Phenyl oxadiazole compound and application thereof

Abstract

The invention discloses a phenyl oxadiazole compound. The structure of the phenyl oxadiazole compound is shown as a general formula I, wherein each substituent group in the formula is defined in the specification. The compound provided by the invention has excellent bactericidal activity, and has excellent prevention and treatment effects on powdery mildew, downy mildew, rust disease and the like.

Description

Technical Field

[0001] This invention belongs to the field of agricultural sterilization, specifically relating to a novel phenyloxadiazole compound and its uses. Background Technology

[0002] Patents WO9636229, CN102336744, and WO2015056806 have successively disclosed some triazolinone and tetraazolinone compounds with bactericidal activity. However, phenyloxadiazole compounds with structures as shown in the general formula I of this invention have not been reported. Summary of the Invention

[0003] The purpose of this invention is to provide a phenyloxadiazole compound that can control harmful bacteria at very low doses, and to be used as a drug for preventing and controlling bacteria in agriculture or other fields.

[0004] To achieve the above objectives, the technical solution of the present invention is as follows:

[0005] Phenylediazole compounds are those represented by general formula I;

[0006]

[0007] In the formula:

[0008] R1 is selected from hydrogen, halogen, cyano, nitro, C1-C 12 Alkyl, halogenated C1-C 12 Alkyl, C3-C 12 cycloalkyl, halogenated C3-C 12 cycloalkyl, C1-C 12 Alkoxy, halogenated C1-C 12 Alkoxy, C1-C 12 Alkylthio, Halogenated C1-C 12 Alkylthio, C1-C 12 Alkylamino, C1-C 12 Alkyl sulfinyl, halogenated C1-C 12 alkyl sulfinyl, C1-C 12 Alkyl sulfonyl, halogenated C1-C 12 Alkyl sulfonyl, C2-C 12 Alkenyl, halogenated C2-C 12 alkenyl, C2-C 12 Alkyne group, halogenated C2-C 12 alkynyl group, C2-C 12 Alkenyl groups, halogenated C2-C 12 Alkenyl groups, C2-C 12 Acryloxy or halogenated C2-C 12 Acryloxy group;

[0009] R2 and R3 may be the same or different, and are selected from CR6 or N;

[0010] Located at the 2, 3, or 4 position of the benzene ring;

[0011] R4 is selected from hydrogen, halogen, cyano, amino, hydroxyl, mercapto, carboxyl, morpholino, C1-C 12 Alkyl, halogenated C1-C 12 Alkyl, cyano C1-C 12 Alkyl, C3-C 12 cycloalkyl, halogenated C3-C 12 cycloalkyl, C1-C 12 Alkoxy, halogenated C1-C 12 Alkoxy, C1-C 12 Alkylthio, Halogenated C1-C 12 Alkylthio, C2-C 12 Alkenyl groups, halogenated C2-C 12 Alkenyl groups, C2-C 12 Acryloxy group, halogenated C2-C 12 Acryloxy group, C1-C 12 Alkyl sulfinyl, halogenated C1-C 12 alkyl sulfinyl, C1-C 12 Alkyl sulfonyl, halogenated C1-C 12 Alkyl sulfonyl, C1-C 12 Alkoxy C1-C 12 Alkyl, halogenated C1-C 12 Alkoxy C1-C 12 Alkyl, C1-C 12 Alkylamino, Halogenated C1-C 12 Alkylamino or di(C1-C) 12 Alkylamino);

[0012] R5 is selected from hydrogen, halogen, cyano, nitro, C1-C. 12 Alkyl, halogenated C1-C 12 Alkyl, C3-C 12 cycloalkyl, halogenated C3-C 12 cycloalkyl, C1-C 12 Alkoxy, halogenated C1-C 12 Alkoxy, C1-C 12 Alkylthio, Halogenated C1-C 12 Alkylthio, C1-C 12 Alkylamino, C1-C 12 Alkyl sulfinyl, halogenated C1-C 12 alkyl sulfinyl, C1-C 12 Alkyl sulfonyl, halogenated C1-C 12 Alkyl sulfonyl, C2-C12 Alkenyl, halogenated C2-C 12 alkenyl, C2-C 12 Alkyne group, halogenated C2-C 12 alkynyl group, C2-C 12 Alkenyl groups, halogenated C2-C 12 Alkenyl groups, C2-C 12 Acryloxy or halogenated C2-C 12 Acryloxy group;

[0013] R6 is selected from hydrogen, halogen, cyano, C1-C. 12 Alkyl, halogenated C1-C 12 Alkyl, C3-C 12 cycloalkyl, halogenated C3-C 12 cycloalkyl, C1-C 12 Alkoxy, halogenated C1-C 12 Alkoxy, C1-C 12 Alkylthio, Halogenated C1-C 12 Alkylthio, C1-C 12 Alkylamino, C1-C 12 Alkyl sulfinyl, halogenated C1-C 12 alkyl sulfinyl, C1-C 12 Alkyl sulfonyl, halogenated C1-C 12 Alkyl sulfonyl, C2-C 12 Alkenyl groups, halogenated C2-C 12 Alkenyl groups, C2-C 12 Acryloxy or halogenated C2-C 12 Acryloxy group;

[0014] n can be selected from 0, 1, 2, 3 or 4; and when n is greater than 1, R5 can be the same or different.

[0015] X is selected from O or S;

[0016] Y is selected from O, S, or NH.

[0017] Furthermore, in compounds of general formula I:

[0018] R1 is selected from hydrogen, halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C1-C6 alkylthio, halo-C1-C6 alkylthio, C1-C6 alkylamino, C1-C6 alkylsulfinyl, halo-C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, halo-C1-C6 alkylsulfonyl, C2-C6 alkenyl, halo-C2-C6 alkenyl, C2-C6 alkynyl, halo-C2-C6 alkynyl, C2-C6 alkenyloxy, halo-C2-C6 alkenyloxy, C2-C6 alkynyloxy, or halo-C2-C6 alkynyloxy.

[0019] R2 and R3 may be the same or different, and are selected from CR6 or N;

[0020] Located at the 2, 3, or 4 position of the benzene ring;

[0021] R4 is selected from hydrogen, halogen, cyano, amino, hydroxyl, mercapto, carboxyl, morpholino, C1-C6 alkyl, halo-C1-C6 alkyl, cyano-C1-C6 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C1-C6 alkylthio, halo-C1-C6 alkylthio, C2-C6 alkenoxy, and halo-C2-C6 alkenoxy. C2-C6 alkynyloxy, halogenated C2-C6 alkynyloxy, C1-C6 alkyl sulfinyl, halogenated C1-C6 alkyl sulfinyl, C1-C6 alkyl sulfonyl, halogenated C1-C6 alkyl sulfonyl, C1-C6 alkoxy-C1-C6 alkyl, halogenated C1-C6 alkoxy-C1-C6 alkyl, C1-C6 alkylamino, halogenated C1-C6 alkylamino or di(C1-C6 alkylamino);

[0022] R5 is selected from hydrogen, halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C1-C6 alkylthio, halo-C1-C6 alkylthio, C1-C6 alkylamino, C1-C6 alkylsulfinyl, halo-C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, halo-C1-C6 alkylsulfonyl, C2-C6 alkenyl, halo-C2-C6 alkenyl, C2-C6 alkynyl, halo-C2-C6 alkynyl, C2-C6 alkenyloxy, halo-C2-C6 alkenyloxy, C2-C6 alkynyloxy, or halo-C2-C6 alkynyloxy.

[0023] R6 is selected from hydrogen, halogen, cyano, C1-C6 alkyl, halo-C1-C6 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C1-C6 alkylthio, halo-C1-C6 alkylthio, C1-C6 alkylamino, C1-C6 alkylsulfinyl, halo-C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, halo-C1-C6 alkylsulfonyl, C2-C6 alkenyloxy, halo-C2-C6 alkenyloxy, C2-C6 alkynyloxy, or halo-C2-C6 alkynyloxy.

[0024] n can be selected from 0, 1, 2, 3 or 4; and when n is greater than 1, R5 can be the same or different.

[0025] X is selected from O or S;

[0026] Y is selected from O or S.

[0027] Furthermore, in compounds of general formula I:

[0028] R1 is selected from hydrogen, halogen, cyano, nitro, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio, halo-C1-C4 alkylthio, C1-C4 alkylsulfinyl, halo-C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, halo-C1-C4 alkylsulfonyl, C2-C4 alkenyl, halo-C2-C4 alkenyl, C2-C4 alkynyl, halo-C2-C4 alkynyl, C2-C4 alkenyloxy, halo-C2-C4 alkenyloxy, C2-C4 alkynyloxy, or halo-C2-C4 alkynyloxy.

[0029] R2 is selected from CR6 or N;

[0030] R3 is selected from N;

[0031] Located at the 2, 3, or 4 position of the benzene ring;

[0032] R4 is selected from hydrogen, halogen, cyano, amino, hydroxyl, mercapto, carboxyl, morpholino, C1-C6 alkyl, halo-C1-C6 alkyl, cyano-C1-C4 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio, halo-C1-C4 alkylthio, C2-C4 alkenoxy, and halo-C2-C4 alkenoxy. C2-C4 alkynyloxy, halogenated C2-C4 alkynyloxy, C1-C4 alkyl sulfinyl, halogenated C1-C4 alkyl sulfinyl, C1-C4 alkyl sulfonyl, halogenated C1-C4 alkyl sulfonyl, C1-C4 alkoxy-C1-C4 alkyl, halogenated C1-C4 alkoxy-C1-C4 alkyl, C1-C4 alkylamino, halogenated C1-C4 alkylamino or di(C1-C4 alkylamino);

[0033] R5 is selected from hydrogen, halogen, cyano, nitro, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio, halo-C1-C4 alkylthio, C1-C4 alkylsulfinyl, halo-C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, halo-C1-C4 alkylsulfonyl, C2-C4 alkenyl, halo-C2-C4 alkenyl, C2-C4 alkynyl, halo-C2-C4 alkynyl, C2-C4 alkenyloxy, halo-C2-C4 alkenyloxy, C2-C4 alkynyloxy, or halo-C2-C4 alkynyloxy.

[0034] R6 is selected from hydrogen, halogen, cyano, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio, halo-C1-C4 alkylthio, C1-C4 alkylamino, C1-C4 alkylsulfinyl, halo-C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, halo-C1-C4 alkylsulfonyl, C2-C4 alkenyloxy, halo-C2-C4 alkenyloxy, C2-C4 alkynyloxy, or halo-C2-C4 alkynyloxy.

[0035] n can be selected from 0, 1, 2 or 3; and when n is greater than 1, R5 can be the same or different;

[0036] X is selected from O or S;

[0037] Y is selected from O or S.

[0038] Furthermore, in compounds of general formula I:

[0039] R1 is selected from hydrogen, halogen, cyano, nitro, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio, halo-C1-C4 alkylthio, C1-C4 alkylsulfinyl, halo-C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, halo-C1-C4 alkylsulfonyl, C2-C4 alkenyl, C2-C4 alkynyl, C2-C4 alkenyloxy, halo-C2-C4 alkenyloxy, C2-C4 alkynyloxy, or halo-C2-C4 alkynyloxy.

[0040] R2 is selected from CR6 or N;

[0041] R3 is selected from N;

[0042] Located at position 4 of the benzene ring;

[0043] R4 is selected from hydrogen, halogen, cyano, amino, hydroxyl, mercapto, C1-C6 alkyl, halo-C1-C6 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio, halo-C1-C4 alkylthio, C2-C4 alkenoxy, halo-C2-C4 alkenoxy, C2-C4 alkynoxy, halo-C2-C4 alkynoxy, C1-C4 alkylsulfinyl, halo-C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, halo-C1-C4 alkylsulfonyl, C1-C4 alkylamino or di(C1-C4 alkylamino);

[0044] R5 is selected from hydrogen, halogen, cyano, nitro, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C2-C4 alkenoxy, halo-C2-C4 alkenoxy, C2-C4 alkynoxy, or halo-C2-C4 alkynoxy.

[0045] R6 is selected from halogens, C1-C4 alkyl, halogenated C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, halogenated C1-C4 alkoxy, C1-C4 alkylthio, halogenated C1-C4 alkylthio, C1-C4 alkylamino, C1-C4 alkylsulfonyl, halogenated C1-C4 alkylsulfonyl, C2-C4 alkenyloxy, halogenated C2-C4 alkenyloxy, C2-C4 alkynyloxy, or halogenated C2-C4 alkynyloxy.

[0046] n can be selected from 0, 1, 2 or 3; and when n is greater than 1, R5 can be the same or different;

[0047] X is selected from O or S;

[0048] Y is selected from O or S.

[0049] Furthermore, in compounds of general formula I:

[0050] R1 is selected from hydrogen, halogen, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl;

[0051] R2 is selected from CR6 or N;

[0052] R3 is selected from N;

[0053] Located at position 4 of the benzene ring;

[0054] R4 is selected from hydrogen, halogen, cyano, amino, hydroxyl, mercapto, C1-C6 alkyl, halo-C1-C6 alkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, C1-C4 alkylthio, halo-C1-C4 alkylthio, C2-C4 alkenoxy, halo-C2-C4 alkenoxy, C2-C4 alkynoxy, halo-C2-C4 alkynoxy, C1-C4 alkylsulfonyl, halo-C1-C4 alkylsulfonyl, or C1-C4 alkylamino.

[0055] R5 is selected from hydrogen, halogen, cyano, nitro, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkoxy or halo-C1-C4 alkoxy;

[0056] R6 is selected from halogens or C1-C4 alkoxy groups;

[0057] n can be selected from 0, 1, 2 or 3; and when n is greater than 1, R5 can be the same or different;

[0058] X is selected from O or S;

[0059] Y is selected from O or S.

[0060] Furthermore, in compounds of general formula I:

[0061] R1 is selected from hydrogen, halogen, or C1-C4 alkyl;

[0062] R2 is selected from CR6 or N;

[0063] R3 is selected from N;

[0064] Located at position 4 of the benzene ring;

[0065] R4 is selected from hydrogen, C1-C6 alkyl, halo-C1-C5 alkyl, C3-C6 cycloalkyl or C1-C4 alkylamino;

[0066] R5 is selected from hydrogen, halogen, nitro, C1-C4 alkyl or C1-C4 alkoxy;

[0067] R6 is selected from halogens or C1-C4 alkoxy groups;

[0068] n is selected from 0, 1, 2, or 3;

[0069] X is selected from O or S;

[0070] Y is selected from O or S.

[0071] Furthermore, in compounds of general formula I:

[0072] R1 is selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, or isopropyl;

[0073] R2 is selected from CR6 or N;

[0074] R3 is selected from N;

[0075] Located at position 4 of the benzene ring;

[0076] R4 is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, difluoromethyl, trifluoromethyl, trifluoroethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylamino, ethylamino, n-propylamino, or isopropylamino;

[0077] R5 is selected from hydrogen, fluorine, chlorine, bromine, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy, or isopropoxy;

[0078] R6 is selected from chlorine, bromine, methoxy, ethoxy, n-propoxy, or isopropoxy;

[0079] n can be selected from 0, 1, 2 or 3; and when n is greater than 1, R5 can be the same or different;

[0080] X is selected from O or S;

[0081] Y is selected from O or S.

[0082] The phenyloxadiazole compounds are used as fungicides in agriculture or other fields.

[0083] In the definitions of compounds of general formula I given above, the terms used in the compilation are generally defined as follows:

[0084] Halogen: Refers to fluorine, chlorine, bromine, or iodine. Alkyl: Straight-chain or branched alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl, or tert-butyl. Cycloalkyl: Substituted or unsubstituted cyclic alkyl, such as cyclopropyl, cyclopentyl, or cyclohexyl. Substituents include methyl, halogen, etc. Haloalkyl: Straight-chain or branched alkyl, where the hydrogen atoms on these alkyl groups may be partially or completely replaced by halogen atoms, such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, etc. Alkylsulfinyl: Straight-chain or branched alkyl groups are attached to the structure via a sulfinyl group (-SO-), such as methylsulfinyl. Haloalkylsulfinyl: Straight-chain or branched alkylsulfinyl, where the hydrogen atoms on the alkyl group may be partially or completely replaced by halogen atoms. Haloalkylsulfonyl: Straight-chain or branched alkylsulfonyl, where the hydrogen atoms on the alkyl group may be partially or completely replaced by halogen atoms. Alkoxy: A straight-chain or branched alkyl group, linked to the structure by an oxygen atom bond. Halogenated alkoxy: A straight-chain or branched alkoxy group where the hydrogen atoms on these alkoxy groups may be partially or completely replaced by halogen atoms. Examples include chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, and trifluoroethoxy. Alkylthio: A straight-chain or branched alkyl group, linked to the structure by a sulfur atom bond. Halogenated alkylthio: A straight-chain or branched alkylthio group where the hydrogen atoms on these alkyl groups may be partially or completely replaced by halogen atoms. Examples include chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, and chlorofluoromethylthio. Alkylthioalkyl: Alkyl-S-alkyl-, e.g., CH3SCH2-. Haloalkylthioalkyl: The hydrogen atoms on the alkyl group of an alkylthioalkyl group may be partially or completely replaced by halogen atoms, such as ClCH2CH2SCH2-, CF3CH2SCH2-, etc. Alkylamino: Straight-chain or branched alkyl groups, linked to the structure by nitrogen atoms. Haloalkylamino: Straight-chain or branched alkylamino groups, where the hydrogen atoms on these alkyl groups may be partially or completely replaced by halogen atoms. Dialkylamino: Such as (CH3)2N-, (CH3CH2)2N-. Alkenyl: Straight-chain or branched alkenes, such as vinyl, 1-propenyl, 2-propenyl, and various butenyl, pentenyl, and hexenyl isomers. Alkenyl groups also include polyenes, such as 1,2-propadienyl and 2,4-hexadienyl. Haloalkenyl: Straight-chain or branched alkenes, where the hydrogen atoms on these alkenyl groups may be partially or completely replaced by halogen atoms. Alkenoxyl: Straight-chain or branched alkenes, linked to the structure by oxygen atoms. Haloalkenyloxy group: Straight-chain or branched alkenyloxy group, in which hydrogen atoms may be partially or completely replaced by halogen atoms. Alkynyl group: Straight-chain or branched alkynes, such as ethynyl, 1-propynyl, 2-propynyl, and various butynyl, pentyynyl, and hexynyl isomers. Alkynyl groups also include groups composed of multiple triple bonds, such as 2,5-hexadiynyl. Haloalkynyl group: Straight-chain or branched alkynes, in which hydrogen atoms may be partially or completely replaced by halogen atoms. Alkynoxy group: Straight-chain or branched alkynes, linked to the structure by oxygen atoms.Halogenated alkynyl groups: Straight-chain or branched alkynyl groups, where the hydrogen atoms on these alkynyl groups may be partially or completely replaced by halogen atoms. Alkyl sulfonyl groups: Straight-chain or branched alkyl groups connected to the structure via a sulfonyl group (-SO2-), such as methylsulfonyl groups. Halogenated alkyl sulfonyl groups: Straight-chain or branched alkyl sulfonyl groups, where the hydrogen atoms on the alkyl group may be partially or completely replaced by halogen atoms.

[0085] Some of the compounds of the present invention can be described using the specific compounds listed in Tables 1 to 10, but this does not limit the present invention.

[0086] Table 1: In general formula I, X = O, Y = O, R2 = C-OCH3, R3 = N. It is attached to the 4th position of the adjacent benzene ring, R1, R4, (R5) n The substituents are shown in Table 1, and the compounds are numbered sequentially from 1-1 to 1-1088.

[0087] Table 1

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102] Table 2: In general formula I, X = 0, Y = 0, R2 = N, R3 = N. Located at position 4 of the benzene ring, with substituents R1, R4, and (R5). nConsistent with Table 1, corresponding to 1-1 to 1-1088 in Table 1, the compound numbers are 2-1 to 2-1088 respectively.

[0103] Table 3: In general formula I, X = 0, Y = 0, R2 = C - Cl, R3 = N. Located at position 4 of the benzene ring, with substituents R1, R4, and (R5). n Consistent with Table 1, corresponding to 1-1 to 1-1088 in Table 1, the compound numbers are 3-1 to 3-1088 respectively.

[0104] Table 4: In general formula I, X = 0, Y = 0, R2 = C - SCH3, R3 = N. Located at position 4 of the benzene ring, with substituents R1, R4, and (R5). n Consistent with Table 1, corresponding to 1-1 to 1-1088 in Table 1, the compound numbers are 4-1 to 4-1088 respectively.

[0105] Table 5: In general formula I, X = 0, Y = 0, R2 = C - SCH3, R3 = N. Located at position 4 of the benzene ring, with substituents R1, R4, and (R5). n Consistent with Table 1, corresponding to 1-1 to 1-1088 in Table 1, the compound numbers are 5-1 to 5-1088 respectively.

[0106] Table 6: In General Formula I, X = S, Y = O, R2 = N, R3 = N Located at position 4 of the benzene ring, with substituents R1, R4, and (R5). n Consistent with Table 1, corresponding to 1-1 to 1-1088 in Table 1, the compound numbers are 6-1 to 6-1088 respectively.

[0107] Table 7: In general formula I, X = S, Y = O, R2 = C-Cl, R3 = N. Located at position 4 of the benzene ring, with substituents R1, R4, and (R5). n Consistent with Table 1, corresponding to 1-1 to 1-1088 in Table 1, the compound numbers are 7-1 to 7-1088 respectively.

[0108] Table 8: In general formula I, X = S, Y = O, R2 = C - SCH3, R3 = N. Located at position 4 of the benzene ring, with substituents R1, R4, and (R5). n Consistent with Table 1, corresponding to 1-1 to 1-1088 in Table 1, the compound numbers are 8-1 to 8-1088 respectively.

[0109] Table 9: In general formula I, X = S, Y = O, R2 = C - SCH3, R3 = N. Located at position 4 of the benzene ring, with substituents R1, R4, and (R5). n Consistent with Table 1, corresponding to 1-1 to 1-1088 in Table 1, the compound numbers are 9-1 to 9-1088 respectively.

[0110] Table 10: In general formula I, X = S, Y = O, R2 = C-OCH3, R3 = N. Located at position 4 of the benzene ring, with substituents R1, R4, and (R5). n Consistent with Table 1, they correspond sequentially to 1-1 to 1-1088 in Table 1, representing compound numbers from 10-1 to 10-1088.

[0111] The compounds of this invention are prepared by the following method, and the reaction formulas are as follows, wherein the groups are defined as above unless otherwise specified:

[0112] The preparation of compound I of general formula is carried out by the following method:

[0113]

[0114] Intermediate II reacts with R4COCl and R4CO-O-COR4 under alkaline conditions in a suitable solvent to give compound of general formula I. II can also be obtained by reacting with R4COOH under condensing agent, alkaline conditions, and a suitable solvent.

[0115] Suitable bases can be selected from triethylamine, diisopropylethylamine, pyridine, 4-N,N-dimethylpyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), etc.

[0116] The reaction is carried out in a suitable solvent, such as dichloromethane, trichloromethane, tetrahydrofuran, acetonitrile, toluene, xylene, benzene, 1,4-dioxane, N,N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, acetone, or butanone.

[0117] The reaction temperature can range from -30℃ to the solvent boiling point, typically from -10℃ to 80℃.

[0118] The reaction time ranges from 30 minutes to 10 hours, typically 1 to 5 hours.

[0119] Intermediate II can be prepared from intermediate III and hydroxylamine or hydroxylamine hydrochloride, referring to relevant literature such as WO200941972, US2009112024, CN111771883, CN107353230, CN114213403.

[0120] Intermediate III can be prepared from intermediates IV and V under suitable alkaline conditions and in a suitable solvent.

[0121]

[0122] Suitable solvents are selected from methanol, ethanol, ethyl acetate, benzene, toluene, xylene, chloroform, dichloromethane, water, tetrahydrofuran, acetonitrile, acetone, butanone, dioxane, N,N-dimethylformamide, N-methylpyrrolidone, or dimethyl sulfoxide, etc.

[0123] Suitable bases can be selected from potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium tert-butoxide, or sodium tert-butoxide, etc.

[0124] The optimal temperature for the reaction is preferably 0–100°C; the reaction time is 30 minutes to 20 hours, preferably 1–10 hours.

[0125] Intermediate V is commercially available, while intermediate IV can be prepared by known methods, such as those described in references WO9636229, CN102336744, and WO2015056806.

[0126] Compounds of general formula I exhibit excellent activity against a variety of pathogens in agriculture or other fields. Therefore, the present invention also includes the use of compounds of general formula I in agriculture or other fields for the preparation of fungicides.

[0127] The examples of diseases mentioned below are only used to illustrate the present invention, and are by no means limiting the present invention.

[0128] Compounds of general formula I can be used to control the following diseases: Oomycete diseases, such as downy mildew (downy mildew of cucumber, rapeseed, soybean, beet, sugarcane, tobacco, pea, loofah, winter melon, cantaloupe, Chinese cabbage, spinach, radish, grape, and onion), white rust (white rust of rapeseed and Chinese cabbage), and damping-off. (Rapeseed damping-off, tobacco damping-off, tomato damping-off, pepper damping-off, eggplant damping-off, cucumber damping-off, cotton seedling damping-off), cottony rot (pepper cottony rot, loofah cottony rot, winter melon cottony rot), blight (broad bean blight, cucumber blight, pumpkin blight, winter melon blight, watermelon blight, cantaloupe blight, pepper blight, leek blight, garlic blight, cotton blight), late blight (potato late blight, tomato late blight), etc.Deuteromycete diseases, such as wilt (sweet potato wilt, cotton wilt, sesame wilt, castor bean wilt, tomato wilt, bean wilt, cucumber wilt, loofah wilt, pumpkin wilt, winter melon wilt, watermelon wilt, cantaloupe wilt, pepper wilt, broad bean wilt, rapeseed wilt, soybean wilt), root rot (pepper root rot, eggplant root rot, bean root rot, cucumber root rot, bitter gourd root rot, cotton black root rot, broad bean root rot), damping-off (cotton seedling damping-off, sesame damping-off, pepper damping-off, cucumber damping-off, cabbage damping-off), anthracnose (sorghum anthracnose, cotton anthracnose, kenaf anthracnose, jute anthracnose, flax anthracnose, tobacco anthracnose, mulberry anthracnose). Anthracnose (including diseases such as anthracnose of peppers, eggplants, beans, cucumbers, bitter melons, zucchini, winter melons, watermelons, cantaloupes, and lychees); Verticillium wilt (including cotton, sunflowers, tomatoes, peppers, and eggplants); Black spot (including zucchini, winter melons, and cantaloupes); Gray mold (including cotton boll mold, kenaf gray mold, tomato gray mold, pepper gray mold, bean gray mold, celery gray mold, spinach gray mold, and kiwifruit gray mold); Brown spot (including cotton brown spot, jute brown spot, beet brown spot, peanut brown spot, pepper brown spot, winter melon brown spot, soybean brown spot, sunflower brown spot, and pea brown spot). Spot disease (broad bean brown spot), black spot (flax false black spot, rapeseed black spot, sesame black spot, sunflower black spot, castor bean black spot, tomato black spot, pepper black spot, eggplant black spot, green bean black spot, cucumber black spot, celery black spot, carrot black rot, carrot black spot, apple black spot, peanut black spot), leaf spot (tomato leaf spot, pepper leaf spot, celery leaf spot), early blight (tomato early blight, pepper early blight, eggplant early blight, potato early blight, celery early blight), ring spot (soybean ring spot, sesame ring spot, green bean ring spot), leaf blight (sesame leaf blight, sunflower leaf blight, watermelon leaf blight, melon leaf blight), stem base rot (tomato stem base rot, vegetable leaf blight). Bean stem base rot), and others (corn round spot, kenaf waist break, rice blast, chestnut black sheath disease, sugarcane eye spot, cotton boll aspergillosis, peanut crown rot, soybean stem blight, soybean black spot, melon large leaf spot, peanut net spot, tea red leaf spot, pepper white star disease, winter melon leaf spot, celery black rot, spinach heart rot, kenaf leaf mold, kenaf spot, jute stem spot, soybean purple spot, sesame leaf spot, castor bean gray spot, tea brown leaf spot, eggplant brown round star disease, common bean red spot, bitter gourd white spot, watermelon spot, jute blight, sunflower root and stem rot, common bean anthracnose, soybean target spot, eggplant scab leaf spot, cucumber target spot, tomato leaf mold, eggplant leaf mold, broad bean red spot, etc.);Basidiomycete diseases, such as rust (wheat stripe rust, wheat stem rust, wheat leaf rust, flower rust, sunflower rust, sugarcane rust, leek rust, onion rust, chestnut rust, soybean rust), smut (corn silk smut, corn smut, sorghum silk smut, sorghum loose smut, sorghum sturdy smut, sorghum pillar smut, chestnut smut, sugarcane smut, bean rust), and others (such as wheat sheath blight, rice sheath blight, etc.); ascomycete diseases, such as powdery mildew (wheat powdery mildew, rapeseed powdery mildew, sesame powdery mildew, etc.). Powdery mildew in sunflowers, beets, eggplants, peas, loofahs, pumpkins, zucchini, winter melons, cantaloupes, grapes, and broad beans; sclerotinia stem rot in flax, rapeseed, soybeans, peanuts, tobacco, peppers, eggplants, beans, peas, cucumbers, bitter melons, winter melons, watermelons, and celery; and black spot in apples and pears.

[0129] Due to their positive properties, the above compounds can be advantageously used to protect important crops, livestock and breeding stock in agriculture and horticulture, as well as environments frequented by humans, from pathogens.

[0130] To achieve the desired effect, the amount of compound used varies depending on various factors, such as the compound used, the crop being protected, the type of pest, the degree of infection, climatic conditions, the application method, and the formulation used.

[0131] A compound dosage of 10 grams to 5 kilograms per hectare can provide adequate control.

[0132] It should be clearly stated that various changes and modifications can be made within the scope defined by this invention.

[0133] Advantages of this invention:

[0134] This invention is structurally novel compared to existing technologies and may have a different target site. It exhibits significant activity against numerous fungal diseases, especially downy mildew and powdery mildew. The synthesis process is simple and easy for industrial production. Detailed Implementation

[0135] The following specific embodiments are used to further illustrate the present invention, but the present invention is by no means limited to these examples (unless otherwise noted, all raw materials used are commercially available).

[0136] Synthesis Examples

[0137] Example 1: Preparation of compounds 1-5

[0138]

[0139] 1) Preparation of 4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-methylbenzonitrile

[0140] In a 100 mL single-necked flask, 4-(2-(bromomethyl)phenyl)-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one (2.25 g, 7.5 mmol; its synthesis is described in reference CN102336744), anhydrous potassium carbonate (2.59 g, 18.7 mmol), and 2-methyl-4-cyanophenol (1 g, 7.5 mmol) were added sequentially to the reaction flask. 40 mL of N,N-dimethylformamide was added, and the mixture was heated to 40 °C and stirred for 4 hours. The reaction was monitored by TLC until it was essentially complete. The mixture was poured into water and extracted with 100 mL of ethyl acetate. The organic phase was washed with 50 mL of saturated brine. After solvent removal, the residue was subjected to column chromatography (eluent: ethyl acetate and petroleum ether, volume ratio 1:5) to give 1.75 g of the product. 1 H NMR(600MHz,Chloroform-d)δ7.61-7.56(m,1H),7.53-7.39(m,3H),7.38-7.23(m,2H) ,6.85(d,J=8.5Hz,1H),5.16(d,J=10.6Hz,2H),3.92(s,3H),3.41(s,3H),2.22(s,3H).

[0141] 2) Preparation of (Z)-N'-hydroxy-4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-methylbenzamidin

[0142] In a 100 mL single-necked reaction flask, 1.5 g (4.28 mmol) of 4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-methylbenzonitrile (obtained in the previous step), 35 mL of ethanol, and 0.42 g (6.4 mmol) of 50% hydroxylamine solution were added dropwise while stirring at room temperature. The mixture was then refluxed for 1 hour. TLC monitoring showed the reaction was essentially complete. After cooling to room temperature, the solution was removed under vacuum, and 50 mL of water was added. Extraction was performed with ethyl acetate (50 mL x 2). The organic phase was dried over anhydrous magnesium sulfate, and after further solvent removal, 1.64 g of product was obtained. This product was used directly in the next step without further purification. HRMS (m / Z): 384.1650 [M+H] + .

[0143] 3) Preparation of compounds 1-5

[0144] In a 50 mL single-necked reaction flask, (Z)-N'-hydroxy-4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-methylbenzamidinium (0.38 g, 1 mmol) and pyridine (0.09 g, 1.2 mmol), and 30 mL of acetonitrile were added sequentially to the reaction flask. Acetic anhydride 0.11 g (1.08 mmol) was added dropwise with stirring at room temperature. After stirring at room temperature for 30 minutes, the mixture was refluxed for 2 hours. After the reaction was completed by TLC monitoring, the solvent was removed by vacuum distillation, and ethyl acetate (2 × 50 mL) was added for extraction. The organic phase was washed with 50 mL of saturated brine. After solvent removal, the residue was subjected to column chromatography (eluent: ethyl acetate and petroleum ether, volume ratio 1:5) to give 0.32 g of compounds 1-5. 1 ¹H-NMR (600MHz, internal standard TMS, solvent CDCl₃) δ (ppm): 7.85-7.79 (m, 2H), 7.65 (d, J = 7.5Hz, 1H), 7.49 (dd, J = 7.7, 1.5Hz, 1H), 7.47-7.42 (m, 1H), 7.25 (s, 1H), 6.86 (d, J = 8.6Hz, 1H), 5.15 (d, J = 10.6Hz, 2H), 3.92 (s, 3H), 3.41 (s, 3H), 2.63 (s, 3H), 2.35 (s, 3H).

[0145] Example 2: Preparation of compounds 1-69

[0146]

[0147] 1) Preparation of 4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)benzonitrile

[0148] In a 100 mL single-necked flask, 4-(2-(bromomethyl)phenyl)-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one (2.50 g, 8.4 mmol; its synthesis is described in reference CN102336744), anhydrous potassium carbonate (2.9 g, 21 mmol), and 4-cyanophenol (1 g, 8.4 mmol) were added sequentially to the reaction flask. 60 mL of N,N-dimethylformamide was added, and the mixture was heated to 40 °C and stirred for 4 hours. The reaction was monitored by TLC until it was basically complete. The mixture was poured into water and extracted with 100 mL of ethyl acetate. The organic phase was washed with 50 mL of saturated brine. After solvent removal, the residue was subjected to column chromatography (eluting agents were ethyl acetate and petroleum ether, volume ratio 1:5) to give 2.1 g of the product. 1H NMR(600MHz,Chloroform-d)δ8.04-8.01(m,2H),7.64-7.59(m,1H),7.47(dtd,J=20.5,7.5,1.6Hz ,2H),7.30-7.26(m,1H),7.00(d,J=8.9Hz,2H),5.16(q,J=12.6Hz,2H),3.94(s,3H),3.40(s,3H).

[0149] 2) Preparation of (Z)-N'-hydroxy-4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)benzamidin

[0150] In a 100 mL single-necked reaction flask, 1.8 g (5.35 mmol) of 4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)benzonitrile (obtained in the previous step), 35 mL of ethanol, and 0.64 g (9.63 mmol) of 50% hydroxylamine solution were added dropwise under stirring at room temperature. The mixture was then refluxed for 1 hour. TLC monitoring showed the reaction was essentially complete. After cooling to room temperature, the solution was removed under vacuum, and 50 mL of water was added. Extraction was performed with ethyl acetate (50 mL x 2). The organic phase was dried over anhydrous magnesium sulfate, and after further solvent removal, 1.84 g of product was obtained. This product was used directly in the next step without further purification. HRMS (m / Z): 370.1508 [M+H] + .

[0151] 3) Preparation of compounds 1-69

[0152] In a 50 mL single-necked reaction flask, 0.37 g (1 mmol) of Z)-N'-hydroxy-4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)benzamide (0.09 g (1.2 mmol)) and 30 mL of acetonitrile were added dropwise to the reaction flask with stirring at room temperature. After stirring at room temperature for 30 minutes, the mixture was refluxed for 2 hours. After the reaction was completed by TLC monitoring, the solvent was removed by vacuum distillation, and the mixture was extracted with ethyl acetate (2 × 50 mL). The organic phase was washed with 50 mL of saturated brine. After solvent removal, the residue was subjected to column chromatography (eluting agent: ethyl acetate and petroleum ether, volume ratio 1:5) to give 0.38 g of compound 1-69. 1¹H-NMR (600MHz, internal standard TMS, solvent CDCl₃) δ (ppm): 8.04–8.01 (m, 2H), 7.64–7.59 (m, 1H), 7.47 (dtd, J = 20.5, 7.5, 1.6 Hz, 2H), 7.30–7.26 (m, 1H), 7.00 (d, J = 8.9 Hz, 2H), 5.16 (q, J = 12.6 Hz, 2H), 3.94 (s, 3H), 3.40 (s, 3H).

[0153] Example 3: Preparation of compounds 1-70

[0154]

[0155] 1) Preparation of 4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-fluorobenzonitrile

[0156] In a 100 mL single-necked flask, 4-(2-(bromomethyl)phenyl)-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one (2.17 g, 7.3 mmol; its synthesis is described in reference CN102336744), anhydrous potassium carbonate (2.51 g, 18.2 mmol), and 2-fluoro-4-cyanophenol (1 g, 7.3 mmol) were added sequentially to the reaction flask. 40 mL of N,N-dimethylformamide was added, and the mixture was heated to 40 °C and stirred for 4 hours. The reaction was monitored by TLC until it was basically complete. The mixture was poured into water and extracted with 100 mL of ethyl acetate. The organic phase was washed with 50 mL of saturated brine. After solvent removal, the residue was subjected to column chromatography (eluting agents were ethyl acetate and petroleum ether, volume ratio 1:5) to give 1.52 g of product. 1 H NMR(600MHz,Chloroform-d)δ7.60-7.56(m,1H),7.48(td,J=6.9,1.8Hz,2H),7.39-7.33(m,2H ),7.29-7.25(m,1H),7.04(t,J=8.4Hz,1H),5.23(d,J=12.7Hz,2H),3.94(s,3H),3.38(s,3H).

[0157] 2) Preparation of (Z)-N'-hydroxy-4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-fluorobenzomididine

[0158] In a 100 mL single-necked reaction flask, 1.3 g (3.67 mmol) of 4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-fluorobenzonitrile (obtained in the previous step), 35 mL of ethanol, and 0.36 g (5.5 mmol) of 50% hydroxylamine solution were added dropwise under stirring at room temperature. The mixture was then refluxed for 1 hour. TLC monitoring showed the reaction was essentially complete. After cooling to room temperature, the solution was removed under vacuum, and 50 mL of water was added. Extraction was performed with ethyl acetate (50 mL x 2). The organic phase was dried over anhydrous magnesium sulfate, and after further solvent removal, 1.41 g of product was obtained. This product was used directly in the next step without further purification. HRMS (m / Z): 388.1397 [M+H] + .

[0159] 3) Preparation of compounds 1-70

[0160] In a 50 mL single-necked reaction flask, (Z)-N'-hydroxy-4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-fluorobenzomidine (0.39 g, 1 mmol) and pyridine (0.09 g, 1.2 mmol), and 30 mL of acetonitrile were added sequentially to the reaction flask. Trifluoroacetic anhydride (0.23 g, 1.08 mmol) was added dropwise with stirring at room temperature. After stirring at room temperature for 30 minutes, the mixture was refluxed for 2 hours. After the reaction was completed by TLC monitoring, the solvent was removed by vacuum distillation, and the mixture was extracted with ethyl acetate (2 × 50 mL). The organic phase was washed with 50 mL of saturated brine. After solvent removal, the residue was subjected to column chromatography (eluent: ethyl acetate and petroleum ether, volume ratio 1:5) to give 0.33 g of compound 1-70. 1 ¹H-NMR (600MHz, internal standard TMS, solvent CDCl₃) δ (ppm): 7.83 (ddd, J = 10.2, 3.8, 2.0 Hz, 2H), 7.65-7.61 (m, 1H), 7.48 (dtd, J = 18.7, 7.5, 1.6 Hz, 2H), 7.28 (dd, J = 7.7, 1.5 Hz, 1H), 7.08 (t, J = 8.5 Hz, 1H), 5.37-5.02 (m, 2H), 3.95 (s, 3H), 3.39 (s, 3H).

[0161] Example 4: Preparation of compounds 1-71

[0162]

[0163] 1) Preparation of 4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-chlorobenzonitrile

[0164] In a 100 mL single-necked flask, 4-(2-(bromomethyl)phenyl)-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one (1.94 g, 6.51 mmol; its synthesis is described in reference CN102336744), anhydrous potassium carbonate (2.25 g, 16.3 mmol), and 2-chloro-4-cyanophenol (1 g, 6.51 mmol) were added sequentially to the reaction flask. 40 mL of N,N-dimethylformamide was added, and the mixture was heated to 40 °C and stirred for 4 hours. The reaction was monitored by TLC until it was basically complete. The mixture was poured into water and extracted with 100 mL of ethyl acetate. The organic phase was washed with 50 mL of saturated brine. After solvent removal, the residue was subjected to column chromatography (eluting agents were ethyl acetate and petroleum ether, volume ratio 1:5) to give 1.45 g of product. 1 H NMR(600MHz,Chloroform-d)δ7.66(d,J=2.1Hz,1H),7.62(d,J=8.1Hz,1H),7.52-7.44(m,3H) ,7.27-7.26(m,1H),7.01(d,J=8.6Hz,1H),5.26(d,J=26.2Hz,2H),3.94(s,3H),3.41(s,3H).

[0165] 2) Preparation of (Z)-N'-hydroxy-4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-chlorobenzamidin

[0166] In a 100 mL single-necked reaction flask, 1.36 g (3.67 mmol) of 4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-chlorobenzonitrile (obtained in the previous step), 35 mL of ethanol, and 0.36 g (5.5 mmol) of 50% hydroxylamine solution were added dropwise while stirring at room temperature. The mixture was then refluxed for 1 hour. TLC monitoring showed the reaction was essentially complete. After cooling to room temperature, the solution was removed under vacuum, and 50 mL of water was added. Extraction was performed with ethyl acetate (50 mL x 2). The organic phase was dried over anhydrous magnesium sulfate, and after further solvent removal, 1.48 g of product was obtained. This product was used directly in the next step without further purification. HRMS (m / Z): 404.1105 [M+H] + .

[0167] 3) Preparation of compounds 1-71

[0168] In a 50 mL single-necked reaction flask, (Z)-N'-hydroxy-4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-chlorobenzamidin (0.4 g, 1 mmol) and pyridine (0.09 g, 1.2 mmol), and 30 mL of acetonitrile were added dropwise. Trifluoroacetic anhydride (0.23 g, 1.08 mmol) was added dropwise with stirring at room temperature. After stirring at room temperature for 30 minutes, the mixture was refluxed for 2 hours. After the reaction was completed by TLC monitoring, the solvent was removed by vacuum distillation, and the mixture was extracted with ethyl acetate (2 × 50 mL). The organic phase was washed with 50 mL of saturated brine. After solvent removal, the residue was subjected to column chromatography (eluent: ethyl acetate and petroleum ether, volume ratio 1:5) to give 0.39 g of compound 1-71. 1 ¹H-NMR (600MHz, internal standard TMS, solvent CDCl₃) δ (ppm): 7.93–7.97 (m, 2H), 7.65–7.61 (m, 1H), 7.48 (dtd, J = 18.7, 7.5, 1.6 Hz, 2H), 7.32 (dd, J = 7.7, 1.5 Hz, 1H), 7.08 (t, J = 8.5 Hz, 1H), 5.35–5.12 (m, 2H), 3.95 (s, 3H), 3.40 (s, 3H).

[0169] Example 5: Preparation of compounds 1-73

[0170] In a 50 mL single-necked reaction flask, (Z)-N'-hydroxy-4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-methylbenzamidinium (0.35 g, 0.9 mmol) and pyridine (0.22 g, 2.7 mmol), and 30 mL of acetonitrile were added sequentially to the reaction flask. Trifluoroacetic anhydride (0.38 g, 1.8 mmol) was added dropwise with stirring at room temperature. After stirring at room temperature for 30 minutes, the mixture was refluxed for 2 hours. After the reaction was completed by TLC monitoring, the solvent was removed by vacuum distillation, and ethyl acetate (2 × 50 mL) was added for extraction. The organic phase was washed with 50 mL of saturated brine. After solvent removal, the residue was subjected to column chromatography (eluent: ethyl acetate and petroleum ether, volume ratio 1:5) to give 0.33 g of compound 1-73. 1¹H-NMR (600MHz, internal standard TMS, solvent CDCl₃) δ (ppm): 7.89 (s, 2H), 7.64 (d, J = 7.7Hz, 1H), 7.48 (dtd, J = 26.7, 7.6, 1.5Hz, 2H), 7.29–7.26 (m, 1H), 6.91 (d, J = 8.3Hz, 1H), 5.18 (d, J = 11.2Hz, 2H), 3.93 (s, 3H), 3.42 (s, 3H), 2.28 (s, 3H).

[0171] Example 6: Preparation of compounds 1-74

[0172]

[0173] 1) Preparation of 4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-methoxybenzonitrile

[0174] In a 100 mL single-necked flask, 4-(2-(bromomethyl)phenyl)-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one (2.0 g, 6.71 mmol; its synthesis is described in reference CN102336744), anhydrous potassium carbonate (2.32 g, 16.8 mmol), and 2-methoxy-4-cyanophenol (1 g, 6.71 mmol) were added sequentially to the reaction flask. 40 mL of N,N-dimethylformamide was added, and the mixture was heated to 40 °C and stirred for 4 hours. The reaction was monitored by TLC until it was essentially complete. The mixture was poured into water and extracted with 100 mL of ethyl acetate. The organic phase was washed with 50 mL of saturated brine. After solvent removal, the residue was subjected to column chromatography (eluting agents were ethyl acetate and petroleum ether, volume ratio 1:5) to give 1.65 g of the product. 1 H NMR(600MHz,Chloroform-d)δ7.60-7.56(m,1H),7.44(ddd,J=11.5,7.5,1.7Hz,2H),7.27-7.22(m,1H),7.19(dd,J=8.4 ,1.9Hz,1H),7.08(d,J=1.9Hz,1H),6.88(d,J=8.4Hz,1H),5.21(d,J=2.8Hz,2H),3.93(s,3H),3.89(s,3H),3.40(s,3H).

[0175] 2) Preparation of (Z)-N'-hydroxy-4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-methoxybenzamidin

[0176] In a 100 mL single-necked reaction flask, 1.42 g (3.88 mmol) of 4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-methoxybenzonitrile (obtained in the previous step), 35 mL of ethanol, and 0.42 g (5.8 mmol) of 50% hydroxylamine solution were added dropwise while stirring at room temperature. The mixture was then refluxed for 1 hour. TLC monitoring showed the reaction was essentially complete. After cooling to room temperature, the solution was removed under vacuum, and 50 mL of water was added. Extraction was performed with ethyl acetate (50 mL x 2). The organic phase was dried over anhydrous magnesium sulfate, and after further solvent removal, 1.51 g of product was obtained. This product was used directly in the next step without further purification. HRMS (m / Z): 400.1612 [M+H] + .

[0177] 3) Preparation of compounds 1-74

[0178] In a 50 mL single-necked reaction flask, (Z)-N'-hydroxy-4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-methoxybenzamidin (0.46 g, 1.15 mmol) and pyridine (0.1 g, 1.38 mmol), and 30 mL of acetonitrile were added dropwise. Trifluoroacetic anhydride (0.26 g, 1.24 mmol) was added dropwise with stirring at room temperature. After stirring at room temperature for 30 minutes, the mixture was refluxed for 2 hours. After the reaction was completed by TLC monitoring, the solvent was removed by vacuum distillation, and the mixture was extracted with ethyl acetate (2 × 50 mL). The organic phase was washed with 50 mL of saturated brine. After solvent removal, the residue was subjected to column chromatography (eluent: ethyl acetate and petroleum ether, volume ratio 1:5) to give 0.41 g of compound 1-74. 1 ¹H-NMR (600MHz, internal standard TMS, solvent CDCl₃) δ (ppm): 7.64 (dd, J = 8.4, 2.0Hz, 1H), 7.57 (d, J = 2.0Hz, 1H), 7.45 (dtd, J = 24.6, 7.5, 1.5Hz, 2H), 7.25 (dd, J = 7.8, 1.5Hz, 2H), 6.93 (d, J = 8.4Hz, 1H), 5.22 (s, 2H), 3.96 (s, 3H), 3.94 (s, 3H), 3.41 (s, 3H).

[0179] Example 7: Preparation of compound 1-138

[0180] In a 50 mL single-necked reaction flask, (Z)-N'-hydroxy-4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-fluorobenzomidine (0.39 g, 1 mmol) and pyridine (0.09 g, 1.2 mmol), and 30 mL of acetonitrile were added dropwise to the reaction flask with stirring at room temperature. After stirring at room temperature for 30 minutes, the mixture was refluxed for 2 hours. After the reaction was completed by TLC monitoring, the solvent was removed by vacuum distillation, and ethyl acetate (2 × 50 mL) was added for extraction. The organic phase was washed with 50 mL of saturated brine. After solvent removal, the residue was subjected to column chromatography (eluting agent: ethyl acetate and petroleum ether, volume ratio 1:5) to give 0.32 g of compound 1-138. 1 ¹H-NMR (600MHz, internal standard TMS, solvent CDCl₃) δ (ppm): 7.85-7.78 (m, 2H), 7.63 (d, J = 7.6Hz, 1H), 7.48 (dt, J = 21.3, 7.8Hz, 2H), 7.34 (dd, J = 22.1, 8.3Hz, 1H), 7.10-7.04 (m, 1H), 6.84 (td, J = 52.3, 3.3Hz, 1H), 5.36-5.10 (m, 2H), 3.95 (s, 3H), 3.40 (s, 3H).

[0181] Example 8: Preparation of Compounds 1-141

[0182] In a 50 mL single-necked reaction flask, (Z)-N'-hydroxy-4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-methylbenzamidinium (0.35 g, 0.9 mmol) and pyridine (0.22 g, 2.7 mmol), and 30 mL of acetonitrile were added sequentially to the reaction flask. 0.32 g (1.8 mmol) of difluoroacetic anhydride was added dropwise with stirring at room temperature. After stirring at room temperature for 30 minutes, the mixture was refluxed for 2 hours. After the reaction was completed by TLC monitoring, the solvent was removed by vacuum distillation, and the mixture was extracted with ethyl acetate (2 × 50 mL). The organic phase was washed with 50 mL of saturated brine. After solvent removal, the residue was subjected to column chromatography (eluent: ethyl acetate and petroleum ether, volume ratio 1:5) to give 0.31 g of compound 1-141. 1¹H-NMR (600MHz, internal standard TMS, solvent CDCl₃) δ (ppm): 7.85-7.79 (m, 2H), 7.65 (d, J = 7.5Hz, 1H), 7.49 (dd, J = 7.7, 1.5Hz, 1H), 7.47-7.42 (m, 1H), 7.25 (s, 1H), 6.86 (d, J = 8.6Hz, 1H), 5.15 (d, J = 10.6Hz, 2H), 3.92 (s, 3H), 3.41 (s, 3H), 2.63 (s, 3H), 2.35 (s, 3H).

[0183] Example 9: Preparation of Compounds 1-142

[0184] In a 50 mL single-necked reaction flask, (Z)-N'-hydroxy-4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-methoxybenzamide (0.46 g, 1.15 mmol) and pyridine (0.1 g, 1.38 mmol), and 30 mL of acetonitrile were added sequentially to the reaction flask. 0.22 g (1.24 mmol) of difluoroacetic anhydride was added dropwise with stirring at room temperature. After stirring at room temperature for 30 minutes, the mixture was refluxed for 2 hours. After the reaction was completed by TLC monitoring, the solvent was removed by vacuum distillation, and ethyl acetate (2 × 50 mL) was added for extraction. The organic phase was washed with 50 mL of saturated brine. After solvent removal, the residue was subjected to column chromatography (eluent: ethyl acetate and petroleum ether, volume ratio 1:5) to give 0.38 g of compound 1-142. 1 ¹H-NMR (600MHz, internal standard TMS, solvent CDCl₃) δ (ppm): 7.65-7.61 (m, 2H), 7.58 (d, J = 1.9 Hz, 1H), 7.48 (td, J = 7.6, 1.4 Hz, 1H), 7.45-7.41 (m, 1H), 7.25 (d, J = 1.4 Hz, 1H), 6.97-6.72 (m, 2H), 5.30 (s, 1H), 5.25-5.14 (m, 2H), 3.96 (s, 3H), 3.94 (s, 3H), 3.42 (s, 3H).

[0185] Example 10: Preparation of compound 1-413

[0186] In a 50 mL single-necked reaction flask, (Z)-N'-hydroxy-4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-methylbenzamidinium (0.35 g, 0.9 mmol) and pyridine (0.22 g, 2.7 mmol), and 30 mL of acetonitrile were added dropwise to the reaction flask with stirring at room temperature. Cyclopropylformyl chloride (0.19 g, 1.8 mmol) was added dropwise. After stirring at room temperature for 30 minutes, the mixture was refluxed for 2 hours. After the reaction was completed by TLC monitoring, the solvent was removed by vacuum distillation, and ethyl acetate (2 × 50 mL) was added for extraction. The organic phase was washed with 50 mL of saturated brine. After solvent removal, the residue was subjected to column chromatography (eluting agent: ethyl acetate and petroleum ether, volume ratio 1:5) to give 0.25 g of compound 1-413. 1 ¹H-NMR (600MHz, internal standard TMS, solvent CDCl₃) δ (ppm): 7.76 (s, 1H), 7.63–7.59 (m, 2H), 7.47 (td, J = 16.4, 15.6, 7.4 Hz, 3H), 6.82 (dd, J = 8.6, 1.9 Hz, 1H), 5.13 (d, J = 9.7 Hz, 2H), 3.92 (s, 3H), 3.42 (s, 3H), 2.23 (m, 1H), 2.19 (s, 3H), 1.00 (m, 2H), 0.93 (m, 2H).

[0187] Example 11: Preparation of compound 1-414

[0188] In a 50 mL single-necked reaction flask, (Z)-N'-hydroxy-4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-methoxybenzamide (0.46 g, 1.15 mmol) and pyridine (0.27 g, 3.45 mmol), and 30 mL of acetonitrile were added dropwise to the reaction flask with stirring at room temperature. Cyclopropanediol chloride 0.18 g (1.72 mmol) and 0.22 g (1.24 mmol) were stirred at room temperature for 30 minutes, then refluxed for 2 hours. After the reaction was completed by TLC monitoring, the solvent was removed by vacuum distillation, and ethyl acetate (2 × 50 mL) was added for extraction. The organic phase was washed with 50 mL of saturated brine. After solvent removal, the residue was subjected to column chromatography (eluting agent was ethyl acetate and petroleum ether, volume ratio 1:5) to give 0.35 g of compound 1-414. 1¹H-NMR (600MHz, internal standard TMS, solvent CDCl₃) δ (ppm): 7.63 (dd, J = 8.4, 2.0Hz, 1H), 7.55 (d, J = 2.0Hz, 1H), 7.42 (dtd, J = 24.6, 7.5, 1.5Hz, 2H), 7.25 (dd, J = 7.8, 1.5Hz, 2H), 6.92 (d, J = 8.4Hz, 1H), 5.22 (s, 2H), 3.96 (s, 3H), 3.94 (s, 3H), 3.41 (s, 3H), 2.23 (m, 1H), 1.00 (m, 2H), 0.93 (m, 2H).

[0189] Example 12: Preparation of compound 1-478

[0190] In a 50 mL single-necked reaction flask, (Z)-N'-hydroxy-4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-fluorobenzomidine (0.39 g, 1 mmol) obtained in step 2) of Example 3 and 20 mL of toluene were added sequentially to the reaction flask, followed by the addition of diisopropylcarbodiimide (0.26 g, 2.1 mmol). The reaction solution was heated to reflux and reacted for 6 hours. After the reaction was completed by TLC monitoring, the solvent was removed by vacuum distillation, and the residue was subjected to column chromatography (eluting agents were ethyl acetate and petroleum ether, volume ratio 1:5) to give 0.2 g of compound 1-478. 1 ¹H-NMR (600MHz, internal standard TMS, solvent CDCl₃) δ (ppm): 7.70-7.62 (m, 3H), 7.51-7.38 (m, 2H), 7.37-7.19 (m, 2H), 6.91-6.99 (m, 1H), 5.27-5.06 (m, 2H), 3.92 (s, 3H), 3.84 (m, 1H), 3.37 (s, 3H), 1.13 (m, 6H).

[0191] Example 13: Preparation of compound 1-482

[0192] In a 50 mL single-necked reaction flask, (Z)-N'-hydroxy-4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-methoxybenzamide (0.46 g, 1.15 mmol) obtained in step 2) of Example 6 and 20 mL of toluene were added sequentially to the reaction flask, followed by the addition of diisopropylcarbodiimide (0.31 g, 2.42 mmol). The reaction solution was heated to reflux and reacted for 6 hours. After the reaction was completed by TLC monitoring, the solvent was removed under reduced pressure, and the residue was subjected to column chromatography (eluting agents were ethyl acetate and petroleum ether, volume ratio 1:5) to give 0.23 g of compound 1-482.1 ¹H-NMR (600MHz, internal standard TMS, solvent CDCl₃) δ (ppm): 7.65-7.62 (m, 1H), 7.51-7.47 (m, 2H), 7.46-7.44 (m, 1H), 7.39-7.42 (m, 1H), 7.23 (dd, J = 7.8, 1.4Hz, 1H), 6.84 (d, J = 8.2Hz, 1H), 5.17 (d, J = 3.3Hz, 2H), 4.02 (m, 1H), 3.93 (s, 3H), 3.92 (s, 3H), 3.40 (s, 3H), 1.32 (d, J = 6.5Hz, 7H).

[0193] Example 14: Preparation of compounds 2-5

[0194] The synthesis was performed according to the preparation of compounds 1-5 in Examples 1, except that 4-(2-(bromomethyl)phenyl)-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one was replaced with 1-(2-bromomethylphenyl)-4-methyl-1,4-dihydro-5H-tetrazole-5-one (synthesis see reference WO2015056806). 1 H NMR(600MHz,Chloroform-d)δ7.84(t,J=0.8Hz,1H),7.82(d,J=2.2Hz,1H),7.71(dt,J=7.9,0.9Hz,1H),7.56 -7.52(m,1H),7.52-7.49(m,2H),6.88(d,J=8.2Hz,1H),5.22(s,2H),3.67(s,3H),2.63(s,3H),2.23(s,3H).

[0195] Example 15: Preparation of compound 2-69

[0196] The synthesis was performed according to the preparation of compounds 1-69 in Example 2, except that 4-(2-(bromomethyl)phenyl)-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one was replaced with 1-(2-bromomethylphenyl)-4-methyl-1,4-dihydro-5H-tetrazole-5-one (synthesis see reference WO2015056806). 1 H NMR(600MHz,Chloroform-d)δ8.05-7.99(m,2H),7.70-7.64(m,1H),7.57-7.49( m,2H),7.39-7.32(m,1H),7.02-6.99(m,2H),5.24(d,J=0.7Hz,2H),3.67(s,3H).

[0197] Example 16: Preparation of compound 2-73

[0198] The synthesis was performed according to the preparation of compounds 1-5 in Examples 1, except that 4-(2-(bromomethyl)phenyl)-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one was replaced with 1-(2-bromomethylphenyl)-4-methyl-1,4-dihydro-5H-tetrazole-5-one (synthesis see reference WO2015056806), and acetic anhydride was replaced with trifluoroacetic anhydride. 1 H NMR(600MHz,Chloroform-d)δ8.09-7.95(m,2H),7.47-7.40(m,2H),7.30(dd, J=7.8,1.5Hz,1H),7.03-6.93(m,2H),5.11(s,2H),3.62(s,3H),2.51(s,3H).

[0199] Example 17: Preparation of compound 2-141

[0200] The synthesis was performed according to the preparation of compounds 1-5 in Examples 1, except that 4-(2-(bromomethyl)phenyl)-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one was replaced with 1-(2-bromomethylphenyl)-4-methyl-1,4-dihydro-5H-tetrazole-5-one (synthesis see reference WO2015056806), and acetic anhydride was replaced with difluoroacetic anhydride. 1 H NMR(600MHz,Chloroform-d)δ7.91-7.84(m,2H),7.71(dt,J=7.9,0.9Hz,1H),7.58-7.5 3(m,1H),7.52-7.49(m,2H),6.94-6.74(m,2H),5.25(s,2H),3.68(s,3H),2.25(s,3H).

[0201] Example 18: Preparation of compound 2-345

[0202] The synthesis was performed according to the preparation of compounds 1-5 in Examples 1, except that 4-(2-(bromomethyl)phenyl)-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one was replaced with 1-(2-bromomethylphenyl)-4-methyl-1,4-dihydro-5H-tetrazole-5-one (synthesis see reference WO2015056806), and acetic anhydride was replaced with 2,2-dimethylbutyryl chloride. 1H NMR(600MHz,Chloroform-d)δ7.87-7.82(m,2H),7.72-7.68(m,1H),7.53(m,1H),7.51-7.47(m,2H),6.89- 6.84(m,1H),5.23(s,2H),3.67(s,3H),2.24(s,3H),1.82(q,J=7.5Hz,2H),1.44(s,6H),0.88-0.84(m,3H).

[0203] Example 19: Preparation of compound 2-481

[0204] The synthesis was performed according to the preparation of compounds 1-478 in Example 12, except that (Z)-N'-hydroxy-4-((2-(3-methoxy-1-methyl-5-oxo-1,5-dihydro-4H-1,2,4-triazol-4-yl)benzyl)oxo)-3-fluorobenzoamidine was replaced with (Z)-N'-hydroxy-3-methyl-4-((2-(4-methyl-5-oxo-4,5-dihydro-1H-tetrazol-1-yl)benzyl)oxo)benzoamidine (the synthesis was performed according to the preparation of compounds 1-5 in Example 1, except that 4-(2-(bromomethyl)phenyl)-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one was replaced with 1-(2-bromomethylphenyl)-4-methyl-1,4-dihydro-5H-tetrazol-5-one (the synthesis is described in reference WO2015056806)). 1 H NMR(600MHz,Chloroform-d)δ7.78-7.66(m,3H),7.56-7.46(m,3H),6.85(d,J=8.2H z,1H),5.21(s,2H),4.05-3.96(m,1H),3.66(s,3H),2.22(s,3H),1.34-1.27(m,6H).

[0205] Example 20: Preparation of compound 2-613

[0206] The synthesis was performed according to the preparation of compounds 1-69 in Example 2, except that 4-(2-(bromomethyl)phenyl)-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one was replaced with 1-(2-bromomethyl-3-methylphenyl)-4-methyl-1,4-dihydro-5H-tetrazole-5-one (synthesis see reference WO2015056806). 1H NMR(600MHz,Chloroform-d)δ8.09-7.95(m,2H),7.47-7.40(m,2H),7.30(dd, J=7.8,1.5Hz,1H),7.03-6.93(m,2H),5.11(s,2H),3.62(s,3H),2.51(s,3H).

[0207] Example 21: Preparation of compound 2-617

[0208] The synthesis was performed according to the preparation of compounds 1-5 in Examples 1, except that 4-(2-(bromomethyl)phenyl)-5-methoxy-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one was replaced with 1-(2-bromomethyl-3-methylphenyl)-4-methyl-1,4-dihydro-5H-tetrazole-5-one (synthesis see reference CN102336744), and acetic anhydride was replaced with trifluoroacetic anhydride. 1 H NMR(600MHz,Chloroform-d)δ7.91(dd,J=8.5,2.2Hz,1H),7.87(dd,J=2.3,1.0Hz,1H),7.52-7.38(m ,2H),7.32-7.28(m,1H),6.94(d,J=8.5Hz,1H),5.12(s,2H),3.63(s,3H),2.52(s,3H),2.15(s,3H).

[0209] Bioactivity Assay Examples

[0210] The compounds of this invention exhibit excellent activity against a variety of pathogens in the agricultural field.

[0211] Example 22: Determination of bactericidal activity

[0212] The compounds of this invention were used to conduct in vivo protective efficacy tests against various fungal diseases of plants. The results of the fungicidal activity assays are shown in the following examples.

[0213] (1) In vivo protective activity assay

[0214] The assay method is as follows: A live pot assay method is used. The sample of the compound to be tested is dissolved in a small amount of solvent (the type of solvent is such as acetone, methanol, DMF, etc., and the solvent is selected according to its solubility in the sample; the volume ratio of solvent to spray volume is equal to or less than 0.05), and diluted with water containing 0.1% Tween 80 to prepare the test solution of the required concentration. The test solution is sprayed onto the diseased host plants (standard potted seedlings cultivated in a greenhouse) using a crop sprayer. Disease inoculation is performed 24 hours later. Based on the characteristics of the disease, diseased plants requiring temperature and humidity control are inoculated and placed in an artificial climate chamber for cultivation. After the disease has fully infected the plants, they are transferred to a greenhouse for cultivation. Diseased plants not requiring humidity control are directly inoculated and cultivated in the greenhouse. The disease control effect of the compound is evaluated after the control group has fully developed the disease (usually one week).

[0215] The results of in vivo protective activity tests for some compounds are as follows:

[0216] In vivo protective activity against cucumber downy mildew:

[0217] Compounds with a control efficacy of over 85% against cucumber downy mildew at a dose of 400 ppm include: 1-5, 2-5, 1-414, 1-482, 1-71, 1-73, and 2-141; CK1 and CK2 have a control efficacy of less than 50% at this dose.

[0218] In vivo protective activity against corn rust:

[0219] Compounds with a control efficacy of over 85% against corn rust at a dose of 400 ppm include: 1-5, 1-69, 1-138, 1-141, 1-142, 1-413, 1-482, 2-73, 2-613, and 2-617; CK1, CK3, and CK4 have a control efficacy of 0 at this dose.

[0220] Compounds with a control efficacy of over 85% against corn rust at a dose of 100 ppm include: 1-5, 1-69, 1-138, 1-141, 1-413, 2-73, 2-613, 2-617, etc.

[0221] Compounds that have a control efficacy of over 85% against corn rust at a dose of 25 ppm include: 1-5, 1-141, 1-69, 2-73, 2-613, 2-617, etc.

[0222] Compounds that have a control efficacy of over 85% against corn rust at a dose of 6.25 ppm include: 1-69, 2-73, and 2-617.

[0223] In vivo protective activity against cucumber anthracnose:

[0224] Compounds with a control efficacy of over 85% against cucumber anthracnose at a dose of 400 ppm include 2-613 and 2-617; CK1, CK3, and CK4 have a control efficacy of 0 at this dose.

[0225] In vivo protective activity against wheat powdery mildew:

[0226] Compounds with a control efficacy of over 85% against wheat powdery mildew at a dosage of 100 ppm include: 1-5, 1-69, 1-70, 1-71, 1-73, 1-74, 1-138, 1-141, 1-413, 2-69, 2-73, 2-345, 2-613, and 2-617; CK1, CK2, CK3, and CK4 have a control efficacy of 0 at this dosage.

[0227] Compounds that have a control efficacy of over 85% against wheat powdery mildew at a dose of 25 ppm include: 1-5, 1-69, 1-70, 1-71, 1-73, 1-138, 1-141, 1-413, 2-73, 2-613, 2-617, etc.

[0228] The compounds that have a control efficacy of over 85% against wheat powdery mildew at a dose of 6.25 ppm are: 1-70, 1-73, 1-138, 1-141, 1-413, 2-613, and 2-617.

[0229] Note:

[0230]

[0231] (2) Test results of some compounds and control drugs

[0232] Activity comparison tests were conducted on some compounds and control agents, and the test results are shown in Table 11.

[0233] Table 11. In vivo protective activity against wheat powdery mildew.

[0234]

Claims

1. A phenyloxadiazole compound, characterized in that: Phenylediazole compounds are those represented by general formula I; In the formula: R1 is selected from hydrogen, halogen, cyano, nitro, C1-C 12 Alkyl, halogenated C1-C 12 Alkyl, C3-C 12 cycloalkyl, halogenated C3-C 12 cycloalkyl, C1-C 12 Alkoxy, halogenated C1-C 12 Alkoxy, C1-C 12 Alkylthio, Halogenated C1-C 12 Alkylthio, C1-C 12 Alkylamino, C1-C 12 Alkyl sulfinyl, halogenated C1-C 12 alkyl sulfinyl, C1-C 12 Alkyl sulfonyl, halogenated C1-C 12 Alkyl sulfonyl, C2-C 12 Alkenyl, halogenated C2-C 12 alkenyl, C2-C 12 Alkyne group, halogenated C2-C 12 alkynyl group, C2-C 12 Alkenyl groups, halogenated C2-C 12 Alkenyl group, C2-C 12 Acryloxy or halogenated C2-C 12 Acryloxy group; R2 and R3 may be the same or different, and are selected from CR6 or N; Located at the 2, 3, or 4 position of the benzene ring; R4 is selected from hydrogen, halogen, cyano, amino, hydroxyl, mercapto, carboxyl, morpholino, C1-C 12 Alkyl, halogenated C1-C 12 Alkyl, cyano C1-C 12 Alkyl, C3-C 12 cycloalkyl, halogenated C3-C 12 cycloalkyl, C1-C 12 Alkoxy, halogenated C1-C 12 Alkoxy, C1-C 12 Alkylthio, Halogenated C1-C 12 Alkylthio, C2-C 12 Alkenyl groups, halogenated C2-C 12 Alkenyl group, C2-C 12 Acryloxy group, halogenated C2-C 12 Acryloxy group, C1-C 12 Alkyl sulfinyl, halogenated C1-C 12 alkyl sulfinyl, C1-C 12 Alkyl sulfonyl, halogenated C1-C 12 Alkyl sulfonyl, C1-C 12 Alkoxy C1-C 12 Alkyl, halogenated C1-C 12 Alkoxy C1-C 12 Alkyl, C1-C 12 Alkylamino, Halogenated C1-C 12 Alkylamino or di(C1-C) 12 Alkylamino); R5 is selected from hydrogen, halogen, cyano, nitro, C1-C. 12 Alkyl, halogenated C1-C 12 Alkyl, C3-C 12 cycloalkyl, halogenated C3-C 12 cycloalkyl, C1-C 12 Alkoxy, halogenated C1-C 12 Alkoxy, C1-C 12 Alkylthio, Halogenated C1-C 12 Alkylthio, C1-C 12 Alkylamino, C1-C 12 Alkyl sulfinyl, halogenated C1-C 12 alkyl sulfinyl, C1-C 12 Alkyl sulfonyl, halogenated C1-C 12 Alkyl sulfonyl, C2-C 12 Alkenyl, halogenated C2-C 12 alkenyl, C2-C 12 Alkyne group, halogenated C2-C 12 alkynyl group, C2-C 12 Alkenyl groups, halogenated C2-C 12 Alkenyl group, C2-C 12 Acryloxy or halogenated C2-C 12 Acryloxy group; R6 is selected from hydrogen, halogen, cyano, C1-C. 12 Alkyl, halogenated C1-C 12 Alkyl, C3-C 12 cycloalkyl, halogenated C3-C 12 cycloalkyl, C1-C 12 Alkoxy, halogenated C1-C 12 Alkoxy, C1-C 12 Alkylthio, Halogenated C1-C 12 Alkylthio, C1-C 12 Alkylamino, C1-C 12 Alkyl sulfinyl, halogenated C1-C 12 alkyl sulfinyl, C1-C 12 Alkyl sulfonyl, halogenated C1-C 12 Alkyl sulfonyl, C2-C 12 Alkenyl groups, halogenated C2-C 12 Alkenyl group, C2-C 12 Acryloxy or halogenated C2-C 12 Acryloxy group; n can be selected from 0, 1, 2, 3 or 4; and when n is greater than 1, R5 can be the same or different. X is selected from O or S; Y is selected from O, S, or NH.

2. The compound according to claim 1, characterized in that, In compounds of general formula I: R1 is selected from hydrogen, halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C1-C6 alkylthio, halo-C1-C6 alkylthio, C1-C6 alkylamino, C1-C6 alkylsulfinyl, halo-C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, halo-C1-C6 alkylsulfonyl, C2-C6 alkenyl, halo-C2-C6 alkenyl, C2-C6 alkynyl, halo-C2-C6 alkynyl, C2-C6 alkenyloxy, halo-C2-C6 alkenyloxy, C2-C6 alkynyloxy, or halo-C2-C6 alkynyloxy. R2 and R3 may be the same or different, and are selected from CR6 or N; Located at the 2, 3, or 4 position of the benzene ring; R4 is selected from hydrogen, halogen, cyano, amino, hydroxyl, mercapto, carboxyl, morpholino, C1-C6 alkyl, halo-C1-C6 alkyl, cyano-C1-C6 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C1-C6 alkylthio, halo-C1-C6 alkylthio, C2-C6 alkenoxy, and halo-C2-C6 alkenoxy. C2-C6 alkynyloxy, halogenated C2-C6 alkynyloxy, C1-C6 alkyl sulfinyl, halogenated C1-C6 alkyl sulfinyl, C1-C6 alkyl sulfonyl, halogenated C1-C6 alkyl sulfonyl, C1-C6 alkoxy-C1-C6 alkyl, halogenated C1-C6 alkoxy-C1-C6 alkyl, C1-C6 alkylamino, halogenated C1-C6 alkylamino or di(C1-C6 alkylamino); R5 is selected from hydrogen, halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C1-C6 alkylthio, halo-C1-C6 alkylthio, C1-C6 alkylamino, C1-C6 alkylsulfinyl, halo-C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, halo-C1-C6 alkylsulfonyl, C2-C6 alkenyl, halo-C2-C6 alkenyl, C2-C6 alkynyl, halo-C2-C6 alkynyl, C2-C6 alkenyloxy, halo-C2-C6 alkenyloxy, C2-C6 alkynyloxy, or halo-C2-C6 alkynyloxy. R6 is selected from hydrogen, halogen, cyano, C1-C6 alkyl, halo-C1-C6 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C1-C6 alkylthio, halo-C1-C6 alkylthio, C1-C6 alkylamino, C1-C6 alkylsulfinyl, halo-C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, halo-C1-C6 alkylsulfonyl, C2-C6 alkenyloxy, halo-C2-C6 alkenyloxy, C2-C6 alkynyloxy, or halo-C2-C6 alkynyloxy. n can be selected from 0, 1, 2, 3 or 4; and when n is greater than 1, R5 can be the same or different. X is selected from O or S; Y is selected from O or S.

3. The compound according to claim 2, characterized in that, In compounds of general formula I: R1 is selected from hydrogen, halogen, cyano, nitro, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio, halo-C1-C4 alkylthio, C1-C4 alkylsulfinyl, halo-C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, halo-C1-C4 alkylsulfonyl, C2-C4 alkenyl, halo-C2-C4 alkenyl, C2-C4 alkynyl, halo-C2-C4 alkynyl, C2-C4 alkenyloxy, halo-C2-C4 alkenyloxy, C2-C4 alkynyloxy, or halo-C2-C4 alkynyloxy. R2 is selected from CR6 or N; R3 is selected from N; Located at the 2, 3, or 4 position of the benzene ring; R4 is selected from hydrogen, halogen, cyano, amino, hydroxyl, mercapto, carboxyl, morpholino, C1-C6 alkyl, halo-C1-C6 alkyl, cyano-C1-C4 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio, halo-C1-C4 alkylthio, C2-C4 alkenoxy, and halo-C2-C4 alkenoxy. C2-C4 alkynyloxy, halogenated C2-C4 alkynyloxy, C1-C4 alkyl sulfinyl, halogenated C1-C4 alkyl sulfinyl, C1-C4 alkyl sulfonyl, halogenated C1-C4 alkyl sulfonyl, C1-C4 alkoxy-C1-C4 alkyl, halogenated C1-C4 alkoxy-C1-C4 alkyl, C1-C4 alkylamino, halogenated C1-C4 alkylamino or di(C1-C4 alkylamino); R5 is selected from hydrogen, halogen, cyano, nitro, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio, halo-C1-C4 alkylthio, C1-C4 alkylsulfinyl, halo-C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, halo-C1-C4 alkylsulfonyl, C2-C4 alkenyl, halo-C2-C4 alkenyl, C2-C4 alkynyl, halo-C2-C4 alkynyl, C2-C4 alkenyloxy, halo-C2-C4 alkenyloxy, C2-C4 alkynyloxy, or halo-C2-C4 alkynyloxy. R6 is selected from hydrogen, halogen, cyano, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio, halo-C1-C4 alkylthio, C1-C4 alkylamino, C1-C4 alkylsulfinyl, halo-C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, halo-C1-C4 alkylsulfonyl, C2-C4 alkenyloxy, halo-C2-C4 alkenyloxy, C2-C4 alkynyloxy, or halo-C2-C4 alkynyloxy. n can be selected from 0, 1, 2 or 3; and when n is greater than 1, R5 can be the same or different; X is selected from O or S; Y is selected from O or S.

4. The compound according to claim 3, characterized in that, In compounds of general formula I: R1 is selected from hydrogen, halogen, cyano, nitro, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio, halo-C1-C4 alkylthio, C1-C4 alkylsulfinyl, halo-C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, halo-C1-C4 alkylsulfonyl, C2-C4 alkenyl, C2-C4 alkynyl, C2-C4 alkenyloxy, halo-C2-C4 alkenyloxy, C2-C4 alkynyloxy, or halo-C2-C4 alkynyloxy. R2 is selected from CR6 or N; R3 is selected from N; Located at position 4 of the benzene ring; R4 is selected from hydrogen, halogen, cyano, amino, hydroxyl, mercapto, C1-C6 alkyl, halo-C1-C6 alkyl, C3-C6 cycloalkyl, halo-C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio, halo-C1-C4 alkylthio, C2-C4 alkenoxy, halo-C2-C4 alkenoxy, C2-C4 alkynoxy, halo-C2-C4 alkynoxy, C1-C4 alkylsulfinyl, halo-C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, halo-C1-C4 alkylsulfonyl, C1-C4 alkylamino or di(C1-C4 alkylamino); R5 is selected from hydrogen, halogen, cyano, nitro, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C2-C4 alkenoxy, halo-C2-C4 alkenoxy, C2-C4 alkynoxy, or halo-C2-C4 alkynoxy. R6 is selected from halogens, C1-C4 alkyl, halogenated C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, halogenated C1-C4 alkoxy, C1-C4 alkylthio, halogenated C1-C4 alkylthio, C1-C4 alkylamino, C1-C4 alkylsulfonyl, halogenated C1-C4 alkylsulfonyl, C2-C4 alkenyloxy, halogenated C2-C4 alkenyloxy, C2-C4 alkynyloxy, or halogenated C2-C4 alkynyloxy. n can be selected from 0, 1, 2 or 3; and when n is greater than 1, R5 can be the same or different; X is selected from O or S; Y is selected from O or S.

5. The compound according to claim 4, characterized in that, In compounds of general formula I: R1 is selected from hydrogen, halogen, C1-C4 alkyl, C2-C4 alkenyl or C2-C4 alkynyl; R2 is selected from CR6 or N; R3 is selected from N; Located at position 4 of the benzene ring; R4 is selected from hydrogen, halogen, cyano, amino, hydroxyl, mercapto, C1-C6 alkyl, halo-C1-C6 alkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, C1-C4 alkylthio, halo-C1-C4 alkylthio, C2-C4 alkenoxy, halo-C2-C4 alkenoxy, C2-C4 alkynoxy, halo-C2-C4 alkynoxy, C1-C4 alkylsulfonyl, halo-C1-C4 alkylsulfonyl, or C1-C4 alkylamino. R5 is selected from hydrogen, halogen, cyano, nitro, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkoxy or halo-C1-C4 alkoxy; R6 is selected from halogens or C1-C4 alkoxy groups; n can be selected from 0, 1, 2 or 3; and when n is greater than 1, R5 can be the same or different; X is selected from O or S; Y is selected from O or S.

6. The compound according to claim 5, characterized in that: In compounds of general formula I: R1 is selected from hydrogen, halogen, or C1-C4 alkyl; R2 is selected from CR6 or N; R3 is selected from N; Located at position 4 of the benzene ring; R4 is selected from hydrogen, C1-C6 alkyl, halo-C1-C5 alkyl, C3-C6 cycloalkyl or C1-C4 alkylamino; R5 is selected from hydrogen, halogen, nitro, C1-C4 alkyl or C1-C4 alkoxy; R6 is selected from halogens or C1-C4 alkoxy groups; n is selected from 0, 1, 2, or 3; X is selected from O or S; Y is selected from O or S.

7. The compound according to claim 6, characterized in that: In compounds of general formula I: R1 is selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, or isopropyl; R2 is selected from CR6 or N; R3 is selected from N; Located at position 4 of the benzene ring; R4 is selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, difluoromethyl, trifluoromethyl, trifluoroethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylamino, ethylamino, n-propylamino, or isopropylamino; R5 is selected from hydrogen, fluorine, chlorine, bromine, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy, or isopropoxy; R6 is selected from chlorine, bromine, methoxy, ethoxy, n-propoxy, or isopropoxy; n can be selected from 0, 1, 2 or 3; and when n is greater than 1, R5 can be the same or different; X is selected from O or S; Y is selected from O or S.

8. Use of a phenyloxadiazole compound according to any one of claims 1-7 as a fungicide in agriculture or other fields.

Images