Amide compounds, processes for their preparation and uses thereof

Abstract

The application provides an amide compound shown in the following formula I and a preparation method and application thereof. The amide compound and a composition comprising the compound have excellent insecticidal and bactericidal effects and have a certain application prospect in preventing and treating diseases and pests and bacterial diseases of crops.

Description

Technical Field

[0001] This invention belongs to the field of pesticide technology, specifically relating to an amide compound with both fungicidal and insecticidal effects. This invention also relates to compositions comprising the compound of this invention and their application in agricultural control of plant diseases and pests. Technical Background

[0002] Amide compounds are used for sterilization primarily by inhibiting mitochondrial respiration by blocking electron transfer in succinate dehydrogenase within the respiratory chain of pathogens, thus exhibiting a broad-spectrum bactericidal effect and good bactericidal efficacy. Existing technologies have also reported that amide compounds possess good insecticidal effects. However, amide compounds exhibiting both excellent bactericidal and good insecticidal effects are rarely reported.

[0003] However, the insecticidal and bactericidal activities of existing amide compounds need further improvement. Summary of the Invention

[0004] The purpose of this invention is to overcome the problem that existing compounds cannot simultaneously achieve both bactericidal and insecticidal effects, and to provide a new amide compound with both insecticidal and bactericidal activities.

[0005] This invention provides a compound of Formula I, including its stereoisomer, racemate, tautomer, nitride, or pharmaceutically acceptable salt thereof:

[0006]

[0007] Among them, R1, R2, and R3 may be the same or different, and are independently selected from hydrogen, halogen, cyano, substituted or unsubstituted C. 1-20 Alkyl, Halogenated C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted 3-20 membered heterocyclic groups, substituted or unsubstituted 5-20 membered heteroaryl groups, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkoxy, halogenated C 3-20 Cycloalkyloxy, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 Alkyne group, substituted or unsubstituted C 1-20 Alkyl carbonyl, substituted or unsubstituted C 1-20 alkoxycarbonyl, substituted or unsubstituted C 6-20 aryl carbonyl, substituted or unsubstituted C 6-20 Aryloxycarbonyl; and the optional substituents are each independently selected from: halogen, C 1-20 Alkyl, Halogenated C 1-20 Alkyl, C 3-20Cycloalkyl, 3-20 membered heterocyclic groups, halogenated C 3-20 cycloalkyl, C 1-20 Alkoxy, halogenated C 1-20 Alkoxy, halogenated C 3-20 cycloalkyl, halogenated C 3-20 At least one of the cycloalkyloxy groups;

[0008] R 11 Selected from C 1-20 Alkyl, Halogenated C 1-20 Alkyl, C 3-20 Cycloalkyl or 3-20 membered heterocyclic groups;

[0009] Q is selected from the following structures shown in Y-1 to Y-93:

[0010]

[0011]

[0012]

[0013]

[0014] Among them, R6, R7, R8, R9 and Z may be the same or different, and are independently selected from hydrogen, halogen, cyano, substituted or unsubstituted C. 1-20 Alkyl, Halogenated C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted 3-20 membered heterocyclic groups, substituted or unsubstituted 5-20 membered heteroaryl groups, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkoxy, halogenated C 3-20 Cycloalkyloxy, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 Alkyne group, substituted or unsubstituted C 1-20 Alkyl carbonyl, substituted or unsubstituted C 1-20 alkoxycarbonyl, substituted or unsubstituted C 6-20 aryl carbonyl, substituted or unsubstituted C 6-20 Aryloxycarbonyl; and the optional substituents are each independently selected from: halogen, C 1-20 Alkyl, Halogenated C 1-20 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic groups, halogenated C 3-20 cycloalkyl, C 1-20 Alkoxy, halogenated C 1-20 Alkoxy, halogenated C 3-20 cycloalkyl, halogenated C 3-20At least one of the cycloalkyloxy groups;

[0015] The substitution is the substitution by one, two, three or more substituents;

[0016] Among the groups represented by Y-1 to Y-93 above The location is the connection point.

[0017] The present invention also provides a composition comprising at least one of the following: a compound represented by Formula I as described above, a stereoisomer, a racemic mixture, a tautomer, a nitrogen oxide, or a pharmaceutically acceptable salt thereof.

[0018] According to an embodiment of the present invention, the composition further includes an adjuvant; the adjuvant is selected from at least one of surfactants, solid diluents, and liquid diluents.

[0019] The present invention also provides at least one of the following: a compound of Formula I, a stereoisomer, a racemic mixture, a tautomer, a nitrogen oxide, or a pharmaceutically acceptable salt thereof, or the use of said composition as a pesticide, such as an insecticide and / or a fungicide.

[0020] The present invention also provides a method for controlling plant fungal and insect pests, comprising applying at least one of the following: a compound of Formula I, its stereoisomer, racemate, tautomer, nitrooxide, or a pharmaceutically acceptable salt thereof, or the composition thereof, to an individual in need of such control.

[0021] Beneficial effects

[0022] The amide compounds and compositions including these compounds provided by this invention have excellent insecticidal and fungicidal effects, and have certain application prospects in the prevention and control of crop diseases, pests and fungal diseases. Detailed Implementation

[0023] To more clearly illustrate the purpose, technical solutions, and advantages of the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments.

[0024] Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without inventive effort are within the scope of protection of this invention.

[0025] Unless otherwise expressly stated, throughout the specification and claims, the term "comprising" or its variations such as "including" or "comprises" shall be understood to include the stated ingredients or steps without excluding other material ingredients or steps.

[0026] Furthermore, to better illustrate the present invention, numerous specific details are provided in the following detailed embodiments.

[0027] Those skilled in the art will understand that the present invention can be practiced even without certain specific details. In some embodiments, materials, methods, and means well known to those skilled in the art are not described in detail in order to highlight the spirit of the invention.

[0028] When the compounds of the present invention can exist in tautomer form, the compounds described above and below should be understood, where applicable, to also include the corresponding tautomer forms, even if such tautomer forms are not explicitly mentioned in each case.

[0029] If the compound represented by Formula I in this invention has one or more chiral centers and is therefore present as an enantiomer or diastereomer, then the pure enantiomer, the racemic version, or the diastereomer can be used in the compositions of this invention.

[0030] Any asymmetric atom (e.g., carbon) in the compounds disclosed in this invention can exist in racemic or enantiomerically enriched forms, such as (R)-, (S)-, or (R,S)- configurations.

[0031] If the compounds of Formula I described in this invention have ionizable functional groups, they can also be used as agricultural salts or mixtures thereof. The pharmaceutically acceptable salts described in this invention can be inorganic salts such as hydrochlorides, hydrobroms, sulfates, nitrates, and phosphates, but are not limited thereto. They can also be organic acid salts such as formates, acetates, oxalates, fumarates, methanesulfonates, and benzenesulfonates, but are not limited thereto.

[0032] The term "C" used in this article 1-20 Alkyl (and in other groups containing alkyl, such as the alkyl moiety of a haloalkyl, the alkyl structural moiety of an alkylsulfinyl, an alkylsulfonyl, or a haloalkylsulfonyl) in each case generally indicates having 1-20 carbon atoms, often 1-12 carbon atoms, preferably 1-6 carbon atoms (C 1-6 ), especially 1-4 carbon atoms (C 1-6 ( ) straight-chain or branched alkyl groups. C 1-4 Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl), and 1,1-dimethylethyl (tert-butyl). 1-6 Examples of alkyl groups except C 1-4In addition to the alkyl groups mentioned, there are n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, or 1-ethyl-2-methylpropyl.

[0033] In this invention, the halogen is typically fluorine, chlorine, bromine, or iodine, preferably fluorine, bromine, or chlorine. Accordingly, this also applies to halogens bonded to other structures, such as halogenated C. 1-20 Alkyl group. Halogenated C 1-20 The alkyl group preferably has a chain length of 1 to 6 carbon atoms, more preferably a chain length of 1 to 4 carbon atoms. The halogenated C 1-20 Alkyl groups, for example, are fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl, and 2,2,2-trichloroethyl; preferably fluoromethyl, difluoromethyl, trifluoromethyl, trichloromethyl, difluorochloromethyl, and dichlorofluoromethyl.

[0034] Term "C" 3-20 "Cycloalkyl" should be understood as representing a saturated monovalent monocyclic, bicyclic, or polycyclic hydrocarbon ring (also called a fused ring hydrocarbon ring) with 3-20 carbon atoms. Bicyclic or polycyclic cycloalkyl includes fused cycloalkyl, bridged cycloalkyl, and spirocyclic cycloalkyl; fused ring refers to a fused ring structure formed by two or more cyclic structures sharing two adjacent ring atoms (i.e., sharing a bond). Bridged ring refers to a fused ring structure formed by two or more cyclic structures sharing two non-adjacent ring atoms. Spirocyclic refers to a fused ring structure formed by two or more cyclic structures sharing a single ring atom. For example, the C 3-20 Cycloalkyl groups can be C 3-8 Monocyclic cycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or C 7-12 Circoalkyl, such as decahydronaphthalene ring; or C 7-12 Bridged cycloalkyl groups, such as norbornene, adamantane, and bicyclo[2,2,2]octane.

[0035] The term "3-20 membered heterocyclic group" refers to a saturated or unsaturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1-5 heteroatoms independently selected from N, O, and S, preferably a "3-10 membered heterocyclic group". The term "3-10 membered heterocyclic group" also refers to a saturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1-5, preferably 1-3, heteroatoms selected from N, O, and S. The heterocyclic group can be connected to the rest of the molecule via any one of the carbon atoms or a nitrogen atom (if present). Specifically, the heterocyclic group can include, but is not limited to: 4-membered rings, such as azirmonobutyl or oxobutyl; 5-membered rings, such as tetrahydrofuranyl, dioxacyclopentenyl, pyrrolyl, imidazoyl, pyrazolyl, or pyrrololinyl; or 6-membered rings, such as tetrahydropyranyl, piperidinyl, morpholinyl, dithiaalkyl, thiomorpholinyl, piperazinyl, or trithiaalkyl; or 7-membered rings, such as diazacycloheptyl. Optionally, the heterocyclic group may be benzo-fused. The heterocyclic group may be bicyclic, for example, but not limited to, a 5,5-membered ring, such as a hexahydrocyclopenta[c]pyrrole-2(1H)-yl ring, or a 5,6-membered bicyclic ring, such as a hexahydropyrrolo[1,2-a]pyrazin-2(1H)-yl ring. The nitrogen-containing ring may be partially unsaturated, i.e., it may contain one, two, or more double bonds, for example, but not limited to, 2,5-dihydro-1H-pyrrole, 4H-[1,3,4]thiadiazinyl, 4,5-dihydrooxazolyl, or 4H-[1,4]thiazinyl, or it may be benzo-fused, for example, but not limited to, dihydroisoquinolinyl, 1,3-benzooxazolyl, or 1,3-benzodioxacyclopentenyl. According to the invention, the heterocyclic group is non-aromatic.

[0036] Term "C" 6-20 "Aryl" should be understood as representing a monocyclic, bicyclic, or tricyclic hydrocarbon ring with 6 to 20 carbon atoms that is monovalent and partially aromatic, preferably "C". 6-14 "Aromatic". The term "C" 6-14 "Aryl" should be understood to preferably represent a monovalent aromatic or partially aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring ("C") having 6, 7, 8, 9, 10, 11, 12, 13, or 14 carbon atoms. 6-14 Aryl), particularly a ring with 6 carbon atoms (“C6 aryl”), such as phenyl; or biphenyl, or a ring with 9 carbon atoms (“C9 aryl”), such as indenyl or indenyl, or a ring with 10 carbon atoms (“C9 aryl”). 10 Aryl groups, such as tetrahydronaphthyl, dihydronaphthyl, or naphthyl, or rings with 13 carbon atoms (“C”). 13 Aryl groups, such as fluorene groups, or rings with 14 carbon atoms (“C”). 14 Aryl), for example, anthracene. When the C 6-20When the aryl group is substituted, it can be monosubstituted or polysubstituted. Furthermore, there are no restrictions on the substitution site; for example, it can be ortho, para, or meta substituted.

[0037] The term "5-20-membered heteroaryl" should be understood to include monovalent monocyclic, bicyclic, or tricyclic aromatic ring systems having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O, and S, such as "5-14-membered heteroaryl". The term "5-14-membered heteroaryl" should also be understood to include monovalent monocyclic, bicyclic, or tricyclic aromatic ring systems having 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 ring atoms, particularly 5, 6, 9, or 10 carbon atoms, and containing 1 to 5, preferably 1 to 3, heteroatoms independently selected from N, O, and S, and in each case, may be benzofused. Specifically, the heteroaryl group is selected from thienyl, furanyl, pyrroleyl, oxazolyl, thiazolyl, imidazoleyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl, and their benzo[derivatives], such as benzofuranyl, benzothienyl, benzooxazolyl, benzoisooxazolyl, benzoimidazolyl, benzotriazolyl, indazole, indolyl, isindolyl, etc.; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and their benzo[derivatives], such as quinolinyl, quinazolinyl, isoquinolinyl, etc.; or acrylinyl, inazinyl, purinyl, and their benzo[derivatives]; or terpenolyl, phthalazinyl, quinazolinyl, quinoxolinyl, naphridinyl, pteridinyl, carbazolyl, acridineyl, phenazinyl, phenothiazinyl, phenothiazinyl, etc.

[0038] As previously stated, a first aspect of the present invention provides a compound of formula I, including its stereoisomer, racemate, pharmaceutically acceptable salt, or solvate:

[0039]

[0040] Among them, R1, R2, and R3 may be the same or different, and are independently selected from hydrogen, halogen, cyano, substituted or unsubstituted C. 1-20 Alkyl, Halogenated C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted 3-20 membered heterocyclic groups, substituted or unsubstituted 5-20 membered heteroaryl groups, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkoxy, halogenated C 3-20 Cycloalkyloxy, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 Alkyne group, substituted or unsubstituted C 1-20 Alkyl carbonyl, substituted or unsubstituted C 1-20alkoxycarbonyl, substituted or unsubstituted C 6-20 aryl carbonyl, substituted or unsubstituted C 6-20 Aryloxycarbonyl; and the optional substituents are each independently selected from: halogen, C 1-20 Alkyl, Halogenated C 1-20 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic groups, halogenated C 3-20 cycloalkyl, C 1-20 Alkoxy, halogenated C 1-20 Alkoxy, halogenated C 3-20 cycloalkyl, halogenated C 3-20 At least one of the cycloalkyloxy groups;

[0041] R 11 Selected from C 1-20 Alkyl, Halogenated C 1-20 Alkyl, C 3-20 Cycloalkyl or 3-20 membered heterocyclic groups;

[0042] Q is selected from the following structures shown in Y-1 to Y-93:

[0043]

[0044]

[0045]

[0046]

[0047] Among them, R6, R7, R8, R9 and Z may be the same or different, and are independently selected from hydrogen, halogen, cyano, substituted or unsubstituted C. 1-20 Alkyl, Halogenated C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted 3-20 membered heterocyclic groups, substituted or unsubstituted 5-20 membered heteroaryl groups, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkoxy, halogenated C 3-20 Cycloalkyloxy, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 Alkyne group, substituted or unsubstituted C 1-20 Alkyl carbonyl, substituted or unsubstituted C 1-20 alkoxycarbonyl, substituted or unsubstituted C 6-20 aryl carbonyl, substituted or unsubstituted C 6-20 Aryloxycarbonyl; and the optional substituents are each independently selected from: halogen, C 1-20 Alkyl, Halogenated C1-20 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic groups, halogenated C 3-20 cycloalkyl, C 1-20 Alkoxy, halogenated C 1-20 Alkoxy, halogenated C 3-20 cycloalkyl, halogenated C 3-20 At least one of the cycloalkyloxy groups;

[0048] The substitution is the substitution by one, two, three or more substituents;

[0049] Among the groups represented by Y-1 to Y-93 above The location is the connection point.

[0050] According to embodiments of the present invention, R1, R2, and R3 may be the same or different, and are independently selected from hydrogen, fluorine, chlorine, bromine, cyano, and C. 1-6 Alkyl, Halogenated C 1-6 Alkyl or C 1-6 Alkyl groups; for example, R1 is selected from fluorine, chlorine, and bromine; R2 and R3 are selected from hydrogen.

[0051] R 11 Selected from C 1-6 Alkyl, Halogenated C 1-6 Alkyl, C 3-12 Cycloalkyl or 3-12 membered heterocyclic groups; for example, R 11 It is selected from cyclopropyl, cyclobutyl, cyclopentyl, monofluoromethyl, difluoromethyl or trifluoromethyl.

[0052] Q is selected from the following structures shown in Y-80 to Y-85:

[0053]

[0054] Among them, R6, R7, and Z may be the same or different, and are independently selected from hydrogen, fluorine, chlorine, bromine, cyano, and C. 1-6 Alkyl, Halogenated C 1-6 Alkyl or C 1-6 Alkyl groups, for example, R6 is selected from halogenated C. 1-6 Alkyl group, R7 is selected from C 1-6 Alkyl, such as C 1-3 Alkyl group, Z is H; for example, R6 is selected from fluorinated C. 1-3 Alkyl groups, such as monofluoromethyl, difluoromethyl, or trifluoromethyl.

[0055] In some embodiments of the present invention, the compound represented by Formula I is selected from the following structures:

[0056]

[0057] The present invention also provides a method for preparing the compound shown in Formula I, comprising the following steps:

[0058]

[0059] Compound Ia reacts with compound Ib to give the compound shown in formula I;

[0060] Among them, R1, R2, R3, R 11 Q has the definitions described above.

[0061] The present invention also provides a composition, such as an insecticidal and / or bactericidal composition, comprising one, two, or more of a compound of formula I, a stereoisomer thereof, a racemic mixture thereof, a tautomer thereof, a nitrogen oxide thereof, or a pharmaceutically acceptable salt thereof, as an active ingredient.

[0062] According to an embodiment of the present invention, the weight percentage of the active ingredient in the composition is 0.1-90%, for example, 0.5-80%.

[0063] According to an embodiment of the present invention, the composition can be administered in the form of a formulation.

[0064] For example, the compound shown in Formula I is dissolved or dispersed in a carrier or formulated as an active ingredient to facilitate dispersion when used as an insecticide and / or bactericide.

[0065] According to an embodiment of the present invention, the composition further includes an adjuvant; the adjuvant is selected from at least one of surfactants, solid diluents, and liquid diluents.

[0066] According to embodiments of the present invention, the formulation includes, but is not limited to, the following forms: wettable powder, oil suspension, water suspension, water emulsion, aqueous solution, emulsifiable concentrate or microcapsule, etc.

[0067] According to embodiments of the invention, a liquid or solid carrier and optionally a surfactant may also be added to the composition.

[0068] The present invention also provides the use of one, two or more of the compounds of Formula I, their stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof, as pesticides, such as insecticides and / or fungicides.

[0069] The present invention also provides the use of one, two or more of the compounds of Formula I, their stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof, in the preparation of pesticides, such as insecticides and / or fungicides.

[0070] The present invention also provides a method for controlling pests and / or plant fungal diseases, comprising applying an effective amount of one, two or more of the following: a compound of formula I, its stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof, or the composition thereof, to an individual in need of such control.

[0071] According to an embodiment of the present invention, the effective amount is 1 gram to 2000 grams per hectare, preferably 10 grams to 1000 grams per hectare.

[0072] The active substances according to the present invention, or the active substances to be used according to the present invention, are suitable for protecting plants and plant organs, increasing harvest yield, improving the quality of harvested products, and controlling pests, particularly in agriculture, horticulture, animal husbandry, forestry, gardens and recreational facilities, warehouse pest control and material protection, and in the sanitation field, where plant fungi and pests are present. They are preferably used as plant protection compositions. They are active against conventionally susceptible and resistant species and against all or individual developmental stages. The aforementioned pests include, but are not limited to, plant parasitic nematodes.

[0073] The plant parasitic nematode mentioned is the root-knot nematode.

[0074] According to an embodiment of the present invention, the plant-borne fungal rot is wheat root rot fungus.

[0075] The following embodiments are used to further explain the present invention, and the following embodiments are merely descriptions of the implementation of the present invention and do not limit the scope of the present invention in any way.

[0076] Example 1. Synthesis of Compound 1

[0077] Synthesis of methyl 2-(5-bromo-3-chloropyridin-2-yl)-2-cyanoacetate

[0078]

[0079] 100 mL of LDMF, 22.4 g of 5-bromo-2,3-dichloropyridine, 16 g of potassium carbonate, and 15 mL of methyl cyanoacetate were added to a 250 mL four-necked flask equipped with a stirrer, thermometer, and condenser. The mixture was heated to 110 °C and reacted for 8 hours. After the reaction was completed, the reaction solution was washed with water, extracted, concentrated, and separated by column chromatography to obtain 15 g of methyl 2-(5-bromo-3-chloropyridin-2-yl)-2-cyanoacetate.

[0080] (2) Synthesis of 2-(5-bromo-3-chloropyridin-2-yl)acetonitrile

[0081]

[0082] 100 mL of methanol, 15 g of methyl 2-(5-bromo-3-chloropyridin-2-yl)-2-cyanoacetate, and 50 mL of sulfuric acid aqueous solution diluted to 50% by mass were added to a 250 mL four-necked flask equipped with a stirrer, thermometer, and condenser. The mixture was heated to reflux and reacted for 24 hours. After the reaction was completed, the reaction solution was washed with water, extracted, concentrated, and separated by column chromatography to obtain 12 g of 2-(5-bromo-3-chloropyridin-2-yl)acetonitrile.

[0083] (3) Synthesis of 1-(5-bromo-3-chloropyridin-2-yl)cyclopropane-1-onitrile

[0084]

[0085] 100 mL of LDM and 12 g of 2-(5-bromo-3-chloropyridin-2-yl)acetonitrile were added to a 250 mL four-necked flask equipped with a stirrer, thermometer, and condenser. After cooling to 0 °C, 4 g of sodium hydroxide was added in portions. After stirring at room temperature for 15 minutes, 10 mL of 1,2-dibromoethane was added dropwise. The reaction was allowed to proceed at room temperature for 4 hours. After the reaction was completed, the reaction solution was washed with water, extracted, concentrated, and separated by column chromatography to obtain 10 g of 1-(5-bromo-3-chloropyridin-2-yl)cyclopropane-1-onitrile.

[0086] (4) Synthesis of 1-(5-bromo-3-chloropyridin-2-yl)cyclobutylamine

[0087]

[0088] Add 50 mL of THF and 10 g of 1-(5-bromo-3-chloropyridin-2-yl)cyclopropane-1-onitrile to a 250 mL four-necked flask equipped with a stirrer, thermometer, and condenser. After cooling to 0 °C, add 20 g of aluminum trichloride in batches. React at room temperature for 4 hours. After monitoring the completion of the reaction, add water to quench the reaction and concentrate to obtain 11 g of crude 1-(5-bromo-3-chloropyridin-2-yl)cyclobutylamine.

[0089] (5) Synthesis of compound 1a

[0090]

[0091] 50 mL of THF, crude 1-(5-bromo-3-chloropyridin-2-yl)cyclopropylmethylamine, 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid, HATU, and TEA were added to a 250 mL four-necked flask equipped with a stirrer, thermometer, and condenser. The mixture was reacted at room temperature for 4 hours. After the reaction was completed, the mixture was washed with water, extracted, concentrated, and subjected to column chromatography to obtain 3 g of compound 1a.

[0092]

[0093] 50 mL of LDM, 3 g of compound 1a, 2.1 g of zinc cyanide, and 1 g of tetraphenylphosphine palladium were added to a 250 mL four-necked flask equipped with a stirrer, thermometer, and condenser. The mixture was reacted at 90 °C for 4 hours under nitrogen protection. After the reaction was completed, the mixture was washed with water, extracted, concentrated, and subjected to column chromatography to obtain 2.5 g of compound 1-1.

[0094]

[0095] To a 250 mL four-necked flask equipped with a stirrer, thermometer, and condenser, add 50 mL of methanol, 2.5 g of compound 1-1, 1.2 g of hydroxylamine hydrochloride, and 3 mL of triethylamine. Reflux for 1.5 hours. After removing the methanol by vacuum distillation, add 50 mL of THF and 2 mL of cyclopropylformyl chloride. Heat and stir for 1 hour until the reaction is complete. After washing with water, extracting, concentrating, and separating by column chromatography, compound 1 is obtained, m / z 449.12 (M+H).

[0096] Biological example: Assay for nematicide activity

[0097] 1. Preparation of root-knot nematode solution:

[0098] (1) Place the root-knot nematode egg mass used in the experiment into a beaker containing pure water, seal it with filter paper, and incubate it at 25°C for 48 hours.

[0099] (2) Preparation of root-knot nematode solution: After culturing the eggs for 48 hours, the eggs were filtered through a filter cloth to remove the egg mass, and second-instar larvae of the same age were obtained.

[0100] (3) Population survey: Take 1 mL of well-mixed liquid containing root-knot nematodes into a counting dish and count them under a dissecting microscope to ensure that there are ≥100 root-knot nematodes per milliliter of the suspension. If the number of nematodes is small, centrifuge at 1000 r / min for 2 minutes, discard the supernatant, centrifuge again, and finally dilute the root-knot nematode solution with pure water to ≥100 nematodes per milliliter for later use.

[0101] (4) Statistical analysis of root-knot nematodes: Under stereomicroscopic examination at various concentrations, the total number of nematodes and the number of dead nematodes were recorded over 24 hours, and the mortality rate was calculated. Statistical analysis of root-knot nematode eggs: Under stereomicroscopic examination at various concentrations, the total number of hatched nematode eggs was recorded over 48 hours, and the inhibitory rate of the compound on nematode egg hatching was calculated.

[0102] Table 1. In vitro activity results of compound 1 against root-knot nematodes (24h)

[0103]

[0104] Table 2. In vitro activity results of compound 1 against root-knot nematode eggs (48 h)

[0105]

[0106] The experimental results showed that after 24 hours of treatment with root-knot nematodes, compound 1 exhibited good killing effects against root-knot nematodes at relatively low doses. Specifically, at concentrations above 1.250 ppm, it showed 100.00% control efficacy against root-knot nematodes, and at a dose of 0.625 ppm of active ingredient, the killing effect reached over 70%, demonstrating excellent nematicidal activity. After 48 hours of treatment with nematode eggs, compound 1 at concentrations above 1.25 ppm showed a good inhibitory effect on egg hatching.

[0107] Indoor activity test against wheat root rot fungi

[0108] (1) Compound 1 was prepared into five concentration gradients: 100 ppm, 50 ppm, 25 ppm, 12.5 ppm, and 6.25 ppm. The required amount of reagent was calculated according to the content of the active ingredient, and a high-concentration 100 ppm stock solution was prepared. Subsequently, the stock solution was diluted by a factor of two to obtain the corresponding concentrations. If the original drug showed poor solubility during the preparation process, an appropriate amount of organic solvent could be added to aid dissolution.

[0109] (2) Taking 95wt% compound 1 as an example, weigh 0.05g of the agent and dissolve it in 1mL of DMF. After complete dissolution, add water to prepare a 5000ppm solution. Then, dilute it in half to 2500ppm-312.5ppm respectively. Each centrifuge tube contains 1mL of solution. When the temperature of the culture medium reaches about 40℃-50℃, add the solution to 50mL of culture medium to prepare a 100ppm solution culture medium. After cooling, inoculate the mycelium.

[0110] (3) Seven days after the first application of the fungicide and inoculation, the colony diameter of Phytophthora soybeanis was investigated using the cross-sectional method. The average diameter of each treatment colony was calculated, and the inhibition rate was calculated using the following formula: Relative inhibition rate (%) = (Control colony diameter - Treatment colony diameter) / (Control colony diameter - Mycelium disc diameter) × 100% Note: The mycelium disc diameter is usually 1 cm.

[0111] Table 3. Indoor activity test efficacy of compound 1 against wheat root rot fungus (7 days)

[0112]

[0113] Experimental results: Based on the above results after 7 days of inoculation, it can be seen that compound 1 achieved a relative inhibition rate of over 90% against wheat root rot fungi in the concentration range of 100ppm-12.5ppm.

[0114] In summary, the compounds of the present invention have superior insecticidal and bactericidal effects.

[0115] The 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 combining the 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. The stereoisomers, racemates, pharmaceutically acceptable salts, or solvates of the compound represented by Formula I: in, R1, R2, and R3 may be the same or different, and are independently selected from hydrogen, halogen, cyano, substituted or unsubstituted C. 1-20 Alkyl, Halogenated C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted 3-20 membered heterocyclic groups, substituted or unsubstituted 5-20 membered heteroaryl groups, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkoxy, halogenated C 3-20 Cycloalkyloxy, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 Alkyne group, substituted or unsubstituted C 1-20 Alkyl carbonyl, substituted or unsubstituted C 1-20 alkoxycarbonyl, substituted or unsubstituted C 6-20 aryl carbonyl, substituted or unsubstituted C 6-20 Aryloxycarbonyl; and the optional substituents are each independently selected from: halogen, C 1-20 Alkyl, Halogenated C 1-20 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic groups, halogenated C 3-20 cycloalkyl, C 1-20 Alkoxy, halogenated C 1-20 Alkoxy, halogenated C 3-20 cycloalkyl, halogenated C 3-20 At least one of the cycloalkyloxy groups; R 11 Selected from C 1-20 Alkyl, Halogenated C 1-20 Alkyl, C 3-20 Cycloalkyl or 3-20 membered heterocyclic groups; Q is selected from the following structures shown in Y-1 to Y-93: Among them, R6, R7, R8, R9 and Z may be the same or different, and are independently selected from hydrogen, halogen, cyano, substituted or unsubstituted C. 1-20 Alkyl, Halogenated C 1-20 Alkyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted 3-20 membered heterocyclic groups, substituted or unsubstituted 5-20 membered heteroaryl groups, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkoxy, halogenated C 3-20 Cycloalkyloxy, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 2-20 Alkyne group, substituted or unsubstituted C 1-20 Alkyl carbonyl, substituted or unsubstituted C 1-20 alkoxycarbonyl, substituted or unsubstituted C 6-20 aryl carbonyl, substituted or unsubstituted C 6-20 Aryloxycarbonyl; and the optional substituents are each independently selected from: halogen, C 1-20 Alkyl, Halogenated C 1-20 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic groups, halogenated C 3-20 cycloalkyl, C 1-20 Alkoxy, halogenated C 1-20 Alkoxy, halogenated C 3-20 cycloalkyl, halogenated C 3-20 At least one of the cycloalkyloxy groups; The substitution is the substitution by one, two, three or more substituents; Among the groups represented by Y-1 to Y-93 above The location is the connection point.

2. The compound of Formula I according to claim 1, wherein its stereoisomer, racemate, pharmaceutically acceptable salt or solvate, wherein, R1, R2, and R3 may be the same or different, and are independently selected from hydrogen, fluorine, chlorine, bromine, cyano, and C. 1-6 Alkyl, Halogenated C 1-6 Alkyl or C 1-6 Alkoxy; R 11 Selected from C 1-6 Alkyl, Halogenated C 1-6 Alkyl, C 3-12 Cycloalkyl or 3-12 membered heterocyclic groups; Q is selected from the following structures shown in Y-80 to Y-85: Among them, R6, R7, and Z may be the same or different, and are independently selected from hydrogen, fluorine, chlorine, bromine, cyano, and C. 1-6 Alkyl, Halogenated C 1-6 Alkyl or C 1-6 Alkyl groups, for example, R6 is selected from halogenated C. 1-6 Alkyl group, R7 is selected from C 1-6 Alkyl group, where Z is H.

3. The compound of formula I according to claim 1 or 2, wherein its stereoisomer, racemate, pharmaceutically acceptable salt or solvate, is, R1 is selected from fluorine, chlorine, and bromine; R2 and R3 are selected from hydrogen. R 11 Selected from cyclopropyl, cyclobutyl, cyclopentyl, monofluoromethyl, difluoromethyl, or trifluoromethyl; Q is selected from the following structures shown in Y-80 to Y-85: Among them, R7 is selected from C 1-3 Alkyl group, Z is H; R6 is selected from fluorinated C. 1-3 alkyl.

4. The compound of formula I according to any one of claims 1-3, wherein its stereoisomer, racemate, pharmaceutically acceptable salt or solvate, is wherein, The compound shown in Formula I is selected from the following structures:

5. A method for preparing the stereoisomer, racemate, pharmaceutically acceptable salt, or solvate of the compound represented by Formula I according to any one of claims 1-4, wherein, Includes the following steps: Compound Ia reacts with compound Ib to give the compound shown in formula I; Among them, R1, R2, R3, R 11 Q has the definition as described in any one of claims 1-4.

6. A composition, such as an insecticidal and / or bactericidal composition, comprising one, two, or more of the compounds of Formula I as described in any one of claims 1-4, their stereoisomers, racemates, tautomers, nitrooxides, or pharmaceutically acceptable salts thereof as active ingredients; Preferably, the composition contains 0.1-90% by weight of the active ingredient; Preferably, the composition further includes an auxiliary agent; the auxiliary agent is selected from at least one of surfactants, solid diluents, and liquid diluents; Preferably, the formulation comprises the following forms: wettable powder, oil suspension, water suspension, water emulsion, aqueous solution, emulsifiable concentrate, or microcapsule. Preferably, a liquid or solid carrier and optionally a surfactant are added to the composition.

7. Use of one, two or more of the compounds of Formula I according to any one of claims 1-4, their stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof as pesticides, such as insecticides and / or fungicides.

8. Use of one, two or more of the compounds of Formula I according to any one of claims 1-4, their stereoisomers, racemates, tautomers, nitrogen oxides or pharmaceutically acceptable salts thereof in the preparation of pesticides, such as insecticides and / or fungicides.

9. A method for controlling pests and / or plant fungal diseases, wherein, This includes applying an effective amount of the compound of Formula I as described in any one of claims 1-4, its stereoisomers, racemates, tautomers, nitrides or pharmaceutically acceptable salts thereof, or the composition of claim 6 to an individual in need of it.

10. The method according to claim 9, wherein, The plant parasitic nematode is a root-knot nematode; Preferably, the plant-borne fungal rot is wheat root rot fungus.

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