A compound containing an oxadiazole structure, its preparation method and application, and a bactericide.

Abstract

This invention relates to the field of pesticides, and discloses a compound containing an oxadiazole structure, its preparation method and application, as well as a fungicide. The compound has the structure shown in formula (I). The compound containing an oxadiazole structure provided by this invention can effectively control oomycete diseases in plants, and has excellent control effects on plant diseases caused by oomycete diseases such as cucumber downy mildew, potato late blight, and pepper blight.

Description

Technical Field

[0001] This invention relates to the field of pesticides, specifically to a compound containing an oxadiazole structure, a method for preparing the compound containing the oxadiazole structure, the application of the compound in controlling oomycete diseases of plants, and a fungicide. Background Technology

[0002] Oomycetes are an important class of eukaryotic organisms that exhibit certain pathogenic effects on all fruits, vegetables, and important staple crops. Once these diseases occur, they are often difficult to control. Fungicides targeting pathogenic Phytophthora, Phytophthora soybeanii, Phytophthora capsici, Pseudomonas columbarium, and other downy mildew pathogens account for a significant market share among fungicides for Oomycete diseases.

[0003] Oomycetes are highly damaging and destructive to crops. For example, downy mildew and Phytophthora can cause diseases with short incubation periods and can sometimes infect plants multiple times, leading to large-scale outbreaks. Downy mildew in cucumbers, for instance, can kill an entire cucumber plant within just a few days. Plant diseases caused by downy mildew can generally be classified into three categories: 1) leaf diseases, mainly downy mildew; 2) root and crown diseases in annual and perennial crops, such as seedling blight, root, neck, and stem rot; 3) systemic diseases, where the plant's roots are infected, the pathogen spreads throughout the plant's vascular system, and symptoms appear on the growing points or leaves. In temperate and tropical climates, most annual or perennial crops, horticultural crops, and ornamental crops (such as grapes, potatoes, tobacco, tomatoes, hops, citrus, sunflowers, vegetables, and soybeans) are susceptible to downy mildew, making it a highly destructive plant pathogen. Therefore, effective control of downy mildew has become an urgent problem to solve.

[0004] Controlling oomycete diseases is becoming increasingly difficult, and chemical control remains the primary method. Commonly used chemical fungicides can be divided into two main categories: protective fungicides and systemic fungicides. Protective fungicides are multi-site fungicides that inhibit the release of spores from oomycete sporangia and spore germination. They have a broad spectrum of action, are less prone to resistance development, and offer strong protection with stable efficacy. However, they lack systemic activity, have relatively low fungicidal activity, and require larger dosages. Therefore, they are generally applied before disease onset for prevention. Systemic fungicides are mostly biosynthesis inhibitors, with strong systemic activity, good safety profile, and high fungicidal activity. They offer both protective and curative effects. Some fungicides are highly resistant to rain washout, but when used alone, they can easily lead to rapid resistance development.

[0005] In the management of airborne diseases such as downy mildew and late blight, the development of resistance has become an urgent problem to be solved. Therefore, the development of fungicides with novel modes of action is of great practical significance. Summary of the Invention

[0006] The purpose of this invention is to provide a new compound containing an oxadiazole structure, in order to overcome the defect that existing oomycete fungicides are not effective against oomycete fungi due to resistance to existing agents.

[0007] To achieve the above objectives, a first aspect of the present invention provides a compound containing an oxadiazole structure or an agriculturally chemically acceptable salt, hydrate, and solvate thereof, the compound having the structure shown in formula (I):

[0008]

[0009] In equation (I),

[0010] M is a group represented by formula (M1) or formula (M2);

[0011] In formulas (M1) and (M2), R2 and R3 are each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted furanyl, substituted or unsubstituted thiophene, substituted or unsubstituted pyrazolyl, or substituted or unsubstituted C containing 1-3 heteroatoms selected from N, O, and S. 2-12 At least one of the unsaturated heterocyclic groups; and the substituents optionally contained in R2 and R3 are each independently selected from nitro, carboxyl, hydroxyl, cyano, C 1-6 alkyl, C 1-10 Alkyl groups, halogens, and C atoms substituted with 1-9 halogens 1-6 Alkyl groups, C substituted with 1-9 halogens 1-6 At least one of the alkoxy groups;

[0012] Q is selected from either the structure shown in equation (Y1) or equation (Y2):

[0013]

[0014] In formula (Y1), R4 is selected from substituted or unsubstituted pyrazolyl groups, substituted or unsubstituted C groups. 2-12 alkenyl, substituted or unsubstituted C 1-6 Alkyl groups, substituted or unsubstituted indolyl groups, substituted or unsubstituted pyrroleyl groups, substituted or unsubstituted azirindolyl groups, and substituted or unsubstituted C groups containing 1-3 heteroatoms selected from N, O, and S. 2-12 An unsaturated heterocyclic group containing 1-3 substituted or unsubstituted C atoms selected from N, O, and S. 2-12 At least one of the saturated heterocyclic groups; and when R4 is pyrazolyl, R2 is not an unsubstituted phenyl group; and each of the optional substituents in R4 is independently selected from nitro, C 1-6 alkyl, C 1-6 alkoxy, C 2-6alkenyl groups, halogens, and C groups substituted with 1-9 halogens 1-6 At least one of the alkyl groups;

[0015] In equation (Y2), R5 is C 1-6 alkoxy groups;

[0016] X is C or N;

[0017] R is selected from H and C. 1-6 alkyl, C 1-6 Alkyl groups and halogens.

[0018] A second aspect of the present invention provides a method for preparing the compound described in the first aspect, the method comprising:

[0019] Under alkaline conditions, the compound represented by formula (N-1) is subjected to a first homogeneous reaction with the compound represented by formula (N-2) or the compound represented by formula (N-3) to obtain the compound of formula (I) containing the group represented by formula (M1); or

[0020] Under alkaline conditions, the compound shown in formula (N-4) and the compound shown in formula (N-5) are subjected to a second homogeneous reaction to obtain the compound of formula (I) containing the group shown in formula (M2);

[0021]

[0022] In formulas (N-1), (N-2), (N-3), (N-4), and (N-5), the definitions of each substituent are the same as those described in the first aspect.

[0023] A third aspect of the invention provides the use of the compounds described in the first aspect, or their agriculturally chemically acceptable salts, hydrates, and solvates, in the control of oomycete diseases in plants.

[0024] A fourth aspect of the invention provides the use of the compounds described in the first aspect, or their agriculturally chemically acceptable salts, hydrates, and solvates, in the preparation of fungicides.

[0025] A fifth aspect of the present invention provides a bactericide comprising an active ingredient and excipients, wherein the active ingredient comprises at least one of the compounds containing an oxadiazole structure as described in the first aspect, or an agriculturally chemically acceptable salt, hydrate, and solvate thereof.

[0026] The compounds containing an oxadiazole structure or their agriculturally chemically acceptable salts, hydrates and solvates provided by this invention can effectively prevent and control oomycete diseases in plants.

[0027] In particular, the compound containing the oxadiazole structure provided by this invention has excellent control effects on plant diseases caused by oomycete diseases such as cucumber downy mildew, potato late blight, and pepper blight. It has especially excellent control effects on plant diseases caused by cucumber downy mildew. Most of its structure is comparable to the currently commercially available oomycete disease control agent fluthiazopyrone (OXA). It has excellent control efficacy at a concentration of 20 mg / L, and even at a low concentration of 1.25 mg / L, it still shows a control efficacy of more than 80%, which has good market development prospects. Detailed Implementation

[0028] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0029] “C 1-6 "alkyl" indicates an alkyl group with a total number of 1-6 carbon atoms, including C64. 1-6 straight-chain alkyl, C 1-6 Branched alkyl groups and C 3-6 The cycloalkyl group can be, for example, a straight-chain alkyl group with a total of 1, 2, 3, 4, 5, or 6 carbon atoms; a branched-chain alkyl group with a total of 1, 2, 3, 4, 5, or 6 carbon atoms; or a cycloalkyl group with a total of 3, 4, 5, or 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclopropyl, methylcyclopropyl, ethylcyclopropyl, cyclopentyl, methylcyclopentyl, cyclohexyl, etc. Regarding "C 1-4 "alkyl" has a similar interpretation, except that the number of carbon atoms is different.

[0030] "C replaced by 1-9 halogens" 1-6 "alkyl" and "C" 1-6 The definition of "alkyl" is similar, except that it refers to "C1-C2 alkyl groups substituted with 1-9 halogens". 1-6 Any 1-9 H atoms in the alkyl group are replaced by any halogen.

[0031] “C 1-6 "alkoxy group" refers to an alkoxy group with a total number of 1-6 carbon atoms, including C64 and C64. 1-6 straight-chain alkoxy, C 1-6 Branched alkoxy groups and C 2-6The cycloalkoxy group can be, for example, a straight-chain alkoxy group with a total of 1, 2, 3, 4, 5, or 6 carbon atoms; a branched-chain alkoxy group with a total of 1, 2, 3, 4, 5, or 6 carbon atoms; or a cycloalkoxy group with a total of 2, 3, 4, 5, or 6 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, etc. Regarding "C 1-10 alkoxy group, C 1-4 The "alkoxy group" has a similar explanation, except that the number of carbon atoms is different.

[0032] "C replaced by 1-9 halogens" 1-6 "alkoxy" and "C" 1-6 The definition of "alkoxy group" is similar, except that it refers to "C643- ... 1-6 The alkoxy group has 1-9 H atoms that are replaced by any halogen.

[0033] “C 2-6 "Alkenyl" refers to a straight-chain or branched hydrocarbon group having one or more double bonds, and the total number of carbon atoms in the alkenyl group is 2-6, and the double bonds in the group can be in any position.

[0034] "Halogen" includes any one or more of fluorine, chlorine, bromine, and iodine.

[0035] "C containing 1-3 heteroatoms selected from N, O, and S, either substituted or unsubstituted" 2-12 "Saturated heterocyclic group" refers to a heterocyclic group with a total number of carbon atoms of 2-12, wherein the cyclic atoms in the heterocycle contain heteroatoms, and the number of heteroatoms is 1-3, and the heteroatoms are selected from at least one of N, O and S, the heterocycle is a saturated group, and optionally at least one H in the group is replaced by a corresponding group as defined herein.

[0036] "C containing 1-3 heteroatoms selected from N, O, and S, either substituted or unsubstituted" 2-12 "Unsaturated heterocyclic group" refers to a heterocyclic group with a total of 2-12 carbon atoms, wherein the cyclic atoms contain heteroatoms, and the number of heteroatoms is 1-3, and the heteroatoms are selected from at least one of N, O, and S, the heterocyclic group is unsaturated, and optionally at least one H in the group is substituted by a corresponding group as defined herein. "Substituted or unsubstituted C containing 1-3 heteroatoms selected from N, O, and S" 2-10 The "unsaturated heterocyclic group" has a similar explanation, except that the number of carbon atoms is different.

[0037] "C replaced or not replaced" 2-12 "Alkenyl" refers to a straight-chain or branched hydrocarbon group having one or more double bonds, and the total number of carbon atoms in the group is 2-12. The double bonds in the group can be in any position and can be selected from C1 to C2. 2-12At least one H in the alkenyl group is substituted by a corresponding group as defined herein. "Substituted or unsubstituted C 2-10 The "alkenyl" has a similar explanation, except that the number of carbon atoms is different.

[0038] "Substituted or unsubstituted phenyl", "Substituted or unsubstituted naphthyl", "Substituted or unsubstituted pyridyl", "Substituted or unsubstituted furanyl", "Substituted or unsubstituted thiophenyl", "Substituted or unsubstituted indolyl", "Substituted or unsubstituted pyrroleyl", and "Substituted or unsubstituted pyrazolyl" have similar definitions, wherein at least one H in phenyl, naphthyl, pyridyl, furanyl, thiophenyl, and pyrazolyl is optionally substituted with the corresponding group defined herein.

[0039] "Substituted or unsubstituted azidoindolyl" means a group formed by replacing a carbon atom on the aromatic ring of an indole structure with at least one nitrogen atom, and optionally at least one H in the group is replaced by a corresponding group as defined below.

[0040] Unless otherwise defined, any substituent of the present invention can be connected to the parent core structure at any position where it can be substituted.

[0041] First aspect

[0042] As previously stated, a first aspect of the present invention provides a compound containing an oxadiazole structure or an agriculturally chemically acceptable salt, hydrate, and solvate thereof, the compound having the structure shown in formula (I):

[0043]

[0044] In equation (I),

[0045] M is a group represented by formula (M1) or formula (M2);

[0046] In formulas (M1) and (M2), R2 and R3 are each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted furanyl, substituted or unsubstituted thiophene, substituted or unsubstituted pyrazolyl, or substituted or unsubstituted C containing 1-3 heteroatoms selected from N, O, and S. 2-12 At least one of the unsaturated heterocyclic groups; and the substituents optionally contained in R2 and R3 are each independently selected from nitro, carboxyl, hydroxyl, cyano, C 1-6 alkyl, C 1-10 Alkyl groups, halogens, and C atoms substituted with 1-9 halogens 1-6 Alkyl groups, C substituted with 1-9 halogens 1-6 At least one of the alkoxy groups;

[0047] Q is selected from either the structure shown in equation (Y1) or equation (Y2):

[0048]

[0049] In formula (Y1), R4 is selected from substituted or unsubstituted pyrazolyl groups, substituted or unsubstituted C groups. 2-12 alkenyl, substituted or unsubstituted C 1-6 Alkyl groups, substituted or unsubstituted indolyl groups, substituted or unsubstituted pyrroleyl groups, substituted or unsubstituted azirindolyl groups, and substituted or unsubstituted C groups containing 1-3 heteroatoms selected from N, O, and S. 2-12 An unsaturated heterocyclic group containing 1-3 substituted or unsubstituted C atoms selected from N, O, and S. 2-12 At least one of the saturated heterocyclic groups; and when R4 is pyrazolyl, R2 is not an unsubstituted phenyl group; and each of the optional substituents in R4 is independently selected from nitro, C 1-6 alkyl, C 1-6 alkoxy, C 2-6 alkenyl groups, halogens, and C groups substituted with 1-9 halogens 1-6 At least one of the alkyl groups;

[0050] In equation (Y2), R5 is C 1-6 alkoxy groups;

[0051] X is C or N;

[0052] R is selected from H and C. 1-6 alkyl, C 1-6 Alkyl groups and halogens.

[0053] The present invention provides several preferred embodiments below to illustrate the preferred use of the compound represented by formula (I) of the present invention.

[0054] Preferred Specific Implementation Method 1:

[0055] In equation (I),

[0056] M is a group represented by formula (M1) or formula (M2);

[0057] In formulas (M1) and (M2), R2 and R3 are each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted furanyl, substituted or unsubstituted thiophene, substituted or unsubstituted pyrazolyl, or substituted or unsubstituted C containing 1-3 heteroatoms selected from N, O, and S. 2-10 At least one of the unsaturated heterocyclic groups; and the substituents optionally contained in R2 and R3 are each independently selected from nitro, carboxyl, hydroxyl, cyano, C1-4 alkyl, C 1-6 Alkyl groups, halogens, and C atoms substituted with 1-9 halogens 1-6 Alkyl groups, C substituted with 1-9 halogens 1-6 At least one of the alkoxy groups;

[0058] Q is selected from either the structure shown in equation (Y1) or equation (Y2):

[0059]

[0060] In formula (Y1), R4 is selected from substituted or unsubstituted pyrazolyl groups, substituted or unsubstituted C groups. 2-10 alkenyl, substituted or unsubstituted C 1-6 Alkyl groups, substituted or unsubstituted indolyl groups, substituted or unsubstituted pyrroleyl groups, substituted or unsubstituted azirindolyl groups, and substituted or unsubstituted C groups containing 1-3 heteroatoms selected from N, O, and S. 2-12 An unsaturated heterocyclic group containing 1-3 substituted or unsubstituted C atoms selected from N, O, and S. 2-12 At least one of the saturated heterocyclic groups; and when R4 is pyrazolyl, R2 is not an unsubstituted phenyl group; and each of the optional substituents in R4 is independently selected from nitro, C 1-4 alkyl, C 1-4 alkoxy, C 2-4 alkenyl groups, halogens, and C groups substituted with 1-9 halogens 1-6 At least one of the alkyl groups;

[0061] In formula (Y2), R5 is methoxy, ethoxy, n-propoxy, or isopropoxy;

[0062] X is C or N; and when X is N, M is the group shown in (M1);

[0063] R is selected from H and C. 1-4 alkyl, C 1-4 Alkyl groups and halogens.

[0064] Preferred Implementation Method 2:

[0065] In equation (I),

[0066] M is a group represented by formula (M1) or formula (M2);

[0067] In formulas (M1) and (M2), R2 and R3 are each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted furanyl, substituted or unsubstituted thiophene, substituted or unsubstituted pyrazolyl, or substituted or unsubstituted C containing 1-3 heteroatoms selected from N, O, and S.2-10 At least one of the unsaturated heterocyclic groups; and the substituents optionally contained in R2 and R3 are each independently selected from nitro, carboxyl, hydroxyl, cyano, C 1-4 alkyl, C 1-4 Alkyl, fluorine, chlorine, bromine, and C atoms substituted with 1-9 halogens 1-6 Alkyl groups, C substituted with 1-9 halogens 1-6 At least one of the alkoxy groups;

[0068] Q is selected from any one of the structures shown in equation (Q1) to equation (Q16):

[0069]

[0070]

[0071] X is C or N; and when X is N, M is the group shown in (M1);

[0072] R is selected from H, methyl, ethyl, n-propyl, and isopropyl.

[0073] Preferred Implementation Method 3:

[0074] In equation (I),

[0075] M is the group represented by formula (M1):

[0076] R, X, Q, and R2 are defined the same as in any of the previous implementation methods.

[0077] In the aforementioned preferred embodiment 3, according to a particularly preferred embodiment, in formula (I),

[0078] M is the group represented by formula (M1);

[0079] R2 is selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted furanyl, substituted or unsubstituted thiophene, substituted or unsubstituted pyrazolyl, or substituted or unsubstituted C containing 1-3 heteroatoms selected from N, O, and S. 2-10 At least one of the unsaturated heterocyclic groups; and the substituents optionally contained in R2 are each independently selected from nitro, carboxyl, hydroxyl, cyano, C 1-4 alkyl, C 1-4 Alkyl, fluorine, chlorine, bromine, and C atoms substituted with 1-9 halogens 1-6 Alkyl groups, C substituted with 1-9 halogens 1-6 At least one of the alkoxy groups;

[0080] Q is selected from any one of the structures shown in equation (Q1) to equation (Q16):

[0081]

[0082]

[0083] X is C or N, and when X is N, M is the group shown in (M1);

[0084] R is selected from H, methyl, ethyl, n-propyl, and isopropyl.

[0085] Preferred Implementation Method 4:

[0086] The compound represented by formula (I) of this invention is any one of the following compounds (Table 1):

[0087] Table 1

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098] Preferred Implementation Method 5:

[0099] In equation (I),

[0100] M is the group represented by formula (M2):

[0101]

[0102] R, X, Q, and R3 are defined in the same way as in any of the previous implementation methods.

[0103] In the aforementioned preferred embodiment 5, according to a particularly preferred embodiment, in formula (I),

[0104] M is the group represented by formula (M2);

[0105] R3 is selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted furanyl, substituted or unsubstituted thiophene, substituted or unsubstituted pyrazolyl, or substituted or unsubstituted C containing 1-3 heteroatoms selected from N, O, and S. 2-10 At least one of the unsaturated heterocyclic groups; and the substituents optionally contained in R3 are each independently selected from nitro, carboxyl, hydroxyl, cyano, C 1-4 alkyl, C 1-4 Alkyl, fluorine, chlorine, bromine, and C atoms substituted with 1-9 halogens 1-6 Alkyl groups, C substituted with 1-9 halogens 1-6 At least one of the alkoxy groups;

[0106] Q is selected from any one of the structures shown in equation (Q1) to equation (Q16):

[0107]

[0108] X is C or N; and when X is N, M is the group shown in (M1);

[0109] R is selected from H, methyl, ethyl, n-propyl, and isopropyl.

[0110] Preferred Implementation Method 6:

[0111] The compound represented by formula (I) of this invention is any one of the following compounds (Table 2):

[0112] Table 2

[0113]

[0114]

[0115]

[0116] Preferred Implementation Method 7:

[0117] The compound represented by formula (I) in this invention is any one of the following compounds (Table 3):

[0118] Table 3

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130] This invention does not specifically limit the method for preparing compounds containing the oxadiazole structure shown in the aforementioned formula (I). Those skilled in the art, with knowledge of the compounds of this invention, can combine existing technologies in the field of organic synthesis and known technical means in the field to obtain a suitable preparation route to synthesize compounds containing the oxadiazole structure shown in the aforementioned formula (I).

[0131] Second aspect

[0132] To obtain a higher product yield, as described above, a second aspect of the present invention provides a method for preparing the aforementioned compound, the method comprising:

[0133] Under alkaline conditions, the compound represented by formula (N-1) is subjected to a first homogeneous reaction with the compound represented by formula (N-2) or with the compound represented by formula (N-3) (that is, the compound represented by formula (N-1) is subjected to a first homogeneous reaction with the compound represented by formula (N-2), or the compound represented by formula (N-1) is subjected to a first homogeneous reaction with the compound represented by formula (N-3), to obtain the compound of formula (I) containing the group represented by formula (M1); or

[0134] Under alkaline conditions, the compound shown in formula (N-4) and the compound shown in formula (N-5) are subjected to a second homogeneous reaction to obtain the compound of formula (I) containing the group shown in formula (M2);

[0135]

[0136] In formulas (N-1), (N-2), (N-3), (N-4), and (N-5), the definitions of each substituent are the same as those described in the first aspect. Further details will not be repeated here, and those skilled in the art should not construe this as a limitation of the invention.

[0137] The following provides several preferred embodiments of the first homogeneous reaction of the present invention.

[0138] Preferably, the first homogeneous reaction is carried out in the presence of an alkaline reagent and in an anhydrous environment.

[0139] Preferably, the first homogeneous reaction is carried out in the presence of a solvent.

[0140] More preferably, in the first homogeneous reaction, the solvent is selected from at least one of dichloromethane (DCM), tetrahydrofuran (THF), N,N-dimethylformamide (DMF), acetonitrile (ACN), and acetone (DMK).

[0141] In a preferred embodiment, the conditions for the first homogeneous reaction include: a reaction temperature of -5°C to 60°C and a reaction time of 1-48 hours.

[0142] According to a preferred embodiment, in the first homogeneous reaction, the alkaline conditions are formed by at least one alkaline substance selected from sodium hydride, cesium carbonate, potassium carbonate, triethylamine, and tetrabutylammonium hydroxide.

[0143] In a preferred embodiment, in the first homogeneous reaction, the molar ratio of the compound represented by formula (N-1) to the compound represented by formula (N-2) or the compound represented by formula (N-3) is 1:(1 to 3); more preferably, it is 1:(1.1 to 2.0).

[0144] The following provides several preferred embodiments of the second homogeneous reaction of the present invention.

[0145] Preferably, the second homogeneous reaction is carried out in the presence of an alkaline reagent and in an anhydrous environment.

[0146] Preferably, the second homogeneous reaction is carried out in the presence of a solvent.

[0147] Particularly preferably, the solvent is selected from at least one of dichloromethane, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, and acetone.

[0148] According to a preferred embodiment, the conditions for the second homogeneous reaction include: a reaction temperature of -5°C to 60°C and a reaction time of 1-48 hours.

[0149] Preferably, the alkaline conditions are formed by at least one alkaline substance selected from sodium hydride, cesium carbonate, potassium carbonate, triethylamine, and tetrabutylammonium hydroxide.

[0150] In a preferred embodiment, in the second homogeneous reaction, the molar ratio of the compound represented by formula (N-4) to the compound represented by formula (N-5) is 1:(1 to 3); more preferably, it is 1:(1.1 to 2.0).

[0151] The aforementioned preparation method of the present invention may also involve various post-processing operations known in the art, such as extraction, washing, filtration, column chromatography, recrystallization, etc. The present invention does not have any particular limitations in this regard, and those skilled in the art should not understand it as a limitation of the present invention.

[0152] The raw materials involved in the preparation method described in this invention can be synthesized according to their structural formulas using organic synthesis methods in the art, or they can be commercially available. The preparation methods for a few raw materials are exemplarily provided below, and should not be construed as limiting the invention by those skilled in the art.

[0153] As previously stated, a third aspect of the present invention provides the use of the compounds described in the first aspect, or their agriculturally chemically acceptable salts, hydrates, and solvates, in the control of oomycete diseases in plants.

[0154] Preferably, the plant oomycete disease is selected from diseases caused by at least one of the following pathogens: cucumber downy mildew, pepper phytoma, litchi downy mildew, tomato gray mold, soybean phytoma, ultimate pythium, tobacco phytoma, and potato late blight.

[0155] As previously stated, a fourth aspect of the present invention provides the use of the compound described in the first aspect, or its agriculturally chemically acceptable salts, hydrates, and solvates, in the preparation of a fungicide.

[0156] As previously described, a fifth aspect of the present invention provides a bactericide comprising an active ingredient and excipients, wherein the active ingredient comprises at least one of the compounds containing an oxadiazole structure as described in the first aspect, or an agriculturally chemically acceptable salt, hydrate, and solvate thereof.

[0157] Preferably, in the bactericide, the content of the active ingredient is 1-99.9% by weight.

[0158] More preferably, in the bactericide, the content of the active ingredient is 5-95% by weight, and exemplarily, the content of the active ingredient is 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, 90% by weight, etc.

[0159] In this invention, the excipients are various excipients commonly used in the art, such as surfactants, solvents, etc.

[0160] Preferably, the formulation of the bactericide is selected from at least one of emulsifiable concentrate, suspension concentrate, powder, granule, aqueous solution, and poison bait.

[0161] More preferably, the formulation of the bactericide is selected from at least one of wettable powder, mother liquor, and masterbatch.

[0162] The present invention will be described in detail below through examples. Unless otherwise specified, all raw materials used in the following examples are commercially available analytical grade products. TLC (thin-layer chromatography) was used to monitor the completion of the reactions in the examples.

[0163] Unless otherwise specified, the following room temperature is 25±3℃.

[0164] Preparation Example 1

[0165]

[0166] Preparation of intermediates 2-6:

[0167] The compound shown in formula (2-5) (1-tert-butoxycarbonylpiperidine-4-thiocarboxamide, 10 mmol) was placed in a 100 mL round-bottom flask, 50 mL of anhydrous ethanol was added, the mixture was stirred thoroughly, and ethyl bromopyruvate (12 mmol) was slowly added dropwise to the reaction system. After the addition was complete, the mixture was refluxed for 12 h. After the reaction was completed by TLC monitoring, most of the solvent was removed under reduced pressure, and the mixture was extracted twice with ethyl acetate. The organic phases were combined, dried with anhydrous sodium sulfate, filtered, concentrated, and the filtrate was prepared by silica gel precipitate and purified by column chromatography to obtain a light yellow solid compound, i.e., intermediate 2-6.

[0168] Preparation of intermediates 2-7:

[0169] Intermediate 2-6 (10 mmol) was placed in a 100 mL round-bottom flask, and 20 mL of 1,4-dioxane solution of 4 mol / L HCl was added to the flask. After reacting for 20 h, the mixture was filtered and washed successively with dried ethyl acetate and petroleum ether. The filter cake was dried to obtain a white solid, namely intermediate 2-7.

[0170] Preparation of intermediates 2-8:

[0171] Intermediate 2-7 (5 mmol) was added to a 100 mL round-bottom flask containing 50 mL of anhydrous dichloromethane. At room temperature, triethylamine (15 mmol), the compound shown in formula (2-9) (7.5 mmol), and 2-(7-azabenzotriazole)-N,N,N',N'-tetramethylurea hexafluorophosphate (HATU, 10 mmol) were added sequentially to the reaction system. After the reaction was completed, the reaction solution was extracted twice with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, the filtrate was concentrated, silica gel was used to prepare sand, and column chromatography was used to purify the solution to obtain a white solid, namely intermediate 2-8.

[0172] Preparation of intermediate 2-10:

[0173] To a 100 mL sealed tube, add a magnetic stir bar, 5 mmol of intermediate 2-8, 30 mL of ethanol, and 5 mL of ammonia water in sequence, and stir the mixture at 100 °C. After the reaction is complete, filter the system, wash the filter cake three times with petroleum ether, and dry it to obtain a white solid, namely intermediate 2-10.

[0174] Preparation of intermediate 2-11:

[0175] Intermediate 2-10 (2 mmol) was added to a 50 mL round-bottom flask, followed by 20 mL of anhydrous dichloromethane. 1,8-diazabicyclo[5.4.0]undec-7-ene (6 mmol) and ethyl dichlorophosphate (4 mmol) were slowly added to the system under ice bath conditions. The reaction was carried out at room temperature for 4 h. The reaction solution was extracted twice with dichloromethane, and the organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated, and purified by silica gel chromatography to obtain a white solid, namely intermediate 2-11.

[0176] Preparation of intermediate 2-1:

[0177] Intermediate 2-11 (2 mmol) was added to a 50 mL round-bottom flask, followed by 20 mL of anhydrous ethanol and 10 mL of a 50% (w / w) aqueous solution of hydroxylamine. The mixture was heated under reflux for 8 h and then cooled to room temperature. The solution was concentrated under reduced pressure to remove the solvent. The reaction mixture was then poured into a beaker containing 150 mL of ice water, resulting in the precipitation of a large amount of white solid. The system was filtered, and the filter cake was washed three times with petroleum ether and dried to obtain a white solid, namely intermediate 2-1.

[0178] Preparation of intermediate N-1a:

[0179] When X in formula (N-1) is C, it is the structure shown in formula (N-1a). The experimental method for preparing the compound with the structure shown in formula (N-1a) is the same as that for preparing the intermediate compound with the structure shown in formula (2-1), only the compound with the structure shown in formula (2-9) needs to be changed.

[0180]

[0181] Preparation Example 2

[0182]

[0183] In formulas (2-4) and (2-12), R is selected from H, methyl, ethyl, n-propyl, and isopropyl;

[0184] In formulas (2-13) and (N-5), R3 is selected from phenyl, and each substituent in R3 is independently selected from nitro, carboxyl, hydroxyl, cyano, C 1-4 alkyl, C 1-4 Alkyl groups, halogens, and C atoms substituted with 1-9 halogens 1-6Alkyl groups, C substituted with 1-9 halogens 1-6 At least one of the alkoxy groups.

[0185] Preparation of intermediates 2-4:

[0186] Intermediate 2-12 (10 mmol) was placed in a 100 mL round-bottom flask, and 10 mL of 2 mol / L sodium hydroxide solution and 20 mL of methanol were added. The mixture was reacted at room temperature for 5 h. After the reaction was complete, the reaction solution was concentrated under reduced pressure. Then, 2 mol / L dilute hydrochloric acid was slowly added dropwise to the solvent-free reaction system to adjust the pH to 5. A large amount of white solid gradually precipitated in the system. The solid was filtered and the filter cake was dried to obtain a white solid compound, namely intermediate 2-4.

[0187] Preparation of intermediate N-4a:

[0188] When X in formula (N-4) is C, it is the structure shown in formula (N-4a). The experimental method for preparing the compound with the structure shown in formula (N-4a) is the same as that for preparing the intermediate compound with the structure shown in formula (2-4), only the compound with the structure shown in formula (2-12) needs to be changed.

[0189]

[0190] Preparation of intermediate N-5:

[0191] Intermediate 2-13 (10 mmol) was added to a 100 mL round-bottom flask, followed by 30 mL of anhydrous ethanol and 20 mL of a 50% (w / w) aqueous solution of hydroxylamine. The mixture was heated under reflux for 8 h and then cooled to room temperature. The solvent was removed by concentration under reduced pressure, and the solution was diluted with 50 mL of ethyl acetate. The solution was then extracted twice with water and once with saturated brine. The separated and collected organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain a white solid compound, namely intermediate N-5.

[0192] For example, when R in formulas (2-4) and (2-12) is selected from H, and R3 in formulas (2-13) and (N-5) is selected from phenyl, and the substituents at positions 2 and 6 on the phenyl are F, intermediates (2-4a) and (N-5a) are prepared.

[0193]

[0194] Preparation of intermediate 2-4a:

[0195] Intermediate 2-8 (10 mmol) was placed in a 100 mL round-bottom flask, and 10 mL of 2 mol / L sodium hydroxide solution and 20 mL of methanol were added. The mixture was reacted at room temperature for 5 h. After the reaction was complete, the reaction solution was concentrated under reduced pressure. Then, 2 mol / L dilute hydrochloric acid was slowly added dropwise to the solvent-free reaction system to adjust the pH to 5. A large amount of white solid gradually precipitated in the system. The solid was filtered and the filter cake was dried to obtain a white solid compound, namely intermediate 2-4a.

[0196] Preparation of intermediate N-5a:

[0197] The compound shown in formula (2-13a) (2,6-difluorobenzonitrile, 10 mmol) was added to a 100 mL round-bottom flask, followed by 30 mL of anhydrous ethanol and 20 mL of a 50% (w / w) aqueous solution of hydroxylamine. The mixture was heated under reflux for 8 h and then cooled to room temperature. The solvent was removed by concentration under reduced pressure, and the mixture was diluted with 50 mL of ethyl acetate. The mixture was then extracted twice with water and once with saturated brine. The separated and collected organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain a white solid compound, namely intermediate N-5a.

[0198] Preparation Example 3

[0199]

[0200] Preparation of intermediates 3-6:

[0201] The compound shown in formula (3-5) (4-Boc-piperazine-1-thioamide, 10 mmol) was placed in a 100 mL round-bottom flask, 50 mL of anhydrous ethanol was added, and ethyl bromide (12 mmol) was slowly added dropwise. After the addition was complete, the mixture was refluxed for 6 h. After the reaction was completed, most of the solvent was removed under reduced pressure, and the mixture was extracted twice with 100 mL of ethyl acetate and an equal volume of water. The organic phases were combined, dried with anhydrous sodium sulfate, filtered, concentrated, and purified by silica gel chromatography to obtain a light yellow solid compound, i.e., intermediate 3-6.

[0202] Preparation of intermediates 3-7:

[0203] Intermediate 3-6 (10 mmol) was placed in a 100 mL round-bottom flask, and 5 mL of HCl in 1,4-dioxane solution (4 mol / L) was added to the flask. After reacting for 10 hours, the mixture was filtered and washed successively with dried ethyl acetate and petroleum ether. The filter cake was dried to obtain a white solid compound, namely intermediate 3-7.

[0204] Preparation of intermediates 3-8:

[0205] Intermediate 3-7 (10 mmol) was added to a 100 mL round-bottom flask and dissolved in 50 mL of anhydrous dichloromethane. At room temperature, triethylamine (20 mmol), the compound shown in formula (2-9) (12 mmol), and HATU (15 mmol) were added sequentially to the reaction system. After the reaction was completed, 100 mL of water was added, and the mixture was extracted twice with 100 mL of dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated, and the filtrate was prepared by silica gel precipitate and purified by column chromatography to obtain a white solid, namely intermediate 3-8.

[0206] Preparation of intermediate 3-10:

[0207] To a 100 mL sealed tube, a magnetic stir bar, 10 mmol of intermediate 3-8, 30 mL of ethanol, and 5 mL of ammonia were added sequentially. The mixture was stirred at 100 °C until the reaction was complete as monitored by TLC, at which point the reaction was stopped. Upon cooling, a large amount of solid precipitated. The system was filtered, and the filter cake was washed three times with petroleum ether and dried to obtain a white solid, namely intermediate 3-10.

[0208] Preparation of intermediate 3-11:

[0209] Intermediate 3-10 (2.5 mmol) was added to a 100 mL round-bottom flask, followed by 15 mL of anhydrous acetonitrile. Under ice bath conditions, dimethyl sulfoxide (0.025 mmol) and triethylamine (7.5 mmol) were added, followed by slow dropwise addition of oxaloyl chloride (5 mmol). The mixture was brought to room temperature, and the reaction was monitored by TLC until the starting material was completely consumed. 50 mL of water and 50 mL of ethyl acetate were added, and the reaction mixture was extracted twice. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated, prepared into silica gel precipitate, and purified by column chromatography to obtain a white solid, intermediate 3-11.

[0210] Preparation of intermediate 3-1:

[0211] Intermediate 3-11 (2 mmol) was added to a 100 mL round-bottom flask, followed by 25 mL of anhydrous ethanol and 10 mL of a 50% (w / w) aqueous solution of hydroxylamine. The mixture was heated under reflux for 8 hours and then cooled to room temperature. The solution was concentrated under reduced pressure to remove the solvent. The reaction mixture was then poured into a beaker containing 150 mL of ice water, resulting in the precipitation of a large amount of white solid. The system was filtered, and the filter cake was washed three times with petroleum ether and dried to obtain a white solid, namely intermediate 3-1.

[0212] Preparation of intermediate N-1b:

[0213] When X in formula (N-1) is N, it is the structure shown in formula (N-1b). The experimental method for preparing the compound with the structure shown in formula (N-1b) is the same as that for preparing the intermediate compound with formula (3-1), only the compound with the structure shown in formula (2-9) needs to be changed.

[0214]

[0215] Example 1:

[0216] This embodiment illustrates a method for preparing compounds of formula (I) containing groups shown in formulas (M1) and (Q1) and where X is C. Exemplarily, the method provided in this embodiment can be used to prepare compounds A1-A20, etc.

[0217]

[0218] In formula (N-3), R2 is selected from substituted phenyl groups, and each substituent in R2 is independently selected from nitro, carboxyl, hydroxyl, cyano, C 1-4 alkyl, C 1-4 Alkyl groups, halogens, and C atoms substituted with 1-9 halogens 1-6 Alkyl groups, C substituted with 1-9 halogens 1-6 At least one of the alkoxy groups.

[0219] At room temperature, intermediate 2-1 (1.0 mmol) was added to a 100 mL round-bottom flask, followed by dichloromethane (DCM, 15 mL) and triethylamine (Et3N, 1.5 mmol). Then, the compound (N-3) (1.2 mmol) was slowly added to the system under ice bath conditions. The reaction was allowed to proceed for 30 min, and the reaction was stopped after TLC monitoring showed that the reaction was complete. The compound was diluted with 20 mL of dichloromethane and extracted once with 30 mL of water and saturated saline solution, respectively. The organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to obtain a white solid compound. This compound was then dissolved in 10 mL of tetrahydrofuran (THF) solution, and 0.26 mL of 50% tetrabutylammonium hydroxide (TBAOH) solution was added. The reaction was continued at room temperature for 2 h. After the reaction was completed by TLC monitoring, the reaction solvent was removed under reduced pressure, diluted with 30 mL of dichloromethane, and extracted once with 30 mL of water and saturated saline solution, respectively. The organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated. The filtrate was prepared into silica gel slurry and purified by column chromatography to obtain a compound of formula (I) containing the groups shown in formula (M1) and (Q1) and where X is C.

[0220] The method for preparing a compound of formula (I) containing the group shown in formula (M1) and where X is C is the same as the method for preparing a compound of formula (I) containing the groups shown in formula (M1) and formula (Q1) and where X is C, except that intermediate (2-1) is replaced with intermediate (N-1a); wherein, in formulas (N-1a) and (N-3), the definitions of Q and R2 are the same as those described in the first aspect.

[0221]

[0222] For example, when R2 in formula (N-3) is selected from phenyl, and the substituents at the 2-position and 6-position of the phenyl group are F, compound A1 is prepared:

[0223]

[0224] At room temperature, intermediate 2-1 (1.0 mmol) was added to a 100 mL round-bottom flask, followed by dichloromethane (15 mL) and triethylamine (1.5 mmol). Then, under ice bath conditions, the compound (2,6-difluorobenzoyl chloride, 1.2 mmol) of formula (N-3a) was slowly added to the system. The reaction was allowed to proceed for 30 min, and the reaction was stopped after TLC monitoring showed completion. The mixture was diluted with 20 mL of dichloromethane, extracted with water, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to obtain a white solid compound. This solid compound was then dissolved in 10 mL of tetrahydrofuran solution, and 0.26 mL of 50% tetrabutylammonium hydroxide solution was added. The reaction was continued at room temperature for 2 h. After TLC monitoring showed completion, the reaction solvent was removed under reduced pressure, diluted with 30 mL of dichloromethane, extracted with water, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated. The filtrate was prepared into silica gel precipitate and purified by column chromatography to obtain compound A1.

[0225] Example 2

[0226] This embodiment illustrates the preparation method of compound (I) containing the groups shown in formula (M1) and formula (Q1) and where X is C. Exemplarily, the method provided in this embodiment can be used to prepare compounds A10, A11, A16 and A17, etc.

[0227]

[0228] In formula (N-2), R2 is selected from substituted phenyl groups, and the substituents in R2 are each independently selected from nitro, carboxyl, hydroxyl, cyano, C 1-4 alkyl, C 1-4 Alkyl groups, halogens, and C atoms substituted with 1-9 halogens 1-6 Alkyl groups, C substituted with 1-9 halogens 1-6 At least one of the alkoxy groups.

[0229] At room temperature, intermediate 2-1 (1.0 mmol) was added to a 100 mL round-bottom flask, followed by dichloromethane (15 mL), the compound shown in formula (N-2) (1.2 mmol), and then 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI, 1.5 mmol) and 4-dimethylaminopyridine (DMAP, 0.1 mmol). The reaction was allowed to proceed for 2 h, and the reaction was stopped after TLC monitoring showed completion. The mixture was diluted with 15 mL of dichloromethane, extracted with water, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to give a white solid compound. The solution was then dissolved in 10 mL of tetrahydrofuran solution, and 0.26 mL of 50% tetrabutylammonium hydroxide solution was added. The reaction was continued at room temperature for 2 h. After the reaction was completed by TLC monitoring, the reaction solvent was removed under reduced pressure, diluted with 30 mL of dichloromethane, extracted with water, dried with anhydrous sodium sulfate, filtered, concentrated, and purified by silica gel sand preparation and column chromatography to obtain compound (I) containing the group shown in formula (M1) and the group shown in formula (Q1) with X being C.

[0230] The method for preparing a compound of formula (I) containing the group shown in formula (M1) and where X is C is the same as the method for preparing a compound of formula (I) containing the groups shown in formula (M1) and formula (Q1) and where X is C, except that intermediate (2-1) is replaced with intermediate (N-1a); wherein, in formulas (N-1a) and (N-2), the definitions of Q and R2 are the same as those described in the first aspect.

[0231]

[0232] For example, when R2 in formula (N-2) is selected from phenyl, and the substituents at the 2 and 6 positions of the phenyl group are methyl, compound A10 is prepared:

[0233]

[0234] At room temperature, intermediate 2-1 (1.0 mmol) was added to a 100 mL round-bottom flask, followed by dichloromethane (15 mL), the compound shown in formula (N-2a) (1.2 mmol), and then 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI, 1.5 mmol) and 4-dimethylaminopyridine (DMAP, 0.1 mmol). The reaction was allowed to proceed for 2 h, and the reaction was stopped after TLC monitoring showed completion. The mixture was diluted with 15 mL of dichloromethane, extracted with water, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to give a white solid compound. The compound was then dissolved in 10 mL of tetrahydrofuran solution, and 0.26 mL of 50% tetrabutylammonium hydroxide solution was added. The reaction was continued at room temperature for 2 h. After the reaction was completed by TLC monitoring, the reaction solvent was removed under reduced pressure, diluted with 30 mL of dichloromethane, extracted with water, dried over anhydrous sodium sulfate, filtered, concentrated, and purified by silica gel sand preparation and column chromatography to obtain compound A10.

[0235] Example 3

[0236] This embodiment illustrates the preparation method of compound (I) containing the groups shown in formula (M2) and formula (Q1) and where X is C. For example, the method provided in this embodiment can be used to prepare compounds B1-B5, etc.

[0237]

[0238] In formula (2-4), R is selected from H and methyl;

[0239] In formula (N-5), R3 is selected from substituted or unsubstituted phenyl groups, and the substituents optionally contained in R3 are each independently selected from nitro, carboxyl, hydroxyl, cyano, C 1-4 alkyl, C 1-4 Alkyl groups, halogens, and C atoms substituted with 1-9 halogens 1-6 Alkyl groups, C substituted with 1-9 halogens 1-6 At least one of the alkoxy groups.

[0240] At room temperature, intermediate 2-4 (1.0 mmol) was added to a 100 mL round-bottom flask, followed by dichloromethane (15 mL), the compound shown in formula (N-5) (1.0 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI, 1.5 mmol), and 4-dimethylaminopyridine (DMAP, 0.1 mmol). The reaction was allowed to proceed for 50 min. After the reaction was complete as monitored by TLC, the reaction was stopped, diluted with 20 mL of dichloromethane, and extracted with water. The organic phase was then treated with anhydrous water. Sodium sulfate was dried, filtered, and the filtrate was concentrated to obtain a white solid compound. This compound was then dissolved in 10 mL of tetrahydrofuran solution, and 0.26 mL of 50% tetrabutylammonium hydroxide solution was added. The reaction was continued at room temperature for 2 h. The reaction was stopped after TLC monitoring showed that the reaction was complete. The reaction solvent was removed under reduced pressure, diluted with 30 mL of dichloromethane, and extracted with water. The organic phase was dried with anhydrous sodium sulfate, filtered, and the filtrate was concentrated. The filtrate was prepared into silica gel sand and purified by column chromatography to obtain compound (I) containing the groups shown in formula (M2) and formula (Q1) and where X is C.

[0241] The method for preparing a compound of formula (I) containing the group shown in formula (M2) and where X is C is the same as the method for preparing a compound of formula (I) containing the groups shown in formula (M2) and formula (Q1) and where X is C, except that intermediate (2-4) is replaced with intermediate (N-4a); wherein, in formulas (N-4a) and (N-5), the definitions of Q, R and R3 are the same as those described in the first aspect.

[0242]

[0243] For example, compound B3 is prepared:

[0244]

[0245] At room temperature, intermediate 2-4a (1.0 mmol) was added to a 100 mL round-bottom flask, followed by dichloromethane (15 mL), the compound shown in formula (N-5a) (1.0 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI, 1.5 mmol), and 4-dimethylaminopyridine (DMAP, 0.1 mmol). The reaction was allowed to proceed for 50 min. After the reaction was complete as monitored by TLC, the reaction was stopped, and 20 mL of dichloromethane was added for dilution. The organic phase was extracted with water, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to obtain a white solid compound. This compound was then dissolved in 10 mL of tetrahydrofuran solution, and 0.26 mL of 50% tetrabutylammonium hydroxide solution was added. The reaction was continued at room temperature for 2 h. After the reaction was completed by TLC monitoring, the reaction was stopped, the reaction solvent was removed under reduced pressure, and the mixture was diluted with 30 mL of dichloromethane. The mixture was then extracted with water, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated. The mixture was then prepared into silica gel slurry and purified by column chromatography to finally obtain a white solid compound B3.

[0246] Example 4:

[0247] This embodiment illustrates the preparation method of compound (I) containing the groups shown in formula (M1) and formula (Q1) and where X is N. Exemplarily, the method provided in this embodiment can be used to prepare compounds C1-C20, etc.

[0248]

[0249] In formula (N-3), R2 is selected from substituted phenyl groups, and each substituent in R2 is independently selected from nitro, carboxyl, hydroxyl, cyano, C 1-4 alkyl, C 1-4 Alkyl groups, halogens, and C atoms substituted with 1-9 halogens 1-6 Alkyl groups, C substituted with 1-9 halogens 1-6 At least one of the alkoxy groups.

[0250] At room temperature, intermediate 3-1 (1.0 mmol) was added to a 100 mL round-bottom flask, followed by dichloromethane (15 mL) and triethylamine (1.5 mmol). Then, the compound (1.2 mmol) shown in formula (N-3) was slowly added to the system under ice bath conditions. The reaction was allowed to proceed for 30 min, and the reaction was stopped after TLC monitoring showed that the reaction was complete. The compound was diluted with 20 mL of dichloromethane and extracted once with 30 mL of water and saturated saline solution, respectively. The organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to obtain a white solid compound. This compound was then dissolved in 10 mL of tetrahydrofuran solution, and 0.26 mL of 50% tetrabutylammonium hydroxide solution was added. The reaction was continued at room temperature for 2 h. After the reaction was completed by TLC monitoring, the reaction solvent was removed under reduced pressure, diluted with 30 mL of dichloromethane, and extracted once with 30 mL of water and saturated saline solution, respectively. The organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated. The filtrate was prepared by silica gel sand preparation and purified by column chromatography to obtain a compound of formula (I) containing the groups shown in formula (M1) and formula (Q1) and where X is N.

[0251] The method for preparing a compound of formula (I) containing the group shown in formula (M1) and where X is N is the same as the method for preparing a compound of formula (I) containing the groups shown in formula (M1) and formula (Q1) and where X is N, except that intermediate (3-1) is replaced with intermediate (N-1b); wherein, in formulas (N-1b) and (N-3), the definitions of Q and R2 are the same as those described in the first aspect.

[0252]

[0253] For example, when R2 in formula (N-3) is selected from phenyl, and the substituents at the 2-position and 6-position of the phenyl group are F,

[0254] Preparation of compound C1:

[0255]

[0256] At room temperature, intermediate 3-1 (1.0 mmol) was added to a 100 mL round-bottom flask, followed by dichloromethane (15 mL) and triethylamine (1.5 mmol). Then, under ice bath conditions, compound (2,6-difluorobenzoyl chloride, 1.2 mmol) of formula (N-3a) was slowly added to the system. The reaction was allowed to proceed for 30 min, and the reaction was stopped after TLC monitoring showed completion. The mixture was diluted with 20 mL of dichloromethane, extracted with water, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to obtain a white solid compound. This solid compound was then dissolved in 10 mL of tetrahydrofuran solution, and 0.26 mL of 50% tetrabutylammonium hydroxide solution was added. The reaction was continued at room temperature for 2 h. After TLC monitoring showed completion, the reaction solvent was removed under reduced pressure, diluted with 30 mL of dichloromethane, extracted with water, dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated, prepared into silica gel precipitate, and purified by column chromatography to obtain compound C1.

[0257] The compounds of the present invention were prepared using a similar method as described above. Proton and carbon NMR data confirmed the availability of the compounds of the present invention; specific characterization data are shown in Table 4.

[0258] Table 4

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271] Test Example 1: The in vivo activity test and investigation method for inhibiting cucumber downy mildew followed the SOP-SC-1098 pot method for cucumber downy mildew in the fungicide volume of "Standard Operating Procedures for Testing the Biological Activity of Pesticides" compiled by Kang Zhuo and Gu Baogen. Fluoxapiprolin (OXA) and Fluoxapiprolin (FOXA) were used as control agents. The test results are shown in Tables 5 and 6. In Tables 5 and 6, A, B, C, and D represent the control efficacy level, with 80% ≤ A ≤ 100%; 70% ≤ B < 80%; 50% ≤ C < 70%; and D < 50%. The structural formulas of the control agents Fluoxapiprolin (OXA) and Fluoxapiprolin (FOXA) are as follows:

[0272]

[0273] Table 5. Preliminary screening activity of some compounds containing oxadiazole ring structures against live fungicides against cucumber downy mildew.

[0274]

[0275] Table 6. Screening activity of some compounds containing oxadiazole ring structures against in vivo fungicidal activity against cucumber downy mildew.

[0276]

[0277] The test results show that the compounds of this invention have good control effects on oomycete diseases such as cucumber downy mildew, and their control effects are comparable to those of the control agents fluoxapiprolin and fluoxapiprolin, indicating significant development value. More specifically, the test results show that most of the compounds of this invention can achieve a control efficacy of over 80% against cucumber downy mildew at a concentration of, for example, 20 mg / L.

[0278] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A compound containing an oxadiazole structure or an agriculturally chemically acceptable salt thereof, characterized in that, The compound has the structure shown in formula (I): Mode( ), Formula (M1) In equation (I), M is the group represented by formula (M1); In formula (M1), R2 is selected from substituted or unsubstituted phenyl groups and substituted or unsubstituted naphthyl groups; and the substituents optionally contained in R2 are each independently selected from halogens and C groups substituted with 1 to 9 halogens. 1-6 At least one of the alkyl groups; Q is selected from formula (Y1): Formula (Y1), In formula (Y1), R4 is selected from substituted or unsubstituted C. 1-6 The alkyl group; and the substituents optionally contained in R4 are each independently selected from C10. 1-4 alkoxy groups; X is C; R is selected from H and C. 1-4 alkyl, C 1-4 Alkyl groups and halogens.

2. The compound according to claim 1, wherein, In formula (I), the substituents in R2 are each independently selected from fluorine, chlorine, bromine, and C substituted with 1-9 halogens. 1-6 At least one of the alkyl groups; Q is selected from the structure shown below: Formula (Q16); X is C; R is selected from H, methyl, ethyl, n-propyl, and isopropyl.

3. The compound according to claim 1 or 2, wherein, The compound represented by formula (I) is any one of the following compounds: 。 4. A method for preparing the compound according to any one of claims 1-3, characterized in that, The method includes: Under alkaline conditions, the compound shown in formula (N-1) is subjected to a first homogeneous reaction with the compound shown in formula (N-2) or the compound shown in formula (N-3) to obtain the compound of formula (I) containing the group shown in formula (M1). Equation (N-1), Equation (N-2). Equation (N-3); In formulas (N-1), (N-2), and (N-3), the definitions of each substituent are the same as those in any one of claims 1-3.

5. The use of the compound of any one of claims 1-3 or its agriculturally chemically acceptable salt in the control of oomycete diseases in plants.

6. The application according to claim 5, wherein the plant oomycete disease is selected from at least one pathogen caused by cucumber downy mildew, pepper phytoma, litchi downy mildew, tomato gray mold, soybean phytoma, ultimate pythium, tobacco phytoma, and potato late blight.

7. The use of the compound of any one of claims 1-3 or an agriculturally chemically acceptable salt thereof in the preparation of a fungicide.

8. A fungicide comprising an active ingredient and excipients, said active ingredient comprising at least one of the compounds containing an oxadiazole structure as described in any one of claims 1-3 or an agriculturally chemically acceptable salt thereof.

9. The bactericide according to claim 8, wherein the content of the active ingredient is 1-99.9% by weight.

10. The bactericide according to claim 9, wherein the content of the active ingredient is 5-95% by weight.

11. The bactericide according to claim 8, wherein, The formulation of the bactericide is selected from at least one of emulsifiable concentrate, suspension concentrate, powder, granule, aqueous solution, and poison bait.

12. The bactericide according to claim 11, wherein, The formulation of this bactericide is selected from at least one of wettable powder, mother liquor, and masterbatch.

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