A class of piperidine amide compounds containing trifluoromethyl oxadiazole linked phenyl, a preparation method thereof and an application thereof

Abstract

The present invention discloses a class of piperidine amide compounds containing trifluoromethyl oxadiazole-linked phenyl groups as shown in the following general formula (T): see the specification for each substituent. The present invention also discloses a preparation method and uses of the piperidine amide compounds containing trifluoromethyl oxadiazole-linked phenyl groups, and the piperidine amide compounds containing trifluoromethyl oxadiazole-linked phenyl groups are particularly suitable for preventing and controlling Rhizoctonia solani, Sclerotinia sclerotiorum, Physalospora piricola or Magnaporthe oryzae, etc.

Description

Technical Field

[0001] The present invention belongs to the field of agricultural fungicides, and particularly relates to a class of piperidine amide compounds containing trifluoromethyl oxadiazole biphenyl, a preparation method thereof, and an application thereof. Background Art

[0002] In agriculture, long-term use of the same pesticide variety is likely to cause diseases to develop drug resistance. Therefore, it is necessary to continuously develop new varieties with different action mechanisms.

[0003] WO2015185485A, WO2019101511A, WO2019052932A, WO2018158365A, WO2018162643A, WO2018202487A, WO2020007658A, WO2020016180A all disclose a class of compounds containing trifluoromethyl oxadiazole benzamide, but there is no report on the same type of compounds with a piperidine structure, and there is no disclosure on the bactericidal activity of the same type of compounds with a piperidine structure. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides a class of piperidine amide compounds containing trifluoromethyl oxadiazole biphenyl represented by the general formula (T):

[0005]

[0006] Wherein:

[0007] R1 is selected from hydrogen, halogen, C1-C6 alkyl or C1-C6 haloalkyl;

[0008] R2 and R3 are independently selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy, cyano-substituted C1-C6 alkyl, C1-C6 alkoxy-substituted C1-C6 alkyl, C3-C6 cycloalkyl or C1-C6 alkyl-substituted C3-C6 cycloalkyl, or a phenyl or 5-membered heteroaryl or 6-membered heteroaryl substituted by at least one of hydrogen, cyano, halogen, nitro, phenoxy, hydroxy, formyl, carboxyl, C1-C6 alkyl, C1-C6 alkenyl, C1-C6 alkynyl, C1-C6 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxycarbonyl or C1-C6 haloalkoxycarbonyl, or a structure represented by the following formula (1):

[0009]

[0010] In the formula, X is selected from -CH2- or -CHR8-, wherein:

[0011] R8 is selected from C1-C6 alkyl, halogenated C1-C6 alkyl, and the carbon atom connected to R8 is a chiral carbon atom, and the chiral carbon atom is in the levorotatory configuration and / or dextrorotatory configuration;

[0012] R9, R 10 , R 11 are independently selected from hydrogen, cyano, halogen, nitro, phenoxy, hydroxy, formyl, carboxyl, C1-C6 alkyl, C1-C6 alkenyl, C1-C6 alkynyl, C1-C6 halogenated alkyl, C1-C6 halogenated alkoxy, C1-C6 alkoxycarbonyl or C1-C6 halogenated alkoxycarbonyl;

[0013] -NR2R3 can also exist in the following cyclized form:

[0014]

[0015] wherein, R 12 , R 13 are independently selected from hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 halogenated alkyl, C1-C6 halogenated alkoxy; when R 12 and R 13 are both not hydrogen, the carbon atom connected to R 12 and / or R 13 is a chiral carbon atom, and the chiral carbon atom is in the levorotatory configuration and / or dextrorotatory configuration; A is selected from carbon or oxygen.

[0016] Preferably, R1 is selected from hydrogen, halogen, C1-C3 alkyl, halogenated C1-C3 halogenated alkyl;

[0017] R2 and R3 are independently selected from hydrogen, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 halogenated alkyl, C1-C3 halogenated alkoxy, cyano-substituted C1-C3 alkyl, C1-C3 alkoxy-substituted C1-C3 alkyl, C3-C6 cycloalkyl or C1-C3 alkyl-substituted C3-C6 cycloalkyl, or phenyl or pyridyl or thiazolyl substituted by at least one of hydrogen, cyano, halogen, nitro, phenoxy, formyl, C1-C3 alkyl, C1-C3 halogenated alkyl, C1-C3 halogenated alkoxy, C1-C3 alkoxycarbonyl or C1-C3 halogenated alkoxycarbonyl, or the structure shown in the following formula (1):

[0018]

[0019] X is selected from -CH2- or -CHR8-, wherein: R8 is selected from C1-C3 alkyl; R9, R 10 , R 11Independently selected from hydrogen, cyano, halogen, nitro, phenoxy, formyl, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkoxycarbonyl, C1-C3 haloalkoxycarbonyl;

[0020] -NR2R3 can also exist in the following cyclized form:

[0021]

[0022] R 12 and R 13 are independently selected from hydrogen, halogen, C1-C3 alkyl, C1-C3 alkoxy, halo C1-C3 alkyl, halo C1-C3 alkoxy; A is selected from carbon or oxygen.

[0023] Further preferably, R1 is selected from hydrogen, halogen, methyl or trifluoromethyl;

[0024] R2 and R3 are independently selected from hydrogen, methyl, ethyl, methoxy, ethoxy, 2,2,2-trifluoroethyl, cyanomethyl or C3-C6 cycloalkyl, or phenyl or pyridyl or thiazolyl substituted by at least one of hydrogen, cyano, halogen, nitro, phenoxy, methyl, ethyl, trifluoromethyl, trifluoromethoxy, methoxycarbonyl, or the structure shown in the following formula (1):

[0025]

[0026] X is selected from -CHR8-, where: R8 is methyl, R9, R 10 , R 11 are independently selected from hydrogen, halogen or methyl;

[0027] -NR2R3 can also exist in the following cyclized form:

[0028]

[0029] R 12 , R 13 are independently selected from hydrogen, halogen, methyl, ethyl; A is selected from carbon or oxygen.

[0030] More preferably, the piperidine amide compounds containing trifluoromethyl oxadiazole biphenyl are selected from the following structures:

[0031]

[0032]

[0033]

[0034] In the substituents of the present invention: alkyl refers to a straight-chain or branched-chain form, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl and other groups; cycloalkyl refers to a form including a cyclic chain, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and other groups; haloalkyl refers to a group in which the alkyl is substituted by one or more halogen atoms; alkoxy refers to a group in which an oxygen atom is connected to the end of the alkyl, such as methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy and the like; haloalkoxy refers to a group in which the alkyl is substituted by one or more halogen atoms and an oxygen atom is connected to the end; halogen refers to fluorine, chlorine, bromine, iodine; 5- or 6-membered heteroaryl group refers to a 5- or 6-membered conjugated ring containing 1 to 3 heteroatoms and the rest being carbon atoms, where the heteroatoms are oxygen, nitrogen, sulfur, such as pyridyl, pyrimidinyl, thiazolyl, pyrazolyl, triazolyl and the like.

[0035] The piperidine amide compounds containing trifluoromethyl oxadiazole-linked phenyl represented by the general formula (T) provided by the present invention, and their typical compounds are listed in Table 1. The typical compounds shown in Table 1 do not limit the scope of the piperidine amide compounds represented by the general formula (T) of the present invention.

[0036]

[0037] Table 1, Some Typical Compounds and 1H NMR Data

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052] In Table 1: s represents a singlet, b represents a broad singlet, d represents a doublet, dd represents a double doublet, t represents a triplet, q represents a quartet, and m represents a multiplet.

[0053] The present invention also provides a preparation method of piperidine amide compounds containing trifluoromethyl oxadiazole-linked phenyl represented by the general formula (T), and the preparation method includes:

[0054]

[0055] Wherein: the definitions of substituents R1, R2, and R3 are as described above, and the acyl chlorination reagent is selected from thionyl chloride and / or oxalyl chloride.

[0056] Specifically, the preparation method includes the following steps:

[0057] (1) In a first solvent, intermediate (I), (II) and a base react to form intermediate (III);

[0058] (2) Intermediate (III) is hydrolyzed and acidified to form intermediate (IV);

[0059] (3) In a second solvent, intermediate (IV) reacts with the acyl chlorination reagent to form an intermediate acyl chloride;

[0060] (4) In a third solvent, in the presence of a base, the intermediate acyl chloride reacts with R2R3-substituted amine to form the piperidine amide compound containing trifluoromethyl oxadiazole-linked phenyl.

[0061] In step (1), the first solvent may be a commonly used organic solvent in the art. Preferably, the first solvent is selected from at least one of N,N-dimethylformamide, toluene, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, acetonitrile or dimethyl sulfoxide. More preferably, the first solvent is selected from at least one of N,N-dimethylformamide, acetonitrile or tetrahydrofuran. The base is selected from potassium carbonate, sodium carbonate or sodium bicarbonate, preferably potassium carbonate. The reaction temperature of step (1) is 0-100 °C, and preferably the reaction temperature is 25-100 °C.

[0062] In step (2), hydrolysis is carried out in a sodium hydroxide-water-water-soluble organic solvent system, and the water-soluble organic solvent is selected from ethanol or tetrahydrofuran; after hydrolysis is completed, it is acidified with hydrochloric acid to form intermediate (IV).

[0063] In step (3), the second solvent may be an organic solvent commonly used in the art. Preferably, the second solvent is selected from at least one of N,N-dimethylformamide, toluene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrahydrofuran, or dimethyl sulfoxide. More preferably, the second solvent is selected from at least one of dichloromethane, chloroform, or carbon tetrachloride. The reaction temperature of step (3) is 0 to 100 °C, and the preferred reaction temperature is 25 °C to the solvent reflux temperature.

[0064] In step (4), the third solvent is selected from at least one of N,N-dimethylformamide, toluene, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, or dimethyl sulfoxide; more preferably, the third solvent is selected from at least one of toluene, dichloromethane, or tetrahydrofuran. The base may be an organic base or an inorganic base, preferably selected from at least one of triethylamine, sodium acetate, sodium carbonate, or potassium carbonate. The reaction temperature of step (4) is 0 to 100 °C, and the preferred reaction temperature is 0 to 25 °C.

[0065] The present invention also provides an application of the piperidine amide compound containing trifluoromethyl oxadiazole biphenyl represented by the general formula (T) as described above in agricultural sterilization.

[0066] As a preferred embodiment, the piperidine amide compound containing trifluoromethyl oxadiazole biphenyl represented by the general formula (T) is suitable for controlling at least one disease selected from Rhizoctonia solani, Sclerotinia sclerotiorum, Physalospora piricola, Magnaporthe oryzae, Puccinia sorghi, Puccinia glycines, or Puccinia triticina.

[0067] As another preferred embodiment, the piperidine amide compound containing trifluoromethyl oxadiazole biphenyl represented by the general formula (T) is particularly suitable for sterilizing crops such as rice, wheat, cotton, corn, soybean, vegetables, and rapeseed.

[0068] The present invention also provides a pesticide formulation, and the pesticide formulation contains 0.001% - 99.99% by weight of the piperidine amide compound containing trifluoromethyl oxadiazole biphenyl represented by the general formula (T). The pesticide formulation can be formulated into emulsifiable concentrates, suspensions, aqueous suspensions, microemulsions, (aqueous) emulsions, powders, wettable powders, soluble powders, (water-dispersible) granules, or capsules, etc.

[0069] The pesticide formulation provided by the present invention, in addition to containing 0.001% - 99.99% by weight of the piperidine amide compound containing trifluoromethyl oxadiazole biphenyl represented by the general formula (T), may further contain an agriculturally acceptable carrier.

[0070] The carrier can be solid or liquid. Suitable solid carriers include natural or synthetic clays and silicates, such as natural silica and diatomaceous earth; magnesium silicate such as talc; magnesium aluminum silicate such as kaolinite, kaolin, montmorillonite and mica; silica white, calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; amine salts such as ammonium sulfate, hexamethylenediamine. Liquid carriers include water and organic solvents. When water is used as the solvent or diluent, organic solvents can also be used as adjuvants or antifreeze additives. Suitable organic solvents include aromatic hydrocarbons such as benzene, xylene, toluene, etc.; chlorinated hydrocarbons, such as chlorobenzene, vinyl chloride, chloroform, dichloromethane, etc.; aliphatic hydrocarbons, such as petroleum fractions, cyclohexane, light mineral oil; alcohols, such as isopropanol, butanol, ethylene glycol, glycerol and cyclohexanol, etc.; and their ethers and esters; and ketones, such as acetone, cyclohexanone and dimethylformamide and N-methyl-pyrrolidone.

[0071] The carrier can also be a surfactant. Suitable surfactants can be emulsifiers, dispersants or wetting agents; they can be ionic or non-ionic. Non-ionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty amines, and commercially available emulsifiers: Nongru 2201B, Nongru 0203B, Nongru 100#, Nongru 500#, Nongru 600#, Nongru 600-2#, Nongru 1601, Nongru 2201, Nongru NP-10, Nongru NP-15, Nongru 507#, Nongru OX-635, Nongru OX-622, Nongru OX-653, Nongru OX-667, Ningru 36#. Dispersants include sodium lignosulfonate, Nekal, calcium lignosulfonate, methylnaphthalenesulfonic acid formaldehyde condensate, etc. Wetting agents are: sodium lauryl sulfate, sodium dodecylbenzenesulfonate, alkylnaphthalenesulfonate, etc.

[0072] The present invention also provides a sterilization method, which includes: applying the piperidine amide compound containing trifluoromethyl oxadiazole biphenyl shown by the general formula (T) to the pathogenic bacteria to be controlled or the medium for its growth. When the piperidine amide compound containing trifluoromethyl oxadiazole biphenyl shown by the general formula (T) is applied to the pathogenic bacteria to be controlled or the medium for its growth, the application rate is 10-1000 per hectare.

[0073] The piperidine amide compound containing trifluoromethyl oxadiazole biphenyl shown by the general formula (T) provided by the present invention has the following advantages compared with the prior art:

[0074] (1) The compound has a novel structure;

[0075] (2) The compound has high bactericidal activity against Rhizoctonia solani, Sclerotinia sclerotiorum, Physalospora piricola, Magnaporthe oryzae, Puccinia sorghi, Puccinia pachyrhizi and Puccinia triticina, etc., and has high bactericidal activity at low concentrations, especially the bactericidal activity against Puccinia pachyrhizi and Puccinia sorghi. Detailed Embodiments

[0076] The present invention will be further described below in conjunction with specific embodiments, but the present invention is not limited to these specific embodiments. Those skilled in the art should recognize that the present invention covers all alternative, improved, and equivalent solutions that may be included within the scope of the claims.

[0077] I. Compound Synthesis

[0078] Example 1. Synthesis of Target Compound T001

[0079] (1) Synthesis of Intermediate (III) (R1 = H)

[0080] Add Intermediate (I) (R1 = H) (24.56 g, 0.08 mol) into a 500 mL round-bottom flask, add 200 mL of acetonitrile, then add anhydrous potassium carbonate (13.80 g, 0.10 mol) and Intermediate (II) (15.70 g, 0.10 mol). Stir at 40 °C and monitor the reaction by TLC. After 6 h, the reaction is complete. Add a small amount of anhydrous magnesium sulfate for drying, filter, concentrate, and separate by column chromatography to obtain Intermediate (III) (R1 = H). The 1H NMR spectrum is as follows:

[0081] 1 H NMR(CDCl3, 400 MHz) δ: 7.96 (d, 2H, J = 8.4 Hz, Ph-H), 7.40 (d, 2H, J = 8.4 Hz, Ph-H), 4.06 (q, 2H, J = 6.8 Hz, CH2), 3.47 (s, 2H, CH2), 2.75 - 2.80 (m, 2H, peridine-H), 2.19 - 2.26 (m, 1H, peridine-H), 1.95 - 2.03 (m, 2H, peridine-H), 1.79 - 1.85 (m, 2H, peridine-H), 1.67 - 1.76 (m, 2H, peridine-H), 1.17 (t, 3H, J = 7.2 Hz, CH3).

[0082] When R1 is other substituents, the synthesis method of Intermediate (III) is the same as above.

[0083] (2) Synthesis of Intermediate (IV) (R1 = H)

[0084] The intermediate (III) (R1 = H) (19.15 g, 0.05 mol) was added to a 500 mL round-bottom flask, 200 mL of tetrahydrofuran was added and stirred until completely dissolved, then 100 mL of water and sodium hydroxide (4.00 g, 0.10 mol) were added, and the mixture was stirred at room temperature. The reaction was monitored by TLC. After 12 h, the reaction was complete and the reaction was stopped. Concentrated hydrochloric acid was added to neutralize, and the pH was adjusted to 1 - 2. White solid precipitated out, filtered, and dried to obtain the intermediate (IV) (R1 = H).

[0085] Its NMR data are as follows: 1 H NMR (DMSO-d6, 400 MHz) δ: 7.99 (d, 2H, J = 8.4 Hz, Ph-H), 7.51 (d, 2H, J = 8.4 Hz, Ph-H), 3.51 (s, 2H, CH2), 2.70 - 2.75 (m, 2H, peridine-H), 2.13 - 2.21 (m, 1H, peridine-H), 1.96 - 2.03 (m, 2H, peridine-H), 1.74 - 1.78 (m, 2H, peridine-H), 1.49 - 1.58 (m, 2H, peridine-H).

[0086] When R1 is other substituents, the synthesis method of the intermediate (IV) is the same as above.

[0087] (3) Synthesis of the target compound T001

[0088] Take the intermediate (IV) (R1 = H) (0.1 g, 0.30 mmol) and add it to a 50 mL round-bottom flask. Add 15 mL of dichloromethane, stir evenly, add 1 drop of DMF, slowly dropwise add 1 mL of oxalyl chloride, heat under reflux at 50 °C. After the reaction is complete, spin-dry all the solvents. Add 15 mL of dichloromethane, add 0.70 mmol of triethylamine and 0.35 mmol of 2-methylaniline during stirring, stir at room temperature for 1 h, and separate by TLC after concentration to obtain the target compound.

[0089]

[0090] Its NMR data are as follows: 11H NMR (400 MHz, CDCl3 / TMS): δ: 8.05 (d, 2H, J = 8.4 Hz, Ph-H), 7.81 (d, 1H, J = 8.4 Hz, Ph-H), 7.48 (d, 2H, J = 8.0 Hz, Ph-H), 7.12 (t, 2H, J = 8.0 Hz, Ph-H), 7.07 (d, 1H, J = 8.0 Hz, Ph-H), 6.99 (s, 1H, NH), 3.58 (s, 2H, CH2), 2.96 - 3.00 (m, 2H, peridine-H), 2.25 - 2.34 (m, 1H, Piperidine-H), 2.24 (s, 3H, CH3), 2.07 - 2.12 (m, 2H, Piperidine-H), 1.87 - 1.96 (m, 4H, Piperidine-H).

[0091] The other compounds described in Table 1 can be synthesized by referring to the same method.

[0092] II. Formulation Preparation

[0093] The following examples illustrate the processing and formulation of the piperidine amide compounds containing trifluoromethyl oxadiazole-linked phenyl as the active ingredient component represented by the general formula (T) provided by the present invention. In the following examples, all "%" refer to weight percentages.

[0094] Example 2. Wettable Powder

[0095] 15% of compound (I) (Table 1), 5% of lignosulfonate (M q ), 1% of lauryl alcohol polyoxyethylene ether (JFC), 40% of diatomaceous earth, and 44% of light calcium carbonate are uniformly mixed and pulverized to obtain the wettable powder.

[0096] Example 3. Emulsifiable Concentrate

[0097] 10% of compound (I) (Table 1), 5% of agricultural emulsifier 500 (calcium salt), 5% of agricultural emulsifier 602, 5% of N-methyl-2-pyrrolidone, and 75% of xylene are heated and stirred evenly to obtain the emulsifiable concentrate.

[0098] Example 4. Granules

[0099] 5% of compound (I) (Table 1), 1% of polyvinyl alcohol (PVA), 4% of naphthalene sulfonate formaldehyde condensate (NMO), and 90% of clay are uniformly mixed and pulverized. Then, 20 parts of water are added to 100 parts of this mixture, kneaded, and granulated with an extrusion granulator to form 14 - 32 mesh granules, which are then dried to obtain the granules.

[0100] Example 5. Water Dispersible Granules

[0101] Mix 20% of compound (I) (Table 1), 4% of naphthalene sulfonate formaldehyde condensate, 1% of naphthalene sulfonate, 2% of silica white and 73% of kaolin, pulverize them, then add water for kneading, and add them into a granulator equipped with a sieve of a certain specification for granulation. Then, after drying and screening (according to the sieve range), the granular product is obtained.

[0102] Example 6, aqueous suspension

[0103] Pre-mix 20% of compound (I) (Table 1), 1% of fatty alcohol polyoxyethylene ether, 3% of rosin block polyoxyethylene polyoxypropylene ether sulfonate, 1% of magnesium aluminum silicate, 0.4% of silicone defoamer, 5% of propylene glycol and deionized water (69.5%) evenly, then add them into a sand mill for sanding, and after filtration, obtain the suspension mother liquor, and add the prepared xanthan gum (0.1%) aqueous solution and shear and mix evenly.

[0104] III. Biological activity test

[0105] The following gives examples of biological activity determination using the compounds of the present invention. It should be noted that the present invention is not limited only to the scope of the following examples.

[0106] Example 7, bactericidal activity determination

[0107] (1) In-vivo bactericidal activity test:

[0108] The target of the bactericidal test is Puccinia sorghi.

[0109] The test method adopts the leaf inoculation method. Select two pots of potted corn seedlings with the same growth at the true leaf stage. Dissolve the sample with an appropriate amount of DMF solvent to prepare medicated solutions with concentrations of 200, 100, 50, and 25 mg / L. Spray the medicated solutions on the leaf surface. After the medicated spray dries, place the inoculation cake on the leaf. After moisturizing in the dark at 24 - 26 °C for 24 hours, restore the natural light and moisturize and culture for about 3 days. After the control is fully diseased, measure the diameter of the disease spots at each inoculation point with a caliper and calculate the control effect.

[0110] After the test treatment, observe and record the disease occurrence situation of the leaves and plants and the mycelial growth situation. According to the disease index and mycelial diameter, refer to the fungicide volume of "SOP for Evaluation of Biological Activity of Newly Developed Pesticides", and calculate the relative control effect according to the disease index.

[0111] Formula for calculating bactericidal efficacy

[0112] Disease index = 100×∑(number of diseased leaves at each level × representative value at each level) / (total number of leaves surveyed × representative value at the highest level);

[0113] Control effect (%) = 100×(control disease index - treatment disease index) / control disease index.

[0114] The evaluation results of bactericidal activity are as follows.

[0115] At a concentration of 200 mg / L, the control effects of compounds T006, T006, T038, T042, T044, T047, T049, T053, T065, T071 against corn rust were greater than 70%;

[0116] At a concentration of 200 mg / L, the control effects of compounds T001, T002, T003, T011, T012, T016, T019, T035, T039, T040, T051, T066, T068, T069, T070, T070, T076 against corn rust were greater than 50%.

[0117] (2) In vitro bactericidal activity test

[0118] Test treatment: Each test compound was dissolved in DMSO to prepare a 1% EC stock solution for standby. The inhibitory circle method was used to evaluate the in vitro bactericidal activity of the test compounds against the test targets at a dose of 50 ppm, and a water control (QCK) was set up separately. Test objects: Alternaria solani, Gibberella zeae, Pyricularia oryae, Phytophthora capsici, Sclerotinia sclerotiorum, Botrytis cinerea, Riziocotinia solani, Fusarium oxysporum, Cercospora arachidicola, and Physalospora piricola.

[0119] Test method: Use a pipette to aspirate 0.15 mL of the above-prepared EC stock solution and dissolve it in 2.85 mL of distilled water to prepare a test solution with an effective concentration of 500 ppm of the test compound. Use a pipette to aspirate 1 mL of the test solution and put it into a sterilized petri dish, then add 9 mL of PDA medium, shake well, and cool. Use a punch to cut out circular bacterial cakes and pick them to the center of the petri dish with an inoculation needle, and then place the petri dish in an incubator at 27 °C for cultivation. After 48 - 72 h, measure the colony diameter. The pure growth amount of the colony is the difference between the average colony diameter and the bacterial cake diameter, and the calculation method of the fungal inhibition rate refers to the following formula.

[0120]

[0121] The pure growth amount of the control colonies in the above calculation formula refers to the pure growth amount of colonies under the test of the clear water control (QCK).

[0122] The in vitro bactericidal results at a concentration of 50 mg / L are as follows:

[0123] A. Rhizoctonia oryzae: The inhibition rates of compounds T006, T019, T038, T042, T044, T047, T049, T051, T053, T065, T069, T071, and T073 against Rhizoctonia oryzae are all above 80%.

[0124] B. Sclerotinia sclerotiorum: The inhibition rates of compounds T006, T019, T038, T042, T044, T047, T049, T051, T053, T065, T069, and T071 against Sclerotinia sclerotiorum are all above 80%.

[0125] C. Physalospora piricola: The inhibition rates of compounds T006, T042, T053, and T065 against Physalospora piricola are all above 80%, and the inhibition rates of compounds T019, T038, T044, T047, T049, T051, T069, T071, and T073 against Physalospora piricola are all above 50%.

[0126] D. Magnaporthe oryzae: The inhibition rate of compound T053 against Magnaporthe oryzae is above 80%, and the inhibition rates of compounds T038, T042, T044, and T073 against Magnaporthe oryzae are above 50%.

Claims

1. A class of piperidine amide compounds containing trifluoromethyl oxadiazole-linked phenyl as shown in the following general formula (T): Wherein: R1 is selected from hydrogen or halogen; R2 and R3 are independently selected from hydrogen, C1-C3 alkyl, cyano-substituted C1-C3 alkyl, C3-C6 cycloalkyl, or phenyl or pyridyl substituted by at least one of hydrogen, halogen, nitro, C1-C3 alkyl, C1-C3 haloalkyl or C1-C3 haloalkoxy, or the structure shown in the following formula (1): X is selected from -CH2- or -CHR8-, where: R8 is selected from C1-C3 alkyl; R9, R 10 , R 11 are independently selected from hydrogen; -NR2R3 can also exist in the following cyclized form: R 12 and R 13 are independently selected from hydrogen; A is selected from oxygen.

2. The piperidine amide compound containing trifluoromethyl oxadiazole biphenyl as shown in the general formula (T) according to claim 1, characterized in that: In the general formula (T): R1 is selected from hydrogen or halogen; R2 and R3 are independently selected from hydrogen, methyl, ethyl, propyl, methoxy, ethoxy, 2,2,2-trifluoroethyl, cyanomethyl or C3-C6 cycloalkyl, or phenyl or pyridyl substituted by at least one of hydrogen, halogen, nitro, methyl, ethyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy, or the structure shown in the following formula (1): X is selected from -CHR8-, where: R8 is methyl, and R9, R 10 , R 11 are independently selected from hydrogen; -NR2R3 can also exist in the following cyclized form: R 12 、R 13 are independently selected from hydrogen; A is selected from oxygen.

3. The piperidine amide compound containing trifluoromethyl oxadiazole biphenyl as shown in the general formula (T) according to claim 2, characterized in that: The piperidine amide compounds containing trifluoromethyl oxadiazole-linked phenyl are selected from the following structures: 。 4. A method for preparing a piperidine amide compound containing a trifluoromethyl oxadiazole-linked phenyl group represented by the general formula (T) according to any one of claims 1-3, characterized in that: The preparation method includes: Wherein: the substituents R1, R 2、 R3 is defined as in claim 1, and the acylating agent is selected from thionyl chloride and / or oxalyl chloride.

5. The preparation method of the piperidine amide compound containing trifluoromethyl oxadiazole biphenyl group shown by the general formula (T) according to claim 4, characterized in that: The preparation method includes the following steps: (1) In a first solvent, intermediate (I), (II) and a base react to form intermediate (III); (2) Intermediate (III) is hydrolyzed and acidified to form intermediate (IV); (3) In a second solvent, intermediate (IV) reacts with an acyl chlorination reagent to form an intermediate acyl chloride; (4) In a third solvent, in the presence of a base, the intermediate acyl chloride reacts with R2R3-substituted amine to form the piperidine amide compounds containing trifluoromethyl oxadiazole-linked phenyl.

6. The preparation method of the piperidine amide compounds containing trifluoromethyl oxadiazole-linked phenyl as shown in the general formula (T) according to claim 5, characterized in that: In step (1), the reaction temperature is 0-100 °C, the first solvent is selected from at least one of N,N-dimethylformamide, toluene, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, acetonitrile and dimethyl sulfoxide; the base is selected from potassium carbonate or triethylamine; In step (2), the hydrolysis and acidification reaction are carried out in a sodium hydroxide-water-water-soluble organic solvent system, and the water-soluble organic solvent is selected from at least one of ethanol, methanol, 1,4-dioxane or tetrahydrofuran; In step (3), the second solvent is selected from at least one of N,N-dimethylformamide, toluene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrahydrofuran or dimethyl sulfoxide; In step (4), the third solvent is selected from at least one of N,N-dimethylformamide, toluene, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran or dimethyl sulfoxide; the base is selected from at least one of organic bases and inorganic bases.

7. The preparation method of the piperidine amide compounds containing trifluoromethyl oxadiazole-linked phenyl as shown in the general formula (T) according to claim 6, characterized in that: In step (1), the reaction temperature is 25-100 °C, the first solvent is selected from at least one of N,N-dimethylformamide, acetonitrile or tetrahydrofuran, and the base is potassium carbonate; In step (2), the water-soluble organic solvent is selected from ethanol or tetrahydrofuran; In step (3), the second solvent is selected from at least one of dichloromethane, chloroform or carbon tetrachloride; In step (4), the third solvent is selected from at least one of toluene, dichloromethane or tetrahydrofuran, and the base is selected from triethylamine or potassium carbonate.

8. Use of a piperidine amide compound containing a trifluoromethyl oxadiazole-linked phenyl group represented by the general formula (T) according to any one of claims 1-3, characterized in that: The piperidine amide compound containing a trifluoromethyl oxadiazole biphenyl group is used for agricultural sterilization.

9. Use of the piperidine amide compound containing trifluoromethyl oxadiazole biphenyl according to claim 8, characterized in that: The piperidine amide compound containing a trifluoromethyl oxadiazole biphenyl group is used for controlling at least one of the diseases of Rhizoctonia solani, Sclerotinia sclerotiorum, Physalospora piricola, Magnaporthe oryzae, Puccinia sorghi, Puccinia glycines or Puccinia triticina.

10. A pesticide formulation, characterized in that: The pesticide formulation contains 0.001%-99.99% by weight of the piperidine amide compound containing a trifluoromethyl oxadiazole biphenyl group represented by the general formula (T) according to any one of claims 1-3, and the rest is an agriculturally acceptable carrier.

11. A method for controlling diseases, characterized in that: The piperidine amide compound containing a trifluoromethyl oxadiazole biphenyl group represented by the general formula (T) according to any one of claims 1-3 is applied to the disease to be controlled or the medium for its growth.

12. The method for controlling diseases according to claim 11, wherein: The effective amount of the piperidine amide compound containing a trifluoromethyl oxadiazole biphenyl group applied to the disease to be controlled or the medium for its growth is 10 g to 1000 g per hectare.

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