A class of piperidine amide compounds containing trifluoromethyl oxadiazole-linked thiophene, a preparation method thereof and applications thereof

Abstract

The present invention discloses a class of piperidine amide compounds of trifluoromethyl oxadiazole - linked thiophene represented by the following general formula (T): Each substituent is as described in the specification. The present invention also discloses a preparation method and applications of the piperidine amide compounds of trifluoromethyl oxadiazole - linked thiophene. The piperidine amide compounds of trifluoromethyl oxadiazole - linked thiophene are particularly suitable for preventing and controlling diseases such as corn rust, soybean rust, rice sheath blight, rape sclerotinia, apple ring rot, or rice blast, 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-linked thiophene, a preparation method thereof, and an application thereof. Background Art

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

[0003] WO2015185485A, WO2019101511A, WO2019052932A, WO2018158365A, WO2018162643A, WO2018202487A, WO2020007658A, WO2020016180A have all disclosed a class of compounds containing trifluoromethyl oxadiazole-linked benzamide, but no reports on the same type of compounds with a piperidine amide structure have been seen, and no reports on the bactericidal activity of the same type of compounds containing a piperidine amide structure have been disclosed. 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-linked thiophene represented by the general formula (T):

[0005]

[0006] Wherein:

[0007] 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, hydroxyl, 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):

[0008]

[0009] In the formula, X is selected from -CH2- or -CHR8-, wherein:

[0010] R8 is selected from C1-C6 alkyl, halo C1-C6 alkyl, and the carbon atom connected to R8 is a chiral carbon atom, and the chiral carbon atom is in the left-handed configuration and / or the right-handed configuration;

[0011] 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 haloalkyl, C1-C6 haloalkoxy, C1-C6 alkoxycarbonyl or C1-C6 haloalkoxycarbonyl;

[0012] -NR2R3 can also exist in the following cyclized forms:

[0013]

[0014] wherein, R 12 , R 13 are independently selected from hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 haloalkyl, C1-C6 haloalkoxy; when R 12 and R 13 are not both 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.

[0015] Preferably, R2 and R3 are independently selected from hydrogen, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 haloalkyl, C1-C3 haloalkoxy, 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 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkoxycarbonyl or C1-C3 haloalkoxycarbonyl, or the structure shown in the following formula (1):

[0016]

[0017] X is selected from -CH2- or -CHR8-, wherein: R8 is selected from C1-C3 alkyl; R9, R 10 , R 11 are independently selected from hydrogen, cyano, halogen, nitro, phenoxy, formyl, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 haloalkoxy, C1-C3 alkoxycarbonyl, C1-C3 haloalkoxycarbonyl;

[0018] -NR2R3 can also exist in the following cyclized forms:

[0019]

[0020] R 12 and R13 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.

[0021] Further preferably, R2 and R3 are independently selected from hydrogen, methyl, ethyl, methoxy, ethoxy, 2,2,2-trifluoroethyl, cyanomethyl or C3-C6 cycloalkyl, or phenyl, 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):

[0022]

[0023] X is selected from -CHR8-, wherein: R8 is methyl, R9, R 10 、R 11 are independently selected from hydrogen, halogen or methyl;

[0024] -NR2R3 can also exist in the following cyclized form:

[0025]

[0026] R 12 、R 13 are independently selected from hydrogen, halogen, methyl, ethyl; A is selected from carbon or oxygen.

[0027] More preferably, the piperidine amide compounds containing trifluoromethyl oxadiazole thiophene are selected from the following structures:

[0028]

[0029]

[0030] 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 group including a cyclic chain form, 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 the alkyl is connected to an oxygen atom at the end, such as methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy and other groups; haloalkoxy refers to a group in which the alkyl is substituted by one or more halogen atoms and is connected to an oxygen atom at 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.

[0031] The piperidine amide compounds containing trifluoromethyl oxadiazole-linked thiophene 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 containing trifluoromethyl oxadiazole-linked thiophene represented by the general formula (T) of the present invention.

[0032]

[0033] Table 1. Some typical compounds and 1H NMR data

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043] In Table 1: s is singlet, b is broad singlet, d is doublet, dd is double doublet, t is triplet, q is quartet, m is multiplet.

[0044] The present invention also provides a preparation method of the piperidine amide compounds containing trifluoromethyl oxadiazole-linked thiophene represented by the general formula (T), and the preparation method includes:

[0045]

[0046] Wherein: the definitions of the substituents R2 and R3 are as described above, and the acyl chlorination reagent is selected from thionyl chloride and / or oxalyl chloride.

[0047] Specifically, the preparation method includes the following steps:

[0048] (1) In a first solvent, the intermediate (I), (II) and a base react to form an intermediate (III);

[0049] (2) The intermediate (III) is hydrolyzed and acidified to form an intermediate (IV);

[0050] (3) In a second solvent, the intermediate (IV) reacts with the acyl chlorination reagent to form an intermediate acyl chloride;

[0051] (4) In a third solvent and in the presence of a base, the intermediate acyl chloride reacts with an R2R3-substituted amine to form the piperidine amide compound containing trifluoromethyl oxadiazole-linked thiophene.

[0052] In step (1), the first solvent may be an organic solvent commonly used 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 to 100 °C, and preferably the reaction temperature is 25 to 100 °C.

[0053] 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 the hydrolysis is completed, it is acidified with hydrochloric acid to form intermediate (IV).

[0054] 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 preferably the reaction temperature is 25 °C to the reflux temperature of the solvent.

[0055] 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 preferably the reaction temperature is 0 to 25 °C.

[0056] The present invention also provides an application of the piperidine amide compound containing trifluoromethyl oxadiazole-linked thiophene represented by the general formula (T) as described above in agricultural sterilization.

[0057] As a preferred embodiment, the piperidine amide compound containing trifluoromethyl oxadiazole-linked thiophene represented by the general formula (T) is suitable for preventing and controlling at least one disease selected from Rhizoctonia solani, Sclerotinia sclerotiorum, Physalospora piricola, Magnaporthe oryzae, Puccinia sorghi, Puccinia glycines or Puccinia triticina.

[0058] As another preferred embodiment, the piperidine amide compounds containing trifluoromethyl oxadiazole - linked thiophene represented by the general formula (T) are particularly suitable for sterilizing agricultural crops such as rice, wheat, cotton, corn, soybean, vegetables, and rapeseed.

[0059] The present invention also provides a pesticide formulation, which contains 0.001% - 99.99% by weight of the piperidine amide compounds containing trifluoromethyl oxadiazole - linked thiophene 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.

[0060] The pesticide formulation provided by the present invention, in addition to containing 0.001% - 99.99% by weight of the piperidine amide compounds containing trifluoromethyl oxadiazole - linked thiophene represented by the general formula (T), may further contain agriculturally acceptable carriers.

[0061] The carriers 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, hexamethylene diamine. Liquid carriers include water and organic solvents. When water is used as a 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 isopropyl alcohol, butanol, ethylene glycol, glycerol, and cyclohexanol, etc.; and their ethers and esters; and ketones, such as acetone, cyclohexanone, as well as dimethylformamide and N - methyl - pyrrolidone.

[0062] The carriers can also be surfactants. 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 lignin sulfonate, Nekal, calcium lignin sulfonate, methylnaphthalene sulfonic acid formaldehyde condensate, etc. Wetting agents are: sodium lauryl sulfate, sodium dodecylbenzenesulfonate, alkylnaphthalene sulfonate, etc.

[0063] The present invention also provides a method for sterilization, which includes: applying the piperidine amide compound containing trifluoromethyl oxadiazole-linked thiophene represented 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-linked thiophene represented 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.

[0064] The piperidine amide compound containing trifluoromethyl oxadiazole-linked thiophene represented by the general formula (T) provided by the present invention has the following advantages compared with the prior art:

[0065] (1) The compound has a novel structure;

[0066] (2) The compound has high bactericidal activity against Rhizoctonia solani, Sclerotinia sclerotiorum, Physalospora piricola, Magnaporthe oryzae, Puccinia sorghi, Puccinia pittieriana, and Puccinia triticina, etc., and has high bactericidal activity at low concentrations, especially against Puccinia pittieriana and Puccinia sorghi. Specific embodiments

[0067] 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 solutions, improvement solutions, and equivalent solutions that may be included within the scope of the claims.

[0068] I. Compound synthesis

[0069] Example 1. Synthesis of the target compound T001

[0070] (1) Synthesis of intermediate (III)

[0071] 0.08 mol of intermediate (I) was added to a 500 mL round-bottom flask, 200 mL of acetonitrile was added, and then anhydrous potassium carbonate (13.80 g, 0.10 mol) and intermediate (II) (15.70 g, 0.10 mol) were added. The mixture was stirred at 40 °C, and the reaction was monitored by TLC. After 6 h, the reaction was complete. The mixture was filtered, concentrated, and separated by column chromatography to obtain intermediate (III). The 1H NMR spectrum is as follows:

[0072] 1H NMR (CDCl3, 400 MHz) δ: 7.67 (d, 1H, J = 3.6 Hz, Thiophene-H), 6.92 (d, 1H, J = 3.6 Hz, Thiophene-H), 4.10 (q, 2H, J = 7.2 Hz, CH2), 3.69 (s, 2H, CH2), 2.86 - 2.89 (m, 2H, peridine-H), 2.21 - 2.29 (m, 1H, peridine-H), 2.06 - 2.13 (m, 2H, peridine-H), 1.84 - 1.89 (m, 2H, peridine-H), 1.70 - 1.80 (m, 2H, peridine-H), 1.22 (t, 3H, J = 7.2 Hz, CH3).

[0073] (2) Synthesis of Intermediate (IV)

[0074] Add 0.05 mol of Intermediate (III) to a 500 mL round-bottom flask, add 100 mL of tetrahydrofuran and stir until completely dissolved. Then add 100 mL of water and sodium hydroxide (4.00 g, 0.10 mol), stir at room temperature, monitor by TLC, stop the reaction after 12 h when the reaction is complete. Neutralize with concentrated hydrochloric acid, adjust the pH to 1 - 2, a white solid precipitates, filter, dry to obtain Intermediate (IV).

[0075] Its NMR data are as follows: 1H NMR (DMSO-d6, 400 MHz) δ: 7.74 (d, 1H, J = 3.6 Hz, Thiophene-H), 7.10 (d, 1H, J = 3.6 Hz, Thiophene-H), 3.72 (s, 2H, CH2), 2.77 - 2.82 (m, 2H, peridine-H), 2.14 - 2.22 (m, 1H, peridine-H), 2.03 - 2.09 (m, 2H, peridine-H), 1.75 - 1.80 (m, 2H, peridine-H), 1.49 - 1.59 (m, 2H, peridine-H).

[0076] (3) Synthesis of Target Compound T001

[0077] Take 0.30 mmol of Intermediate (IV) and add it to a 50 mL round-bottom flask. Add 15 mL of dichloromethane, stir evenly, add 1 drop of DMF, slowly add 1 mL of oxalyl chloride dropwise, heat under reflux for 4 hours. After the reaction is complete, evaporate all the solvents. Add 15 mL of dichloromethane, add 0.70 mmol of triethylamine and 0.35 mmol of 2-methylaniline while stirring, stir at room temperature for 1 h, concentrate and separate by TLC to obtain the target compound.

[0078]

[0079] Its NMR data are as follows: 1H NMR (400 MHz, CDCl3 / TMS): δ: 7.77 (d, 1H, J = 8.0 Hz, Ph-H), 7.71 (d, 1H, J = 3.6 Hz, Thiophene-H), 7.15 - 7.21 (m, 2H, Ph-H), 7.04 - 7.08 (m, 1H, Ph-H), 6.97 (d, 1H, J = 3.6 Hz, Thiophene-H), 3.76 (s, 2H, CH2), 3.01 - 3.06 (m, 2H, Piperidine-H), 2.26 - 2.34 (m, 1H, Piperidine-H), 2.23 (s, 3H, CH3), 2.12 - 2.18 (m, 2H, Piperidine-H), 1.87 - 1.99 (m, 4H, Piperidine-H). For other compounds described in Table 1, the same method can be referred to for synthesis.

[0080] II. Preparation Formulation

[0081] The following examples illustrate the processing and formulation of preparations using the piperidine amide compounds containing trifluoromethyl oxadiazole - linked thiophene represented by the general formula (T) provided by the present invention as the active ingredient component. In the following examples, all "%" refer to weight percentages.

[0082] Example 2. Wettable Powder

[0083] Mix 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 evenly, and then pulverize to obtain the wettable powder.

[0084] Example 3. Emulsifiable Concentrate

[0085] Mix 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 by heating and stirring evenly to obtain the emulsifiable concentrate.

[0086] Example 4. Granules

[0087] Mix 5% of compound (I) (Table 1), 1% of polyvinyl alcohol (PVA), 4% of naphthalene sulfonate formaldehyde condensate (NMO), and 90% of clay evenly, and then pulverize. Then add 20 parts of water to 100 parts of this mixture, knead, and use an extrusion granulator to make granules with a mesh size of 14 - 32, and dry to obtain the granules.

[0088] Example 5, Water Dispersible Granules

[0089] 20% of Compound (I) (Table 1), 4% of naphthalene sulfonate formaldehyde condensate, 1% of naphthalene sulfonate, 2% of silica white, and 73% of kaolin were mixed and pulverized, then kneaded with water, and granulated in a granulator equipped with a sieve of a certain specification. Then, it was dried and screened (according to the sieve range) to obtain the granular product.

[0090] Example 6, Aqueous Suspension Concentrate

[0091] 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%) were pre-mixed evenly, then sanded in a sand mill, and the filtered suspension mother liquor was added with a prepared xanthan gum (0.1%) aqueous solution and shear-mixed evenly.

[0092] III. Biological Activity Tests

[0093] The following are 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.

[0094] Example 7, Determination of Bactericidal Activity

[0095] (1) In vivo bactericidal activity test:

[0096] The target of the bactericidal test was Puccinia sorghi.

[0097] The leaf inoculation method was adopted for the test. Two pots of potted corn seedlings with the same growth at the true leaf stage were selected. The sample was dissolved in an appropriate amount of DMF solvent and formulated into liquid medicines with concentrations of 200, 100, 50, and 25 mg / L. The liquid medicines were sprayed on the leaf surface. After the medicine spray was dried, the inoculation cakes were placed on the leaves. After moisturizing in the dark at 24 - 26°C for 24 hours, the natural light was restored and the plants were cultured with moisturizing for about 3 days. After the control was fully diseased, the diameter of the disease spots at each inoculation point was measured with a caliper, and the control efficacy was calculated.

[0098] After the test treatment, the disease occurrence and mycelial growth of the leaves and plants were observed and recorded. According to the disease index and mycelial diameter, referring to the fungicide volume of "SOP for the Evaluation of the Biological Activity of Novel Pesticides", the relative control efficacy was calculated according to the disease index.

[0099] Formula for calculating the bactericidal efficacy

[0100] Disease index = 100 × ∑(number of diseased leaves at each level × representative value at each level) / (total number of leaves investigated × representative value at the highest level);

[0101] Control effect (%) = 100 × (control disease index - treated disease index) / control disease index.

[0102] The results of the bactericidal activity evaluation are as follows.

[0103] At a concentration of 200 mg / L, the control effects of compounds T006, T007, T010, T023, T025, T027, T028, T029, T030, T032, T033, T038, T039, T041, T045, T046 against corn rust were greater than 70%;

[0104] At a concentration of 200 mg / L, the control effects of compounds T001, T002, T003, T011, T012, T016, T019, T035, T040 against corn rust were greater than 50%;

[0105] (2) In vitro bactericidal activity test

[0106] Test treatment: Each test compound was dissolved in DMSO to prepare a 1% EC stock solution for standby. The inhibitory zone 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. Test objects: Alternaria solani, Gibberella zeae, Pyricularia oryae, Phytophthora capsici, Sclerotinia sclerotiorum, Botrytis cinerea, Riziocotinia solani, Fusarium oxysporum, Cercospora arachidicola, and Physalospora piricola.

[0107] 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 into a sterilized petri dish, then add 9 mL of PDA medium, shake well, and cool. Use a punch to cut out circular agar discs 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 incubation. 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 agar disc diameter. The calculation method of the fungal inhibition rate refers to the following formula.

[0108]

[0109] 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).

[0110] In vitro bactericidal results at a concentration of 50 mg / L:

[0111] A. Rhizoctonia oryzae: The inhibition rates of compounds T006, T007, T010, T023, T025, T028, T029, T030, T032, T033, T038, T039, T041, T045, and T046 against Rhizoctonia oryzae are all above 80%, and the inhibition rate of compound T027 against Rhizoctonia oryzae is above 60%.

[0112] B. Sclerotinia sclerotiorum: The inhibition rates of compounds T007, T010, T023, T025, T027, T028, T029, T030, T033, T038, T039, T041, T045, and T046 against Sclerotinia sclerotiorum are all above 80%, and the inhibition rates of compounds T006 and T032 against Sclerotinia sclerotiorum are above 60%.

[0113] C. Physalospora piricola: The inhibition rates of compounds T007 and T028 against Physalospora piricola are all above 80%, and the inhibition rates of compounds T006, T010, T023, T025, T027, T029, T030, T032, T033, T038, T039, T041, T045, and T046 against Physalospora piricola are all above 60%.

[0114] D. Magnaporthe oryzae: The inhibition rates of compounds T027 and T028 against Magnaporthe oryzae are above 60%.

Claims

1. A class of piperidine amide compounds containing trifluoromethyl oxadiazole - linked thiophene as shown in the following general formula (T): Wherein: R2 and R3 are independently selected from hydrogen, C1 - C3 alkyl, C1 - C3 alkoxy, C3 - C6 cycloalkyl, or phenyl substituted by at least one of hydrogen, halogen, nitro, C1 - C3 alkyl, and C1 - C3 haloalkyl.

2. The piperidine amide compound containing trifluoromethyl oxadiazole-linked thiophene represented by the general formula (T) according to claim 1, characterized in that: In the general formula (T): R2 and R3 are independently selected from hydrogen, methyl, ethyl, methoxy, ethoxy, 2,2,2 - trifluoroethyl or C3 - C6 cycloalkyl, or phenyl substituted by at least one of hydrogen, halogen, nitro, methyl, ethyl, and trifluoromethyl.

3. The piperidine amide compound containing trifluoromethyl oxadiazole-linked thiophene represented by the general formula (T) according to claim 2, characterized in that: The piperidine amide compounds containing trifluoromethyl oxadiazole - linked thiophene are selected from the following structures: 。 4. A method for preparing a piperidine amide compound containing trifluoromethyl oxadiazole - linked thiophene represented by the general formula (T) according to any one of claims 1 - 3, characterized in that: The preparation method includes: Wherein: The definitions of substituents R2 and R3 are as in claim 1, and the acyl chlorination reagent is selected from thionyl chloride and / or oxalyl chloride.

5. The preparation method of the piperidine amide compound containing trifluoromethyl oxadiazole-linked thiophene represented 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) undergoes hydrolysis and acidification reactions to form intermediate (IV); (3) In a second solvent, intermediate (IV) reacts with the 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 thiophene.

6. The preparation method of the piperidine amide compounds containing trifluoromethyl oxadiazole - linked thiophene 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 reactions 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, and tetrahydrofuran; In step (3), the second solvent is selected from at least one of N,N - dimethylformamide, toluene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrahydrofuran, and dimethyl sulfoxide; In step (4), the third solvent is selected from at least one of N,N - dimethylformamide, toluene, dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, and 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 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, and 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, and 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 trifluoromethyl oxadiazole-linked thiophene represented by the general formula (T) according to any one of claims 1-3, characterized in that: The piperidine amide compound containing trifluoromethyl oxadiazole-linked thiophene is used for agricultural sterilization.

9. Use of the piperidine amide compound containing trifluoromethyl oxadiazole-linked thiophene according to claim 8, characterized in that: The piperidine amide compound 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 preparation contains 0.001%-99.99% by weight of the piperidine amide compound containing trifluoromethyl oxadiazole-linked thiophene 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 trifluoromethyl oxadiazole-linked thiophene 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, characterized in that: The effective amount of the piperidine amide compound containing trifluoromethyl oxadiazole-linked thiophene 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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