Preparation method of novel phosphorus-containing agricultural compound synergist and application of novel phosphorus-containing agricultural compound synergist in agriculture

Abstract

The invention discloses a preparation method of a novel phosphorus-containing agricultural compound synergist and an application of the novel phosphorus-containing agricultural compound synergist in agriculture, and is characterized in that the general formula of the synergist is as follows: # imgabs0 #, wherein R1 is hydrogen, 5-methoxypyrimidine, acetaldehyde, pyridine, 2, 4-dimethoxypyrimidine, 3, 4-dimethylisoxazole, benzaldehyde, 2-methoxypyrazine, 4, 4 '-dimethoxypyrimidine, 3, 4-dimethylisoxazole, 4, 4'-dimethoxypyrimidine, 4, 4 '-dimethoxypyrimidine, 4, 4'-dimethoxypyrimidine, 4, 4 '-dimethoxypyrimidine, 4, 4'-dimethoxypyrimidine, 4, 4 '-dimethoxypyrimidine, 4, 4'-dimethoxypyrimidine, 4, 4 ' R1 is methyl, ethyl or n-butyl, R2 is methyl, ethyl or n-butyl, and R3 is 2, 5-dimethoxypyrimidine, thiazole, 5-methylisoxazole or morpholine. The novel agricultural compound synergist disclosed by the invention has a relatively good inhibition effect on kiwifruit canker germs.

Description

Technical Field

[0001] The present invention relates to the field of chemical technology, and specifically to a preparation method of a novel agricultural compound synergist and its application in antibacterial effects against Xanthomonas oryzae pv. oryzae, Xanthomonas citri subsp. citri, and Xanthomonas oryzae pv. oryzicola. Background Art

[0002] The frequent occurrence of bacterial diseases such as bacterial blight of rice and bacterial leaf streak of rice seriously threatens the rice yield, resulting in a 20% to 50% decrease in rice yield. Therefore, exploring effective methods for controlling bacterial diseases of rice has become a hot topic for plant protection scientists. Currently, chemical control is the most direct and effective method for controlling bacterial diseases, but the effects of bacteriostatic agents on the market are often not satisfactory, and overuse may disrupt the ecological balance. Therefore, developing highly efficient, environmentally friendly, and low-toxic green antibacterial agents is the goal pursued by pesticide researchers.

[0003] Phosphate drugs are a class of drugs containing phosphate groups and have wide applications in fields such as chemical engineering, medicine, pesticides, plastics, and rubber. They can be used as plastic additives to improve the flame retardancy, thermal stability, and mechanical properties of plastics; as lubricant additives to improve the anti-wear, extreme pressure, and antioxidant properties of lubricants; as pharmaceutical intermediates for synthesizing antibacterial drugs, anticancer drugs, etc.; and as pesticides with insecticidal and bactericidal effects, which has attracted the attention of many researchers.

[0004] Based on this, in this study, using phosphate as the parent structure and introducing various heterocyclic structures, targeting agricultural bacterial diseases Xanthomonas oryzae pv. oryzae, Xanthomonas citri subsp. citri, and Xanthomonas oryzae pv. oryzicola, it is expected to find compounds with good activity and specificity, enabling these compounds to play an important role in the prevention and control of agricultural bacterial diseases. Summary of the Invention

[0005] The technical problem to be solved by the present invention is: to provide a preparation method of a novel phosphorus-containing agricultural compound synergist with bactericidal effects and its application in agriculture.

[0006] Another object is the use of having inhibitory effects on Xanthomonas oryzae pv. oryzae, Xanthomonas citri subsp. citri, and Xanthomonas oryzae pv. oryzicola.

[0007] The technical solution of the present invention is: a novel phosphorus-containing agricultural compound synergist, and the general formula of the synergist is as follows:

[0008] R 1 is hydrogen, 5-methoxypyrimidine, acetaldehyde, pyridine, 2,4-dimethoxypyrimidine, 3,4-dimethylisoxazole, benzaldehyde, 2-methoxypyrazine, 4,5-dimethoxypyrimidine, thiazole, 5-methylisoxazole, or morpholine, R 2is methyl, ethyl or n-butyl.

[0009] The preparation method of the novel phosphorus-containing agricultural compound synergist includes the following steps:

[0010]

[0011] The synthesis steps of the preparation method of the novel phosphorus-containing agricultural compound synergist are as follows: A mixture of 4-cyanobenzaldehyde, substituted p-aminobenzenesulfonamide, dialkyl phosphite and aluminum trifluoromethanesulfonate is stirred and reacted in an 80 °C oil bath; The reaction is monitored by thin layer chromatography until the raw material spots disappear; After the reaction is completed, filtration is carried out at room temperature, and the filter cake is repeatedly washed with ACN to obtain the target compound.

[0012] The dosage ratio of the 4-cyanobenzaldehyde, substituted p-aminobenzenesulfonamide, dialkyl phosphite and aluminum trifluoromethanesulfonate is: 1:1:1.2:0.01.

[0013] The application of the novel phosphorus-containing agricultural compound synergist in agriculture.

[0014] The application of the novel phosphorus-containing agricultural compound synergist in the preparation of drugs for preventing and treating Xanthomonas oryzae pv. oryzae, Xanthomonas citri subsp. citri and Xanthomonas oryzae pv. oryzicola.

[0015] The synergist is ((4-cyanophenyl)((4-(N-substituted)phenyl)amino)methyl)dialkyl phosphate.

[0016] A compound synergist, wherein the composition contains the synergist as claimed in claim 1 and abscisic acid (ABA).

[0017] The mass ratio of the synergist and ABA is 2:1.

[0018] The application of the compound synergist in the preparation of drugs for preventing and treating Xanthomonas oryzae pv. oryzae, Xanthomonas citri subsp. citri and Xanthomonas oryzae pv. oryzicola

[0019] Advantages of the present invention: A preparation method of a novel agricultural compound synergist with activities against Xanthomonas oryzae pv. oryzae, Xanthomonas citri subsp. citri, and Xanthomonas oryzae pv. oryzicola is synthesized in the present invention. The advantages of the present invention are that raw materials are easily available, the process is simple, and the reaction conditions are mild. In the present invention, the antibacterial activity of the target compound against Pseudomonas syringae pv. actinidiae was systematically evaluated. The results are shown in Table 2. According to the results, the synthesized derivatives have certain activities against Xanthomonas oryzae pv. oryzae, Xanthomonas citri subsp. citri, and Xanthomonas oryzae pv. oryzicola. Among them, compound II-1 has the best activity against Xanthomonas citri subsp. citri, and the inhibition rate of Xanthomonas citri subsp. citri at a concentration of 100 mg / L is 74.1%, which is better than the control agents thiodiazole copper and thiazole zinc (the inhibition rates are 62.8% and 53.9% respectively). Compound II-12 has the best inhibitory activity against Xanthomonas oryzae pv. oryzicola, and the inhibition rate at a concentration of 100 mg / L is 76.9%, which is better than the control agents thiodiazole copper and thiazole zinc (the inhibition rates are 50.7% and 51.7% respectively). The inhibitory activity of compound I-6 against Xanthomonas oryzae pv. oryzae is 79.2%, slightly lower than that of the control agent thiodiazole copper (79.4%). The antibacterial effect is increased after compounding. Detailed implementation mode

[0020] Example 1: Synthesis of dimethyl ((4-cyanophenyl)((4-(N-phenylsulfonamido)amino)methyl)phosphonate (compound number II-1), including the following steps:

[0021] A mixture of 4-cyanobenzaldehyde (1.0 mmol), p-aminobenzenesulfonamide (1.0 mmol), dimethyl phosphite (1.2 mmol), and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin-layer chromatography (TLC) until the raw material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was repeatedly washed with ACN to obtain the target compound dimethyl ((4-cyanophenyl)((4-(N-phenylsulfonamido)amino)methyl)phosphonate.

[0022] Example 2: Synthesis of diethyl ((4-cyanophenyl)((4-(N-phenylsulfonamido)amino)methyl)phosphonate (compound number II-2), including the following steps:

[0023] A mixture of 4-cyanobenzaldehyde (1.0 mmol), p-aminobenzenesulfonamide (1.0 mmol), diethyl phosphite (1.2 mmol), and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin-layer chromatography (TLC) until the raw material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was repeatedly washed with ACN to obtain the target compound diethyl ((4-cyanophenyl)((4-(N-phenylsulfonamido)amino)methyl)phosphonate.

[0024] Example 3: Synthesis of ((4-cyanophenyl)((4-(N-phenylsulfonamido)amino)methyl) dibutyl phosphate (Compound No. II-3), including the following steps:

[0025] A mixture of 4-cyanobenzaldehyde (1.0 mmol), p-aminobenzenesulfonamide (1.0 mmol), dibutyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the starting material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-phenylsulfonamido)amino)methyl) dibutyl phosphate.

[0026] Example 4: Synthesis of ((4-cyanophenyl)((4-(N-(5-methoxypyrimidine)phenylsulfonamido)amino)methyl) dimethyl phosphate (Compound No. II-4), including the following steps:

[0027] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(5-methoxypyrimidine)benzenesulfonamide (1.0 mmol), dimethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the starting material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-phenylsulfonamido)amino)methyl) dimethyl phosphate.

[0028] Example 5: Synthesis of ((4-cyanophenyl)((4-(N-(5-methoxypyrimidine)phenylsulfonamido)amino)methyl) ethyl phosphate (Compound No. II-5), including the following steps:

[0029] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(5-methoxypyrimidine)benzenesulfonamide (1.0 mmol), diethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the starting material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-phenylsulfonamido)amino)methyl) ethyl phosphate.

[0030] Example 6: Synthesis of ((4-cyanophenyl)((4-(N-(5-methoxypyrimidine)phenylsulfonamido)amino)methyl) dibutyl phosphate (Compound No. II-6), including the following steps:

[0031] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(5-methoxypyrimidine)benzenesulfonamide (1.0 mmol), dibutyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the raw material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was repeatedly washed with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-benzenesulfonamido)amino)methyl) dibutyl phosphate).

[0032] Example 7: Synthesis of ((4-cyanophenyl)((4-(N-(acetyl)benzenesulfonamido)amino)methyl) dimethyl phosphate (Compound No. II-7), comprising the following steps:

[0033] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(acetyl)benzenesulfonamide (1.0 mmol), dimethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the raw material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was repeatedly washed with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-benzenesulfonamido)amino)methyl) dimethyl phosphate).

[0034] Example 8: Synthesis of ((4-cyanophenyl)((4-(N-(acetyl)benzenesulfonamido)amino)methyl) diethyl phosphate (Compound No. II-8), comprising the following steps:

[0035] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(acetyl)benzenesulfonamide (1.0 mmol), diethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the raw material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was repeatedly washed with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-benzenesulfonamido)amino)methyl) diethyl phosphate).

[0036] Example 9: Synthesis of bis((4-cyanophenyl)((4-(N-(acetyl)benzenesulfonamido)amino)methyl) dibutyl phosphate (Compound No. II-9), comprising the following steps:

[0037] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(acetyl)benzenesulfonamide (1.0 mmol), dibutyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the starting material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-benzenesulfonamido)amino)methyl)dibutyl phosphate).

[0038] Example 10: Synthesis of ((4-cyanophenyl)((4-(N-(pyridinyl)benzenesulfonamido)amino)methyl)dimethyl phosphate (Compound No. II-10), comprising the following steps:

[0039] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(pyridinyl)benzenesulfonamide (1.0 mmol), dimethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the starting material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-(pyridinyl)benzenesulfonamido)amino)methyl)dimethyl phosphate).

[0040] Example 11: Synthesis of ((4-cyanophenyl)((4-(N-(pyridinyl)benzenesulfonamido)amino)methyl)diethyl phosphate (Compound No. II-11), comprising the following steps:

[0041] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(pyridinyl)benzenesulfonamide (1.0 mmol), diethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the starting material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-(pyridinyl)benzenesulfonamido)amino)methyl)diethyl phosphate).

[0042] Example 12: Synthesis of ((4-cyanophenyl)((4-(N-(pyridinyl)benzenesulfonamido)amino)methyl)dibutyl phosphate (Compound No. II-12), comprising the following steps:

[0043] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(pyridyl)benzenesulfonamide (1.0 mmol), dibutyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the starting material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-(pyridyl)benzenesulfonamido)amino)methyl)dibutyl phosphate).

[0044] Example 13: Synthesis of ((4-cyanophenyl)((4-(N-(2,4-dimethoxypyrimidinyl)benzenesulfonamido)amino)methyl)dimethyl phosphate (Compound No. II-13), comprising the following steps:

[0045] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(2,4-dimethoxypyrimidinyl)benzenesulfonamide (1.0 mmol), dimethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the starting material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-benzenesulfonamido)amino)methyl)dimethyl phosphate).

[0046] Example 14: Synthesis of ((4-cyanophenyl)((4-(N-(2,4-dimethoxypyrimidinyl)benzenesulfonamido)amino)methyl)diethyl phosphate (Compound No. II-14), comprising the following steps:

[0047] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(2,4-dimethoxypyrimidinyl)benzenesulfonamide, diethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the starting material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-benzenesulfonamido)amino)methyl)diethyl phosphate).

[0048] Example 15: Synthesis of ((4-cyanophenyl)((4-(N-(2,4-dimethoxypyrimidinyl)benzenesulfonamido)amino)methyl)dibutyl phosphate (Compound No. II-15), comprising the following steps:

[0049] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(2,4-dimethoxypyrimidinyl)benzenesulfonamide, dibutyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the raw material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-benzenesulfonamido)amino)methyl)dibutyl phosphate).

[0050] Example 16: Synthesis of dimethyl ((4-cyanophenyl)((4-(N-(3,4-dimethylisoxazolyl)benzenesulfonamido)amino)methyl)phosphonate (Compound No. II-16), comprising the following steps:

[0051] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(3,4-dimethylisoxazolyl)benzenesulfonamide (1.0 mmol), dimethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the raw material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound dimethyl ((4-cyanophenyl)((4-(N-benzenesulfonamido)amino)methyl)phosphonate).

[0052] Example 17: Synthesis of diethyl ((4-cyanophenyl)((4-(N-(3,4-dimethylisoxazolyl)benzenesulfonamido)amino)methyl)phosphonate (Compound No. II-17), comprising the following steps:

[0053] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(3,4-dimethylisoxazolyl)benzenesulfonamide (1.0 mmol), diethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the raw material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound diethyl ((4-cyanophenyl)((4-(N-benzenesulfonamido)amino)methyl)phosphonate).

[0054] Example 18: Synthesis of dibutyl ((4-cyanophenyl)((4-(N-(3,4-dimethylisoxazolyl)benzenesulfonamido)amino)methyl)phosphonate (Compound No. II-18), comprising the following steps:

[0055] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(3,4-dimethylisoxazolyl)benzenesulfonamide (1.0 mmol), dibutyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the starting material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-benzenesulfonamido)amino)methyl)dibutyl phosphate).

[0056] Example 19: Synthesis of ((4-cyanophenyl)((4-(N-(formyl)benzenesulfonamido)amino)methyl)dimethyl phosphate (Compound No. II-19), comprising the following steps:

[0057] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(formyl)benzenesulfonamide (1.0 mmol), dimethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the starting material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-(formyl)benzenesulfonamido)amino)methyl)dimethyl phosphate).

[0058] Example 20: Synthesis of ((4-cyanophenyl)((4-(N-(formyl)benzenesulfonamido)amino)methyl)diethyl phosphate (Compound No. II-20), comprising the following steps:

[0059] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(acetyl)benzenesulfonamide (1.0 mmol), diethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the starting material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-(formyl)benzenesulfonamido)amino)methyl)diethyl phosphate).

[0060] Example 21: Synthesis of ((4-cyanophenyl)((4-(N-(formyl)benzenesulfonamido)amino)methyl)dibutyl phosphate (Compound No. II-21), comprising the following steps:

[0061] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(butyryl)benzenesulfonamide (1.0 mmol), dibutyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the raw material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was repeatedly washed with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-(formyl)benzenesulfonamido)amino)methyl) dibutyl phosphate).

[0062] Example 22: Synthesis of ((4-cyanophenyl)((4-(N-(2-methoxypyrazinyl)benzenesulfonamido)amino)methyl) dimethyl phosphate (Compound No. II-22), comprising the following steps:

[0063] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(2-methoxypyrazinyl)benzenesulfonamide (1.0 mmol), dimethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the raw material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was repeatedly washed with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-(formyl)benzenesulfonamido)amino)methyl) dimethyl phosphate).

[0064] Example 23: Synthesis of ((4-cyanophenyl)((4-(N-(2-methoxypyrazinyl)benzenesulfonamido)amino)methyl) diethyl phosphate (Compound No. II-23), comprising the following steps:

[0065] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(2-methoxypyrazinyl)benzenesulfonamide (1.0 mmol), diethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the raw material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was repeatedly washed with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-(formyl)benzenesulfonamido)amino)methyl) diethyl phosphate).

[0066] Example 24: Synthesis of ((4-cyanophenyl)((4-(N-(2-methoxypyrazinyl)benzenesulfonamido)amino)methyl) dibutyl phosphate (Compound No. II-24), comprising the following steps:

[0067] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(2-methoxypyrazinyl)benzenesulfonamide (1.0 mmol), dibutyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the raw material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-(formyl)benzenesulfonamido)amino)methyl)dibutyl phosphate).

[0068] Example 25: Synthesis of ((4-cyanophenyl)((4-(N-(4,5-dimethoxypyrimidinyl)benzenesulfonamido)amino)methyl)dimethyl phosphate (Compound No. II-25), comprising the following steps:

[0069] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(4,5-dimethoxypyrimidinyl)benzenesulfonamide (1.0 mmol), dimethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the raw material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-(4,5-dimethoxypyrimidinyl)benzenesulfonamido)amino)methyl)dimethyl phosphate).

[0070] Example 26: Synthesis of ((4-cyanophenyl)((4-(N-(4,5-dimethoxypyrimidinyl)benzenesulfonamido)amino)methyl)diethyl phosphate (Compound No. II-26), comprising the following steps:

[0071] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(4,5-dimethoxypyrimidinyl)benzenesulfonamide (1.0 mmol), diethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the raw material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-(4,5-dimethoxypyrimidinyl)benzenesulfonamido)amino)methyl)diethyl phosphate).

[0072] Example 27: Synthesis of ((4-cyanophenyl)((4-(N-(4,5-dimethoxypyrimidinyl)benzenesulfonamido)amino)methyl)dibutyl phosphate (Compound No. II-27), comprising the following steps:

[0073] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(4,5-dimethoxypyrimidinyl)benzenesulfonamide (1.0 mmol), dibutyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the starting material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-(4,5-dimethoxypyrimidinyl)benzenesulfonamido)amino)methyl) dibutyl phosphate).

[0074] Example 28: Synthesis of ((4-cyanophenyl)((4-(N-(thiazolyl)benzenesulfonamido)amino)methyl) dimethyl phosphate (Compound No. II-28), comprising the following steps:

[0075] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(thiazolyl)benzenesulfonamide (1.0 mmol), dimethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the starting material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-(thiazolyl)benzenesulfonamido)amino)methyl) dimethyl phosphate).

[0076] Example 29: Synthesis of ((4-cyanophenyl)((4-(N-(thiazolyl)benzenesulfonamido)amino)methyl) diethyl phosphate (Compound No. II-29), comprising the following steps:

[0077] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(thiazolyl)benzenesulfonamide (1.0 mmol), diethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the starting material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-(thiazolyl)benzenesulfonamido)amino)methyl) diethyl phosphate).

[0078] Example 30: Synthesis of ((4-cyanophenyl)((4-(N-(thiazolyl)benzenesulfonamido)amino)methyl) dibutyl phosphate (Compound No. II-30), comprising the following steps:

[0079] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(thiazolyl)benzenesulfonamide (1.0 mmol), dibutyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the raw material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-(thiazolyl)benzenesulfonamido)amino)methyl)dibutyl phosphate).

[0080] Example 31: Synthesis of ((4-cyanophenyl)((4-(N-(5-methylisoxazolyl)benzenesulfonamido)amino)methyl)dimethyl phosphate (Compound No. II-31), including the following steps:

[0081] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(5-methylisoxazolyl)benzenesulfonamide (1.0 mmol), dimethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the raw material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-(5-methylisoxazolyl)benzenesulfonamido)amino)methyl)dimethyl phosphate).

[0082] Example 32: Synthesis of ((4-cyanophenyl)((4-(N-(5-methylisoxazolyl)benzenesulfonamido)amino)methyl)diethyl phosphate (Compound No. II-32), including the following steps:

[0083] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(5-methylisoxazolyl)benzenesulfonamide (1.0 mmol), diethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the raw material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-(5-methylisoxazolyl)benzenesulfonamido)amino)methyl)diethyl phosphate).

[0084] Example 33: Synthesis of ((4-cyanophenyl)((4-(N-(5-methylisoxazolyl)benzenesulfonamido)amino)methyl)dibutyl phosphate (Compound No. II-33), including the following steps:

[0085] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(5-methylisoxazolyl)benzenesulfonamide (1.0 mmol), dibutyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the starting material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-(5-methylisoxazolyl)benzenesulfonamido)amino)methyl)dibutyl phosphate).

[0086] Example 34: Synthesis of dimethyl ((4-cyanophenyl)((4-(N-(5-morpholinyl)benzenesulfonamido)amino)methyl)phosphonate (Compound No. II-34), comprising the following steps:

[0087] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(5-morpholinyl)benzenesulfonamide (1.0 mmol), dimethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the starting material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound dimethyl ((4-cyanophenyl)((4-(N-(5-morpholinyl)benzenesulfonamido)amino)methyl)phosphonate).

[0088] Example 35: Synthesis of diethyl ((4-cyanophenyl)((4-(N-(5-morpholinyl)benzenesulfonamido)amino)methyl)phosphonate (Compound No. II-35), comprising the following steps:

[0089] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(5-morpholinyl)benzenesulfonamide (1.0 mmol), diethyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the starting material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound diethyl ((4-cyanophenyl)((4-(N-(5-morpholinyl)benzenesulfonamido)amino)methyl)phosphonate).

[0090] Example 36: Synthesis of dibutyl ((4-cyanophenyl)((4-(N-(5-morpholinyl)benzenesulfonamido)amino)methyl)phosphonate (Compound No. II-36), comprising the following steps:

[0091] A mixture of 4-cyanobenzaldehyde (1.0 mmol), 4-amino-(N)-(5-morpholinyl)benzenesulfonamide (1.0 mmol), dibutyl phosphite (1.2 mmol) and aluminum trifluoromethanesulfonate (0.01 mmol) was stirred and reacted in an 80 °C oil bath. The reaction was monitored by thin layer chromatography (TLC) until the starting material spots disappeared. After the reaction was completed, filtration was carried out at room temperature, and the filter cake was washed repeatedly with ACN to obtain the target compound ((4-cyanophenyl)((4-(N-(5-morpholinyl)benzenesulfonamido)amino)methyl)dibutyl phosphate).

[0092] For the nuclear magnetic resonance hydrogen spectrum ( 1 1H NMR), carbon spectrum ( 13 13C NMR) and high resolution mass spectrometry (HRMS) data of the synthetic derivatives in the above Examples II-1 to II-36 are shown in Table 1.

[0093] Table 1. Spectral data of compounds II-1 to II-36

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110] Example 37: Inhibitory Activity of the Target Compound against Xanthomonas oryzae pv. oryzae, Xanthomonas citri subsp. citri, and Xanthomonas oryzae pv. oryzicola

[0111] (1) Test Method

[0112] The bactericidal activity of the compound was determined by the turbidimetric method (Yng L.; et al., 2017). Prepare the test compound at a concentration of 100 μg / mL. Prepare NB medium (3.0 g beef extract, 5.0 g peptone, 1.0 g yeast extract, 10.0 g glucose, 1000 mL distilled water, pH 7.0 - 7.2). Use an inoculating loop to pick a small piece of medium containing Xanthomonas oryzae pv. oryzae, Xanthomonas citri subsp. citri, and Xanthomonas oryzae pv. oryzicola and place it into two NB media respectively. Plug the stopper and incubate in a constant temperature shaker at 28°C and 180 rpm until the logarithmic growth phase (OD 595 = 0.6 - 0.8) for standby. Take 40 μL of the bacterial solution, 4 mL of water - Tween (1% Tween - 20), and 1 mL of the prepared compound solution. Incubate the test tubes at 28 ± 1°C and shake continuously at 180 rpm for 1 - 3 days. Monitor the growth of bacteria by measuring the optical density at 600 nm (OD 600 ). Use the same concentration of solvent and 0.1% Tween 20 as the blank control, and thiazole copper and thiazole zinc as the control agents. Each treatment was repeated three times. Calculate the inhibition rate of the agent against bacteria using the following formula:

[0113] I = (Ctur - Ttur) / Ctur × 100%

[0114] 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.

[0115] (2) Biological Test Results

[0116] Table 2 Inhibitory Activity of the Target Compound against Xanthomonas oryzae pv. oryzae, Xanthomonas citri subsp. citri, and Xanthomonas oryzae pv. oryzicola

[0117]

[0118]

[0119] Note: The experiment was repeated three times. Thiazole copper and thiazole zinc were used as positive controls.

[0120] The antibacterial activity of the target compounds was systematically evaluated. The results are shown in Table 2. According to the results, the synthesized derivatives have certain activities against Xanthomonas oryzae pv. oryzae, Xanthomonas axonopodis pv. citri, and Acidovorax avenae subsp. avenae. Among them, Compound II1 has the best activity against Xanthomonas axonopodis pv. citri. At a concentration of 100 mg / L, the inhibition rate of Xanthomonas axonopodis pv. citri is 74.1%, which is better than that of the control agents thiodiazole copper and thiazole zinc (the inhibition rates are 62.8% and 53.9% respectively). Compound II12 has the best inhibitory activity against Acidovorax avenae subsp. avenae. At a concentration of 100 mg / L, the inhibition rate is 76.9%, which is better than that of the control agents thiodiazole copper and thiazole zinc (the inhibition rates are 50.7% and 51.7% respectively). The inhibitory activity of Compound II6 against Xanthomonas oryzae pv. oryzae is 79.2%, slightly lower than that of the control agent thiodiazole copper (79.4%).

[0121] Example 38: Preparation of the compositions of Compounds II1, II6, and II12 with abscisic acid (ABA)

[0122] Some of the preparations used below were prepared by adjusting the concentration of commercially available preparations. The following examples further illustrate the present invention, but the present invention is not limited to the ratios, preparation types, and uses in these examples. In the following examples, the target compounds II1, II6, and II12 and ABA are prepared into compositions. In each composition, the ratios of the target compounds II1, II6, and II12 and abscisic acid (ABA) are calculated according to the mass ratio. The following preparations of the target compounds II1, II6, and II12 and abscisic acid (ABA) are prepared as needed.

[0123] Composition 1: II1: Abscisic acid (ABA) = 1:1

[0124] Composition 2: II1: Abscisic acid (ABA) = 1:2

[0125] Composition 3: II1: Abscisic acid (ABA) = 2:1

[0126] Composition 4: II6: Abscisic acid (ABA) = 1:1

[0127] Composition 5: II6: Abscisic acid (ABA) = 1:2

[0128] Composition 6: II6: Abscisic acid (ABA) = 2:1

[0129] Composition 7: II12: Abscisic acid (ABA) = 1:1

[0130] Composition 8: II12: Abscisic acid (ABA) = 1:2

[0131] Composition 9: II12: Abscisic acid (ABA) = 2:1

[0132] Example 39: Inhibitory Activity of the Compound Mixture against Xanthomonas oryzae pv. oryzae, Xanthomonas axonopodis pv. citri, and Xanthomonas oryzae pv. oryzicola

[0133] According to the method described in Example 37, the inhibitory activity of the composition of Example 38 against Xanthomonas oryzae pv. oryzae, Xanthomonas axonopodis pv. citri, and Xanthomonas oryzae pv. oryzicola was tested.

[0134] Table 4 Inhibitory Activity of the Compound Mixture against Phytopathogens

[0135]

[0136] It can be seen from Table 4 that when the composition ratio of the composition is compound: abscisic acid (ABA) = 2:1, the compound mixture has the best synergistic effect against Xanthomonas axonopodis pv. citri, Xanthomonas oryzae pv. oryzicola, and Xanthomonas oryzae pv. oryzae at the test concentrations of 50 and 100 mg / mL. Its inhibitory activities against Xanthomonas axonopodis pv. citri, Xanthomonas oryzae pv. oryzicola, and Xanthomonas oryzae pv. oryzae at 100 and 50 mg / mL are 83.6%, 69.4%, 84.2%, 76.5%, 80.5%, and 56.7% respectively.

[0137] The examples of the present invention assist in explaining the technical solutions of the present invention. The effects of the present invention are that the synthesis route is simple, the yield is relatively high, and a preparation method of a novel and highly efficient phosphorus-containing agricultural compound synergist and its application in agriculture are obtained.

Claims

1. A novel phosphorus-containing agricultural compound synergist, characterized in that: The general formula of the synergist is as follows: R1 is hydrogen, 5-methoxypyrimidine, acetaldehyde, pyridine, 2,4-dimethoxypyrimidine, 3,4-dimethylisoxazole, benzaldehyde, 2-methoxypyrazine, 4,5-dimethoxypyrimidine, thiazole, 5-methylisoxazole or morpholine, and R2 is methyl, ethyl or n-butyl.

2. The method for preparing a novel phosphorus-containing agricultural compound synergist as claimed in claim 1, characterized in that: The following steps are involved:

3. The method for preparing a novel phosphorus-containing agricultural compound synergist according to claim 2, characterized in that: The synthesis steps are as follows: stirring a mixture of 4-cyanobenzaldehyde, substituted p-aminobenzenesulfonamide, dialkyl phosphite and aluminum trifluoromethanesulfonate in an oil bath for reaction; monitoring the reaction by thin layer chromatography until the raw material point disappears; filtering at room temperature after the reaction is completed, and repeatedly washing the filter cake with ACN to obtain the target compound.

4. The method for preparing a novel phosphorus-containing agricultural compound synergist according to claim 3, characterized in that: The usage ratio of the 4-cyanobenzaldehyde, substituted p-aminobenzenesulfonamide, dialkyl phosphite and aluminum trifluoromethanesulfonate is 1:1:1.2:0.

01.

5. Use of the novel phosphorus-containing agricultural compound synergist as claimed in claim 1 in agriculture.

6. Use of the novel phosphorus-containing agricultural compound synergist as claimed in claim 1 in the preparation of drugs for preventing and controlling rice bacterial blight, citrus canker and rice streak pathogen.

7. The use according to claim 6, characterized in that: The synergist is ((4-cyanobenzene)((4-(N-substituted)phenyl)amino)methyl)dialkyl phosphate.

8. A composite synergist, characterized in that: The composition comprises the synergist according to claim 1 and abscisic acid (ABA).

9. The composite synergist according to claim 7, characterized in that: The mass ratio of the synergist to ABA is 2:

1.

10. Use of the composite synergist according to claim 7 or 8 in the preparation of drugs for preventing and controlling Xanthomonas oryzae, Xanthomonas citri var. citri, and Pseudomonas dasyphyllae of rice.

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