-C 18 Alkane tricarboxylic acid, C5-C 18 Alkanetetracarboxylic acid, C3-C 18 Encarboxylic acids, C4-C 18 olefinic acid, C3-C 18 Alkynic acid, C4-C 18 Alkyne dicarboxylic acid, benzoic acid, phthalic acid, C1-C 18 Alkanesulfonic acid, C3-C 18 Enyl sulfonic acid, C3-C 18 In acetylsulonic acids, the hydrogen atoms can be partially or completely substituted by the same or different substituents from the following: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C. 18 Alkyl, C1-C 18 Alkoxy, C1-C 18 Alkylthio, C1-C 18 Alkylamine group, C1-C 18 Alkyl carbonyl, C1-C 18 Alkoxycarbonyl; the inorganic acid is selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, or carbonic acid; In the definition given in equation (I) above, the terms used, whether alone or in compound words, represent the following substituents: Halogens: refer to fluorine, chlorine, bromine, and iodine; Alkyl: refers to straight-chain or branched alkyl groups; Cycloalkyl: refers to saturated or unsaturated cycloalkyl groups; Alkenyl; refers to a straight-chain or branched alkyl group, and may have one or more double bonds at any position; Alkynyl group; refers to a straight-chain or branched alkyl group, and may have one or more triple bonds at any position; Halogenation: refers to the replacement of some or all of the hydrogen atoms with halogen atoms.

2. The pyrimidine amine benzoate compound according to claim 1, characterized in that: In compound (I): R is selected from methyl, propyl, isopropyl, cyclopropyl, and C1-C3 haloalkyl; W is selected from H, halogen, cyano, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 heterocyclic, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylamine, and C1-C6 dialkylamine. The hydrogen atoms in W may be partially or completely substituted by substituents selected from the following same or different substituents: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylamine, C1-C6 alkylcarbonyl, and C1-C6 alkoxycarbonyl. X is selected from halogens; R 1 R 2 R 3 R 4 R 5 It is the same or different, selected from hydrogen, halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 heterocyclic, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylsilyl, C1-C6 alkylamine, C1-C6 dialkylamine, C1-C6 alkylcarbonyl, C1-C6 alkylcarbonyloxy, C1-C6 alkoxycarbonyloxy, C1-C6 alkoxycarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthiocarbonyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyloxy, C1-C6 alkylsulfinyloxy, C1-C6 alkylsulfonyloxy, phenyl, phenoxy, phenylthio, heteroaryl, heteroaryloxy, heteroarylthio, R 1 R 2 R 3 R 4 R 5 The hydrogen atom can be partially or completely substituted by the same or different substituents selected from the following: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylamine, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, R 1 R 2 R 3 R 4 R 5 It can also form five-, six-, seven-, or eight-membered rings containing C, N, O, or S with the connected benzene ring; R' represents H; R 6 R 7 R 8 R 9 R 10 R 11 They are the same or different, selected from H, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl; n is 0 or 1.

3. The pyrimidine amine benzoate compound according to claim 1, characterized in that: In compound (I): R is selected from methyl, fluoromethyl, and fluoroethyl; W is selected from H, halogen, C1-C3 alkyl, cyclopropyl, C1-C3 alkoxy, C1-C3 alkylthio, C1-C3 alkylamine, and C1-C3 dialkylamine. X is selected from halogens; R 1 R 2 R 3 R 4 R 5 It is the same or different, selected from hydrogen, halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 heterocyclic, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylsilyl, C1-C6 alkylamine, C1-C6 dialkylamine, C1-C6 alkylcarbonyl, C1-C6 alkylcarbonyloxy, C1-C6 alkoxycarbonyloxy, C1-C6 alkoxycarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthiocarbonyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyloxy, C1-C6 alkylsulfinyloxy, C1-C6 alkylsulfonyloxy, phenyl, phenoxy, phenylthio, heteroaryl, heteroaryloxy, heteroarylthio, R 1 R 2 R 3 R 4 R 5 The hydrogen atom can be partially or completely substituted by the same or different substituents selected from the following: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylamine, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, R 1 R 2 R 3 R 4 R 5 It can also form five-, six-, seven-, or eight-membered rings containing C, N, O, or S with the connected benzene ring; R' represents H; R 6 R 7 R 8 R 9 R 10 R 11 They may be the same or different, and are selected from hydrogen, C1-C3 alkyl, and cyclopropyl; n is 0 or 1.

4. The pyrimidine amine benzoate compound according to claim 1, characterized in that: Compounds of formula (I) are compounds represented by formulas IA, IB, IC, ID, IE, IF, IG, IH, II, IJ, IK, IL, IM, IN, IO, IP, IQ, IR, IS, and IT. in: R is selected from H, halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, and C3-C6 heterocyclic. The hydrogen atom in R may be partially or completely substituted by the same or different substituents selected from the following: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 alkylamine, and C1-C6 alkylcarbonyl. W is selected from H, halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, and C3-C6 heterocyclic. The hydrogen atoms in W may be partially or completely substituted by the same or different substituents selected from the following: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 alkylamine, C1-C6 alkylcarbonyl, and C1-C6 alkoxycarbonyl. X is selected from halogens; R 1 R 2 R 3 R 4 R 5 It is the same or different, selected from hydrogen, halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C3-C6 heterocyclic, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 alkylsilyl, C1-C6 alkylamine, C1-C6 dialkylamine, C1-C6 alkylcarbonyl, C1-C6 alkylcarbonyloxy, C1-C6 alkoxycarbonyloxy, C1-C6 alkoxycarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkylthiocarbonyl, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyloxy, C1-C6 alkylsulfinyloxy, C1-C6 alkylsulfonyloxy, phenyl, phenoxy, phenylthio, heteroaryl, heteroaryloxy, heteroarylthio, R 1 R 2 R 3 R 4 R 5 The hydrogen atom can be partially or completely substituted by the same or different substituents selected from the following: halogen, cyano, nitro, amino, hydroxyl, mercapto, carboxyl, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylamine, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, R 1 R 2 R 3 R 4 R 5 It can also form five-, six-, seven-, or eight-membered rings containing C, N, O, or S with the connected benzene ring; Salts of Formula (I): Salts of compounds of Formula (I) with organic or inorganic acids; the organic acids are selected from formic acid, acetic acid, propionic acid, butyric acid, cyclopentanoic acid, oxalic acid, adipic acid, benzoic acid, phthalic acid, lauric acid, maleic acid, fumaric acid, sorbic acid, malic acid, citric acid, tartaric acid, coconut oil acid, methanesulfonic acid, ethanesulfonic acid, and benzenesulfonic acid. The hydrogen atoms in the organic acid may be partially or completely substituted by the following same or different substituents: halogen, amino group, hydroxyl group, mercapto group, C1-C... 12 Alkyl, C1-C 12 Haloalkyl, C1-C 12 Alkoxy, C1-C 12 Halogenated alkoxy group; inorganic acid selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or carbonic acid.

5. The pyrimidine amine benzoate compound according to claim 1, characterized in that: The compound of formula (I) is: (S)-2-((5-chloro-6-(difluoromethyl)-2-methylpyrimidin-4-yl)amino)propylbenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 4-chlorobenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 4-methylbenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-4-difluoromethyl benzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-4-(trifluoromethyl)benzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-4-tert-butylbenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 4-phenylbenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl4-(difluoromethoxy)benzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl4-(trifluoromethoxy)benzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-3-(trifluoromethyl)benzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 3,4,5-trimethoxybenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 2-fluorobenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 2,6-difluorobenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 2,3,4,5-tetrafluorobenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 2,3,4,5,6-pentafluorobenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 2,6-dichlorobenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 2,4-dichlorobenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 2,4,6-trichlorobenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 2,4-dichloro-5-fluorobenzoate; (S)-2-((5-bromo-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-chloro-4-methylbenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-chloro-4-(trifluoromethyl)benzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-chloro-4-nitrobenzene ester; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-iodobenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 2-methylbenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-fluoro-6-methylbenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-chloro-6-methylbenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-bromo-6-methylbenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-methyl-4-fluorobenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-methyl-3,4-difluorobenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-methyl-4-chlorobenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-methyl-4,5-dichlorobenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-methyl-3-chlorobenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-methyl-4-bromobenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 2,6-dimethylbenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 2,4-dimethylbenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 2,3-dimethylbenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 2,4,6-trimethylbenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-methyl-4-methoxybenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-methyl-4-nitrobenzene ester; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-methyl-4-phenoxybenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-(difluoromethyl)benzoate; (R)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-(trifluoromethyl)benzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-(trifluoromethyl)benzoate; (RS)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-(trifluoromethyl)benzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-chloro-6-(trifluoromethyl)benzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-(trifluoromethyl)-4-fluorobenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-(trifluoromethyl)-4-chlorobenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-(trifluoromethyl)-4-bromobenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-(trifluoromethyl)-4-(4-chlorophenoxy)benzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-(trifluoromethyl)-4-nitrobenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 2-ethylbenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 2-methoxybenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-(trifluoromethoxy)benzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 2-ethoxybenzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-nitro-4-(trifluoromethyl)benzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-1-naphthyl carboxylate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-naphthyl carboxylate; (S)-2-((5-bromo-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-4-(trifluoromethyl)benzoate; (S)-2-((5-bromo-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl4-(difluoromethoxy)benzoate; (S)-2-((5-bromo-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl 2-methylbenzoate; (S)-2-((5-bromo-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-methyl-4-fluorobenzoate; (S)-2-((5-bromo-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-methyl-4-chlorobenzoate; (S)-2-((5-bromo-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-(trifluoromethyl)benzoate; (S)-2-((5-chloro-6-(difluoromethyl)-2-methylpyrimidin-4-yl)amino)propyl 4-methylbenzoate; (S)-2-((5-chloro-6-(difluoromethyl)-2-methylpyrimidin-4-yl)amino)propyl-4-(trifluoromethyl)benzoate; (S)-2-((5-chloro-6-(difluoromethyl)-2-methylpyrimidin-4-yl)amino)propyl 2-methylbenzoate; (S)-2-((5-chloro-6-(difluoromethyl)-2-methylpyrimidin-4-yl)amino)propyl-2-(trifluoromethyl)benzoate; (S)-2-((5-chloro-6-methylpyrimidin-4-yl)amino)propyl-2-(trifluoromethyl)benzoate; (S)-2-((5-bromo-6-methylpyrimidin-4-yl)amino)propyl-2-(trifluoromethyl)benzoate; (R)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)butyl-2-(trifluoromethyl)benzoate; (S)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)butyl-2-(trifluoromethyl)benzoate; (RS)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)butyl-2-(trifluoromethyl)benzoate; (S)-1-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-yl-2-chlorobenzoate; (R)-1-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-yl-2-(trifluoromethyl)benzoate; (S)-1-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-yl-2-(trifluoromethyl)benzoate; (RS)-1-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)propyl-2-yl-2-(trifluoromethyl)benzoate; (RS)-1-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)but-2-yl-2-(trifluoromethyl)benzoate; 2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)ethyl 2,6-dichlorobenzoate; 2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)ethyl 2-(trifluoromethyl)benzoate; (S)-2-((5-fluoro-2-chloropyrimidin-4-yl)amino)propyl 2-methylbenzoate; (S)-2-((5-fluoro-2-chloropyrimidin-4-yl)amino)propyl 2-fluorobenzoate; (S)-2-((2,5-dichloro-6-methylpyrimidin-4-yl)amino)propyl 2-(trifluoromethyl)benzoate; 2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)(methyl)amino)ethyl 2-(trifluoromethyl)benzoate; 2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)(methyl)amino)ethyl 2-methylbenzoate; (RS)-2-((5-chloro-6-(difluoromethyl)pyrimidin-4-yl)amino)-2-phenylethyl 2-(trifluoromethyl)benzoate.

6. The pyrimidine amine benzoate compound according to claim 1, characterized in that: Compounds of formula (I) include their salts, Z or E isomers, R or S isomers, cis or trans isomers, or mixtures thereof in any proportion.

7. The method for preparing the pyrimidine amine benzoate compound according to any one of claims 1 to 6, characterized in that: The pyrimidine amine benzoate compound shown in formula (I) is prepared by the reaction shown below. Reaction 1: Reaction 2: Reaction 3: In solvents such as dichloromethane, dichloroethane, toluene, xylene, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, pyridine, tetrahydrofuran, methanol, ethanol, isopropanol, acetone, butanone, methyl isobutyl ketone, acetonitrile, ethyl acetate, or dioxane, at -10°C to reflux temperature, in the presence of a dehydrating agent and a base, compound (II) reacts with compound (III) to yield compound (I), wherein the dehydrating agent is selected from dicyclohexylcarbodiimide, 1 -Ethyl-(3-dimethylaminopropyl)carbodiimide, 2-(7-azabenzotriazole)-N,N,N',N'-tetramethylurea hexafluorophosphate or benzotriazole-1-yloxytripyrrolidinephosphine hexafluorophosphate, wherein the base is selected from alkali metal hydrides such as sodium hydride, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, alkali metal carbonates such as sodium carbonate or potassium carbonate, alkali metal alkoxides such as sodium methoxide or sodium ethoxide, organic amines such as pyridine, methylpyridine, triethylamine or diisopropylethylamine; or In the solvents dichloromethane, dichloroethane, toluene, xylene, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, pyridine, tetrahydrofuran, methanol, ethanol, isopropanol, acetone, butanone, methyl isobutyl ketone, acetonitrile, ethyl acetate, or dioxane, at -10°C to reflux temperature, in the absence of a base or in the presence of a base, compound (II) reacts with compound (IV) to obtain compound (I), wherein the base is selected from alkali metal hydrides such as sodium hydride, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, alkali metal carbonates such as sodium carbonate or potassium carbonate, alkali metal alkoxides such as sodium methoxide or sodium ethoxide, organic amines such as pyridine, methylpyridine, triethylamine, or diisopropylethylamine; In solvents such as dichloromethane, dichloroethane, toluene, xylene, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, pyridine, tetrahydrofuran, methanol, ethanol, isopropanol, acetone, butanone, methyl isobutyl ketone, acetonitrile, ethyl acetate, or dioxane, at -10°C to reflux temperature, in the absence of or in the presence of a base, compound (V) reacts with compound (VI) to yield compound (II), wherein the base is selected from alkali metal hydrides such as sodium hydride, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, alkali metal carbonates such as sodium carbonate or potassium carbonate, alkali metal alkoxides such as sodium methoxide or sodium ethoxide, organic amines such as pyridine, methylpyridine, triethylamine, or diisopropylethylamine; In one or two solvents at 0°C to reflux temperature, the compound of formula (I) reacts with acid to obtain a salt of the compound of formula (I), wherein the solvent is selected from dichloromethane, dichloroethane, trichloromethane, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, N,N-dimethylformamide, tetrahydrofuran, ethyl acetate, methanol, ethanol, isopropanol or dioxane; In the formula, R, R', R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 W, X, n, and acid have the definition in claim 1, and L is a leaving group, chlorine or bromine.

8. Use of the pyrimidine amine benzoate compound according to any one of claims 1 to 6, characterized in that: Use for the preparation of a medicine having bactericidal or insecticidal / miticidal activity in the agricultural, forestry or health fields, or for the prevention and control of harmful pathogens or pests / mites in the agricultural, forestry or health fields.

9. A method for controlling harmful bacteria or pests / mites, characterized in that: Apply the pyrimidine amine benzoate compound of any one of claims 1 to 6 to harmful pathogens or pests / mites that need to be controlled, or their growth medium.

10. A bactericidal, insecticidal / mite-killing composition, characterized in that: The composition contains a pyrimidine amine benzoate compound as an active ingredient as described in any one of claims 1 to 6, wherein the weight percentage of the active ingredient in the composition is 0.5-99%.

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