A 2-amido tert-butyl sulfonamide compound and its preparation method and application

Abstract

The present invention relates to the technical field of agricultural chemicals, and in particular to a 2-amido tert-butyl sulfonamide compound and a preparation method and application thereof. The compound has the following general formula: 1 The group is 2,4,5-trichlorophenyl, 2,4,6-tribromophenyl or 2-trifluoromethyl-4-chlorophenyl; R 2 The group is an alkyl, benzyl, phenyl or heterocyclic group. The 2-amido tert-butyl sulfonamide compounds provided by the present invention are used for the prevention and treatment of diseases caused by fungi and oomycetes such as rape sclerotinia, tomato gray mold, rice sheath blight, rice blast, graminearum sickle, pepper phytophthora, and the like; and for the prevention and treatment of diseases caused by bacteria such as citrus canker, rice bacterial blight, cabbage soft rot, melon fruit spot, and tomato canker.

Description

Technical Field

[0001] The present invention relates to the technical field of agricultural chemicals, and in particular to a 2-amido tert-butyl sulfonamide compound and a preparation method and application thereof. Background Art

[0002] Sulfonamide compounds have been the focus of scientific researchers since their discovery. Compounds containing sulfonamide groups have a wide range of biological activities and are widely used in the field of drug molecule design. They are a very important type of active compound. Sulfonamide compounds are the first drugs discovered by humans that have selective effects on bacteria, and they can be systematically applied to various problems caused by bacterial infections. Sulfonamide compounds have a wide range of biological activities in medicine and pesticides, such as bactericidal, weed-killing, insecticidal, anti-cancer, anti-diabetic, etc. In recent years, there have been many studies on sulfonamide compounds, and highly effective and low-toxic fungicides such as Flusulfamide and Tolnifanide have been developed. In the field of fungicides, sulfonamide products are rare, and the only widely used one on the market is Cyazofamid. 2-Oxocyclododecanesulfonamide has good inhibitory activity against a variety of plant pathogens. Based on this, 2-oxocycloalkylsulfonamide compounds were studied in depth, and a candidate fungicide variety, chesulfamide, was developed for the prevention and control of tomato gray mold (Botrytis cinerea) and cucumber leaf spot (Corynes poracassiicola).

[0003]

[0004] In the process of designing new pesticide molecules, the introduction of active fragments requires the help of bridging groups. Amide groups are the most common bridging groups in compound molecules, used to bridge other active fragments, and play a very important role in the creation of new pesticides. Most amide compounds have the advantages of high efficiency, low toxicity, low residue, and easy degradation. These unique biological activities also meet the conditions for creating green pesticides.

[0005] Therefore, how to provide a 2-amido tert-butyl sulfonamide compound and a preparation method and application thereof is a technical problem that needs to be solved urgently by those skilled in the art. Summary of the invention

[0006] The purpose of the present invention is to provide a 2-amido tert-butyl sulfonamide compound and a preparation method and application thereof in view of the deficiencies in the prior art, so as to solve the technical problems of low efficiency, high toxicity, easy residue and difficult degradation existing in the existing fungicides.

[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0008] The present invention provides a 2-amido tert-butyl sulfonamide compound having the following structure:

[0009]

[0010] Where: R 1 The group is 2,4,5-trichlorophenyl, 2,4,6-tribromophenyl or 2-trifluoromethyl-4-chlorophenyl; R 2 The group is an alkyl group, a benzyl group, a phenyl group or a heterocyclic group.

[0011] Preferably, the R 2 The groups are ClCH2-, Cl2CH-, Cl3C-, CH3-, CH3CH2-, CH3(CH2)2-, CH3(CH2)6-, C6H5-CH2-, 4-F-C6H4-CH2-, 4-F-C6H4-, 3-F-C6H4-, 2-F-C6H4-, 4-Br-C6H4-, 3-Br-C6H4-, 2-Br-C6H4-, 4-Cl-C6H4-, 3 -Cl-C6H4-, 2-Cl-C6H4-, 4-CF3-C6H4-, 3-CF3-C6H4-, 2-CF3-C6H4-, C6H5-, 4-CH3-C6H4-, 3-CH 3-C6H4-, 2-CH3-C6H4-, 4-CF3O-C6H4-, 2,6-Cl2-C6H3-, 5-Cl-2-OCH3-C6H3-, 3,5-CH3-C6H3- or

[0012] The present invention also provides a method for preparing a 2-amido tert-butyl sulfonamide compound, comprising the following steps:

[0013] (1) mixing 3,3-dimethyl-2-oxobutanesulfonic acid potassium salt and oxalyl chloride in a solvent for reaction to obtain a solution of 3,3-dimethyl-2-oxobutanesulfonyl chloride; mixing the obtained solution of 3,3-dimethyl-2-oxobutanesulfonyl chloride with a substituted amine, triethylamine and dichloromethane, and then performing an amination reaction to obtain N-substituted-3,3-dimethyl-2-oxobutanesulfonamide;

[0014] (2) mixing N-substituted-3,3-dimethyl-2-oxobutanesulfonamide, tetraisopropyl titanate and sodium borohydride in a solvent for an amination reaction under the condition of introducing ammonia gas to obtain N-substituted-3,3-dimethyl-2-aminobutanesulfonamide;

[0015] (3) Mixing substituted acid chloride, N-substituted-3,3-dimethyl-2-aminobutanesulfonamide and triethylamine in a solvent for amidation reaction to obtain 2-amido tert-butylsulfonamide compounds.

[0016] Preferably, in step (1), step (2) and step (3), the reaction temperature is independently 20 to 40° C., and the reaction time is independently 2 to 5 h.

[0017] Preferably, in step (1), the solvent is a mixed solution of N,N-dimethylformamide and dichloromethane; the dosage ratio of the potassium salt of 3,3-dimethyl-2-oxobutanesulfonic acid, N,N-dimethylformamide, dichloromethane and oxalyl chloride is 0.05-0.20 mol: 2-7 mL: 70-300 mL: 0.05-0.20 mol.

[0018] Preferably, in step (1), the usage ratio of the potassium salt of 3,3-dimethyl-2-oxobutanesulfonic acid, the substituted amine, triethylamine and dichloromethane is 0.05-0.15 mol: 0.03-0.10 mol: 0.03-0.10 mol: 60-180 mL.

[0019] Preferably, in step (2), the solvent is ethanol; the dosage ratio of the N-substituted-3,3-dimethyl-2-oxobutanesulfonamide, tetraisopropyl titanate, sodium borohydride and ethanol is 0.01-0.08 mol: 0.01-0.08 mol: 0.03-0.30 mol: 10-250 mL.

[0020] Preferably, in step (3), the solvent is dichloromethane, and the amount ratio of the N-substituted-3,3-dimethyl-2-aminobutanesulfonamide, substituted acid chloride, triethylamine and dichloromethane is 1-5 mmol: 1.5-9 mmol: 1.5-9 mmol: 10-60 mL.

[0021] The present invention also provides the use of 2-amido tert-butyl sulfonamide compounds in agricultural fungicides, wherein the 2-amido tert-butyl sulfonamide compounds are used for preventing and controlling one or several pathogenic fungi, oomycetes and pathogenic bacteria; for preventing and controlling one or several fungi and oomycetes diseases selected from rapeseed sclerotinia rot, tomato gray mold, rice sheath blight, rice blast, graminearum sclerotinia and pepper phytophthora; and for preventing and controlling one or several bacterial diseases selected from citrus canker, rice white leaf blight, cabbage soft rot, melon fruit spot and tomato canker.

[0022] Beneficial effects of the present invention:

[0023] The 2-amido tert-butyl sulfonamide compounds prepared by the present invention are used for preventing and controlling pathogenic fungi, oomycetes and pathogenic bacteria in plants; for preventing and controlling diseases caused by fungi and oomycetes such as rape sclerotinia, tomato gray mold, rice sheath blight, rice blast, graminearum sickle and pepper phytophthora; and for preventing and controlling diseases caused by bacteria such as citrus canker, rice bacterial leaf blight, cabbage soft rot, melon fruit spot and tomato canker. DETAILED DESCRIPTION

[0024] The present invention provides a 2-amido tert-butyl sulfonamide compound having the following structure:

[0025]

[0026] Where: R 1 The group is 2,4,5-trichlorophenyl, 2,4,6-tribromophenyl or 2-trifluoromethyl-4-chlorophenyl; R 2 The group is an alkyl group, a benzyl group, a phenyl group or a heterocyclic group.

[0027] In the present invention, the R 1 The group is preferably 2,4,5-trichlorophenyl or 2-trifluoromethyl-4-chlorophenyl, and more preferably 2,4,5-trichlorophenyl; R 2 The group is preferably an alkyl group, a phenyl group or a heterocyclic group, and more preferably an alkyl group or a phenyl group.

[0028] In the present invention, the R 2 The groups are ClCH2-, Cl2CH-, Cl3C-, CH3-, CH3CH2-, CH3(CH2)2-, CH3(CH2)6-, C6H5-CH2-, 4-F-C6H4-CH2-, 4-F-C6H4-, 3-F-C6H4-, 2-F-C6H4-, 4-Br-C6H4-, 3-Br-C6H4-, 2-Br-C6H4-, 4-Cl-C6H4-, 3-Cl-C6H4-, 2-Cl-C6H4-, 4-CF3-C6H4-, 3-CF 3- C6H4-, 2-CF3-C6H4-, C6H5-, 4-CH 3- C6H4-、3-CH 3- C6H4-, 2-CH3-C6H4-, 4-CF3O-C6H4-, 2,6-Cl2-C6H3-, 5-Cl-2-OCH3-C6H3-, 3,5-CH3-C6H3- or Preferably, ClCH2-, Cl2CH-, Cl3C-, CH3-, CH3CH2-, CH3(CH2)2-, CH3(CH2)6-, C6H5-CH2-, 4-F-C6H4-CH2-, 4-F-C6H4-, 3-F-C6H4-, 2-F-C6H4-, 4-Br-C6H4-, 3-Br-C6H4-, 2-Br-C6H4-, 4-Cl-C6H4-, 3-Cl-C6H4-, 2-Cl-C6H4-, 4-CF3-C6H4-, 3-CF 3- C6H4-, 2-CF3-C6H4-, C6H5-, 4-CH 3- C6H4-、3-CH 3- C6H4-, 2-CH3-C6H4-, 4-CF3O-C6H4-, 2,6-Cl2-C6H3-, 5-Cl-2-OCH3-C6H3-, or 3,5-CH3-C6H3-, and more preferably ClCH2-, Cl2CH-, Cl3C-, CH3-, CH3CH2-, CH3(CH2)2-, CH3(CH2)6-, C6H5-CH2-, 4-F-C6H4-CH2-, 4-F-C6H4-, 3-F-C6H4-, 2-F-C6H4-, 4-Br-C6H4-, 3-Br-C6H4-, 2-Br-C6H4-, 4-Cl-C6H4-, 3-Cl-C6H4-, 2-Cl-C6H4-, 4-CF3-C6H4-, 3-CF 3- C6H4-, 2-CF3-C6H4-, C6H5-, 4-CH 3- C6H4-、3-CH 3- C6H4-, 2-CH3-C6H4-, 4-CF3O-C6H4-, 2,6-Cl2-C6H3- or 5-Cl-2-OCH3-C6H3-.

[0029] The present invention also provides a method for preparing a 2-amido tert-butyl sulfonamide compound, comprising the following steps:

[0030] (1) mixing 3,3-dimethyl-2-oxobutanesulfonic acid potassium salt and oxalyl chloride in a solvent for reaction to obtain a solution of 3,3-dimethyl-2-oxobutanesulfonyl chloride; mixing the obtained solution of 3,3-dimethyl-2-oxobutanesulfonyl chloride with a substituted amine, triethylamine and dichloromethane, and then performing an amination reaction to obtain N-substituted-3,3-dimethyl-2-oxobutanesulfonamide;

[0031] (2) mixing N-substituted-3,3-dimethyl-2-oxobutanesulfonamide, tetraisopropyl titanate and sodium borohydride in a solvent for an amination reaction under the condition of introducing ammonia gas to obtain N-substituted-3,3-dimethyl-2-aminobutanesulfonamide;

[0032] (3) Mixing substituted acid chloride, N-substituted-3,3-dimethyl-2-aminobutanesulfonamide and triethylamine in a solvent for amidation reaction to obtain 2-amido tert-butylsulfonamide compounds.

[0033] In the present invention, in step (1), step (2) and step (3), the reaction temperature is independently 20 to 40°C, preferably 22 to 38°C, and more preferably 25 to 35°C; the reaction time is independently 2 to 5h, preferably 2.5 to 4.5h, and more preferably 3 to 4h.

[0034] In the present invention, in step (1), the substituted amine, triethylamine and dichloromethane are first cooled in an ice-water bath, and then a solution of 3,3-dimethyl-2-oxobutanesulfonyl chloride is added to react.

[0035] In the present invention, in step (1), the temperature at which the solution of 3,3-dimethyl-2-oxobutanesulfonyl chloride is mixed with the substituted amine, triethylamine and dichloromethane is 0 to 5°C, preferably 1 to 4°C, and more preferably 2 to 3°C.

[0036] In the present invention, in step (1), the solvent is a mixed solution of N,N-dimethylformamide and dichloromethane; the dosage ratio of the potassium salt of 3,3-dimethyl-2-oxobutanesulfonic acid, N,N-dimethylformamide, dichloromethane and oxalyl chloride is 0.05-0.20 mol: 2-7 mL: 70-300 mL: 0.05-0.20 mol, preferably 0.08-0.18 mol: 3-6 mL: 100-250 mL: 0.08-0.18 mol, and more preferably 0.10-0.15 mol: 4-5 mL: 150-200 mL: 0.10-0.15 mol.

[0037] In the present invention, in step (1), the usage ratio of the potassium salt of 3,3-dimethyl-2-oxobutanesulfonic acid, the substituted amine, triethylamine and dichloromethane is 0.05-0.15 mol: 0.03-0.10 mol: 0.03-0.10 mol: 60-180 mL, preferably 0.07-0.13 mol: 0.04-0.08 mol: 0.04-0.08 mol: 80-160 mL, and further preferably 0.09-0.12 mol: 0.05-0.07 mol: 0.05-0.07 mol: 100-130 mL.

[0038] In the present invention, in step (2), the solvent is ethanol; the dosage ratio of the N-substituted-3,3-dimethyl-2-oxobutanesulfonamide, tetraisopropyl titanate, sodium borohydride and ethanol is 0.01-0.08 mol: 0.01-0.08 mol: 0.03-0.30 mol: 10-250 mL, preferably 0.03-0.07 mol: 0.03-0.07 mol: 0.05-0.25 mol: 50-200 mL, and further preferably 0.04-0.06 mol: 0.04-0.06 mol: 0.10-0.20 mol: 100-150 mL.

[0039] In the present invention, in step (3), the solvent is dichloromethane, and the amount ratio of the N-substituted-3,3-dimethyl-2-aminobutanesulfonamide, substituted acid chloride, triethylamine and dichloromethane is 1-5mmol:1.5-9mmol:1.5-9mmol:10-60mL, preferably 2-4.5mmol:2-8mmol:2-8mmol:15-55mL, and more preferably 2.5-4mmol:2.5-7mmol:3-7mmol:25-50mL.

[0040] In the present invention, the synthetic route of the 2-amido tert-butyl sulfonamide compounds is as follows:

[0041]

[0042] In the present invention, the potassium salt of 3,3-dimethyl-2-oxobutanesulfonic acid can be obtained by mixing 3,3-dimethyl-2-butanone, sulfur trioxide·dioxane adduct and anhydrous potassium carbonate in a solvent for sulfonation reaction.

[0043] In the present invention, the temperature of the sulfonation reaction is -5 to 5°C, preferably -4 to 4°C, more preferably -3 to 3°C, and the time of the sulfonation reaction is 1 to 4h, preferably 1.5 to 3h, more preferably 2 to 2.5h.

[0044] In the present invention, the molar ratio of the 3,3-dimethyl-2-butanone solution, sulfur trioxide·dioxane adduct and anhydrous potassium carbonate is 0.5-1.5:0.5-1.8:0.25-1.8, preferably 0.8-1.3:0.8-1.5:0.6-1.5, and more preferably 0.9-1.1:0.9-1.2:0.8-1.2.

[0045] The present invention also provides the use of 2-amido tert-butyl sulfonamide compounds in agricultural fungicides, wherein the 2-amido tert-butyl sulfonamide compounds are used for preventing and controlling one or several pathogenic fungi, oomycetes and pathogenic bacteria; for preventing and controlling one or several fungi and oomycetes diseases selected from rapeseed sclerotinia rot, tomato gray mold, rice sheath blight, rice blast, graminearum sclerotinia and pepper phytophthora; and for preventing and controlling one or several bacterial diseases selected from citrus canker, rice white leaf blight, cabbage soft rot, melon fruit spot and tomato canker.

[0046] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0047] Example 1

[0048] Taking compound LCJ-1 as an example, the specific preparation process is as follows:

[0049]

[0050] The preparation process is as follows: under nitrogen, 150mL of dichloromethane, 0.09mol of 3,3-dimethyl-2-oxo-butanesulfonic acid potassium, and 3.6mL of DMF are stirred evenly, and 0.10mol of oxalyl chloride is slowly added dropwise, and the reaction is stirred at 25°C for 3h; the filtrate is filtered and slowly added dropwise to the reaction solution composed of 0.06mol2,4,5-trichloroaniline, 0.06mol triethylamine, and 120mL of dichloromethane, which has been cooled in an ice water bath, and the reaction temperature is controlled at 0°C during the addition. After the addition is completed, the temperature is naturally raised and the reaction is carried out for 3h. At this time, the reaction solution is an orange transparent solution. The reaction progress is monitored by TLC [V (petroleum ether): V (ethyl acetate) = 4:1]. The result shows that the reaction is stopped when there is no raw material in the reaction solution, and the post-treatment operation is carried out. The reaction solution is washed three times with 75mL3mol / L hydrochloric acid, 50mL saturated sodium bicarbonate, and 50mL distilled water. The washed reaction solution was dried with anhydrous Na2SO4 for 3 hours, filtered, and the filtrate was evaporated to dryness using a rotary evaporator to obtain a crude product. Recrystallization was performed using acetone + petroleum ether to obtain N-substituted-3,3-dimethyl-2-oxobutanesulfonamide;

[0051] Ammonia gas was introduced into a mixed solution of 120 mL of ethanol, 0.03 mol of N-substituted-3,3-dimethyl-2-oxobutanesulfonamide, and 0.03 mol of tetraisopropoxytitanium to react for 5 h; 0.08 mol of sodium borohydride was added in small amounts and multiple times to react for 5 h, and N-substituted-3,3-dimethyl-2-aminobutanesulfonamide was obtained after post-treatment and recrystallization with methanol;

[0052] 4.5 mmol chloroacetyl chloride was added dropwise into a mixture of 30 mL dry dichloromethane, 3 mmol N-substituted-3,3-dimethyl-2-aminobutanesulfonamide and 4.5 mmol dry triethylamine to react for 3 h. After post-treatment, the compound LCJ-1 was separated by column chromatography (V petroleum ether: V ethyl acetate = 10:1).

[0053] Embodiments 2 to 30

[0054] The substituents of the above-mentioned substituted acid chlorides are respectively Cl2CH-, Cl3C-, CH3-, CH3CH2-, CH3(CH2)2-, CH3(CH2)6-, C6H5-CH2-, 4-F-C6H4-CH2-, 4-F-C6H4-, 3-F-C6H4-, 2-F-C6H4-, 4-Br-C6H4-, 3-Br-C6H4-, 2-Br-C6H4-, 4-Cl-C6H4-, 3-Cl-C6H4-, 2-Cl-C 6H4-, 4-CF3-C6H4-, 3-CF3-C6H4-, 2-CF3-C6H4-, C6H5-, 4-CH3-C6H4-, 3-CH3-C6H4-, 2-CH3-C6H4-, 4-CF3O-C6H4-, 2,6-Cl2-C6H3-, 5-Cl-2-OCH3-C6H3-, 3,5-CH3-C6H3-, SC4H3-, to obtain compounds LCJ-2 to LCJ-30 of Examples 2 to 30, respectively.

[0055] Embodiment 31

[0056] When the substituted amine is 2,4,5-tribromoaniline and the substituent of the substituted acid chloride is ClCH2-, compound LCJ-31 is obtained.

[0057] Embodiments 32 to 34

[0058] When the substituted amine is 2-trifluoromethyl-4-chloroaniline and the substituents of the substituted acid chloride are ClCH2-, 3-Br-C6H4-, and SC4H3-, respectively, compounds LCJ-32 to LCJ-34 of Examples 32 to 34 are obtained.

[0059] The physicochemical data of the compounds LCJ-1 to LCJ-34 prepared in Examples 1 to 34 are shown in Table 1 below; 1 HNMR and 13 The CNMR data are shown in Table 2; their HRMS data are shown in Table 3.

[0060] Table 1 Physicochemical data of compounds LCJ-1 to LCJ-34

[0061]

[0062]

[0063]

[0064]

[0065] Table 2 Compounds LCJ-1 to LCJ-34 1 HNMR and 13 CNMR Data

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075] Table 3 HRMS data of compounds LCJ-1 to LCJ-34

[0076]

[0077]

[0078]

[0079] The above embodiments 1 to 34 were tested for performance:

[0080] (I) Determination of fungicidal activity of compounds LCJ-1 to LCJ-34 against various plant pathogens

[0081] The mycelium growth rate method was used to determine the fungicidal activity of the compounds against various plant pathogens. The specific method is as follows:

[0082] The sample compounds were weighed and dissolved in acetone, and the concentration was 5000μg / mL test reagents were prepared and placed in a low-temperature refrigerator for activity determination. Under sterile conditions, 0.33mL of the agent with a concentration of 5000μg / mL was mixed evenly with 33mL of melted (60±5℃) PDA medium to prepare 33mL of toxic medium with a concentration of 50μg / mL, and then 33mL of toxic medium was evenly poured into 3 culture dishes with a diameter of 9cm, 11mL per dish. Compound 1 (structure shown below), compound 2 (structure shown below), boscalid, carbendazim, procymidone, and metalaxyl were used as control agents, and acetone solvent was set as a blank control. The general screening concentration was 50μg / mL. After the toxic medium in the dish was condensed, the cultured pathogenic bacteria blocks with a diameter of 0.5cm were inoculated respectively. Place in a 26℃ incubator for culture. After the colonies in the blank control have grown fully, the colony diameters of each treatment are measured by the cross method and the average value is taken. The inhibition rate is calculated based on the average diameters of the blank control and the treated colonies after correction, and the inhibitory activity of each compound against Sclerotinia sclerotiorum is determined by the mycelial growth rate method. After inoculation and cultivation, the colony diameter is measured, the inhibition rate is calculated according to the calculation formula, and the EC50 value of the corresponding compound is calculated. Each compound and control agent are repeated 3 times. After calculation, the fungicidal activity of compounds LCJ-1 to LCJ-34 against various plant pathogens is shown in Table 4 below.

[0083]

[0084] Table 4 Bactericidal activity of compounds LCJ-1 to LCJ-34 against various plant pathogens

[0085]

[0086]

[0087]

[0088]

[0089] Note: “ / ” indicates that this test was not conducted

[0090] As can be seen from Table 4, this series of compounds can not only inhibit the growth of plant pathogenic fungi such as tomato gray mold, rice blast, rapeseed sclerotinia, melon wilt and rice sheath blight, but also have a good control effect on the growth of oomycetes (capsicum frutescens), with a broad spectrum. However, different compounds have different active effects on the same plant pathogen. In general, R 2Compounds with alkyl groups showed better fungicidal effects. Compounds LCJ-1, LCJ-2, LCJ-6, LCJ-9, LCJ-21, LCJ-31, and LCJ-34 showed good inhibitory effects on three types of gray mold, which were better than the control agents boscalid, procymidone, and carbendazim; among them, compounds LCJ-1 and LCJ-21 performed the best; there were 5 target compounds with an inhibition rate of more than 80% on rice blast fungus, namely compound LCJ-1 (80.36%), The inhibitory rates of the four compounds against Sclerotinia sclerotiorum were higher than 80%, among which the compound LCJ-34 had the highest activity (89.39%), which was better than the commercial fungicide carbendazim (85.71%) and slightly lower than boscalid (98.57%) and The inhibition rates of three compounds screened out from procymidone (100%) against melon wilt pathogen were higher than 80%, namely LCJ-1 (85.82%), LCJ-2 (81.56%), and LCJ-32 (85.61%), which were better than the commercial fungicide procymidone (60.28%), but lower than boscalid (98.58%) and carbendazim (100%). Compound LCJ-3 had the highest activity against rice sheath blight pathogen, with an inhibition rate of 91.2 4%, which is better than the commercial fungicide boscalid (90.78%), and slightly lower than procymidone (98.62%) and carbendazim (100%); the inhibition rate of 4 compounds screened out against pepper phytophthora was higher than 80%, namely LCJ-1 (84.83%), LCJ-4 (93.79%), LCJ-5 (82.07%), and LCJ-7 (80.69%), which is slightly lower than the commercial fungicide metalaxyl (97.93%). This experiment proves the broad-spectrum fungicidal activity of this series of compounds, and the activity of most compounds is better than the control agent compound 1 and compound 2.

[0091] (II) Determination of bactericidal activity of compounds LCJ-1 to LCJ-34 against various plant pathogens

[0092] The bactericidal activity of the target compound against 5 kinds of bacteria was determined by the 96-well cell culture plate method (turbidimetry). First, the strain must be activated. The bacteria stored in 25% sterilized glycerol at ultra-low temperature (-80°C) were activated by streaking on LB plate culture medium, placed in a dark environment, and cultured at 28°C for 3 days. After a single colony is produced, it is transferred into 100mL of LB liquid culture medium, sealed and placed in an oscillating shaker, and the temperature is controlled at 28°C, and the speed is 180r / min. The culture is shaken for 48-72h (different bacteria have different culture times) to allow the activated strains to enter a stable growth period, and then the next test can be carried out.

[0093] Take 10mL of bacterial culture that has entered the stable growth phase and add it to 100mL of LB liquid culture medium, shake it to mix it evenly. Use a multichannel pipette to add 196μL of bacterial culture to each well of the 96-well plate. Then add 4μL of the target compound solution with a concentration of 5000μg / mL to each well of the cell culture plate, mix the drug solution evenly with the existing LB liquid culture medium with bacteria in the well, and prepare the target compound to have a concentration of 100μg / mL in each well. Use streptomycin sulfate as the control agent, DMSO as the solvent control, LB liquid culture medium as the blank control, and culture medium containing only bacterial solution as the growth control. Each compound and control are repeated 3 times. Seal with sealing film, shake and culture at 28℃, 180r / min for 2d until the bacterial solution in the blank control well enters the stable growth phase, and then start the investigation. Use a UV spectrophotometer to evaluate the bactericidal effect of the compound by detecting the absorbance of the solution in each well of the cell culture plate. The inhibition rate is calculated using the following formula:

[0094] Corrected OD value = OD value of bacterial culture medium - OD value of sterile culture medium

[0095]

[0096] Table 5 Bactericidal activity determination of compounds LCJ-1 to LCJ-34

[0097]

[0098]

[0099]

[0100] As can be seen from Table 5, this series of compounds have certain bactericidal effects on various plant pathogenic bacteria, but different compounds have different active effects on the same plant pathogen. The inhibition rates of compounds LCJ-5, LCJ-12, LCJ-21, LCJ-29, and LCJ-30 on citrus canker pathogens are 62.21%, 63.41%, 100%, 100%, and 87.14%, respectively, which are better than the positive control streptomycin (56.92%); the activity of compounds LCJ-32 and LCJ-33 on cucurbit fruit spot pathogens is equivalent to streptomycin, and the inhibition rates are all 100%; the inhibition rates of compounds LCJ-1, LCJ-4, and LCJ-5 on rice bacterial blight pathogens are 72.28%, 78.36%, and 84.47%, respectively, which are slightly lower than the commercial agent streptomycin (88.74%). The series of compounds had poor activity against Chinese cabbage soft rot pathogen and tomato canker pathogen, with the highest inhibition rates being 14.17% (LCJ-19) and 30.26% (LCJ-12), respectively, which were much lower than the positive control streptomycin (inhibition rates were 100% and 83.22%, respectively).

[0101] As can be seen from the above embodiments, the present invention provides a 2-amido tert-butyl sulfonamide compound and its preparation method and application. The 2-amido tert-butyl sulfonamide compound of the present invention is used for preventing and controlling one or several pathogenic fungi, oomycetes and pathogenic bacteria in plant diseases; for preventing and controlling one or several fungi and oomycetes in rapeseed sclerotinia, tomato gray mold, rice sheath blight, rice blast, graminearum sickle and pepper phytophthora; for preventing and controlling one or several bacterial diseases in citrus canker, rice bacterial leaf blight, cabbage soft rot, melon fruit spot and tomato canker.

[0102] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A 2-amido tert-butyl sulfonamide compound, characterized in that: It has the following structure: ， Where: R 1 The group is 2,4,5-trichloro-C6H2-, 2,4,5-tribromo-C6H2- or 2-CF3-4-Cl-C6H3-; The R 2 The groups are ClCH2-, Cl2CH-, Cl3C-, CH3-, 2-F-C6H4-, 2-Cl-C6H4-, 2-CF3-C6H4-, 2-CH3-C6H4-, , 3-Br-C6H4- or SC4H3-.

2. The method for preparing the 2-amido tert-butyl sulfonamide compound according to claim 1, characterized in that: The steps include: (1) mixing 3,3-dimethyl-2-oxobutanesulfonic acid potassium salt and oxalyl chloride in a solvent for reaction to obtain a solution of 3,3-dimethyl-2-oxobutanesulfonyl chloride; mixing the obtained solution of 3,3-dimethyl-2-oxobutanesulfonyl chloride with a substituted amine, triethylamine and dichloromethane, and then performing an amination reaction to obtain N-substituted-3,3-dimethyl-2-oxobutanesulfonamide; (2) Under the condition of introducing ammonia gas, N-substituted-3,3-dimethyl-2-oxobutanesulfonamide, tetraisopropyl titanate and sodium borohydride are mixed in a solvent for amination reaction to obtain N-substituted-3,3-dimethyl-2-aminobutanesulfonamide; (3) mixing substituted acid chloride, N-substituted-3,3-dimethyl-2-aminobutanesulfonamide and triethylamine in a solvent for amidation reaction to obtain 2-amido tert-butylsulfonamide compounds; The substituted amine is 2,4,5-trichloroaniline, 2,4,5-tribromoaniline or 2-trifluoromethyl-4-chloroaniline; The substituents of the substituted acid chloride are ClCH2-, Cl2CH-, Cl3C-, CH3-, 2-F-C6H4-, 2-Cl-C6H4-, 2-CF3-C6H4-, 2-CH3-C6H4-, , 3-Br-C6H4- or SC4H3-.

3. The preparation method according to claim 2, characterized in that: In step (1), step (2) and step (3), the reaction temperature is independently 20-40° C., and the reaction time is independently 2-5 h.

4. The preparation method according to claim 3, characterized in that: In step (1), the solvent is a mixed solution of N,N-dimethylformamide and dichloromethane; the dosage ratio of the potassium salt of 3,3-dimethyl-2-oxobutanesulfonic acid, N,N-dimethylformamide, dichloromethane and oxalyl chloride is 0.05-0.20 mol: 2-7 mL: 70-300 mL: 0.05-0.20 mol.

5. The preparation method according to claim 4, characterized in that: In step (1), the usage ratio of the potassium salt of 3,3-dimethyl-2-oxobutanesulfonic acid, the substituted amine, triethylamine and dichloromethane is 0.05-0.15 mol: 0.03-0.10 mol: 0.03-0.10 mol: 60-180 mL.

6. The preparation method according to any one of claims 2 to 5, characterized in that In step (2), the solvent is ethanol; the dosage ratio of the N-substituted-3,3-dimethyl-2-oxobutanesulfonamide, tetraisopropyl titanate, sodium borohydride and ethanol is 0.01~0.08 mol: 0.01~0.08 mol: 0.03~0.30 mol: 10~250 mL.

7. The preparation method according to claim 6, characterized in that: In step (3), the solvent is dichloromethane, and the amount ratio of the N-substituted-3,3-dimethyl-2-aminobutanesulfonamide, substituted acid chloride, triethylamine and dichloromethane is 1~5mmol:1.5~9mmol:1.5~9mmol:10~60mL.

8. The use of the 2-amido tert-butyl sulfonamide compound according to claim 1 in agricultural fungicides, characterized in that: The 2-amido tert-butyl sulfonamide compound is used for preventing and controlling one or more of the following diseases: rapeseed sclerotinia disease, tomato gray mold, rice sheath blight, rice blast, graminearum sclerotinia disease and pepper blight; and is used for preventing and controlling one or more of the following bacterial diseases: citrus canker, rice bacterial leaf blight, cabbage soft rot, melon fruit spot and tomato canker.

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