Oxadiazole compound and its application

Abstract

The present invention discloses a novel oxadiazole compound, as shown in general formula I: #imgabs0#. The compound of general formula I has excellent fungicidal activity and has a good control effect on plant fungal diseases, especially soybean rust. The present invention includes the use of the compound of general formula I as a fungicide in agriculture and other fields.

Description

Technical Field

[0001] The present invention belongs to the field of agricultural fungicides, and specifically relates to an oxadiazole compound and its application. Background Art

[0002] Patents WO2013008162A1, WO2015185485A1, WO2017174158A1, WO2017198852A1, US20170015655A1, and WO2018015447A1 relate to oxadiazole compounds and their use as fungicides; however, the activity of these compounds is still unsatisfactory, and there is a need to continuously develop new compounds with higher activity.

[0003] In the prior art, there has been no report on the oxadiazole compounds and their fungicidal activities as shown in the present invention. Summary of the Invention

[0004] The present invention aims to provide an oxadiazole compound capable of controlling a variety of plant fungal diseases, and its use in preparing a drug for preventing and controlling pathogens in agriculture and other fields.

[0005] To achieve the above object, the technical solution of the present invention is as follows:

[0006] An oxadiazole compound, as shown in the general formula I:

[0007]

[0008] Where:

[0009] X1 and X2 are each independently selected from hydrogen, halogen or C1-C6 alkyl;

[0010] n is selected from 0 or 1;

[0011] L is selected from -C(=O)- or -S(=O) m -, m is selected from 1 or 2;

[0012] R1, R2, R3, R4, and R5 are each independently selected from hydrogen, halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C1-C6 alkylthio, halo-C1-C6 alkylthio, phenyl or phenoxy which is unsubstituted or substituted with 1, 2, 3, 4, or 5 R6, and when the number of substituents is greater than 1, R6 may be the same or different;

[0013] R6 is selected from halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C1-C6 alkylthio or halo-C1-C6 alkylthio;

[0014] or a salt of a compound of formula I.

[0015] In one possible implementation, in Formula I,

[0016] X1 and X2 are each independently selected from hydrogen, halogen or C1-C4 alkyl;

[0017] n is selected from 0 or 1;

[0018] L is selected from -C(=O)- or -S(=O) m -, m is selected from 1 or 2;

[0019] R1, R2, R3, R4, and R5 are each independently selected from hydrogen, halogen, cyano, nitro, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio, halo-C1-C4 alkylthio, phenyl or phenoxy which is unsubstituted or substituted with 1, 2, 3, 4, or 5 R6, and when the number of substituents is greater than 1, R6 may be the same or different;

[0020] R6 is selected from halogen, cyano, nitro, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio or halo-C1-C4 alkylthio;

[0021] or a salt formed by a compound of formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.

[0022] In one possible implementation, in Formula I,

[0023] X1 and X2 are each independently selected from hydrogen, halogen or C1-C4 alkyl;

[0024] n is selected from 0 or 1;

[0025] L is selected from -C(=O)- or -S(=O) m -, m is selected from 1 or 2;

[0026] R1, R2, R4, and R5 are each independently selected from hydrogen, halogen, cyano, nitro, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio, or halo-C1-C4 alkylthio;

[0027] R3 is selected from hydrogen, halogen, cyano, nitro, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio, halo-C1-C4 alkylthio, phenyl or phenoxy which is unsubstituted or substituted with 1, 2, 3, 4 or 5 R6, and when the number of substituents is greater than 1, R6 may be the same or different;

[0028] R6 is selected from halogen, cyano, nitro, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio or halo-C1-C4 alkylthio;

[0029] or a salt formed by a compound of formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.

[0030] In one possible implementation, in Formula I,

[0031] X1 and X2 are each independently selected from hydrogen, fluorine, chlorine, bromine, methyl or ethyl;

[0032] n is selected from 0 or 1;

[0033] L is selected from -C(=O)- or -S(=O) m -, m is selected from 1 or 2;

[0034] R1, R2, R3, R4, R5 are each independently selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, perfluoroethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl , methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, monofluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, phenyl or phenoxy which is unsubstituted or substituted with 1, 2, 3, 4 or 5 R6, and when the number of substituents is greater than 1, R6 may be the same or different;

[0035] R6 is selected from fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, perfluoroethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, monofluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, trifluoromethylthio or 2,2,2-trifluoroethylthio;

[0036] or a salt formed by a compound of formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.

[0037] In one possible implementation, in Formula I,

[0038] X1 and X2 are each independently selected from hydrogen, fluorine, chlorine, bromine, methyl or ethyl;

[0039] n is selected from 0 or 1;

[0040] L is selected from -C(=O)- or -S(=O) m -, m is selected from 1 or 2;

[0041] R1, R2, R4, R5 are each independently selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, perfluoroethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, monofluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, trifluoromethylthio, or 2,2,2-trifluoroethylthio;

[0042] R3 is selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, perfluoroethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, monofluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, phenyl or phenoxy which is unsubstituted or substituted with 1, 2, 3, 4 or 5 R6, and when the number of substituents is greater than 1, R6 may be the same or different;

[0043] R6 is selected from fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, perfluoroethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, monofluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, trifluoromethylthio or 2,2,2-trifluoroethylthio;

[0044] or a salt formed by a compound of formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.

[0045] In one possible implementation, the compound of formula I is selected from any one of the following compounds:

[0046]

[0047]

[0048] In the definitions of the compounds of the general formula given above, the terms used collectively generally represent the following substituents:

[0049] Halogen: refers to fluorine, chlorine, bromine or iodine.

[0050] Alkyl: straight-chain or branched alkyl, for example methyl, ethyl, n-propyl, isopropyl or the different butyl, pentyl or hexyl isomers.

[0051] Cycloalkyl: refers to a substituted or unsubstituted cyclic alkyl group, such as cyclopropyl, cyclopentyl or cyclohexyl; substituents include methyl, halogen, etc.

[0052] Haloalkyl: a straight-chain or branched alkyl group, in which the hydrogen atoms may be partially or completely replaced by halogen, for example, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, perfluoroethyl, etc.

[0053] Alkoxy: a straight or branched chain alkyl group connected to the structure through an oxygen atom bond, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, etc.

[0054] Haloalkoxy: The hydrogen atoms on the alkoxy group may be partially or completely replaced by halogen, for example, monochloromethoxy, dichloromethoxy, trichloromethoxy, monofluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, 2,2,2-trifluoroethoxy, etc.

[0055] Alkylthio: a straight or branched chain alkyl group connected to the structure through a sulfur atom bond, such as methylthio, ethylthio, etc.

[0056] Haloalkylthio: The hydrogen atoms on the alkylthio group may be partially or completely substituted by halogen, for example chloromethylthio, difluoromethylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, and the like.

[0057] Some of the compounds of formula I of the present invention are shown below, but the present invention is by no means limited to these compounds.

[0058]

[0059] Table 1: In general formula I, when X1=X2=H, n=0 and L is -C(=O)-, R1, R2, R3, R4, and R5 are different substituents as shown in Table 1, and the representative compounds are numbered 1.1-1.280.

[0060] Table 1

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071] In general formula I, when X1=X2=H, n=1 and L is -C(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compounds are numbered 2.1-2.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0072] In general formula I, when X1=F, X2=H, n=0 and L is -C(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compounds are numbered 3.1-3.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0073] In general formula I, when X1=F, X2=H, n=1 and L is -C(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compounds are numbered 4.1-4.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0074] In general formula I, when X1=H, X2=F, n=0 and L is -C(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compounds are numbered 5.1-5.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0075] In general formula I, when X1=H, X2=F, n=1 and L is -C(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compounds are numbered 6.1-6.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0076] In general formula I, when X1=CH3, X2=H, n=0 and L is -C(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with Table 1, and the representative compounds are numbered 7.1-7.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0077] In general formula I, when X1=CH3, X2=H, n=1 and L is -C(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with Table 1, and the representative compounds are numbered 8.1-8.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0078] In general formula I, when X1=H, X2=CH3, n=0 and L is -C(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compounds are numbered 9.1-9.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0079] In general formula I, when X1=H, X2=CH3, n=1 and L is -C(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compounds are numbered 10.1-10.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0080] In general formula I, when X1=X2=F, n=0 and L is -C(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compounds are numbered 11.1-11.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0081] In general formula I, when X1=X2=F, n=1 and L is -C(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compounds are numbered 12.1-12.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0082] In general formula I, when X1=X2=H, n=0 and L is -S(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compounds are numbered 13.1-13.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0083] In general formula I, when X1=X2=H, n=1 and L is -S(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compounds are numbered 14.1-14.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0084] In general formula I, when X1=F, X2=H, n=0 and L is -S(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compounds are numbered 15.1-15.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0085] In general formula I, when X1=F, X2=H, n=1 and L is -S(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compounds are numbered 16.1-16.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0086] In general formula I, when X1=H, X2=F, n=0 and L is -S(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compounds are numbered 17.1-17.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0087] In general formula I, when X1=H, X2=F, n=1 and L is -S(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compounds are numbered 18.1-18.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0088] In general formula I, when X1=CH3, X2=H, n=0 and L is -S(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with Table 1, and the representative compound numbers are 19.1-19.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0089] In general formula I, when X1=CH3, X2=H, n=1 and L is -S(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with Table 1, and the representative compound numbers are 20.1-20.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0090] In general formula I, when X1=H, X2=CH3, n=0 and L is -S(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with Table 1, and the representative compounds are numbered 21.1-21.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0091] In general formula I, when X1=H, X2=CH3, n=1 and L is -S(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with Table 1, and the representative compound numbers are 22.1-22.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0092] In general formula I, when X1=X2=F, n=0 and L is -S(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compounds are numbered 23.1-23.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0093] In general formula I, when X1=X2=F, n=1 and L is -S(=O)-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compounds are numbered 24.1-24.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0094] In general formula I, when X1=X2=H, n=0 and L is -S(=O)2-, the substituents R1, R2, R3, R4, and R5 are consistent with Table 1, and the representative compound numbers are 25.1-25.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0095] In general formula I, when X1=X2=H, n=1 and L is -S(=O)2-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compound numbers are 26.1-26.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0096] In general formula I, when X1=F, X2=H, n=0 and L is -S(=O)2-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compound numbers are 27.1-27.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0097] In general formula I, when X1=F, X2=H, n=1 and L is -S(=O)2-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compounds are numbered 28.1-28.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0098] In general formula I, when X1=H, X2=F, n=0 and L is -S(=O)2-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compounds are numbered 29.1-29.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0099] In general formula I, when X1=H, X2=F, n=1 and L is -S(=O)2-, the substituents R1, R2, R3, R4, and R5 are consistent with those in Table 1, and the representative compound numbers are 30.1-30.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0100] In general formula I, when X1=CH3, X2=H, n=0 and L is -S(=O)2-, the substituents R1, R2, R3, R4, and R5 are consistent with Table 1, and the representative compound numbers are 31.1-31.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0101] In general formula I, when X1=CH3, X2=H, n=1 and L is -S(=O)2-, the substituents R1, R2, R3, R4, and R5 are consistent with Table 1, and the representative compound numbers are 32.1-32.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0102] In general formula I, when X1=H, X2=CH3, n=0 and L is -S(=O)2-, the substituents R1, R2, R3, R4, and R5 are consistent with Table 1, and the representative compound numbers are 33.1-33.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0103] In general formula I, when X1=H, X2=CH3, n=1 and L is -S(=O)2-, the substituents R1, R2, R3, R4, and R5 are consistent with Table 1, and the representative compound numbers are 34.1-34.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0104] In general formula I, when X1=X2=F, n=0 and L is -S(=O)2-, the substituents R1, R2, R3, R4, and R5 are consistent with Table 1, and the representative compound numbers are 35.1-35.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0105] In general formula I, when X1=X2=F, n=1 and L is -S(=O)2-, the substituents R1, R2, R3, R4, and R5 are consistent with Table 1, and the representative compound numbers are 36.1-36.280, corresponding to 1.1-1.280 in Table 1, respectively.

[0106] The compounds of the general formula I of the present invention can be prepared according to the following method (unless otherwise specified, the groups in the formula have the same definitions as above, wherein LG = Cl, Br or I):

[0107]

[0108] Step 1: Preparation of compound of formula III

[0109] The compound of formula III can be prepared by reacting the compound of formula II with thionyl chloride, oxalyl chloride, phosgene, phosphorus oxychloride, phosphorus pentachloride, phosphorus trichloride, triphosgene, etc. using conventional methods.

[0110] Step 2: Preparation of compounds of formula V

[0111] The compound of formula III is reacted with the compound of formula IV in a suitable solvent at a temperature ranging from -10°C to the boiling point of the solvent for 0.5-48 hours to obtain the compound of formula V; the reaction can be carried out in the presence of a base.

[0112] Step 3: Preparation of compound of formula VI

[0113] The compound of formula VI can be prepared by conventional methods by hydrolyzing the compound of formula V with hydrochloric acid to form a salt.

[0114] Step 4: Preparation of compounds of formula I

[0115] The compound of formula VI and the compound of formula VII are reacted in a suitable solvent in the presence of a base at a temperature ranging from -10°C to the boiling point of the solvent for 0.5-48 hours to obtain the compound of formula I.

[0116] In the above reaction, suitable solvents may be aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; halogenated hydrocarbons such as chloroform and dichloromethane; esters such as methyl acetate and ethyl acetate; ethers such as tetrahydrofuran, dioxane, diethyl ether, and 1,2-dimethoxyethane; polar solvents such as water, acetonitrile, N,N-dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide; or mixed solvents thereof; and bases which may be the same or different may be organic bases such as trimethylamine, triethylamine, pyridine, DBU, 4-dimethylaminopyridine, N,N-diisopropylmethylamine, and N,N-diisopropylethylamine.

[0117] The sources of the raw materials and intermediates involved in the above preparation method are as follows:

[0118] The compound of general formula II can be prepared according to a known method, for example, with reference to the methods reported in WO2015185485, WO2017076935, WO2017211652, WO2017211650, WO2017093019, WO2017076739, WO2013008162 or CN113788800.

[0119] The compound of formula IV, the compound of formula VII and other conventional raw materials and reagents are usually commercially available or can be prepared in-house according to conventional methods.

[0120] The compounds represented by the general formula I of the present invention are used to prevent and control diseases on various crops caused by various fungi such as Oomycetes, Basidiomycetes, Ascomycetes and Deuteromycetes. For example, at relatively low dosages, they have excellent preventive effects on diseases such as cucumber downy mildew, cucumber gray mold, cucumber anthracnose, cucumber powdery mildew, tomato early blight, tomato late blight, pepper blight, grape downy mildew, grape white rot, apple ring rot, apple leaf spot, rice sheath blight, rice blast, wheat rust, wheat leaf spot, wheat powdery mildew, rapeseed sclerotinia, corn leaf spot, and soybean rust.

[0121] Due to their positive properties, the above-mentioned compounds can be advantageously used for protecting important agricultural and horticultural crops, domestic and breeding stock, and the environment frequented by humans from pathogens.

[0122] To obtain the desired effect, the amount of compound used will vary depending on various factors, such as the compound used, the crop to be protected, the type of pest, the degree of infestation, climatic conditions, the method of application, the formulation used, etc.

[0123] Doses of 5 g to 5 kg of compound per hectare provide adequate control.

[0124] The present invention also includes a fungicide containing the compound of formula I as the active ingredient. The weight percentage of the active ingredient in the fungicide is between 0.1-99%. The fungicide also includes agricultural, forestry, and sanitary acceptable carriers and adjuvants.

[0125] The fungicide of the present invention can be applied in the form of a formulation. The compound of formula I as the active ingredient is dissolved or dispersed in a carrier and / or adjuvant or formulated into a formulation so as to be more easily dispersed when used as a fungicide.

[0126] The present invention uses the compound of general formula I as the active ingredient, and the compound of general formula I can be prepared into various formulation types in accordance with methods well known in the art, including aqueous solutions, soluble liquids, emulsifiable concentrates, microemulsions, aqueous emulsions, suspensions, suspension seed coatings, dispersible oil suspensions, ultra-low volume concentrates, powders, wettable powders, soluble powders, emulsifiable powders, granules, water-dispersible granules, soluble granules, emulsifiable granules, dry suspensions, effervescent granules, floating granules, tablets, soluble tablets, effervescent tablets, microcapsule powders, and microcapsule suspensions. In any case, the selection of the formulation type depends on the physical, chemical, and biological properties of the compound of general formula I.

[0127] The fungicidal preparations of the compounds of formula I of the present invention can be prepared by conventional processing methods, i.e., mixing the active substance with a liquid carrier or a solid carrier and then adding one or more surfactants such as an emulsifier, dispersant, wetting agent, thickener, stabilizer, and defoamer. Typically, the composition contains at least one carrier and at least one surfactant. In each case, it should be ensured that the active ingredient of the composition of the present invention is evenly distributed.

[0128] Aqueous solutions are prepared by uniformly mixing the compound of formula I, a surfactant, and water to form a homogeneous, transparent liquid, typically containing 5-50% of the active ingredient, 5-20% of an emulsifier, 0-10% of other additives such as penetrants, and the balance being water.

[0129] The soluble liquid is prepared by uniformly mixing the compound of formula I, a surfactant, and a non-aqueous polar solvent to form a homogeneous transparent liquid. The soluble liquid typically contains 5-60% of the active ingredient, 5-20% of an emulsifier, 0-10% of other additives such as a penetrant, and the balance being a liquid carrier.

[0130] Emulsifiable concentrates are prepared by uniformly mixing the compound of formula I, a surfactant, and an organic solvent to form a homogeneous oily liquid. The emulsifiable concentrate typically contains 1-70% of the active ingredient, 5-20% of an emulsifier, 0-10% of other additives such as penetrants and stabilizers, and the balance being a liquid carrier.

[0131] Microemulsions are prepared by uniformly mixing the compound of formula I, a surfactant, water, and an organic solvent to form a homogeneous, transparent liquid. Microemulsions typically contain 1-50% active ingredient, 5-30% emulsifier, 2-10% antifreeze, 0-10% other additives such as penetrants and stabilizers, and the balance liquid carrier.

[0132] For aqueous emulsions, uniformly mix the compound of formula I, a surfactant, and an organic solvent to form an oil phase; then mix water and an antifreeze agent to form an aqueous phase. A high-shear emulsifier is used to shear the oil phase at high speed while slowly adding the aqueous phase to the oil phase to produce a uniformly dispersed aqueous emulsion. Typically, the emulsion contains 5-50% active ingredient, 5-20% emulsifier, 2-5% antifreeze agent, and the balance a liquid carrier.

[0133] Suspension concentrates are prepared by uniformly mixing the compound of formula I, a dispersant, a wetting agent, an antifreeze agent, and water, followed by sand milling to obtain a stable, non-precipitating, flowable liquid. Suspension concentrates typically contain 5-50% active ingredient, 2-10% dispersant, 2-5% wetting agent, 2-5% antifreeze agent, 0-10% other additives such as defoamers, thickeners, and preservatives, and the balance being a liquid carrier.

[0134] Suspension seed coatings are prepared by uniformly mixing a compound of formula I, a dispersant, a wetting agent, a film-forming agent, and water, followed by sand milling to obtain a stable, non-precipitating, flowable liquid. Suspension seed coatings typically contain 1-50% active ingredient, 2-10% dispersant, 2-5% wetting agent, 2-5% antifreeze, 2-10% film-forming agent, 0-10% other additives such as defoamers, thickeners, preservatives, and warning colors, and the balance is a liquid carrier.

[0135] Dispersible oil suspension concentrates are prepared by uniformly mixing the compound of formula I, a surfactant, and an oil-based carrier, followed by sand milling to obtain a stable, non-settling, flowable liquid. Dispersible oil suspension concentrates typically contain 5-50% active ingredient, 5-30% surfactant, 0-10% other additives such as thickeners and stabilizers, and the balance being the liquid carrier.

[0136] Ultra-low volume formulations are prepared by uniformly mixing the compound of formula I, a surfactant, and an organic solvent to form a homogeneous, transparent oil phase, which typically contains 1-30% active ingredient, 5-30% emulsifier, 0-10% other additives such as stabilizers, and the balance being a liquid carrier.

[0137] Powders are prepared by mixing the compound of formula I, an adjuvant, and a carrier, and pulverizing the mixture to obtain a powder. Powders typically contain 5-85% of the active ingredient, 5-10% of a dispersant, 0-10% of other additives such as a stabilizer, and the balance being a solid carrier.

[0138] Wettable powders are prepared by mixing a compound of formula I, a dispersant, a wetting agent, and a carrier, and pulverizing the mixture to obtain a powder. Wettable powders typically contain 5-85% active ingredient, 5-10% dispersant, 1-10% wetting agent, 0-10% other additives such as stabilizers, and the balance being a solid carrier.

[0139] Soluble powders are prepared by mixing the compound of formula I, a dispersant, a wetting agent, and a carrier, and pulverizing the mixture to obtain a powder. Soluble powders typically contain 5-80% of the active ingredient, 5-10% of the dispersant, 1-10% of the wetting agent, 0-10% of other additives such as stabilizers, and the balance being a solid carrier.

[0140] Emulsifiable powders are prepared by mixing the compound of formula I, a surfactant, and an organic solvent to form a homogeneous, transparent oil phase, which is then evenly sprayed onto a pre-ground carrier. Emulsifiable powders typically contain 5-50% active ingredient, 5-30% emulsifier, 5-10% wetting and dispersing agent, 0-15% organic solvent, and the balance solid carrier.

[0141] Granules are prepared by mixing the compound of formula I, adjuvants, and carriers, followed by kneading, granulation, drying, and coating. Granules typically contain 0.5-20% of the active ingredient, 0.1-10% of a binder, 0-10% of other additives such as stabilizers, and the balance being a solid carrier.

[0142] Water-dispersible granules are prepared by mixing the compound of formula I, a dispersant, a wetting agent, a disintegrant, and a carrier, followed by kneading, granulation, and drying. Water-dispersible granules typically contain 5-85% of the active ingredient, 1-10% of the dispersant, 1-10% of the wetting agent, 0.1-10% of the binder, and 0-10% of other additives such as disintegrants and stabilizers, with the balance being a solid carrier.

[0143] Soluble granules are prepared by mixing the compound of formula I, a dispersant, a wetting agent, a disintegrant, and a carrier, followed by kneading, granulation, and drying. Soluble granules typically contain 5-85% of the active ingredient, 1-10% of the dispersant, 1-10% of the wetting agent, 0.1-10% of the binder, and 0-10% of other additives such as disintegrants and stabilizers, with the balance being a solid carrier.

[0144] Emulsifiable granules are prepared by mixing the compound of formula I, a surfactant, and an organic solvent to form a homogeneous, transparent oil phase. This oil phase is then evenly sprayed onto a pre-crushed carrier, kneaded, granulated, and dried. Emulsifiable granules typically contain 5-50% active ingredient, 5-30% emulsifier, 5-10% wetting and dispersing agent, 0-15% organic solvent, and 0-10% other additives such as disintegrants, stabilizers, and binders. The balance is a solid carrier.

[0145] Dry suspension concentrates are prepared by uniformly mixing the compound of formula I, a dispersant, a wetting agent, a carrier, and water, sand milling the mixture, and then spray drying. Dry suspension concentrates typically contain 5-80% active ingredient, 2-20% dispersant, 2-10% wetting agent, and 0-10% other additives such as defoamers and thickeners, with the balance being a solid carrier.

[0146] Effervescent granules are prepared by mixing the compound of formula I, a wetting and dispersing agent, an effervescent disintegrant, and a carrier, followed by kneading and granulation. Effervescent granules typically contain 0.5-30% of the active ingredient, 2-20% of the wetting and dispersing agent, 2-20% of the effervescent disintegrant, 0-10% of other additives such as stabilizers and binders, and the balance being a solid carrier.

[0147] Floating granules are prepared by mixing the compound of formula I, a wetting and dispersing agent, floating beads, and a carrier, followed by kneading and granulation. Floating granules typically contain 0.5-30% active ingredient, 2-20% wetting and dispersing agent, 5-20% floating beads, 0-10% other additives such as stabilizers, binders, and disintegrants, and the balance solid carrier.

[0148] Tablets are prepared by mixing the compound of formula I, a dispersant, a wetting agent, a disintegrant, and a carrier, followed by kneading, tableting, and drying. Tablets typically contain 5-50% active ingredient, 1-10% dispersant, 1-10% wetting agent, 0.1-10% binder, 0-10% other additives such as disintegrants and stabilizers, and the balance being a solid carrier.

[0149] Soluble tablets are prepared by mixing the compound of formula I, a dispersant, a wetting agent, a disintegrant, and a carrier, followed by kneading, tableting, and drying. Soluble tablets typically contain 5-50% of the active ingredient, 1-10% of the dispersant, 1-10% of the wetting agent, 0.1-10% of the binder, 0-10% of other additives such as disintegrants and stabilizers, and the balance being a solid carrier.

[0150] Effervescent tablets are prepared by mixing the compound of formula I, a wetting and dispersing agent, an effervescent disintegrant, and a carrier, kneading the mixture, and tableting. Effervescent tablets typically contain 0.5-30% of the active ingredient, 2-20% of the wetting and dispersing agent, 2-20% of the effervescent disintegrant, 0-10% of other additives such as stabilizers and binders, and the balance being a solid carrier.

[0151] Microcapsule powders are prepared by dissolving the compound of formula I in a solvent, adding an emulsifier and a wall material, and stirring to obtain an oil phase. A dispersant is then added to water to obtain an aqueous phase. The oil phase is then added to the aqueous phase under high-speed stirring to form an oil-in-water emulsion. A curing agent is then added to the emulsion under stirring, and the mixture is heated and insulated to form capsules, which are then filtered and dried. Microcapsule powders typically contain 0.5-30% active ingredient, 2-10% emulsifier, 2-10% wetting and dispersing agent, 5-30% other additives such as wall materials, defoamers, curing agents, stabilizers, and the balance solid carrier.

[0152] The microcapsule suspension is prepared by dissolving the compound of formula I in a solvent, adding an emulsifier and wall material, and stirring to obtain an oil phase. A dispersant is then added to water to obtain an aqueous phase. The oil phase is then added to the aqueous phase under high-speed stirring to form an oil-in-water emulsion. A curing agent is then added to the emulsion under stirring, and the mixture is heated and insulated to form microcapsules. Microcapsule suspensions typically contain 0.5-30% active ingredient, 2-10% emulsifier, 2-10% wetting and dispersing agent, 5-30% other additives such as wall material, defoamer, preservative, thickener, curing agent, stabilizer, and the balance is a liquid carrier.

[0153] The bactericidal preparation of the compound of formula I of the present invention can be prepared using (liquid or solid) carriers and various adjuvants known to those skilled in the art, including but not limited to the following substances.

[0154] Suitable surfactants in the fungicide formulations of the compound of general formula I of the present invention can be emulsifiers, dispersants, or wetting agents; they can be one or more of nonionic or ionic types. Ionic surfactants are selected from sulfonates, sulfates, carboxylates, phosphates, succinates, lignin sulfonates, acrylamide acrylic acid copolymers, and the like. Nonionic surfactants are selected from fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, fatty amine polyoxyethylene ethers, fatty acid polyoxyethylene ethers, acid alcohol esters and their polyoxyethylene ethers, alkyl polyethylene glycol ethers, alkylphenyl polyethylene glycol ethers, fatty amides and their polyoxyethylene ethers, alkanolamides and their polyoxyethylene ethers, polyoxyethylene polyoxypropylene ether block copolymers, sodium alkylnaphthalenesulfonate fatty alcohol polyoxyethylene ethers, and sorbitan fatty acid ester polyoxyethylene ethers.

[0155] The above-mentioned surfactant can be selected from one or more of the surfactants shown, such as: sodium or calcium salt of lignin sulfonate, polyoxyethylene (n20) phenylethylphenol ether oleate, alkylaryl polyoxyethylene polyoxypropylene ether, tristyrylphenol polyoxyethylene (n20) ether phosphorylated triethanolamine salt, Nongru 0201B, Nongru 0203B, Nongru 100#, Nongru 600#, Nongru 700#, Nongru 1601#, Nongru AEO-3, Nongru AEO-5, Nongru AEO-7, Nongru T-20, Nongru T-80, Nongru T-85, Nongru S-80, Nongru S-85, Nongru NP-7, Nongru NP-10, Nongru NP-15, Nongru OX-2681, Nongru OX-8686, Nongru OX- 690, Agricultural Milk 2201#, Polycarboxylate Dispersant GY-D800, Polycarboxylate Dispersant GY-D04, Polycarboxylate Dispersant GY-D02, Alkyl Naphthalene Sulfonate Formaldehyde Condensate (NNO), Naphthol Sulfonic Acid Formaldehyde Condensate Sodium Salt, Alkylphenol Polyoxyethylene Polyoxypropylene Ether, Styrene Maleic Anhydride, Methylnaphthalene Sulfonic Acid Formaldehyde Condensate, Castor Oil Ethylene Oxide Adduct, Alkylphenol Polyoxyethylene Polyoxypropylene Ether, Alkyl-Diethylene Glycol Ether-Sulfonate Sodium, N-Methyl-Oleoyl-Taurate Sodium, Detergent LS, Sodium Methylene Naphthalene Sulfonate, Sodium Oleic Acid Methylaminoethyl Sulfonate, Dispersant SP-28F, Dispersant SP-SC3, Darun Dispersant D909S, Alkyl Aryl Polyoxyethylene Ether, Dodecyl Polyoxyethylene Ether Phosphate, Alkyl Phenol polyoxyethylene ether formaldehyde condensate, sodium dibutylnaphthalene sulfonate (pulling powder BX), dibutylnaphthalene sulfonic acid formaldehyde condensate, dispersant SD-811, dispersant SD815, dispersant SK-24, dispersant SK-20TX, dispersant SK-5218, dispersant SK-33H, dispersant SK-10LX, dispersant SK-551, dispersant Atlox4913, dispersant EL-20, dispersant EL-40, dispersant EL-90, dispersant YUS-NV1203, dispersant YUS-NV1420, dispersant YUS-WG4, dispersant YUS-TG285, dispersant YUS-WP1, dispersant YUS-110, dispersant YUS-EP60P, dispersant Powder YUS-CH1100, dispersant SP-OF3468, dispersant SP-OF3472, dispersant SP-2728, dispersant SP-SC29, dispersant Supragil MNS / 90, dispersant Soprophor FD, dispersant YUS-FS1, dispersant YUS-PQ100, dispersant YUS-WG5, YUS-D935, octylphenol polyoxyethylene ether sulfate, Morwet EFW, wetting agent Igepal BC / 10, wetting agent GEROPONL-WET / P, wetting agent Rhodasurf 860 / p, wetting agent SP-SC3266, wetting agent PICO-SW2, wetting agent PICO-SW3,Wetting agent YUS-LXC, wetting agent YUS-204, sodium alkyl alcohol polyoxyethylene ether sulfate, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, alkyl succinic acid sulfonate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, calcium dodecylbenzene sulfonate, etc.

[0156] Suitable liquid carriers in the bactericidal preparations of the compound of general formula I of the present invention can be one or more of water, organic solvents, and oily media. Suitable organic solvents are selected from aromatic hydrocarbons, chlorinated aromatic hydrocarbons, aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons, alcohols, and their ethers and esters, ketones, and the like, such as benzene, xylene, toluene, alkylbenzenes, alkylnaphthalenes, chlorobenzenes, vinyl chloride, trichloroethane, dichloromethane, chloroform, carbon tetrachloride, polychlorinated ethanes, petroleum fractions, cyclohexane, methanol, ethanol, isopropyl alcohol, butanol, ethylene glycol, propylene glycol, glycerol, sorbitol, benzyl alcohol, furfuryl alcohol, cyclohexanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, N-methyl-pyrrolidone, tributyl phosphate, dimethylformamide, and dimethyl sulfoxide. Suitable oily media are selected from soybean oil, methyl oleate, light mineral oil, liquid paraffin, kerosene, turpentine, and the like.

[0157] Suitable solid carriers in the bactericidal preparations of the compound of general formula I of the present invention include natural or synthetic ones. They can be selected from, but are not limited to, clay, rock powder, chalk, quartz, clay, montmorillonite, sodium sulfate, silicon dioxide, diatomaceous earth, pumice, gypsum, talc, bentonite, kaolin, attapulgite, light calcium carbonate, pottery clay, montmorillonite, magnesium aluminum silicate, atavistic clay, white carbon black, ammonium sulfate, coumarone resin, superphosphate, aluminum oxide, calcite, marble, pumice etc. Suitable particle carriers include crushed and graded natural rocks such as sepiolite and dolomite and synthetic particles made of organic and inorganic powders.

[0158] Suitable binders and thickeners include synthetic or natural water-soluble polymers. They can be selected from, but not limited to, carbonyl methyl alcohol, polyvinyl alcohol, polyvinyl acetate, xanthan gum, gelatin, gum arabic, polyvinyl pyrrolidone, magnesium aluminum silicate, polyvinyl alcohol, polyethylene glycol, phenolic resin, shellac, methylcellulose, soluble starch, carboxymethyl cellulose, and sodium alginate, and can be added to the preparation in the form of powder, granules, or latex.

[0159] Suitable defoaming agents can be selected from but are not limited to defoaming agent SAG1522, silicones, C8-10 fatty alcohols, phosphates, C10-20 saturated fatty acids (such as capric acid) and amides.

[0160] Suitable antifreeze agents can be selected from, but are not limited to, ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol, ethylene glycol butyl ether, propylene glycol butyl ether, ethylene glycol butyl ether acetate, urea, and the like.

[0161] Suitable penetrants can be selected from, but are not limited to, silicone, penetrant T, penetrant JFC, and the like.

[0162] Suitable film-forming agents include natural products and modified products thereof and synthetic polymers. They may be selected from, but are not limited to, sodium carboxymethyl starch, soluble starch, phosphorylated starch, oxidized starch, chitosan and its derivatives, polypropylene graft copolymers, xanthan gum, sodium alginate, agar, gelatin, gum arabic, polyethylene glycol, polyvinyl alcohol, polyvinyl acetate, polyacrylamide, polyvinyl pyrrolidone, polyacrylic acid, and the like.

[0163] Suitable preservatives may be selected from, but are not limited to, sodium benzoate, kasone, potassium sorbate, and the like.

[0164] Suitable disintegrants can be selected from, but are not limited to, sodium carboxymethyl starch, cross-linked sodium carboxymethyl starch, cross-linked sodium carboxymethyl cellulose, modified starch, cross-linked polyvinyl pyrrolidone, ammonium sulfate, sodium sulfate, sodium chloride, ammonium chloride, and the like.

[0165] The effervescent disintegrant can be an acidic component and / or an alkaline component, wherein the acidic component can be selected from organic acids, inorganic acids, such as tartaric acid, citric acid, salicylic acid, phosphoric acid, etc.; the alkaline component can be selected from basic carbonates, carbonates, such as sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, ammonium bicarbonate, etc.

[0166] Suitable warning colors can be selected from, but are not limited to, inorganic pigments such as iron oxide, titanium oxide or Prussian blue; organic dyes such as alizarin, acid scarlet G, basic rhodamine, azo dyes, metal phthalocyanines, etc.

[0167] Suitable wall materials include one or more of natural polymer materials, semi-synthetic polymer materials, and fully synthetic polymer materials. Natural polymer materials may be selected from, but are not limited to, gelatin, gum arabic, agar, alginate, chitosan, fibrin, and zein; semi-synthetic polymer materials may be selected from, but are not limited to, methyl (ethyl) cellulose, sodium carboxymethyl cellulose, cellulose acetate and its esters, and some glycerides; and fully synthetic polymer materials may be selected from, but are not limited to, polyacrylic resin, urea-formaldehyde resin, polyamide, polyester, polymethyl methacrylate, polyurea, and polyurethane.

[0168] Suitable curing agents include one or more of polyols and polyamines. Polyols may be selected from, but are not limited to, ethylene glycol, glycerol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, and the like; polyamines may be selected from, but are not limited to, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, diethanolamine, triethanolamine, hexamethylenetetramine, and isophoronediamine.

[0169] The bactericidal preparation of the compound of general formula I of the present invention can be diluted by the user or sprayed with water before use, or can be used directly.

[0170] The technical solution of the present invention also includes a method for controlling pathogens: applying the fungicide of the present invention to the pathogens or their growth medium. The effective amount is usually selected to be 10 to 1000 grams per hectare, and preferably 10 to 500 grams per hectare.

[0171] It should be understood that various changes and modifications can be made within the scope of the present invention as defined by the claims. DETAILED DESCRIPTION

[0172] The following specific examples are used to further illustrate the present invention, but the present invention is in no way limited to these examples. (Unless otherwise noted, all raw materials used are commercially available)

[0173] Synthesis Example

[0174] According to the synthetic route described above, different raw materials can be used to prepare the compounds represented by the general formula I of the present invention, which are further described in detail as follows:

[0175] Example 1: Preparation of intermediate N-(piperidin-4-yl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide hydrochloride (VI-1):

[0176]

[0177] To the reaction flask, 1.70 g (6.59 mmol) of 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzoic acid (intermediate II-1, prepared according to the method reported in WO2015185485) and 20 mL of thionyl chloride were added, and the mixture was heated under reflux for 4 hours. After the reaction was completed as monitored by TLC, the thionyl chloride was evaporated under reduced pressure to obtain intermediate III-1.

[0178] To another reaction flask, 1.26 g (6.30 mmol) of 1-tert-butyloxycarbonylaminomethylpiperidine (intermediate IV-1), 0.52 g (6.57 mmol) of pyridine and 20 mL of dichloromethane were added, and the mixture was cooled to 0-5°C in an ice bath; the intermediate III-1 prepared in the previous step (diluted with 10 mL of dichloromethane) was added dropwise to the reaction solution under stirring, and the reaction was stirred for 1 hour; after the completion of the reaction monitored by TLC, the solvent was removed under reduced pressure, and the residue was purified by column chromatography to obtain 1.5 g of a white solid, namely, intermediate V-1.

[0179] After dissolving 1.5 g of the intermediate V-1 obtained in the previous step in 40 mL of ethyl acetate, 10 mL of concentrated hydrochloric acid was slowly added dropwise thereto with stirring. During this process, solids were continuously precipitated. The solids were filtered, washed with an appropriate amount of ethyl acetate, and dried to obtain 0.76 g of a white solid, namely the intermediate N-(piperidin-4-yl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide hydrochloride (VI-1).

[0180] Example 2: Preparation of intermediate N-(piperidin-4-methylene)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide hydrochloride (VI-2):

[0181]

[0182] Referring to the synthesis method of Example 1, intermediate III-1 and intermediate IV-2 were subjected to condensation reaction to obtain intermediate V-2, which was then treated with concentrated hydrochloric acid to obtain intermediate VI-2.

[0183] Example 3: Preparation of Compound 1.1

[0184]

[0185] To a reaction flask were added 0.20 g (0.53 mmol) of N-(piperidin-4-yl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide hydrochloride (Intermediate VI-1), 0.04 g (0.51 mmol) of pyridine, 15 mL of toluene, and 0.09 g (0.64 mmol) of benzoyl chloride. The mixture was heated under reflux for 5 hours. After completion of the reaction, as monitored by TLC, the solvent was removed under reduced pressure, and the residue was purified by column chromatography to obtain 0.16 g of a white solid, Compound 1.1.

[0186] Compound 1.1 1 HNMR and LC-MS data are as follows:

[0187] 1 HNMR(600MHz,Chloroform-d)δ8.13(d,2H),7.92(d,2H),7.46–7.34(m,5H),6.73(d,1H),4.75(s,1H),4.33–4.2 3(m,1H),3.82(s,1H),3.19(s,1H),2.98(s,1H),2.10(d,2H),1.72–1.36(m,2H).LC-MS(m / z,ESI):445.22(M+H) + .

[0188] Example 4: Preparation of Compound 1.2

[0189]

[0190] Compound 1.2 (white solid) was prepared by referring to the synthesis method of Example 3. 1 HNMR and LC-MS data are as follows:

[0191] 1 HNMR(600MHz,Chloroform-d)δ8.18–8.14(m,2H),7.93–7.89(m,2H),7.43– 7.35(m,2H),7.21(td,1H),7.12–7.08(m,1H),6.40(s,1H),4.81(d,1H),4. 32–4.23(m,1H),3.66–3.59(m,1H),3.20(s,1H),2.99(s,1H),2.21–2.15(m ,1H),2.12–2.06(m,1H),1.67–1.58(m,2H).LC-MS(m / z,ESI):463.14(M+H) + .

[0192] Example 5: Preparation of Compound 1.3

[0193]

[0194] Compound 1.3 (white solid) was prepared by referring to the synthesis method of Example 3. 1 HNMR and LC-MS data are as follows:

[0195] 1 HNMR(600MHz,Chloroform-d)δ8.20–8.17(m,2H),7.92–7.89(m,2H),7.39(td,1H),7.17(dt,1H),7.15–7.09(m,2H),6.30(d,1H),4.73 (s,1H),4.34–4.23(m,1H),3.79(s,1H),3.21(s,1H),3.00(s,1H),2.25–2.06(m,2H),1.63–1.37(m,2H).LC-MS(m / z,ESI):463.17(M+H) + .

[0196] Example 6: Preparation of Compound 1.4

[0197]

[0198] Compound 1.4 (white solid) was prepared by referring to the synthesis method of Example 3. 1The HNMR data are as follows:

[0199] 1 HNMR(600MHz,Chloroform-d)δ8.18(d,2H),7.91(d,2H),7.42(dd,2H),7.10(t,2H),6.27(d,1 H),4.72(s,1H),4.35–4.22(m,1H),3.83(s,1H),3.11(d,2H),2.14(s,2H),1.77–1.34(m,2H).

[0200] Example 7: Preparation of Compound 1.20

[0201]

[0202] Compound 1.20 (white solid) was prepared by referring to the synthesis method of Example 3. 1 The HNMR data are as follows:

[0203] 1 HNMR(400MHz,Chloroform-d)δ8.15(d,2H),7.93(d,2H),7.35–7.12(m,4H),6.67(d,1H),4.85(d,1H),4. 38–4.19(m,1H),3.56(d,1H),3.24–2.90(m,2H),2.43–1.96(m,5H),1.75–1.56(m,1H),1.47–1.32(m,1H).

[0204] Example 8: Preparation of Compound 1.21

[0205]

[0206] Compound 1.21 (white solid) was prepared by referring to the synthesis method of Example 3. 1 The HNMR data are as follows:

[0207] 1 HNMR(400MHz,Chloroform-d)δ8.12(dd,2H),7.93(dd,2H),7.32–7.12(m,4H),6.94–6.72(m,1H),4. 74(s,1H),4.37–4.19(m,1H),3.83(s,1H),3.08(d,2H),2.35(s,3H),2.10(s,2H),1.79–1.33(m,2H).

[0208] Example 9: Preparation of Compound 1.22

[0209]

[0210] Compound 1.22 (white solid) was prepared by referring to the synthesis method of Example 3. 1 The HNMR data are as follows:

[0211] 1 HNMR(400MHz,Chloroform-d)δ8.10(d,2H),7.94(d,2H),7.28(d,2H),7.19(d,2H),6.99(d,1H),4.73( s,1H),4.36–4.21(m,1H),3.86(s,1H),3.33–2.82(m,2H),2.36(s,3H),2.09(d,2H),1.76–1.33(m,2H).

[0212] Example 10: Preparation of Compound 1.151

[0213]

[0214] Compound 1.151 (white solid) was prepared by referring to the synthesis method of Example 3. 1 The HNMR data are as follows:

[0215] 1 HNMR(600MHz,Chloroform-d)δ8.17(d,2H),7.92(d,2H),7.62(d,2H),7.58(d,2H),7.48(d,2H),7.45(t,2H),7.38(t,1H),6.44(d,1H) ,4.78(s,1H),4.37–4.25(m,1H),3.93(s,1H),3.25(s,1H),3.03(s,1H),2.16(s,2H),1.74–1.38(m,2H).LC-MS(m / z,ESI):521.29(M+H) + .

[0216] Example 11: Preparation of Compound 1.217

[0217]

[0218] Compound 1.217 (white solid) was prepared by referring to the synthesis method of Example 3. 1 HNMR and LC-MS data are as follows:

[0219] 1HNMR(600MHz,Chloroform-d)δ8.18(d,2H),7.92(d,2H),7.43–7.34(m,4H),7.16(t,1H),7.04(d,2H),7.02–6.98(m,2H),6.34–6.2 6(m,1H),4.72(s,1H),4.36–4.22(m,1H),3.93(s,1H),3.12(d,2H),2.13(s,2H),1.76–1.39(m,2H).LC-MS(m / z,ESI):537.32(M+H) + .

[0220] Example 12: Preparation of Compound 2.1

[0221]

[0222] Compound 2.1 (white solid) was prepared by referring to the synthesis method of Example 3. 1 HNMR and LC-MS data are as follows:

[0223] 1 HNMR(600MHz,Chloroform-d)δ8.10(d,2H),7.91(d,2H),7.43–7.32(m,5H),7.02(t,1H),4.71(s,1H),3. 76(s,1H),3.36(d,2H),2.87(d,2H),2.09–1.59(m,3H),1.47–1.07(m,2H).LC-MS(m / z,ESI):459.25(M+H) + .

[0224] Example 13: Preparation of Compound 25.1

[0225]

[0226] Compound 25.1 (white solid) was prepared by referring to the synthesis method of Example 3. 1 HNMR and LC-MS data are as follows:

[0227] 1HNMR(600MHz,Chloroform-d)δ8.16(d,2H),7.90(d,2H),7.78(d,2H),7.65(t,1H),7.58(t,2H),6.27(d,1H),4 .02–3.92(m,1H),3.92–3.83(m,2H),2.46(td,2H),2.13(dd,2H),1.73(qd,2H).LC-MS(m / z,ESI):481.16(M+H) + .

[0228] Example 14: Preparation of Compound 26.1

[0229]

[0230] Compound 26.1 (white solid) was prepared by referring to the synthesis method of Example 3. 1 HNMR and LC-MS data are as follows:

[0231] 1 HNMR(600MHz,Chloroform-d)δ8.15(d,2H),7.87(d,2H),7.77–7.71(m,2H),7.59(t,1H),7.52(t,2H),6.60–6.53(m,1H),3 .81(dt,2H),3.33(t,2H),2.27(td,2H),1.81(dd,2H),1.73–1.61(m,1H),1.45–1.34(m,2H).LC-MS(m / z,ESI):495.18(M+H) + .

[0232] Biological activity assay

[0233] Example 15: Determination of fungicidal activity against soybean rust

[0234] Protective activity testing method: A live pot assay is used. The test compound sample is dissolved in a small amount of solvent (e.g., acetone, methanol, DMF, etc., selected based on its solubility for the sample, with a volume ratio of solvent to spray volume equal to or less than 0.05). This solution is then diluted with water containing 0.1% Tween 80 to produce the desired test concentration. A separate solvent-water solution serves as a blank control. Using a crop sprayer, the test solution is sprayed onto the diseased host plant (standard potted seedlings grown in a greenhouse). Twenty-four hours later, the disease is inoculated. Depending on the characteristics of the disease, plants requiring temperature and humidity control are inoculated and cultured in an artificial climate chamber. Once infection is complete, they are transferred to the greenhouse. Plants not requiring humidity control are inoculated and cultured directly in the greenhouse. The compound's protective efficacy is evaluated after the control plant has fully developed disease (usually one week).

[0235] The in vivo protective activity against soybean rust is as follows:

[0236] When the concentration of the solution was 100 mg / L, compounds 1.1, 1.2, 1.3, 1.4, 1.20, 1.21, 1.22, 1.151, 1.217, 2.1, 25.1, and 26.1 showed a control effect of not less than 90% against soybean rust;

[0237] When the concentration of the solution was 25 mg / L, compounds 1.1, 1.2, 1.3, 1.20, 1.21, 1.22, 1.151, 1.217, 2.1, and 26.1 showed a control effect of not less than 90% against soybean rust;

[0238] When the concentration of the solution was 6.25 mg / L, the control efficacy of compounds 1.1, 2.1, and 26.1 against soybean rust was no less than 90%;

[0239] When the concentration of the drug solution is 3.125 mg / L, the control efficiency of compounds 1.1 and 2.1 against soybean rust is not less than 90%.

Claims

1. An oxadiazole compound, characterized in that The compound is shown in the general formula I: In the general formula I: X1 and X2 are each independently selected from hydrogen, halogen or C1-C6 alkyl; n is selected from 0 or 1; L is selected from -C(=O)- or -S(=O) m -, m is selected from 2; R1, R2, R3, R4, and R5 are each independently selected from hydrogen, halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C1-C6 alkylthio, halo-C1-C6 alkylthio, phenyl or phenoxy which is unsubstituted or substituted with 1, 2, 3, 4, or 5 R6, and when the number of substituents is greater than 1, R6 may be the same or different; R6 is selected from halogen, cyano, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C1-C6 alkylthio or halo-C1-C6 alkylthio; or a salt of a compound of formula I.

2. The compound according to claim 1, characterized in that In the general formula I, X1 and X2 are each independently selected from hydrogen, halogen or C1-C4 alkyl; n is selected from 0 or 1; L is selected from -C(=O)- or -S(=O) m -, m is selected from 2; R1, R2, R3, R4, and R5 are each independently selected from hydrogen, halogen, cyano, nitro, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio, halo-C1-C4 alkylthio, phenyl or phenoxy which is unsubstituted or substituted with 1, 2, 3, 4, or 5 R6, and when the number of substituents is greater than 1, R6 may be the same or different; R6 is selected from halogen, cyano, nitro, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio or halo-C1-C4 alkylthio; or a salt formed by a compound of formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.

3. The compound according to claim 2, characterized in that In the general formula I, X1 and X2 are each independently selected from hydrogen, halogen or C1-C4 alkyl; n is selected from 0 or 1; L is selected from -C(=O)- or -S(=O) m -, m is selected from 2; R1, R2, R4, and R5 are each independently selected from hydrogen, halogen, cyano, nitro, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio, or halo-C1-C4 alkylthio; R3 is selected from hydrogen, halogen, cyano, nitro, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio, halo-C1-C4 alkylthio, phenyl or phenoxy which is unsubstituted or substituted with 1, 2, 3, 4 or 5 R6, and when the number of substituents is greater than 1, R6 may be the same or different; R6 is selected from halogen, cyano, nitro, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio or halo-C1-C4 alkylthio; or a salt formed by a compound of formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.

4. The compound according to claim 2, characterized in that In the general formula I, X1 and X2 are each independently selected from hydrogen, fluorine, chlorine, bromine, methyl or ethyl; n is selected from 0 or 1; L is selected from -C(=O)- or -S(=O) m -, m is selected from 2; R1, R2, R3, R4, R5 are each independently selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, perfluoroethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl , methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, monofluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, phenyl or phenoxy which is unsubstituted or substituted with 1, 2, 3, 4 or 5 R6, and when the number of substituents is greater than 1, R6 may be the same or different; R6 is selected from fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, perfluoroethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, monofluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, trifluoromethylthio or 2,2,2-trifluoroethylthio; or a salt formed by a compound of formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.

5. The compound according to claim 3, characterized in that In the general formula I, X1 and X2 are each independently selected from hydrogen, fluorine, chlorine, bromine, methyl or ethyl; n is selected from 0 or 1; L is selected from -C(=O)- or -S(=O) m -, m is selected from 2; R1, R2, R4, R5 are each independently selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, perfluoroethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, monofluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, trifluoromethylthio, or 2,2,2-trifluoroethylthio; R3 is selected from hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, perfluoroethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, monofluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, trifluoromethylthio, 2,2,2-trifluoroethylthio, phenyl or phenoxy which is unsubstituted or substituted with 1, 2, 3, 4 or 5 R6, and when the number of substituents is greater than 1, R6 may be the same or different; R6 is selected from fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, tribromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, heptafluoroisopropyl, perfluoroethyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, monofluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, trifluoromethylthio or 2,2,2-trifluoroethylthio; or a salt formed by a compound of formula I and hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, methanesulfonic acid, 4-toluenesulfonic acid, malic acid, fumaric acid, lactic acid, maleic acid, salicylic acid, tartaric acid or citric acid.

6. The compound according to any one of claims 1 to 5, characterized in that The compound is selected from any one of the following compounds:

7. Use of the compound of general formula I according to claim 1 as a fungicide in the agricultural field.

8. A bactericidal composition, characterized in that: The composition comprises the compound of general formula I according to claim 1 and an agriculturally acceptable carrier, wherein the weight percentage of the active component in the composition is 0.1-99%.

9. A method for preventing and controlling pathogens, characterized in that: Applying a fungicidal effective amount of the fungicidal composition according to claim 8 to crops or the growing medium or site of crops.

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