Preparation method of novel agricultural compound synergist and application of novel agricultural compound synergist in agriculture

Abstract

The invention discloses a preparation method of a novel agricultural compound synergist and application of the novel agricultural compound synergist in agriculture, and is characterized in that the general formula of the novel agricultural compound synergist is as follows: # imgabs0 #, wherein R is hydrogen, 4-hydroxyl, 4-chlorine, 4-methoxyl, 4-methyl, 2-bromo, 2-chlorine, 4-hydroxy-3-methoxyl, 4-nitro, 3-hydroxyl, 2, 3-dimethoxy, 2, 3-dimethoxy, 2, 3-dimethoxy, 2, 3-dimethoxy, 2, 3-dimethoxy, 2, 3-dimethoxy, 2, 3-dimethoxy, 2, 3-dimethoxy, 2, 3-dimethoxy, 2, 3-dimethoxy, 2, 3-dimethoxy, 2, 3-dimethoxy, 2, 3-dimethoxy, 2, 3 the structural formula is shown in the specification, and the structural formula is shown in the specification. The structural formula is shown in the specification. The structural formula is shown in the specification. The novel agricultural compound synergist disclosed by the invention has a relatively good inhibition effect on kiwifruit canker germs.

Description

Technical Field

[0001] The invention relates to the field of chemical technology, and in particular to a preparation method of a novel agricultural compound synergist and its application in the antibacterial effect on citrus canker bacteria. Background Art

[0002] Kiwi fruit is rich in vitamin C, sugar, protein, amino acids, organic matter and various trace elements, so it is known as the "king of fruits". Due to its high economic value and good production efficiency, kiwi fruit has become an important pillar industry in economic development.

[0003] Kiwifruit disease (actinidia sclerotiorum) is a global bacterial disease caused by pathogenic strains of kiwifruit (Psa) in the genus Pseudomonas. The disease is highly contagious, rapidly spreading and destructive, causing serious damage to the kiwifruit planting industry and seriously reducing the yield and quality of kiwifruit. In recent years, with the continuous expansion of the planting area, the promotion of new varieties, the influence of climatic factors and unreasonable cultivation and management measures, the disease has spread widely and become increasingly serious, becoming one of the most serious diseases threatening kiwifruit production. At present, chemical control is the most direct, simple and effective method for preventing and controlling kiwifruit Psa. In actual production, due to the wide variety of agents, unclear differences in prevention and control effects, and lack of scientific basis, the prevention and control effects are not satisfactory. Sulfonamides (SAs) refer to a class of drugs with a p-aminobenzenesulfonamide structure, which is a class of chemotherapy drugs used to prevent and treat bacterial infections. It is characterized by a broad antibacterial spectrum, good antibacterial effect and rapid absorption. In addition, sulfonamide compounds also have antiviral, antiproliferative, antifungal and insecticidal activities, which have attracted the attention of many researchers. Common commercial sulfonamide drugs include sodium sulfonamide (SD), sulfaquinoline (SQ), sulfamethoxazole (SMZ), sulfadimethoxine (SMM), sulfadimethoxine (SDM) and sulfadimethyl bromide (SG). The antibacterial mechanism of sulfonamide drugs is to compete with para-aminobenzoic acid (PABA) for dihydrofolate synthase, thereby inhibiting the growth and reproduction of bacteria and interfering with bacterial folate metabolism.

[0004] Based on this, this study used sulfonamides as the basic compounds, introduced phosphate structures with the same antibacterial activity, and targeted agricultural bacterial diseases Psa, hoping to find compounds with good activity and specificity so that these compounds can play an important role in the prevention and control of agricultural bacterial diseases. Summary of the invention

[0005] The present invention aims to provide a method for preparing a novel agricultural compound synergist with bactericidal effect and its application in agriculture.

[0006] Another object of the present invention is to use the invention to inhibit kiwifruit canker bacteria.

[0007] The technical solution of the present invention is: a novel agricultural compound synergist, wherein the derivative has the general formula (I):

[0008]

[0009] Wherein: R is phenyl, heterocyclic or one or two substituted phenyl groups among o-, m- or p-, and the substituents are hydroxyl, halogen, methoxy, nitro, alkane, vinyl and cyano.

[0010] Further, R is phenyl, 4-hydroxyphenyl, 4-chlorophenyl, 4-methoxyphenyl, 4-methylphenyl, 2-bromophenyl, 2-chlorophenyl, 4-hydroxy-3-methoxyphenyl, 4-nitrophenyl, 3-hydroxyphenyl, 3-furyl, 2,4-dichlorophenyl, 2-hydroxy-3-bromophenyl, 4-vinylphenyl, 3-bromophenyl, 4-bromophenyl, 2-nitrophenyl, 3-nitrophenyl, 3-chlorophenyl, 4-cyanophenyl.

[0011] A new type of agricultural compound synergist, the specific compounds are as follows:

[0012] II-1: diethyl ((4-(N-cyclopropylsulfonamido)phenyl)amino)(phenyl)methyl phosphate;

[0013] II-2: diethyl ((4-(N-cyclopropylsulfonamido)phenyl)amino)(4-hydroxyphenyl)methyl phosphate;

[0014] II-3: diethyl ((4-chlorophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate;

[0015] II-4: diethyl ((4-(N-cyclopropylsulfonamido)phenyl)amino)(4-methoxyphenyl)methyl phosphate;

[0016] II-5: diethyl ((4-(N-cyclopropylsulfonamido)phenyl)amino)(p-tolyl)methyl phosphate; II-6: diethyl ((2-bromophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate;

[0017] II-7: diethyl ((2-chlorophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate;

[0018] II-8: diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(4-hydroxy-3-methoxyphenyl)methyl)phosphate;

[0019] II-9: diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(4-nitrophenyl)methyl)phosphate;

[0020] II-10: diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(3-hydroxyphenyl)methyl)phosphate;

[0021] II-11: diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(2,4-dichlorophenyl)methyl) phosphate;

[0022] II-12: diethyl ((5-bromo-2-hydroxyphenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate;

[0023] II-13: diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(4-vinylphenyl)methyl)phosphate;

[0024] II-14: diethyl ((3-bromophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate;

[0025] II-15: diethyl ((4-bromophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate;

[0026] II-16: diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(2-nitrophenyl)methyl)phosphate;

[0027] II-17: diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(3-nitrophenyl)methyl)phosphate;

[0028] II-18: diethyl ((3-chlorophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate;

[0029] II-19: diethyl ((4-cyanophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate;

[0030] A method for preparing a novel agricultural compound synergist comprises the following steps:

[0031]

[0032] The synthesis steps are: 4-amino-N-cyclopropylbenzenesulfonamide, substituted aldehyde and different phosphates, then acetonitrile is added as a solvent, and after stirring, boron trifluoride diethyl ether complex is added, the temperature is raised to 75°C, and a yellow-white solid appears after 24 hours. Stirring is continued for two hours, and the reaction is monitored by thin layer chromatography (TLC) until the raw material point disappears. After the reaction is completed, it is filtered at room temperature, and the filter cake is repeatedly washed with ACN to obtain the target compound.

[0033] The novel agricultural compound synergist is used in the preparation of medicine for preventing and treating kiwifruit canker pathogens.

[0034] The application of the novel agricultural compound synergist in agriculture.

[0035] The novel agricultural compound synergist is ((4-(N-cyclopropylsulfonylamino)phenyl)amino)

[0036] (Substituted phenyl)methyl phosphates.

[0037] A composition comprising the novel agricultural compound synergist according to claim 1 and zinc thiazole.

[0038] The mass ratio of the novel agricultural compound synergist to zinc thiazole is 4:1-1:4.

[0039] The composition is used in preparing medicine for preventing and treating bacterial diseases of crops.

[0040] Diethyl ((4-(N-cyclopropylsulfonylamino)phenyl)amino)(substituted phenyl)methyl phosphate:

[0041] Beneficial effects of the invention: The invention synthesizes a method for preparing a novel agricultural compound synergist with anti-kiwifruit canker pathogen activity. The invention has the advantages of easy availability of raw materials, simple process and mild reaction conditions. Compounds II2 and II13 in the invention have good anti-Psa activity, EC 50 The value was 59.4 mg / L, slightly lower than the EC of the control agent zinc thiazole 50 Compound II2 had the best antibacterial effect on Xoc, EC 50 The results showed that the concentrations of thiazolone and zinc thiazolidine in the control group were 48.3 and 43.4 mg / L, respectively, which were better than those of the control group thiazolone and zinc thiazolidine (EC 50 The values ​​were 53.1 and 50.1 mg / L respectively). The antibacterial effect was enhanced after compounding. DETAILED DESCRIPTION

[0042] Example 1: Synthesis of diethyl ((4-(N-cyclopropylsulfonamido)phenyl)amino)(phenyl)methyl phosphate (compound number II-1), comprising the following steps:

[0043] 4-amino-N-cyclopropylbenzenesulfonamide, benzaldehyde and diethyl phosphate are placed in a reaction flask. Then add 10 ml of acetonitrile (ACN) as a solvent, stir for 5 minutes and then add 0.2 ml of boron trifluoride diethyl ether complex. The temperature is raised to 75°C, and a yellow-white solid appears after 24 hours. Continue stirring for two hours. Monitor the reaction by thin layer chromatography (TLC) until the raw material spot disappears. After the reaction is completed, filter at room temperature and repeatedly wash the filter cake with ACN to obtain the target compound diethyl ((4-(N-cyclopropylsulfonamido)phenyl)amino)(phenyl)methyl phosphate.

[0044] Example 2: Synthesis of diethyl((4-(N-cyclopropylsulfonamido)phenyl)amino)(4-hydroxyphenyl)methylphosphonic acid (compound number II-2), comprising the following steps:

[0045] 4-amino-N-cyclopropylbenzenesulfonamide, 4-hydroxybenzaldehyde and diethyl phosphate were placed in a reaction flask. Then 10 ml of acetonitrile (ACN) was added as a solvent, and after stirring for 5 minutes, 0.2 ml of boron trifluoride diethyl ether complex was added. The temperature was raised to 75°C, and a yellow-white solid appeared after 24 hours. Stirring was continued for two hours. The reaction was monitored by thin layer chromatography (TLC) until the raw material spot disappeared. After the reaction was completed, it was filtered at room temperature and the filter cake was repeatedly washed with ACN to obtain the target compound diethyl ((4-(N-cyclopropylsulfonamido)phenyl)amino)(4-hydroxyphenyl)methylphosphonic acid.

[0046] Example 3: Synthesis of diethyl ((4-chlorophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate (compound number II-3), comprising the following steps:

[0047] 4-amino-N-cyclopropylbenzenesulfonamide, 4-chlorobenzaldehyde and diethyl phosphate were placed in a reaction flask. Then 10 ml of acetonitrile (ACN) was added as a solvent, and 0.2 ml of boron trifluoride diethyl ether complex was added after stirring for 5 minutes. The temperature was raised to 75°C, and a yellow-white solid appeared after 24 hours. Stirring was continued for two hours. The reaction was monitored by thin layer chromatography (TLC) until the raw material point disappeared. After the reaction was completed, it was filtered at room temperature and the filter cake was repeatedly washed with ACN to obtain the target compound diethyl ((4-chlorophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate.

[0048] Example 4: Synthesis of diethyl ((4-(N-cyclopropylsulfonamido)phenyl)amino)(4-methoxyphenyl)methyl phosphate (compound number II-4), comprising the following steps:

[0049] 4-amino-N-cyclopropylbenzenesulfonamide, 4-methoxybenzaldehyde and diethyl phosphate were placed in a reaction flask. Then 10 ml of acetonitrile (ACN) was added as a solvent, and after stirring for 5 minutes, 0.2 ml of boron trifluoride diethyl ether complex was added. The temperature was raised to 75°C, and a yellow-white solid appeared after 24 hours. Stirring was continued for two hours. The reaction was monitored by thin layer chromatography (TLC) until the raw material point disappeared. After the reaction was completed, it was filtered at room temperature and the filter cake was repeatedly washed with ACN to obtain the target compound diethyl ((4-(N-cyclopropylsulfonamido)phenyl)amino)(4-methoxyphenyl)methyl phosphate.

[0050] Example 5: Synthesis of diethyl ((4-(N-cyclopropylsulfonamido)phenyl)amino)(p-tolyl)methyl phosphate (compound number II-5), comprising the following steps:

[0051] 4-amino-N-cyclopropylbenzenesulfonamide, 4-methylbenzaldehyde and diethyl phosphate are placed in a reaction flask. Then add 10 ml of acetonitrile (ACN) as a solvent, stir for 5 minutes and add 0.2 ml of boron trifluoride diethyl ether complex. The temperature is raised to 75°C, and a yellow-white solid appears after 24 hours. Continue stirring for two hours. Monitor the reaction by thin layer chromatography (TLC) until the raw material point disappears. After the reaction is completed, filter at room temperature and repeatedly wash the filter cake with ACN to obtain the target compound diethyl ((4-(N-cyclopropylsulfonamido)phenyl)amino)(p-tolyl)methyl phosphate.

[0052] Example 6: Synthesis of diethyl ((2-bromophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate (compound number II-6), comprising the following steps:

[0053] 4-amino-N-cyclopropylbenzenesulfonamide, 2-bromobenzaldehyde and diethyl phosphate were placed in a reaction flask. Then 10 ml of acetonitrile (ACN) was added as a solvent, and 0.2 ml of boron trifluoride diethyl ether complex was added after stirring for 5 minutes. The temperature was raised to 75°C, and a yellow-white solid appeared after 24 hours. Stirring was continued for two hours. The reaction was monitored by thin layer chromatography (TLC) until the raw material point disappeared. After the reaction was completed, it was filtered at room temperature and the filter cake was repeatedly washed with ACN to obtain the target compound diethyl ((2-bromophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate.

[0054] Example 7: Synthesis of diethyl ((2-chlorophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate (compound number II-7), comprising the following steps:

[0055] 4-amino-N-cyclopropylbenzenesulfonamide, 2-chlorobenzaldehyde and diethyl phosphate were placed in a reaction flask. Then 10 ml of acetonitrile (ACN) was added as a solvent, and 0.2 ml of boron trifluoride diethyl ether complex was added after stirring for 5 minutes. The temperature was raised to 75°C, and a yellow-white solid appeared after 24 hours. Stirring was continued for two hours. The reaction was monitored by thin layer chromatography (TLC) until the raw material point disappeared. After the reaction was completed, it was filtered at room temperature and the filter cake was repeatedly washed with ACN to obtain the target compound diethyl ((2-chlorophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate.

[0056] Example 8: Synthesis of diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(4-hydroxy-3-methoxyphenyl)methyl)phosphate (compound number II-8), comprising the following steps:

[0057] 4-Amino-N-cyclopropylbenzenesulfonamide, 4-hydroxy-3-methoxybenzaldehyde and diethyl phosphate were placed in a reaction flask. Then 10 ml of acetonitrile (ACN) was added as a solvent, and 0.2 ml of boron trifluoride diethyl ether complex was added after stirring for 5 minutes. The temperature was raised to 75°C, and a yellow-white solid appeared after 24 hours. Stirring was continued for two hours. The reaction was monitored by thin layer chromatography (TLC) until the raw material point disappeared. After the reaction was completed, it was filtered at room temperature and the filter cake was repeatedly washed with ACN to obtain the target compound diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(4-hydroxy-3-methoxyphenyl)methyl) phosphate.

[0058] Example 9: Synthesis of diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(4-nitrophenyl)methyl)phosphate (compound number II-9), comprising the following steps:

[0059] 4-Amino-N-cyclopropylbenzenesulfonamide, 4-nitrobenzaldehyde and diethyl phosphate were placed in a reaction flask. Then 10 ml of acetonitrile (ACN) was added as a solvent, and after stirring for 5 minutes, 0.2 ml of boron trifluoride diethyl ether complex was added. The temperature was raised to 75°C, and a yellow-white solid appeared after 24 hours. Stirring was continued for two hours. The reaction was monitored by thin layer chromatography (TLC) until the raw material spot disappeared. After the reaction was completed, it was filtered at room temperature and the filter cake was repeatedly washed with ACN to obtain the target compound diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(4-nitrophenyl)methyl) phosphate.

[0060] Example 10: Synthesis of diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(3-hydroxyphenyl)methyl)phosphate (compound number II-10), comprising the following steps:

[0061] 4-amino-N-cyclopropylbenzenesulfonamide, 3-hydroxybenzaldehyde and diethyl phosphate were placed in a reaction flask. Then 10 ml of acetonitrile (ACN) was added as a solvent, and after stirring for 5 minutes, 0.2 ml of boron trifluoride diethyl ether complex was added. The temperature was raised to 75°C, and a yellow-white solid appeared after 24 hours. Stirring was continued for two hours. The reaction was monitored by thin layer chromatography (TLC) until the raw material spot disappeared. After the reaction was completed, it was filtered at room temperature and the filter cake was repeatedly washed with ACN to obtain the target compound diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(3-hydroxyphenyl)methyl)phosphate.

[0062] Example 11: Synthesis of diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(2,4-dichlorophenyl)methyl)phosphate (compound number II-12), comprising the following steps:

[0063] 4-Amino-N-cyclopropylbenzenesulfonamide, 2,4-dichlorobenzaldehyde and diethyl phosphate were placed in a reaction flask. Then 10 ml of acetonitrile (ACN) was added as a solvent, and 0.2 ml of boron trifluoride diethyl ether complex was added after stirring for 5 minutes. The temperature was raised to 75°C, and a yellow-white solid appeared after 24 hours. Stirring was continued for two hours. The reaction was monitored by thin layer chromatography (TLC) until the raw material spot disappeared. After the reaction was completed, it was filtered at room temperature and the filter cake was repeatedly washed with ACN to obtain the target compound diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(2,4-dichlorophenyl)methyl)phosphate.

[0064] Example 12: Synthesis of diethyl ((5-bromo-2-hydroxyphenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate (compound number II-13), comprising the following steps:

[0065] 4-amino-N-cyclopropylbenzenesulfonamide, 3-bromo-2-hydroxybenzaldehyde and diethyl phosphate were placed in a reaction flask. Then 10 ml of acetonitrile (ACN) was added as a solvent, and 0.2 ml of boron trifluoride diethyl ether complex was added after stirring for 5 minutes. The temperature was raised to 75°C, and a yellow-white solid appeared after 24 hours. Stirring was continued for two hours. The reaction was monitored by thin layer chromatography (TLC) until the raw material point disappeared. After the reaction was completed, it was filtered at room temperature and the filter cake was repeatedly washed with ACN to obtain the target compound diethyl ((5-bromo-2-hydroxyphenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate.

[0066] Example 13: Synthesis of diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(4-vinylphenyl)methyl)phosphate (compound number II-14), comprising the following steps:

[0067] 4-Amino-N-cyclopropylbenzenesulfonamide, 4-vinylbenzaldehyde and diethyl phosphate were placed in a reaction flask. Then 10 ml of acetonitrile (ACN) was added as a solvent, and after stirring for 5 minutes, 0.2 ml of boron trifluoride diethyl ether complex was added. The temperature was raised to 75°C, and a yellow-white solid appeared after 24 hours. Stirring was continued for two hours. The reaction was monitored by thin layer chromatography (TLC) until the raw material spot disappeared. After the reaction was completed, it was filtered at room temperature and the filter cake was repeatedly washed with ACN to obtain the target compound diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(4-vinylphenyl)methyl) phosphate.

[0068] Example 14: Synthesis of diethyl ((3-bromophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate (compound number II-15), comprising the following steps:

[0069] 4-amino-N-cyclopropylbenzenesulfonamide, 3-bromobenzaldehyde and diethyl phosphate were placed in a reaction flask. Then 10 ml of acetonitrile (ACN) was added as a solvent, and 0.2 ml of boron trifluoride diethyl ether complex was added after stirring for 5 minutes. The temperature was raised to 75°C, and a yellow-white solid appeared after 24 hours. Stirring was continued for two hours. The reaction was monitored by thin layer chromatography (TLC) until the raw material point disappeared. After the reaction was completed, it was filtered at room temperature and the filter cake was repeatedly washed with ACN to obtain the target compound diethyl ((3-bromophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate.

[0070] Example 15: Synthesis of diethyl ((4-bromophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate (compound number II-16), comprising the following steps:

[0071] 4-amino-N-cyclopropylbenzenesulfonamide, 4-bromobenzaldehyde and diethyl phosphate were placed in a reaction flask. Then 10 ml of acetonitrile (ACN) was added as a solvent, and 0.2 ml of boron trifluoride diethyl ether complex was added after stirring for 5 minutes. The temperature was raised to 75°C, and a yellow-white solid appeared after 24 hours. Stirring was continued for two hours. The reaction was monitored by thin layer chromatography (TLC) until the raw material point disappeared. After the reaction was completed, it was filtered at room temperature and the filter cake was repeatedly washed with ACN to obtain the target compound diethyl ((4-bromophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate.

[0072] Example 16: Synthesis of diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(2-nitrophenyl)methyl)phosphate (compound number II-17), comprising the following steps:

[0073] 4-amino-N-cyclopropylbenzenesulfonamide, 2-nitrobenzaldehyde and diethyl phosphate were placed in a reaction flask. Then 10 ml of acetonitrile (ACN) was added as a solvent, and after stirring for 5 minutes, 0.2 ml of boron trifluoride diethyl ether complex was added. The temperature was raised to 75°C, and a yellow-white solid appeared after 24 hours. Stirring was continued for two hours. The reaction was monitored by thin layer chromatography (TLC) until the raw material spot disappeared. After the reaction was completed, it was filtered at room temperature and the filter cake was repeatedly washed with ACN to obtain the target compound diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(2-nitrophenyl)methyl) phosphate.

[0074] Example 17: Synthesis of diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(3-nitrophenyl)methyl)phosphate (compound number II-18), comprising the following steps:

[0075] 4-amino-N-cyclopropylbenzenesulfonamide, 3-nitrobenzaldehyde and diethyl phosphate were placed in a reaction flask. Then 10 ml of acetonitrile (ACN) was added as a solvent, and after stirring for 5 minutes, 0.2 ml of boron trifluoride diethyl ether complex was added. The temperature was raised to 75°C, and a yellow-white solid appeared after 24 hours. Stirring was continued for two hours. The reaction was monitored by thin layer chromatography (TLC) until the raw material spot disappeared. After the reaction was completed, it was filtered at room temperature and the filter cake was repeatedly washed with ACN to obtain the target compound diethyl (((4-(N-cyclopropylsulfonamido)phenyl)amino)(3-nitrophenyl)methyl)phosphate.

[0076] Example 18: Synthesis of diethyl ((3-chlorophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate (compound number II-19), comprising the following steps:

[0077] 4-amino-N-cyclopropylbenzenesulfonamide, 3-chlorobenzaldehyde and diethyl phosphate were placed in a reaction flask. Then 10 ml of acetonitrile (ACN) was added as a solvent, and 0.2 ml of boron trifluoride diethyl ether complex was added after stirring for 5 minutes. The temperature was raised to 75°C, and a yellow-white solid appeared after 24 hours. Stirring was continued for two hours. The reaction was monitored by thin layer chromatography (TLC) until the raw material point disappeared. After the reaction was completed, it was filtered at room temperature and the filter cake was repeatedly washed with ACN to obtain the target compound diethyl ((3-chlorophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate.

[0078] Example 19: Synthesis of diethyl ((4-cyanophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate (compound number II-20), comprising the following steps:

[0079] 4-Amino-N-cyclopropylbenzenesulfonamide, 4-cyanobenzaldehyde and diethyl phosphate were placed in a reaction flask. Then 10 ml of acetonitrile (ACN) was added as a solvent, and 0.2 ml of boron trifluoride diethyl ether complex was added after stirring for 5 minutes. The temperature was raised to 75°C, and a yellow-white solid appeared after 24 hours. Stirring was continued for two hours. The reaction was monitored by thin layer chromatography (TLC) until the raw material point disappeared. After the reaction was completed, it was filtered at room temperature and the filter cake was repeatedly washed with ACN to obtain the target compound diethyl ((4-cyanophenyl)((4-(N-cyclopropylsulfonamido)phenyl)amino)methyl) phosphate.

[0080] The nuclear magnetic resonance hydrogen spectra of the derivatives synthesized in the above examples II-1 to II-20 ( 1 H NMR), carbon spectrum ( 13 C NMR) and high resolution mass spectrometry (HRMS) data are shown in Table 1.

[0081] Table 1. Spectral data of compounds II-1 to II-20

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093] Example 20: Inhibitory activity of target compounds against kiwifruit canker pathogens

[0094] (1) Test method

[0095] The bactericidal activity of the compound was determined by turbidity method (Yng L.; et IIl., 2017). The test compound was prepared at a concentration of 100 μg / mL. NB medium (3.0 g beef extract, 5.0 g peptone, 1.0 g yeast powder, 10.0 g glucose, 1000 mL distilled water, pH 7.0-7.2) was prepared. A small piece of medium containing kiwifruit canker bacteria was cut into two NB mediums with a bacterial loop, plugged, and cultured at 28°C, 180 rpm constant temperature shaker until the logarithmic growth phase (OD 595 =0.6-0.8) for later use. Take 40 μL of bacterial solution, 4 mL of water-Tween (1% Tween-20), and 1 mL of the prepared compound solution, incubate the test tube at 28±1°C, and shake continuously at 180 rpm for 1-3 days. Measure the OD at 600 nm. 600 ) to monitor bacterial growth, but with the same concentration of solvent and 0.1% Tween 20 as a blank control, copper thiazole and zinc thiazole as control agents, each treatment was repeated three times. The inhibition rate of the agent on bacteria was calculated by the following formula:

[0096] I=(Ctur-Ttur) / Ctur×100%

[0097] Where I is the inhibition rate, Ctur represents the corrected turbidity value of bacterial growth in the test tube without drug treatment (blank control), and Ttur represents the corrected turbidity value of bacterial growth in the test tube treated with the compound.

[0098] (2) Biological test results

[0099] Table 2 Inhibitory activity of target compounds against kiwifruit canker pathogens

[0100]

[0101]

[0102] Note: The experiment was repeated three times. Zinc thiazole was used as a positive control.

[0103] The antibacterial activity of the target compounds against kiwifruit canker pathogen was systematically evaluated. The results are shown in Table 2. According to the results, the synthesized derivatives have certain antibacterial activity against kiwifruit canker pathogen. Among them, compounds A2 and A13 showed good anti-Psa activity, and their EC 50 The values ​​were 48.3 and 43.4 mg / L, respectively, which were better than the control agent zinc thiazole (EC 50 The value is 50.1mg / L).

[0104] Example 21: Compounding of II 13 and zinc thiazole

[0105] The zinc thiazole used below is prepared by adjusting the concentration of a commercially available preparation. The following examples are further explanations of the present invention. In the following examples, the target compound II-13 and zinc thiazole are used to prepare a composite composition. In each composition, the target compound II-13 and zinc thiazole are used to prepare a composite composition. The following preparations are prepared according to the requirements.

[0106] Table 3 Compound formulation

[0107]

[0108] Example 22: Inhibitory activity of the composite compound against kiwifruit canker pathogens

[0109] According to the method described in Example 23, the concentration of the compound of Example 24 was tested for its inhibitory activity against kiwifruit canker bacteria.

[0110] Table 4 Inhibitory activity of the compound against kiwifruit canker pathogens

[0111]

[0112]

[0113] From Table 4, it can be seen that at the test concentrations of 50 and 100 mg / mL, the protective inhibition rate of the compound against kiwifruit canker pathogens was significantly enhanced after compound II 13 and thiazole zinc were compounded. When the ratio of compound II 13 and thiazole zinc was between 4:1 and 1:4, the inhibition rate against kiwifruit canker pathogens was better than that of a single agent. When the ratio was 4:1, at the test concentrations of 50 and 100 mg / mL, the inhibition rate was 85.5% and 65.4%, and the synergistic effect was the best.

[0114] The embodiments of the present invention are used to illustrate the technical solution of the present invention. The effects of the present invention are that the synthesis route is simple, the yield is high, and a new and efficient preparation method of a new agricultural compound synergist is obtained and its application in agriculture.

Claims

1. A novel agricultural compound synergist, characterized in that: The general formula of the novel agricultural compound synergist is as follows: Wherein, R is a group substituted at one or two positions in the ortho, meta or para of the benzene ring, and the substituent is hydroxyl, halogen, methoxy, nitro, alkane, vinyl and cyano.

2. A novel agricultural compound synergist according to claim 1, characterized in that: R is hydrogen, 4-hydroxy, 4-chloro, 4-methoxy, 4-methyl, 2-bromo, 2-chloro, 4-hydroxy-3-methoxy, 4-nitro, 3-hydroxy, 2,4-dichloro, 2-hydroxy-3-bromo, 4-vinyl, 3-bromophenyl, 4-bromo, 2-nitro, 3-nitro, 3-chloro, 4-cyano.

3. The method for preparing a novel agricultural compound synergist according to claim 1, characterized in that: The following steps are involved:

4. The method for preparing a novel agricultural compound synergist according to claim 3, characterized in that: The synthesis steps are: 4-amino-N-cyclopropylbenzenesulfonamide, substituted aldehyde and different phosphates, then acetonitrile is added as a solvent, and after stirring, boron trifluoride diethyl ether complex is added, the temperature is raised to 75°C, and a yellow-white solid appears after 24 hours. Stirring is continued for two hours, and the reaction is monitored by thin layer chromatography (TLC) until the raw material point disappears. After the reaction is completed, it is filtered at room temperature, and the filter cake is repeatedly washed with ACN to obtain the target compound.

5. Use of a novel agricultural compound synergist as claimed in claim 1 or 2 in the preparation of drugs for preventing and treating kiwifruit canker pathogens.

6. Use of the novel agricultural compound synergist as claimed in claim 1 or 2 in agriculture.

7. The use according to claim 7, characterized in that: The novel agricultural compound synergist is ((4-(N-cyclopropylsulfonylamino)phenyl)amino)(substituted phenyl)methyl phosphate.

8. A composition, characterized in that: The invention comprises the novel agricultural compound synergist as claimed in claim 1 and zinc thiazole.

9. The composition according to claim 8, characterized in that: The mass ratio of the novel agricultural compound synergist to zinc thiazole is 4:1-1:

4.

10. Use of the composition according to claim 8 in the preparation of drugs for preventing and controlling bacterial diseases of crops.

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