Triazolethiol derivative and use thereof

Abstract

The present invention belongs to the technical field of agricultural fungicides / bactericides, and specifically relates to a triazolethiol derivative and the use thereof. The triazolethiol derivative is as represented by general formula (I). The compound of general formula (I) exhibits good activity against a variety of fungal and bacterial diseases in the agricultural field, and can be used as a fungicide / bactericide in the agricultural field.

Description

A triazole thiol derivative and its uses Technical Field

[0001] This invention belongs to the field of agricultural fungicides and bactericides, specifically relating to a triazole thiol derivative, its preparation method, and its uses. Background Technology

[0002] To date, numerous crop protectants have been developed to combat or prevent microbial infection. However, there remains a need to develop new compounds that are effective against a broad spectrum of plant pathogenic microorganisms, such as fungi and bacteria. These compounds should exhibit low toxicity, high selectivity, or be applicable at low application rates while still effectively controlling harmful pathogens. This invention provides novel compounds for controlling plant pathogenic microorganisms, such as fungi and bacteria.

[0003] However, no compounds or complexes with structures as shown in Formula I of this invention have been reported. Summary of the Invention

[0004] To address the above problems, the present invention aims to provide a method for preparing and using a triazole thiol derivative.

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

[0006] A triazole thiol derivative, a compound or complex of general formula I.

[0007] In the formula:

[0008] R1 is selected from C1-C 12 Alkyl, halogenated C1-C 12 Alkyl, C3-C 12 cycloalkyl, halogenated C3-C 12 cycloalkyl, C2-C 12 alkenyl, C2-C 12 Alkyne group, halogenated C2-C 12 Alkenyl, halogenated C2-C 12 Alkynyl, unsubstituted or phenyl with 1-5 R5 substituted groups;

[0009] R2 and R3 may be the same or different, and each can be independently selected from hydrogen, fluorine, chlorine, bromine, iodine, and C1-C. 12 Alkyl, halogenated C1-C 12 Alkyl, C3-C 12 cycloalkyl or halogenated C3-C 12 cycloalkyl;

[0010] R4 is selected from hydrogen, halogen, hydroxyl, nitro, amino, cyano, C1-C. 12 Alkyl, halogenated C1-C 12Alkyl, C1-C 12 Alkoxy, halogenated C1-C 12 Alkoxy, C1-C 12 Alkylthio, Halogenated C1-C 12 Alkylthio, C3-C 12 cycloalkyl, C3-C 12 Epoxyalkyl, C1-C 12 Alkoxy carbonyl, halogenated C1-C 12 Alkoxy carbonyl, unsubstituted or phenoxy with 1-5 R5 substituted groups;

[0011] R5 is selected from hydrogen, halogen, nitro, cyano, C1-C. 12 Alkyl, halogenated C1-C 12 Alkyl, C1-C 12 Alkoxy, halogenated C1-C 12 Alkoxy or C3-C 12 cycloalkyl;

[0012] Y is selected from N or CH;

[0013] m is 1, 2, 3, 4 or 5;

[0014] n is 1, 2, or 3;

[0015] M is selected from Li, Na, K, Zn, Cu, Mn, Fe, Co, Mg, Ca, Cr, Mo, Ni, Sn, or Se.

[0016] Preferably, in the compound or complex of general formula I

[0017] R1 is selected from C1-C8 alkyl, halo-C1-C8 alkyl, C3-C8 cycloalkyl, halo-C3-C8 cycloalkyl, C2-C8 alkenyl, C2-C8 ynyl, halo-C2-C8 alkenyl, halo-C2-C8 ynyl, unsubstituted or phenyl substituted with 1-4 R5s.

[0018] R2 and R3 may be the same or different, and each can be independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C8 alkyl, halogenated C1-C8 alkyl, C3-C8 cycloalkyl or halogenated C3-C8 cycloalkyl.

[0019] R4 is selected from hydrogen, halogen, hydroxyl, nitro, amino, cyano, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxy, halo-C1-C8 alkoxy, C1-C8 alkylthio, halo-C1-C8 alkylthio, C3-C8 cycloalkyl, C3-C8 epoxyalkyl, C1-C8 alkoxycarbonyl, halo-C1-C8 alkoxycarbonyl, unsubstituted or phenoxy groups substituted with 1-4 R5 groups;

[0020] R5 is selected from hydrogen, halogen, nitro, cyano, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxy, halo-C1-C8 alkoxy, or C3-C8 cycloalkyl;

[0021] Y is selected from N or CH;

[0022] m is 1, 2, 3, 4 or 5;

[0023] n is 1, 2, or 3;

[0024] M is selected from Li, Na, K, Zn, Cu, Mn, Fe, Co, Mg, Ca, Cr, Mo, Ni, Sn, or Se.

[0025] Further preferably, in the compound or complex of general formula I

[0026] R1 is selected from C1-C4 alkyl, halo-C1-C4 alkyl, C3-C4 cycloalkyl, halo-C3-C4 cycloalkyl, C2-C4 alkenyl, C2-C4 ynyl, halo-C1-C4 alkenyl, halo-C1-C4 ynyl, unsubstituted or phenyl substituted with 1-4 R5s.

[0027] R2 and R3 may be the same or different, and each can be independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C4 cycloalkyl or halo-C3-C4 cycloalkyl.

[0028] R4 is selected from hydrogen, halogen, hydroxyl, nitro, amino, cyano, C1-C4 alkyl, halo-C1-C4 alkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio, halo-C1-C4 alkylthio, C3-C4 cycloalkyl, C3-C4 epoxyalkyl, C1-C4 alkoxycarbonyl, halo-C1-C4 alkoxycarbonyl, unsubstituted or phenoxy groups substituted with 1-4 R5 groups;

[0029] R5 is selected from hydrogen, halogen, nitro, cyano, C1-C4 alkyl, halo-C1-C4 alkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, or C3-C4 cycloalkyl;

[0030] Y is selected from N or CH;

[0031] m is 1, 2, 3, 4 or 5;

[0032] n is 1, 2, or 3;

[0033] M is selected from Li, Na, K, Zn, Cu, Mn, Fe, Co, Mg, Ca, Cr, Mo, Ni, Sn, or Se.

[0034] In a further preferred embodiment, the compound or complex of general formula I contains...

[0035] R1 is selected from methyl, ethyl, monochloromethyl, monofluoromethyl, cyclopropyl, monochlorocyclopropyl, monofluorocyclopropyl, vinyl, ethynyl, monochlorovinyl, monochloroacetylene, unsubstituted or phenyl substituted with 1-4 R5s;

[0036] R2 and R3 may be the same or different, and each can be independently selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, monochloromethyl, cyclopropyl or monochlorocyclopropyl.

[0037] R4 is selected from hydrogen, fluorine, chlorine, bromine, hydroxyl, nitro, amino, cyano, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, methylthio, monochloromethylthio, cyclopropyl, ethylene oxide, methoxycarbonyl, difluoromethoxycarbonyl, unsubstituted or phenoxy groups substituted with 1-4 R5 groups.

[0038] R5 is selected from hydrogen, fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, or cyclopropyl.

[0039] Y is selected from N or CH;

[0040] m is 1, 2, 3, 4 or 5;

[0041] n is 1, 2, or 3;

[0042] M is selected from Li, Na, K, Zn, Cu, Mn, Fe, Co, Mg, Ca, Cr, Mo, Ni, Sn, or Se.

[0043] More preferably, in the compound or complex of general formula I

[0044] R1 is selected from methyl, ethyl, monochloromethyl, cyclopropyl, monochlorocyclopropyl, monofluorocyclopropyl, unsubstituted or phenyl substituted with 1-4 R5s;

[0045] R2 and R3 may be the same or different, and each can be independently selected from hydrogen, fluorine, chlorine, bromine, methyl, cyclopropyl or monochlorocyclopropyl;

[0046] R4 is selected from hydrogen, fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio, cyclopropyl, unsubstituted or phenoxy groups substituted with 1-4 R5 groups;

[0047] R5 is selected from hydrogen, fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy, or trifluoromethoxy.

[0048] Y is selected from N or CH;

[0049] m is 1, 2, or 3;

[0050] n is 1 or 2;

[0051] M is selected from Li, Na, K, Zn, Cu, or Mn.

[0052] Most preferably, in the compound or complex of general formula I

[0053] R1 is selected from methyl, ethyl, cyclopropyl, monochlorocyclopropyl, or monofluorocyclopropyl;

[0054] R2 and R3 are hydrogen;

[0055] R4 is selected from hydrogen, fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, or trifluoromethoxy.

[0056] Y represents CH;

[0057] m is 1 or 2;

[0058] n is 1 or 2;

[0059] M is selected from Li, K, Zn or Mn.

[0060] A method for preparing compounds or complexes of general formula I as described, comprising the following reaction formula:

[0061] The use of a triazole thiol derivative of general formula I in agriculture for the preparation of fungicides and bactericides.

[0062] In the definitions of compounds of general formula I given above, the terms used in the compilation are generally defined as follows:

[0063] 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. Halogenated alkyl: 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. Alkoxy: Straight-chain or branched alkoxy. Halogenated alkoxy: Straight-chain or branched alkoxy, 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, trifluoroethoxy, etc. 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. Alkynyl: Straight-chain or branched alkynes, such as ethynyl, 1-propynyl, 2-propynyl, and various butynyl, pentynyl, and hexynyl isomers. Alkynyl groups also include groups composed of multiple triple bonds, such as 2,5-hexadiynyl.

[0064] Some of the compounds of this invention can be described using the specific compounds listed in Tables 1-2, but this does not limit the invention.

[0065] When R1 = 1-chlorocyclopropyl, R2 = R3 = H, R4 = 2-Cl, Y = CH, and m = 1, the substituents M and n are shown in Table 1, and the compounds are numbered 1-1 to 1-16 in sequence.

[0066] Table 2: When R1 = 1-fluorocyclopropyl, R2 = R3 = H, R4 = 2-Cl, Y = CH, and m = 1, the M and n substituents are shown in Table 1, and the compound numbers are 2-1 to 2-16 in sequence.

[0067] Table 3: When R1 = 1-chlorocyclopropyl, R2 = R3 = H, R4 = 3-Cl, Y = CH, and m = 1, the M and n substituents are shown in Table 1, and the compound numbers are 3-1 to 3-16 in sequence.

[0068] Table 4: When R1 = 1-fluorocyclopropyl, R2 = R3 = H, R4 = 3-Cl, Y = CH, and m = 1, the M and n substituents are shown in Table 1, and the compound numbers are 4-1 to 4-16 in sequence.

[0069] Table 5: When R1 = 1-chlorocyclopropyl, R2 = R3 = H, R4 = 4-Cl, Y = CH, and m = 1, the M and n substituents are shown in Table 1, and the compound numbers are 5-1 to 5-16 in sequence.

[0070] Table 6: When R1 = 1-fluorocyclopropyl, R2 = R3 = H, R4 = 4-Cl, Y = CH, and m = 1, the M and n substituents are shown in Table 1, and the compound numbers are 6-1 to 6-16 in sequence.

[0071] Table 7: When R1 = 1-chlorocyclopropyl, R2 = R3 = H, R4 = 2,4-Cl, Y = CH, and m = 2, the M and n substituents are shown in Table 1, and the compounds are numbered 7-1 to 7-16 in sequence.

[0072] Table 8: When R1 = 1-fluorocyclopropyl, R2 = R3 = H, R4 = 2,4-Cl, Y = CH, and m = 2, the M and n substituents are shown in Table 1, and the compound numbers are 8-1 to 8-16 in sequence.

[0073] Table 9: When R1 = 1-chlorocyclopropyl, R2 = R3 = H, R4 = 3,5-Cl, Y = CH, and m = 2, the M and n substituents are shown in Table 1, and the compounds are numbered 9-1 to 9-16 in sequence.

[0074] Table 10: When R1 = 1-fluorocyclopropyl, R2 = R3 = H, R4 = 3,5-Cl, Y = CH, and m = 2, the M and n substituents are shown in Table 1, and the compound numbers are 10-1 to 10-16 in sequence.

[0075] Table 11: When R1 = 1-chlorocyclopropyl, R2 = R3 = H, R4 = 2,6-Cl, Y = CH, and m = 2, the M and n substituents are shown in Table 1, and the compound numbers are 11-1 to 11-16 in sequence.

[0076] Table 12: When R1 = 1-fluorocyclopropyl, R2 = R3 = H, R4 = 2,6-Cl, Y = CH, and m = 2, the M and n substituents are shown in Table 1, and the compound numbers are 12-1 to 12-16 in sequence.

[0077] Table 13: When R1 = cyclopropyl, R2 = R3 = H, R4 = 2-Cl, Y = CH, and m = 1, the M and n substituents are shown in Table 1, and the compound numbers are 13-1 to 13-16 in sequence.

[0078] Table 1

[0079] Table 14: In general formula I, when R1 = 2,4-difluorophenyl, R2 = R3 = F, R4 = 5-(4-CNPhO)-, Y = N, and m = 1, the substituents M and n are consistent with the substituents shown in Table 1, corresponding to 1-1 to 1-16 in Table 1, and the compound numbers are 14-1 to 14-16 in sequence.

[0080] Table 15: In general formula I, when R1 = 2,4-difluorophenyl, R2 = R3 = F, R4 = 5-(4-CF3PhO)-, Y = N, and m = 1, the substituents M and n are consistent with the substituents shown in Table 1, corresponding to 1-1 to 1-16 in Table 1, and the compound numbers are 15-1 to 15-16 in sequence.

[0081] Table 16: In general formula I, when R1 = 2,4-difluorophenyl, R2 = R3 = F, R4 = 5-(4-NO2PhO)-, Y = N, and m = 1, the substituents M and n are consistent with the substituents shown in Table 1, corresponding to 1-1 to 1-16 in Table 1, and the compound numbers are 16-1 to 16-16 in sequence.

[0082] 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:

[0083] When M is Li, Na, or K, the compound of general formula I can be obtained by reacting intermediate V with lithium hydroxide, sodium hydroxide, or potassium hydroxide in an organic solvent such as methanol, ethanol, toluene, xylene, or water.

[0084] When M is Zn, Cu, Mn, Mg, Ca, Fe, Co, Cr, Mo, Ni, Sn, or Se, it can be obtained by first reacting intermediate V with sodium hydroxide, potassium hydroxide, or lithium hydroxide to form sodium salt, potassium salt, or lithium salt, and then reacting with a compound containing a metal cation.

[0085] The reaction is carried out in a suitable solvent, which can be selected from organic solvents such as methanol, ethanol, n-propanol, isopropanol, DMF, DMSO, acetonitrile, triethylamine, toluene, xylene, or water. The reaction temperature can range from 0 to 100°C, typically 20 to 80°C. The reaction time is from 10 minutes to 20 hours, typically 30 minutes to 8 hours.

[0086] The inorganic substances mentioned are zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, copper chloride, copper sulfate, copper acetate, copper nitrate, manganese chloride, manganese sulfate, manganese acetate, manganese nitrate, ferric chloride, ferric sulfate, ferric nitrate, ferrous acetate, ferrous chloride, ferrous sulfate, ferrous nitrate, cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt acetate, magnesium chloride, magnesium sulfate, magnesium nitrate, calcium chloride, calcium sulfate, calcium carbonate, calcium nitrate, calcium acetate, chromium chloride, chromium sulfate, chromium nitrate, chromium acetate, molybdenum chloride, molybdenum sulfate, molybdenum nitrate, molybdenum acetate, nickel chloride, nickel sulfate, nickel nitrate, nickel acetate, stannous chloride, or selenium dioxide, etc.

[0087] The molar ratio of intermediate V to lithium hydroxide, sodium hydroxide, or potassium hydroxide is 1:1 to 1:3; preferably 1:1 to 1:1.5.

[0088] The molar ratio of divalent inorganic substances to V is 1:1 to 1:2; preferably 1:1.5 to 1:2.

[0089] The molar ratio of trivalent inorganic substances to V is 1:1 to 1:3; preferably 1:2 to 1:3.

[0090] Intermediate V is commercially available or referenced in publications such as WO9616048, CN1058712, CN118772072, CN116655548, CN116162067, WO2023056714, CN115894387, CN115448889, CN114805227, CN114805228, and CN11477328. 0, CN114478411, CN113429357, CN111303059; WO2018094147, WO2018094138, WO2018094129, WO2017087592, WO2017087597, WO2017087643, WO2017087619, WO2015143192, etc.

[0091] Although the compounds of general formula I of this invention also belong to the triazole thiol class of compounds disclosed in the prior art, their structural features are significantly different. Furthermore, these structural differences result in the compounds of this invention exhibiting superior antifungal and / or antibacterial activity.

[0092] The compound of general formula I of this invention can be used to control plant diseases, and can be used to prevent and control diseases caused by various fungi such as Basidiomycetes, Ascomycetes, Fusarium graminearum, Fusarium pseudograminearum, Fusarium truncatum, Fusarium oxysporum, and Deuteromycetes on a variety of crops. For example, at low doses, it has good preventive effects against diseases such as cucumber gray mold, cucumber anthracnose, cucumber powdery mildew, tomato early blight, grape white rot, apple ring rot, apple leaf spot, rice sheath blight, rice blast, wheat scab, corn stem base rot, wheat stem base rot, corn ear rot, rice bakanae disease, cotton wilt, cucumber wilt, wheat rust, wheat leaf spot, wheat powdery mildew, rapeseed sclerotinia rot, corn small leaf spot, peanut net blotch, vegetable gray mold, grape gray mold, and peanut white mold.

[0093] The compound of general formula I of this invention is used for controlling bacterial diseases of plants. It can be used to prevent and control a variety of bacterial diseases of plants, such as fruit spot (e.g., melon fruit spot), leaf spot (e.g., tomato bacterial leaf spot), bacterial wilt (e.g., tomato bacterial wilt, potato bacterial wilt), bacterial blight, canker (e.g., citrus canker, kiwifruit canker, tomato canker), soft rot (e.g., Chinese cabbage soft rot), bacterial angular leaf spot (e.g., cucumber bacterial angular leaf spot), bacterial stripe (e.g., rice bacterial stripe), leaf blight, bacterial leaf blight (e.g., rice bacterial leaf blight), black rot (e.g., cabbage black rot), crown gall (e.g., grape crown gall), wildfire (e.g., tobacco wildfire), bacterial basal rot (e.g., rice bacterial basal rot), black spot (e.g., walnut black spot), bacterial shot-hole (e.g., peach bacterial shot-hole), and bacterial scab. Attached Figure Description

[0094] Figure 1-1 shows the infrared spectra of compounds 1-9 in the embodiments of the present invention.

[0095] Figures 1-2 are infrared spectra of prothioconazole provided in the embodiments of the present invention.

[0096] Figure 2-1 shows the XPS broad spectrum of compounds 1-9 in the embodiments of the present invention.

[0097] Figure 2-2 is an XPS broad spectrum of prothioconazole provided in the embodiments of the present invention.

[0098] Figures 2-3 show the Zn2p spectra of compounds 1-9 in the embodiments of the present invention. Detailed Implementation

[0099] 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).

[0100] Synthesis Examples

[0101] Example: Preparation of compounds 1-9

[0102] 10.33 g (0.03 mol) of prothioconazole and 200 ml of water were added to a 500 ml single-necked reaction flask. The mixture was stirred at room temperature, and 50 ml of an aqueous solution containing 1.68 g of potassium hydroxide was added dropwise until a clear liquid was obtained. Then, 50 ml of an aqueous solution containing 2.40 g of zinc sulfate was added dropwise. A white precipitate was quickly formed in the reaction solution. After reacting for 2 hours, the mixture was filtered, washed three times with water and three times with methanol, and dried to obtain compound 1-9, 10.05 g of white solid, with a yield of 73% and a melting point of 266-271 °C. The infrared spectra of the target compounds 1-9 and prothioconazole are shown in Figures 1-1 and 1-2, respectively; the XPS spectra of compounds 1-9 and prothioconazole are shown in Figures 2-1 and 2-2, respectively; the Zn2p spectrum of compound 1-9 is shown in Figure 2-3; and the elemental contents of compounds 1-9 and prothioconazole are shown in Tables 14-1 and 14-2.

[0103] Table 14-1 shows the elemental contents of compounds 1-9.

[0104] Table 14-2 shows the elemental content of prothioconazole.

[0105] The other compounds of the present invention described in Tables 1-13 above can be synthesized by referring to the synthesis described in Example 1 above.

[0106] Bioactivity Assay Examples

[0107] The compounds of this invention exhibit excellent activity against a variety of pathogens in the agricultural field.

[0108] Example 1: Assay for antifungal activity

[0109] In vivo protective activity assay

[0110] 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).

[0111] The results of in vivo protective activity tests for some compounds are as follows:

[0112] In vivo protective activity against wheat scab:

[0113] At a dose of 50 ppm, compounds 1-9 are 100% effective against wheat scab.

[0114] At a dosage of 12.5 ppm, compounds 1-9 showed a control efficacy of over 95% against wheat scab.

[0115] At a dosage of 3.13 ppm, compounds 1-9 showed a control efficacy of over 90% against wheat scab.

[0116] In vivo protective activity against wheat powdery mildew:

[0117] At a dose of 5 ppm, compounds 1-9 are 100% effective against wheat powdery mildew.

[0118] At a dosage of 2.5 ppm, compounds 1-9 showed a control efficacy of over 80% against wheat powdery mildew.

[0119] In vivo protective activity against wheat rust:

[0120] At a dose of 25 ppm, compounds 1-9 provide 100% control of wheat rust.

[0121] At a dose of 6.25 ppm, compounds 1-9 showed a control efficacy of over 95% against wheat rust.

[0122] (2) Test results of some compounds and control drugs

[0123] The activity comparison tests of some compounds with the control drug are shown in Tables 15-17.

[0124] Table 15 Comparison of the activities of compounds 1-9 with prothioconazole

[0125] Table 16 Comparison of wheat scab activity

[0126] The CK1 structure is The CK2 structure is CK3 is prothioconazole mancozeb [(C 14 H 14 Cl2N3OS)2(Mn) 0.5 (Zn) 0.5 ]2. Hydrocarbons.

[0127] As can be seen from the above, the compounds of the present invention have outstanding structural features compared with existing commercial products and similar compounds, and achieve unexpected effects on specific targets. Furthermore, the activity of compounds 1-9 of the present invention against wheat scab at low doses was determined and the results are shown in Table 17. It can be seen that the compounds have outstanding effects at low doses.

[0128] Table 17 Comparison of wheat scab activity

[0129] Example 2: Determination of bactericidal activity

[0130] (1) Indoor bioactivity assay

[0131] In vivo efficacy testing methods for bacterial fruit spot disease of melon, bacterial angular leaf spot disease of cucumber, and soft rot disease of Chinese cabbage: Dissolve the test compound in a small amount of dimethyl sulfoxide and dilute to the required concentration, while setting up a blank control. Ensure even coverage on both sides of the leaves during spraying. Adjust the cultured pathogenic bacteria suspension to the required concentration and spray the plant leaves with the pathogen for inoculation. Place the treated plants in an artificial climate chamber, then transfer them to a greenhouse for normal cultivation. After the blank control develops disease, investigate the control effect of the agent.

[0132] Methods for testing the in vivo control efficacy against citrus canker: Cryopreserved citrus canker pathogens were streaked onto a solid culture medium. Activated single colonies were picked and transferred to a liquid culture medium, shaken, centrifuged, and the supernatant was discarded. The bacterial cells were then resuspended in sterile water for inoculation. Two-year-old disease-free citrus trees grown in a greenhouse were selected. The tested pesticide was sprayed onto both the upper and lower surfaces of the leaves. Then, a suspension of citrus canker pathogens was inoculated by spraying, ensuring the bacterial suspension covered both the upper and lower surfaces of the leaves. An investigation was conducted 5-7 days later.

[0133] Some of the compounds in this invention also show certain preventive effects against bacterial diseases such as soft rot of Chinese cabbage, angular leaf spot of cucumber, and fruit spot of melon, such as compounds 1-9.

Claims

1. A triazole thiol derivative, characterized in that: Compounds or complexes represented by general formula I, In the formula: R1 is selected from C1-C 12 Alkyl, halogenated C1-C 12 Alkyl, C3-C 12 cycloalkyl, halogenated C3-C 12 cycloalkyl, C2-C 12 alkenyl, C2-C 12 Alkyne group, halogenated C2-C 12 Alkenyl, halogenated C2-C 12 Alkynyl, unsubstituted or phenyl with 1-5 R5 substituted groups; R2 and R3 may be the same or different, and each can be independently selected from hydrogen, fluorine, chlorine, bromine, iodine, and C1-C. 12 Alkyl, halogenated C1-C 12 Alkyl, C3-C 12 cycloalkyl or halogenated C3-C 12 cycloalkyl; R4 is selected from hydrogen, halogen, hydroxyl, nitro, amino, cyano, C1-C. 12 Alkyl, halogenated C1-C 12 Alkyl, C1-C 12 Alkoxy, halogenated C1-C 12 Alkoxy, C1-C 12 Alkylthio, Halogenated C1-C 12 Alkylthio, C3-C 12 cycloalkyl, C3-C 12 Epoxyalkyl, C1-C 12 Alkoxy carbonyl, halogenated C1-C 12 Alkoxy carbonyl, unsubstituted or phenoxy with 1-5 R5 substituted groups; R5 is selected from hydrogen, halogen, nitro, cyano, C1-C. 12 Alkyl, halogenated C1-C 12 Alkyl, C1-C 12 Alkoxy, halogenated C1-C 12 Alkoxy or C3-C 12 cycloalkyl; Y is selected from N or CH; m is 1, 2, 3, 4 or 5; n is 1, 2, or 3; M is selected from Li, Na, K, Zn, Cu, Mn, Fe, Co, Mg, Ca, Cr, Mo, Ni, Sn, or Se.

2. The triazole thiol derivative according to claim 1, characterized in that: In the compound or complex of general formula I R1 is selected from C1-C8 alkyl, halo-C1-C8 alkyl, C3-C8 cycloalkyl, halo-C3-C8 cycloalkyl, C2-C8 alkenyl, C2-C8 ynyl, halo-C2-C8 alkenyl, halo-C2-C8 ynyl, unsubstituted or phenyl substituted with 1-4 R5s. R2 and R3 may be the same or different, and each can be independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C8 alkyl, halogenated C1-C8 alkyl, C3-C8 cycloalkyl or halogenated C3-C8 cycloalkyl. R4 is selected from hydrogen, halogen, hydroxyl, nitro, amino, cyano, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxy, halo-C1-C8 alkoxy, C1-C8 alkylthio, halo-C1-C8 alkylthio, C3-C8 cycloalkyl, C3-C8 epoxyalkyl, C1-C8 alkoxycarbonyl, halo-C1-C8 alkoxycarbonyl, unsubstituted or phenoxy groups substituted with 1-4 R5 groups; R5 is selected from hydrogen, halogen, nitro, cyano, C1-C8 alkyl, halo-C1-C8 alkyl, C1-C8 alkoxy, halo-C1-C8 alkoxy, or C3-C8 cycloalkyl; Y is selected from N or CH; m is 1, 2, 3, 4 or 5; n is 1, 2, or 3; M is selected from Li, Na, K, Zn, Cu, Mn, Fe, Co, Mg, Ca, Cr, Mo, Ni, Sn, or Se.

3. The triazole thiol derivative according to claim 1, characterized in that: In the compound or complex of general formula I R1 is selected from C1-C4 alkyl, halo-C1-C4 alkyl, C3-C4 cycloalkyl, halo-C3-C4 cycloalkyl, C2-C4 alkenyl, C2-C4 ynyl, halo-C1-C4 alkenyl, halo-C1-C4 ynyl, unsubstituted or phenyl substituted with 1-4 R5s. R2 and R3 may be the same or different, and each can be independently selected from hydrogen, fluorine, chlorine, bromine, iodine, C1-C4 alkyl, halo-C1-C4 alkyl, C3-C4 cycloalkyl or halo-C3-C4 cycloalkyl. R4 is selected from hydrogen, halogen, hydroxyl, nitro, amino, cyano, C1-C4 alkyl, halo-C1-C4 alkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, C1-C4 alkylthio, halo-C1-C4 alkylthio, C3-C4 cycloalkyl, C3-C4 epoxyalkyl, C1-C4 alkoxycarbonyl, halo-C1-C4 alkoxycarbonyl, unsubstituted or phenoxy groups substituted with 1-4 R5 groups; R5 is selected from hydrogen, halogen, nitro, cyano, C1-C4 alkyl, halo-C1-C4 alkyl, C1-C4 alkoxy, halo-C1-C4 alkoxy, or C3-C4 cycloalkyl; Y is selected from N or CH; m is 1, 2, 3, 4 or 5; n is 1, 2, or 3; M is selected from Li, Na, K, Zn, Cu, Mn, Fe, Co, Mg, Ca, Cr, Mo, Ni, Sn, or Se.

4. The triazole thiol derivative according to claim 1, characterized in that: In the compound or complex of general formula I R1 is selected from methyl, ethyl, monochloromethyl, monofluoromethyl, cyclopropyl, monochlorocyclopropyl, monofluorocyclopropyl, vinyl, ethynyl, monochlorovinyl, monochloroacetylene, unsubstituted or phenyl substituted with 1-4 R5s; R2 and R3 may be the same or different, and each can be independently selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, monochloromethyl, cyclopropyl or monochlorocyclopropyl. R4 is selected from hydrogen, fluorine, chlorine, bromine, hydroxyl, nitro, amino, cyano, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, methylthio, monochloromethylthio, cyclopropyl, ethylene oxide, methoxycarbonyl, difluoromethoxycarbonyl, unsubstituted or phenoxy groups substituted with 1-4 R5 groups. R5 is selected from hydrogen, fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, or cyclopropyl. Y is selected from N or CH; m is 1, 2, 3, 4 or 5; n is 1, 2, or 3; M is selected from Li, Na, K, Zn, Cu, Mn, Fe, Co, Mg, Ca, Cr, Mo, Ni, Sn, or Se.

5. The triazole thiol derivative according to claim 1, characterized in that: In the compound or complex of general formula I R1 is selected from methyl, ethyl, monochloromethyl, cyclopropyl, monochlorocyclopropyl, monofluorocyclopropyl, unsubstituted or phenyl substituted with 1-4 R5s; R2 and R3 may be the same or different, and each can be independently selected from hydrogen, fluorine, chlorine, bromine, methyl, cyclopropyl or monochlorocyclopropyl; R4 is selected from hydrogen, fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio, cyclopropyl, unsubstituted or phenoxy groups substituted with 1-4 R5 groups; R5 is selected from hydrogen, fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy, or trifluoromethoxy. Y is selected from N or CH; m is 1, 2, or 3; n is 1 or 2; M is selected from Li, Na, K, Zn, Cu, or Mn.

6. The triazole thiol derivative according to claim 1, characterized in that: In the compound or complex of general formula I R1 is selected from methyl, ethyl, cyclopropyl, monochlorocyclopropyl, or monofluorocyclopropyl; R2 and R3 are hydrogen; R4 is selected from hydrogen, fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, difluoromethyl, trifluoromethyl, methoxy, or trifluoromethoxy. Y represents CH; m is 1 or 2; n is 1 or 2; M is selected from Li, K, Zn or Mn.

7. A method for preparing the compound or complex of general formula I as described in claim 1, wherein the reaction formula is as follows:

8. The use of a triazole thiol derivative of general formula I in agriculture for the preparation of fungicides and bactericides.

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