Preparation method and application of active substance with functions of disease resistance and plant growth regulation

Abstract

The invention discloses a substance with both disease resistance and plant growth regulation activity, and particularly relates to a sulfonamide-containing abietic acid derivative, the general formula of the derivative is as follows: # imgabs0 #, wherein R is N-(4, 6-dimethyl pyrimidine-2-yl) benzenesulfonamide, N-(pyrimidine-2-yl) benzenesulfonamide, N-(3, 4-dimethyl pyrimidine-2-yl) benzenesulfonamide or N-(3, 4-dimethyl pyrimidine-2-yl) benzenesulfonamide; the preparation method comprises the following steps: preparing N-(5, 4-dimethylisoxazole-5-yl) benzenesulfonamide, N-(3-methoxypyrazine-2-yl) benzenesulfonamide, N-(6-methoxypyrimidine-4-yl) benzenesulfonamide, 3-amino-N-phenylbenzenesulfonamide, N-((4-aminophenyl) sulfonyl) benzamide, N-(5, 6-dimethyl-2, 4-dimethylisoxazole-5-yl) benzenesulfonamide, N-(4-aminophenyl) sulfonyl) benzamide, N 2, 6-dimethoxypyrimidine-4-yl) benzenesulfonamide, N-(6-chloropyridazine-3-yl) benzenesulfonamide and the like or disubstitution of any combination of the above substituent groups are selected. The derivative has a good inhibition effect on rice bacterial leaf streak, tobacco bacterial wilt, potato late blight and tobacco mosaic disease. The compound I-3 and kasugamycin show a synergistic effect in the process of preventing and treating the rice streak pathogen, and the purposes of pesticide reduction and synergism can be achieved. The plant growth regulator activity of part of the compounds is tested, and the compound I-3 is found to have good auxin activity and cytokinin activity.

Description

Technical Field

[0001] The present invention relates to the field of chemical technology, and particularly to a plant growth regulator of sulfonamide-containing rosin acid compounds, a preparation method of the compound, and a use of the composition thereof for inhibiting Xanthomonas oryzae pv. oryzicola, Ralstonia solanacearum, Phytophthora infestans, and tobacco mosaic virus. Background Art

[0002] Plant diseases caused by bacteria and viruses have led to a significant decline in the grain yield of crops. Diseases caused by pathogens or viruses such as Ralstonia solanacearum, Phytophthora infestans, and tobacco mosaic virus have caused huge economic losses to agriculture. At present, the commonly used antibacterial agents on the market not only have poor field control effects and are not conducive to the sustainable development of the environment, but also continuously enhance the drug resistance of bacteria. Therefore, it is urgent to develop a highly efficient, low-toxic, and environmentally friendly antiviral agent and antibacterial agent.

[0003] Plant growth regulators, that is, some substances produced by humans through microbial fermentation or chemical synthesis and having similar physiological and biological effects to natural phytohormones, are collectively called plant growth substances with natural phytohormones. At present, the research and wide application of new plant growth regulators are reflected in the fact that the sales volume of plant growth hormones in the world has increased from 260 million US dollars in 1974 to 700 million US dollars in 2007, and the growth rate is greater than that of any type of pesticide. Moreover, they are applied to cultivating short and strong seedlings of rice and rapeseed, preventing lodging of rice and wheat, regulating the plant type of cotton, regulating the flowering period of hybrid rice, increasing the latex yield of rubber, promoting rooting, fruit setting, and improving the quality of crops. Therefore, the development and research of plant growth regulators are of certain significance to the development of the national economy.

[0004] Kasugamycin is a highly efficient aminoglycoside agricultural antibiotic produced by Streptomyces kasugaensis, and has good control effects on bacteria such as Magnaporthe oryzae of rice, Clavibacter michiganensis subsp. sepedonicus of potato, Alternaria solani of celery, Fulvia fulva of tomato, Colletotrichum gloeosporioides of citrus, and Pseudomonas syringae pv. lachrymans of cucumber. Kasugamycin has the characteristics of low toxicity, low pollution, and low residue, meeting the requirements of modern green health. However, kasugamycin is easily affected by factors such as photolysis, acid-base destruction, and oxidative decomposition in the natural environment, and the efficiency is low in production applications. Therefore, the compounding work of kasugamycin is particularly important.

[0005] The natural organic acid abietic acid extracted from rosin has attracted much attention in the fields of drug and pesticide development due to its various biological activities. It not only has significant antibacterial and antifungal activities, can inhibit the growth of a variety of pathogenic microorganisms, reduce crop disease losses, and improve crop yield and quality, but also its antiviral and anti-inflammatory properties provide potential for drug applications. In addition, as a natural product, abietic acid is environmentally friendly and biodegradable, which gives it obvious advantages in the fields of ecological agriculture and green chemistry. The diversity of its structure provides a broad space for chemical modification. By introducing structural fragments with antibacterial activity, its biological activity can be further improved to develop more efficient and environmentally friendly pesticide products.

[0006] In summary, abietic acid derivatives have shown certain bactericidal activities, providing a reference for the creation of novel and highly efficient antiviral and bactericidal agents. Based on the previous work, the present invention designed and synthesized a series of sulfonamide-containing abietic acid compounds and studied their plant growth regulator activities, hoping to screen out highly active antiviral and antibacterial plant growth regulating drugs. Summary of the Invention

[0007] The object of the present invention is to provide a preparation method of a sulfonamide-containing abietic acid derivative plant growth regulator with bactericidal and antiviral activities and its composition.

[0008] Another object of the present invention is its use for inhibiting rice bacterial leaf streak, tobacco bacterial wilt, potato late blight, and tobacco mosaic disease.

[0009] The technical solution of the present invention: A sulfonamide-containing abietic acid compound, and the general formula of the derivative is the following formula (I):

[0010]

[0011] Wherein: R is N-(4,6-dimethylpyrimidin-2-yl)benzenesulfonamide, N-(pyrimidin-2-yl)benzenesulfonamide, N-(3,4-dimethylisoxazol-5-yl)benzenesulfonamide, N-(3-methoxypyrazin-2-yl)benzenesulfonamide, N-(6-methoxypyrimidin-4-yl)benzenesulfonamide, 3-amino-N-phenylbenzenesulfonamide, N-((4-aminophenyl)sulfonyl)benzamide, N-(5,6-dimethoxypyrimidin-4-yl)benzenesulfonamide, N-(6-chloropyridazin-3-yl)benzenesulfonamide, N-(6-methoxypyridazin-3-yl)benzenesulfonamide, N-(2,6-dimethoxypyrimidin-4-yl)benzenesulfonamide, N-(pyridin-2-yl)benzenesulfonamide, N-(5-methoxypyrimidin-2-yl)benzenesulfonamide, N-methylbenzenesulfonamide, N,N-dimethylbenzenesulfonamide, N-cyclopropylbenzenesulfonamide, N-(thiazol-2-yl)benzenesulfonamide, N-(4-methylpyrimidin-2-yl)benzenesulfonamide, 4-(morpholinosulfonyl)aniline, N-(4-aminophenyl)-4-methylbenzenesulfonamide, 6-amino-N-methylnaphthalene-2-sulfonamide or a disubstitution of any combination of the above substituents.

[0012] Preferably, R is N-(4,6-dimethylpyrimidin-2-yl)benzenesulfonamide, N-(pyrimidin-2-yl)benzenesulfonamide, N-(3,4-dimethylisoxazol-5-yl)benzenesulfonamide, N-(3-methoxypyrazin-2-yl)benzenesulfonamide, N-(6-methoxypyrimidin-4-yl)benzenesulfonamide, 3-amino-N-phenylbenzenesulfonamide, N-((4-aminophenyl)sulfonyl)benzamide, N-(5,6-dimethoxypyrimidin-4-yl)benzenesulfonamide, N-(6-chloropyridazin-3-yl)benzenesulfonamide, N-(6-methoxypyridazin-3-yl)benzenesulfonamide, N-(2,6-dimethoxypyrimidin-4-yl)benzenesulfonamide, N-(pyridin-2-yl)benzenesulfonamide, N-(5-methoxypyrimidin-2-yl)benzenesulfonamide, N-methylbenzenesulfonamide, N,N-dimethylbenzenesulfonamide, N-cyclopropylbenzenesulfonamide, N-(thiazol-2-yl)benzenesulfonamide, N-(4-methylpyrimidin-2-yl)benzenesulfonamide, 4-(morpholinosulfonyl)aniline, N-(4-aminophenyl)-4-methylbenzenesulfonamide, 6-amino-N-methylnaphthalene-2-sulfonamide or a disubstitution of any combination of the above substituents.

[0013] Sulfonamide-containing rosin acid derivatives, specific compounds are as follows:

[0014] Compound II-1: (1S,4S,10S)-N-(4-(N-(4,6-dimethylpyrimidin-2-yl)aminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide;

[0015] Compound II-2: (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-(N-(pyrimidin-2-yl)sulfamoyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide;

[0016] Compound II-3: (1S,4S,10S)-N-(4-(N-(3,4-dimethylisoxazol-5-yl)sulfamoyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide;

[0017] Compound II-4: (1S,4S,10S)-7-isopropyl-N-(4-(N-(3-methoxypyrazin-2-yl)sulfamoyl)phenyl)-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide;

[0018] Compound II-5: (1S,4S,10S)-7-isopropyl-N-(4-(N-(6-methoxypyrimidin-4-yl)sulfamoyl)phenyl)-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide;

[0019] Compound II-6: (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(3-(N-phenylsulfamoyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide;

[0020] Compound II-7: (1S,4S,10S)-N-(4-(N-benzoylsulfamoyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide;

[0021] Compound II-8: (1S,4S,10S)-N-(4-(N-(5,6-dimethoxypyrimidin-4-yl)sulfamoyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide;

[0022] Compound II-9: (1S,4S,10S)-N-(4-(N-(6-chloropyridazin-3-yl)sulfamoyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide;

[0023] Compound II-10: (1S,4S,10S)-7-isopropyl-N-(4-(N-(6-methoxypyridazin-3-yl)sulfamoyl)phenyl)-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide;

[0024] Compound II-11: (1S,4S,10S)-N-(4-(N-(2,6-dimethoxypyrimidin-4-yl)aminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide;

[0025] Compound II-12: (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-(N-(pyridin-2-yl)aminosulfonyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide;

[0026] Compound II-13: (1S,4S,10S)-7-isopropyl-N-(4-(N-(5-methoxypyrimidin-2-yl)aminosulfonyl)phenyl)-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide;

[0027] Compound II-14: (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-(N-methylaminosulfonyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide;

[0028] Compound II-15: (1S,4S,10S)-N-(4-(N,N-dimethylaminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide;

[0029] Compound II-16: (1S,4S,10S)-N-(4-(N-cyclopropylaminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide;

[0030] Compound II-17: (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-(N-(thiazol-2-yl)aminosulfonyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide;

[0031] Compound II-18: (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-(N-(4-methylpyrimidin-2-yl)aminosulfonyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide;

[0032] Compound II-19: (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-(morpholinosulfonyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide;

[0033] Compound II-20: (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-((4-methylphenyl)sulfonamido)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide;

[0034] Compound II-21: (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(6-(N-methylsulfamoyl)naphthalen-2-yl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide.

[0035] A preparation method of a sulfonamide-containing dehydroabietic acid derivative, comprising the following steps:

[0036] (1) Charge rosin acid and thionyl chloride at a ratio of 1:3, heat under reflux for 1 - 3 h. After the reaction ends and the temperature drops to room temperature, evaporate under reduced pressure to obtain 1-formyl chloride rosin acid;

[0037]

[0038] (2) Charge 1-formyl chloride rosin acid, substituted sulfonamide, and triethylamine at a ratio of 1:1 - 1.2:0.5, add 5 mL of dichloromethane, stir in an ice bath for 20 min. After the reaction ends, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and separate and purify by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain the target compound.

[0039]

[0040] Use of the said derivative in the preparation of drugs and agents for preventing and treating bacterial leaf streak of rice, bacterial wilt of tobacco, late blight of potato, and tobacco mosaic virus.

[0041] A compound pesticide composition, characterized in that: the said composition contains the said derivative and kasugamycin. The mass ratio of the said derivative to kasugamycin is 1:2 - 2:1. The said derivative is (1S,4S,10S)-N-(4-(N-(3,4-dimethylisoxazol-5-yl)aminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide.

[0042] Use of the said composition in the preparation of drugs for preventing and treating plant bacterial diseases. The plant bacterial disease is bacterial leaf streak of rice.

[0043] A novel plant growth regulator is the compound (1S,4S,10S)-N-(4-(N-(3,4-dimethylisoxazol-5-yl)aminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide, the compound of formula (7) below:

[0044]

[0045] Advantages of the present invention: The present invention synthesizes sulfonamide-containing abietic acid derivatives with antibacterial activity against Xanthomonas oryzae pv. oryzicola. The advantages of the present invention are that the raw materials are easily available, the process is simple, and the reaction conditions are mild. The inhibition rate of compound II-3 in the present invention against Xanthomonas oryzae pv. oryzicola is 62.1% at a concentration of 100 mg / L, exceeding the inhibition rate of the commercial agent thiodiazole copper of 55.4%. In addition, for the selected composition of the present invention, compound II-3 and kasugamycin show a synergistic effect in the control of Xanthomonas oryzae pv. oryzicola, which can further reduce the production cost and usage cost, achieving the purpose of reducing the amount of medicine and increasing the efficacy. The experimental results show that compound II-3 has good plant growth regulation activity, providing a basis for the subsequent research on abietic acid-based plant growth regulating agents. Specific Embodiments

[0046] Example 1: Synthesis of (1S,4S,10S)-N-(4-(N-(4,6-dimethylpyrimidin-2-yl)aminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (compound number II-1), including the following steps:

[0047] (1) Charge abietic acid and thionyl chloride at a ratio of 1:3, heat under reflux for 1 - 3 h. After the reaction is completed and the temperature drops to room temperature, evaporate under reduced pressure to obtain 1-formyl chloride abietic acid.

[0048] (2) Charge 1-formyl chloride abietic acid, 4-amino-N-(4,6-dimethylpyrimidin-2-yl)benzenesulfonamide, and triethylamine at a ratio of 1:1 - 1.2:0.5, add 5 mL of dichloromethane, stir in an ice bath for 20 min. After the reaction is completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and perform separation and purification by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-N-(4-(N-(4,6-dimethylpyrimidin-2-yl)aminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide, with a yield of 67%.

[0049] Example 2: Synthesis of (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-(N-(pyrimidin-2-yl)aminosulfonyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (Compound No. II-2), which comprises the following steps:

[0050] (1) Charge rosin acid and thionyl chloride at a ratio of 1:3, heat under reflux for 1 - 3 h. After the reaction is completed and the temperature drops to room temperature, evaporate under reduced pressure to obtain 1-formyl chloride rosin acid.

[0051] (2) Charge 1-formyl chloride rosin acid, 4-amino-N-(pyrimidin-2-yl)benzenesulfonamide, and triethylamine at a ratio of 1:1 - 1.2:0.5, add 5 mL of dichloromethane, stir in an ice bath for 20 min. After the reaction is completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and separate and purify by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-(N-(pyrimidin-2-yl)aminosulfonyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide with a yield of 44%.

[0052] Example 3: Synthesis of (1S,4S,10S)-N-(4-(N-(3,4-dimethylisoxazol-5-yl)aminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (Compound No. II-3), which comprises the following steps:

[0053] (1) Charge rosin acid and thionyl chloride at a ratio of 1:3, heat under reflux for 1 - 3 h. After the reaction is completed and the temperature drops to room temperature, evaporate under reduced pressure to obtain 1-formyl chloride rosin acid.

[0054] (2) Charge 1-formyl chloride rosin acid, 4-amino-N-(3,4-dimethylisoxazol-5-yl)benzenesulfonamide, and triethylamine at a ratio of 1:1 - 1.2:0.5, add 5 mL of dichloromethane, stir in an ice bath for 20 min. After the reaction is completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and separate and purify by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-N-(4-(N-(3,4-dimethylisoxazol-5-yl)aminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide with a yield of 56%.

[0055] Example 4: Synthesis of (1S,4S,10S)-7-isopropyl-N-(4-(N-(3-methoxypyrazin-2-yl)aminosulfonyl)phenyl)-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (Compound No. II-4), which comprises the following steps:

[0056] (1) Charge rosin acid and thionyl chloride at a ratio of 1:3, heat under reflux for 1 - 3 h. After the reaction is completed and the temperature drops to room temperature, evaporate under reduced pressure to obtain 1-formyl chloride rosin acid.

[0057] (2) Charge 1-formyl chloride rosin acid, 4-amino-N-(3-methoxypyrazin-2-yl)benzenesulfonamide, and triethylamine at a ratio of 1:1 - 1.2:0.5, add 5 mL of dichloromethane, stir in an ice bath for 20 min. After the reaction is completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and perform separation and purification by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-7-isopropyl-N-(4-(N-(3-methoxypyrazin-2-yl)aminosulfonyl)phenyl)-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide with a yield of 39%.

[0058] Example 5: Synthesis of (1S,4S,10S)-7-isopropyl-N-(4-(N-(6-methoxypyrimidin-4-yl)aminosulfonyl)phenyl)-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (Compound No. II-5), which comprises the following steps:

[0059] (1) Charge rosin acid and thionyl chloride at a ratio of 1:3, heat under reflux for 1 - 3 h. After the reaction is completed and the temperature drops to room temperature, evaporate under reduced pressure to obtain 1-formyl chloride rosin acid.

[0060] (2) Charge 1-formyl chloride rosin acid, 4-amino-N-(6-methoxypyrimidin-4-yl)benzenesulfonamide, and triethylamine at a ratio of 1:1 - 1.2:0.5, add 5 mL of dichloromethane, stir in an ice bath for 20 min. After the reaction is completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and perform separation and purification by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-7-isopropyl-N-(4-(N-(6-methoxypyrimidin-4-yl)aminosulfonyl)phenyl)-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide with a yield of 59%.

[0061] Example 6: Synthesis of (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(3-(N-phenylaminosulfonyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (Compound No. II-6), which comprises the following steps:

[0062] (1) Charge rosin acid and thionyl chloride at a ratio of 1:3, heat under reflux for 1 - 3 h. After the reaction is completed and the temperature drops to room temperature, evaporate under reduced pressure to obtain 1-formyl chloride rosin acid.

[0063] (2) Charge 1-formyl chloride rosin acid, 3-amino-N-phenylbenzenesulfonamide, and triethylamine at a ratio of 1:1 - 1.2:0.5, add 5 mL of dichloromethane, stir in an ice bath for 20 min. After the reaction is completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and perform separation and purification by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(3-(N-phenylaminosulfonyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide with a yield of 61%.

[0064] Example 7: Synthesis of (1S,4S,10S)-N-(4-(N-benzoylaminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (Compound No. II-7), which comprises the following steps:

[0065] (1) Charge rosin acid and thionyl chloride at a ratio of 1:3, heat under reflux for 1 - 3 h. After the reaction is completed and the temperature drops to room temperature, evaporate under reduced pressure to obtain 1-formyl chloride rosin acid.

[0066] (2) Charge 1-formyl chloride rosin acid, N-((4-aminophenyl)sulfonyl)benzamide, and triethylamine at a ratio of 1:1 - 1.2:0.5, add 5 mL of dichloromethane, stir in an ice bath for 20 min. After the reaction is completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and perform separation and purification by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-N-(4-(N-benzoylaminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide with a yield of 57%.

[0067] Example 8: Synthesis of (1S,4S,10S)-N-(4-(N-(5,6-dimethoxypyrimidin-4-yl)aminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (Compound No. II-8), comprising the following steps:

[0068] (1) Charge rosin acid and thionyl chloride at a ratio of 1:3, heat under reflux for 1 - 3 h. After the reaction is completed and the temperature drops to room temperature, evaporate under reduced pressure to obtain 1-formylchloride rosin acid.

[0069] (2) Charge 1-formylchloride rosin acid, 4-amino-N-(5,6-dimethoxypyrimidin-4-yl)benzenesulfonamide, and triethylamine at a ratio of 1:1 - 1.2:0.5, add 5 mL of dichloromethane, stir in an ice bath for 20 min. After the reaction is completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and separate and purify by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-N-(4-(N-(5,6-dimethoxypyrimidin-4-yl)aminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide, with a yield of 63%.

[0070] Example 9: Synthesis of (1S,4S,10S)-N-(4-(N-(6-chloropyridazin-3-yl)aminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (Compound No. II-9), comprising the following steps:

[0071] (1) Charge rosin acid and thionyl chloride at a ratio of 1:3, heat under reflux for 1 - 3 h. After the reaction is completed and the temperature drops to room temperature, evaporate under reduced pressure to obtain 1-formylchloride rosin acid.

[0072] (2) Charge 1-formylchloride rosin acid, 4-amino-N-(6-chloropyridazin-3-yl)benzenesulfonamide, and triethylamine at a ratio of 1:1 - 1.2:0.5, add 5 mL of dichloromethane, stir in an ice bath for 20 min. After the reaction is completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and separate and purify by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-N-(4-(N-(6-chloropyridazin-3-yl)aminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide, with a yield of 63%.

[0073] Example 10: Synthesis of (1S,4S,10S)-7-isopropyl-N-(4-(N-(6-methoxypyridazin-3-yl)aminosulfonyl)phenyl)-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (Compound No. II-10), which comprises the following steps:

[0074] (1) Charge rosin acid and thionyl chloride at a ratio of 1:3, heat under reflux for 1 - 3 h. After the reaction is completed and the temperature drops to room temperature, evaporate under reduced pressure to obtain 1-formyl chloride rosin acid.

[0075] (2) Charge 1-formyl chloride rosin acid, 4-amino-N-(6-methoxypyridazin-3-yl)benzenesulfonamide, and triethylamine at a ratio of 1:1 - 1.2:0.5, add 5 mL of dichloromethane, stir in an ice bath for 20 min. After the reaction is completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and perform separation and purification by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-7-isopropyl-N-(4-(N-(6-methoxypyridazin-3-yl)aminosulfonyl)phenyl)-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide with a yield of 68%.

[0076] Example 11: Synthesis of (1S,4S,10S)-N-(4-(N-(2,6-dimethoxypyrimidin-4-yl)aminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (Compound No. II-11), which comprises the following steps:

[0077] (1) Charge rosin acid and thionyl chloride at a ratio of 1:3, heat under reflux for 1 - 3 h. After the reaction is completed and the temperature drops to room temperature, evaporate under reduced pressure to obtain 1-formyl chloride rosin acid.

[0078] (2) Charge 1-formyl chloride rosin acid, 4-amino-N-(2,6-dimethoxypyrimidin-4-yl)benzenesulfonamide, and triethylamine at a ratio of 1:1 - 1.2:0.5, add 5 mL of dichloromethane, stir in an ice bath for 20 min. After the reaction is completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and perform separation and purification by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-N-(4-(N-(2,6-dimethoxypyrimidin-4-yl)aminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide with a yield of 56%.

[0079] Example 12: Synthesis of (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-(N-(pyridin-2-yl)aminosulfonyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (Compound No. II-12), comprising the following steps:

[0080] (1) Rosin acid and thionyl chloride were fed in a ratio of 1:3, heated under reflux for 1 - 3 h. After the reaction ended and the temperature dropped to room temperature, evaporation under reduced pressure was carried out to obtain 1-formylchloride rosin acid.

[0081] (2) 1-Formylchloride rosin acid, 4-amino-N-(pyridin-2-yl)benzenesulfonamide, and triethylamine were fed in a ratio of 1:1 - 1.2:0.5. 5 mL of dichloromethane was added, and the mixture was stirred in an ice bath for 20 min. After the reaction ended, the reaction system was poured into saturated brine, extracted with dichloromethane, and the organic layer was collected. Separation and purification were carried out by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-(N-(pyridin-2-yl)aminosulfonyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide, with a yield of 43%.

[0082] Example 13: Synthesis of (1S,4S,10S)-7-isopropyl-N-(4-(N-(5-methoxypyrimidin-2-yl)aminosulfonyl)phenyl)-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (Compound No. II-13), comprising the following steps:

[0083] (1) Rosin acid and thionyl chloride were fed in a ratio of 1:3, heated under reflux for 1 - 3 h. After the reaction ended and the temperature dropped to room temperature, evaporation under reduced pressure was carried out to obtain 1-formylchloride rosin acid.

[0084] (2) 1-Formylchloride rosin acid, 4-amino-N-(5-methoxypyrimidin-2-yl)benzenesulfonamide, and triethylamine were fed in a ratio of 1:1 - 1.2:0.5. 5 mL of dichloromethane was added, and the mixture was stirred in an ice bath for 20 min. After the reaction ended, the reaction system was poured into saturated brine, extracted with dichloromethane, and the organic layer was collected. Separation and purification were carried out by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-7-isopropyl-N-(4-(N-(5-methoxypyrimidin-2-yl)aminosulfonyl)phenyl)-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide, with a yield of 52%.

[0085] Example 14: Synthesis of (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-(N-methylaminosulfonyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (Compound No. II-14), comprising the following steps:

[0086] (1) Charge rosin acid and thionyl chloride at a ratio of 1:3, heat under reflux for 1 - 3 h. After the reaction is completed and the temperature drops to room temperature, evaporate under reduced pressure to obtain 1-formylchloride rosin acid.

[0087] (2) Charge 1-formylchloride rosin acid, 4-amino-N-methylbenzenesulfonamide, and triethylamine at a ratio of 1:1 - 1.2:0.5, add 5 mL of dichloromethane, stir in an ice bath for 20 min. After the reaction is completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and separate and purify by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-(N-methylaminosulfonyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide with a yield of 68%.

[0088] Example 15: Synthesis of (1S,4S,10S)-N-(4-(N,N-dimethylaminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (Compound No. II-15), comprising the following steps:

[0089] (1) Charge rosin acid and thionyl chloride at a ratio of 1:3, heat under reflux for 1 - 3 h. After the reaction is completed and the temperature drops to room temperature, evaporate under reduced pressure to obtain 1-formylchloride rosin acid.

[0090] (2) Charge 1-formylchloride rosin acid, 4-amino-N,N-dimethylbenzenesulfonamide, and triethylamine at a ratio of 1:1 - 1.2:0.5, add 5 mL of dichloromethane, stir in an ice bath for 20 min. After the reaction is completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and separate and purify by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-N-(4-(N,N-dimethylaminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide with a yield of 47%.

[0091] Example 16: Synthesis of (1S,4S,10S)-N-(4-(N-cyclopropylaminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (Compound No. II-16), which comprises the following steps:

[0092] (1) Charge rosin acid and thionyl chloride at a ratio of 1:3, heat under reflux for 1 - 3 h. After the reaction is completed and the temperature drops to room temperature, evaporate under reduced pressure to obtain 1-formyl chloride rosin acid.

[0093] (2) Charge 1-formyl chloride rosin acid, 4-amino-N-cyclopropylbenzenesulfonamide, and triethylamine at a ratio of 1:1 - 1.2:0.5, add 5 mL of dichloromethane, stir in an ice bath for 20 min. After the reaction is completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and separate and purify by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-N-(4-(N-cyclopropylaminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide with a yield of 66%.

[0094] Example 17: Synthesis of (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-(N-(thiazol-2-yl)aminosulfonyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (Compound No. II-17), which comprises the following steps:

[0095] (1) Charge rosin acid and thionyl chloride at a ratio of 1:3, heat under reflux for 1 - 3 h. After the reaction is completed and the temperature drops to room temperature, evaporate under reduced pressure to obtain 1-formyl chloride rosin acid.

[0096] (2) Charge 1-formyl chloride rosin acid, 4-amino-N-(thiazol-2-yl)benzenesulfonamide, and triethylamine at a ratio of 1:1 - 1.2:0.5, add 5 mL of dichloromethane, stir in an ice bath for 20 min. After the reaction is completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and separate and purify by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-(N-(thiazol-2-yl)aminosulfonyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide with a yield of 38%.

[0097] Example 18: Synthesis of (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-(N-(4-methylpyrimidin-2-yl)aminosulfonyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (Compound No. II-18), which comprises the following steps:

[0098] (1) Charge rosin acid and thionyl chloride at a ratio of 1:3, heat under reflux for 1 - 3 h. After the reaction is completed and the temperature drops to room temperature, evaporate under reduced pressure to obtain 1-formyl chloride rosin acid.

[0099] (2) Charge 1-formyl chloride rosin acid, 4-amino-N-(4-methylpyrimidin-2-yl)benzenesulfonamide, and triethylamine at a ratio of 1:1 - 1.2:0.5, add 5 mL of dichloromethane, stir in an ice bath for 20 min. After the reaction is completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and perform separation and purification by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-(N-(4-methylpyrimidin-2-yl)aminosulfonyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide with a yield of 48%.

[0100] Example 19: Synthesis of (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-(morpholinosulfonyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (Compound No. II-19), which comprises the following steps:

[0101] (1) Charge rosin acid and thionyl chloride at a ratio of 1:3, heat under reflux for 1 - 3 h. After the reaction is completed and the temperature drops to room temperature, evaporate under reduced pressure to obtain 1-formyl chloride rosin acid.

[0102] (2) Charge 1-formyl chloride rosin acid, 4-(morpholinosulfonyl)aniline, and triethylamine at a ratio of 1:1 - 1.2:0.5, add 5 mL of dichloromethane, stir in an ice bath for 20 min. After the reaction is completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and perform separation and purification by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-(morpholinosulfonyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide with a yield of 53%.

[0103] Example 20: Synthesis of (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-((4-methylphenyl)sulfamoyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (Compound No. II-20), including the following steps:

[0104] (1) Charge rosin acid and thionyl chloride at a ratio of 1:3, heat under reflux for 1 - 3 h. After the reaction is completed and the temperature drops to room temperature, evaporate under reduced pressure to obtain 1-formyl chloride rosin acid.

[0105] (2) Charge 1-formyl chloride rosin acid, N-(4-aminophenyl)-4-methylbenzenesulfonamide, and triethylamine at a ratio of 1:1 - 1.2:0.5, add 5 mL of dichloromethane, stir in an ice bath for 20 min. After the reaction is completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and separate and purify by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(4-((4-methylphenyl)sulfamoyl)phenyl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide, with a yield of 61%.

[0106] Example 21: Synthesis of (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(6-(N-methylaminosulfonyl)naphthalen-2-yl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide (Compound No. II-21), including the following steps:

[0107] (1) Charge rosin acid and thionyl chloride at a ratio of 1:3, heat under reflux for 1 - 3 h. After the reaction is completed and the temperature drops to room temperature, evaporate under reduced pressure to obtain 1-formyl chloride rosin acid.

[0108] (2) Charge 1-formyl chloride rosin acid, 6-amino-N-methylnaphthalene-2-sulfonamide, and triethylamine at a ratio of 1:1 - 1.2:0.5, add 5 mL of dichloromethane, stir in an ice bath for 20 min. After the reaction is completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, and separate and purify by column chromatography (petroleum ether:ethyl acetate = 3:1 - 1:1) to obtain (1S,4S,10S)-7-isopropyl-1,4-dimethyl-N-(6-(N-methylaminosulfonyl)naphthalen-2-yl)-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide, with a yield of 52%.

[0109] For the nuclear magnetic resonance hydrogen spectrum ( 1 HNMR), carbon spectrum ( 13The \(^{13}\)C NMR and high-resolution mass spectrometry (HRMS) data are shown in Table 1.

[0110] Table 1. Spectral data of Compounds II-1 to II-21

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120] Example 22: Inhibitory Activity of the Target Compound against Xanthomonas oryzae pv. oryzicola, Ralstonia solanacearum, and Phytophthora infestans

[0121] (1) Test Method

[0122] The bactericidal activity of the compound was determined by the turbidimetric method (Yang L., et al., 2017). A test compound with a concentration of 100 mg / L was prepared. NB medium was prepared (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). A small piece of medium containing Xanthomonas oryzae pv. oryzicola, Ralstonia solanacearum, and Phytophthora infestans was respectively picked with an inoculation loop and placed into two NB media. The plugs were inserted, and the cultures were shaken in a constant temperature shaker at 28 °C and 180 rpm until the logarithmic growth phase (OD 595 = 0.6 - 0.8) for standby. 40 μL of the bacterial solution, 4 mL of water-Tween (1% Tween-20), and 1 mL of the prepared compound solution were taken, and the test tubes were cultured at 28 ± 1 °C and continuously shaken at 180 rpm for 1 - 3 days. The growth of bacteria was monitored by measuring the optical density at 595 nm (OD 595 ), but the same concentration of solvent and 0.1% Tween 20 were used as the blank control, and kasugamycin was used as the control agent. Each treatment was repeated three times. The inhibition rate of the agent against bacteria was calculated by the following formula:

[0123] I = (Ctur - Ttur) / Ctur × 100%

[0124] 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.

[0125] (2) Biological test results

[0126] Table 2 Inhibitory activities of the target compounds against Xanthomonas oryzae pv. oryzicola, Ralstonia solanacearum, and Phytophthora infestans

[0127]

[0128]

[0129] Using the turbidimetry method, the antibacterial activities of the target compounds were tested at a concentration of 100 mg / L, with thiodiazole copper and thiazole zinc as the control agents. It can be seen from the biological activity determination results in Table 2 that the sulfonamide-containing rosin acid compounds have moderate to excellent inhibitory activities against Pseudomonas syringae pv. actinidiae. Among them, II-2 and II-3 have the best activities, with an inhibitory activity of 62.1% against Xanthomonas oryzae pv. oryzicola, which is higher than that of the control agent thiodiazole copper (55.4%).

[0130] Example 23: Therapeutic, inactivation, and protective activities of the target compounds against tobacco mosaic virus

[0131] (1) Test method

[0132] A. Virus purification

[0133] Using the Gooding method (Gooding; et al. 1967), select the upper leaves of Nicotiana glutinosa L. plants that have been inoculated for more than 3 weeks and are systemically infected with TMV. Homogenize them in a phosphate buffer, filter through double-layer gauze, centrifuge at 1000 rpm, treat with polyethylene glycol twice, and then centrifuge again. Suspend the precipitate in a phosphate buffer to obtain a crude extract of TMV. The entire experiment is carried out at 4°C. Measure the absorbance value at a wavelength of 260 nm using an ultraviolet spectrophotometer, and calculate the virus concentration according to the formula.

[0134] Virus concentration (mg / mL) = (A260 × dilution factor) / E0.1%1cm 260nm

[0135] Where E represents the extinction coefficient, that is, the light absorption (optical density) value of a suspension with a concentration of 0.1% (1 mg / mL) at a wavelength of 260 nm and a light path of 1 cm. The E0.1%1cm 260nm of TMV is 3.1.

[0136] B. Active therapeutic effect of the agent on TMV infection: Select Nicotiana glutinosa plants with consistent growth. First, use a writing brush to dip into the virus sap and inoculate the virus on the whole leaf. After inoculation, rinse with clean water. After the leaf dries, apply the agent on the right half leaf and apply the corresponding dose of solvent on the left half leaf as a control. Then, culture in a light incubator under humid conditions, control the temperature at 23 ± 1 °C, light intensity at 10,000 Lux. After 3 - 4 days, observe and record the number of necrotic spots. Set 3 plants for each agent treatment, with 3 - 4 leaves per plant. Repeat each agent 3 times according to the above method, and calculate the inhibition rate according to the following formula.

[0137] C. Active protective effect of the agent on TMV infection

[0138] Active protective effect of the agent on TMV infection: Select Nicotiana glutinosa plants with consistent growth. First, use a writing brush to apply the agent on the right half leaf and apply the corresponding dose of solvent on the left half leaf as a control. After the leaf dries, dip the writing brush into the virus sap and inoculate the virus on the whole leaf. After inoculation, rinse with clean water. Then, culture in a light incubator under humid conditions, control the temperature at 23 ± 1 °C, light intensity at 10,000 Lux. After 3 - 4 days, observe and record the number of necrotic spots. Set 3 plants for each agent treatment, with 3 - 4 leaves per plant. Repeat each agent 3 times according to the above method, and calculate the inhibition rate according to the following formula.

[0139] D. Active inactivation effect of the agent on TMV infection

[0140] Active inactivation effect of the agent on TMV infection: Select Nicotiana glutinosa plants with consistent growth. Evenly spread carborundum on the whole leaf. Mix the compound with an equal volume of virus sap and inactivate for 30 minutes. Use a brush to manually rub and inoculate on the right half leaf of suitable-age Chenopodium amaranticolor with carborundum spread. Mix the corresponding dose of solvent with virus sap and inoculate on the left half leaf of suitable-age Chenopodium amaranticolor with carborundum spread. After 3 - 4 days, observe and record the number of necrotic spots. Set 3 plants for each agent treatment, with 3 - 4 leaves per plant. Repeat each agent 3 times according to the above method, and calculate the inhibition rate according to the following formula.

[0141] Y = (C - A) / C × 100%

[0142] Where: Y is the inhibition rate of the compound on tobacco mosaic virus; C is the number of necrotic spots on the control group (left half leaf), and A is the number of necrotic spots on the treatment group (right half leaf).

[0143] (2) Biological test results

[0144] Table 3 Therapeutic, protective, and inactivation activities of the target compound against tobacco mosaic virus

[0145]

[0146]

[0147] The anti-TMV activity of the target compound was tested using the half-leaf spot method at a concentration of 500 μg / mL and ningnanmycin as the control agent. From the biological activity assay results in Table 3, it can be seen that the rosin acid compounds containing sulfonamide structure have moderate to excellent inhibitory activity against TMV, among which II-7 is superior to the control agent ningnanmycin in both treatment and protection.

[0148] Example 24: Preparation of target compound II-3 composition

[0149] Some of the preparations used below are prepared by adjusting the concentration of commercially available preparations. The following examples are further explanations of the present invention, but the present invention is not limited to the ratios, preparation types and uses in the present examples. In the following examples, wettable powders of target compound II-3 and kasugamycin are used to prepare composite compositions, and in each composition, the ratio of target compound II-3 to kasugamycin is calculated according to the mass ratio. The following preparations of target compound II-3 and kasugamycin are prepared as needed.

[0150] Composition 1: II-3: Kasugamycin wettable powder = 1:1

[0151] Composition 2: II-3: Kasugamycin wettable powder = 1:2

[0152] Composition 3: II-3: Kasugamycin wettable powder = 2:1

[0153] Example 25: Anti-rice streak disease activity of the composition of target compound II-3

[0154] According to the antibacterial activity test method mentioned in Example 22, the antibacterial activity of the combination of target compound II-3 and zhongshengmycin was tested for its activity against rice streak pathogen.

[0155] Table 4 Inhibitory activity of drugs against rice streak pathogen

[0156]

[0157] The in vitro growth rate method was used to test the anti-kiwifruit canker pathogen activity of the composition at a concentration of 100 μg / mL. From the biological activity assay results in Table 4, it can be seen that the anti-kiwifruit canker pathogen activity of the composite composition is improved compared with the compound before compounding. The inhibitory activity of composition 3 (II-3: kasugamycin wettable powder = 2:1) against kiwifruit canker pathogen reached 70.4%. Therefore, the composite composition of II-3 and kasugamycin has a synergistic effect on kiwifruit canker.

[0158] Example 26: Determination of plant growth regulating activity of some target compounds

[0159] (1) Test method

[0160] The plant growth regulatory activities of the target compounds were determined by using the wheat coleoptile cutting test method and the radish cotyledon expansion method (Song Yangyang. Research on the Synthesis and Biological Activities of Novel Plant Growth Regulators Containing Ferrocene Groups [D]. Northwest University, 2011.). Prepare the required solutions: Weigh 1.019 g of citric acid, 2.350 g of dipotassium hydrogen phosphate trihydrate, and 20 g of sugar, mix and make up the volume to 1 L to obtain a citric acid-phosphate buffer solution with a pH of 5. In the wheat coleoptile test method, indoleacetic acid (IAA) was used as the standard control, and in the radish cotyledon expansion method, kinetin (KT) was used as the standard control. Weigh an appropriate amount of the target compound and the control sample, dissolve them with a few drops of DMF, add one drop of emulsifier (Tween-80), and prepare sample solutions with a concentration of 100 μg / mL using the buffer solution, and then dilute them successively to 50, 10, and 1 μg / mL. Weigh 2.4 g of agar, heat it with 400 mL of water until it dissolves, pour it into a porcelain dish and let it cool to obtain the germination bed.

[0161] Wheat coleoptile cutting test method: Take about 50 g of wheat seeds, soak them for 4 h, rinse them several times with clean water, drain the water, evenly place them in the germination bed, seal them with a film, and place them in an artificial climate chamber at 25 ± 1 °C for dark cultivation. When the wheat coleoptiles grow to 2.5 - 3 cm, select sections with consistent growth, take the sensitive sections with a blade, take one section from each bud, shade them, and place them in distilled water for rinsing for one hour. Take 8 mL of each sample solution and place it in a culture dish with a diameter of 9 cm, add two filter papers to each, and evenly place 10 cut coleoptile segments in each treatment, then place them in an artificial climate chamber at 25 ± 1 °C for dark cultivation. After 48 h, measure the total length of 10 segments, compare it with the blank buffer solution control, and at the same time compare it with the standard solution of the same concentration, calculate the inhibitory or promoting effect, and use it as an evaluation index for the function of the drug auxin. The calculation method is as follows:

[0162] Effect = (Treatment - Blank) / Blank * 100%

[0163] If the calculated result is positive, it indicates a promoting effect; if it is negative, it indicates an inhibitory effect. Then, the drug efficacy evaluation is carried out. The evaluation criteria are as follows:

[0164]

[0165] Radish cotyledon expansion method: Take about 30 g of radish seeds, soak them in warm water until the seeds show white tips, wash them with clear water, drain the water, put them in a germination bed and seal it with a film, and place it in an artificial climate chamber at 25 ± 1 °C for dark cultivation for about 72 h for standby. Take 8 mL of each sample solution and add two pieces of filter paper to each Petri dish with a diameter of 9 cm. Select radish seedlings with uniform growth and consistent cotyledon size, then cut off the cotyledons without petioles, put 10 pieces in each treatment, and at the same time weigh the fresh weight of the cotyledons before each group of treatments, record the data, cover the Petri dish lid, and cultivate in the dark in the artificial climate chamber. After 72 h, take out the cotyledons of each group, blot the water attached to the surface of the cotyledons with absorbent paper, weigh the fresh weight of the cotyledons after each group of treatments, record the data, calculate the percentage increase in the fresh weight of the cotyledons after cultivation, and use it as an evaluation index for the cytokinin function of the drug sample. The calculation method and evaluation criteria are the same as those of the wheat coleoptile cutting test method.

[0166] (2) Biological test results

[0167] Table 5 Plant growth regulator activities of some target compounds

[0168]

[0169]

[0170] The test results of the plant growth activities of this series of target compounds are shown in Table 5. The preliminary biological activity test results show that the target compounds have certain plant growth regulating activities. Among them, compound I-9 has good auxin activity, but is inferior to kinetin activity. Within a certain range, the activity at high concentration is better than that at low concentration, such as compound I-4.

[0171] The examples of the present invention are used to illustrate 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 new type of high-efficiency plant growth regulating agent for controlling rice bacterial leaf streak disease is obtained.

Claims

1. A rosin acid derivative containing sulfonamide, characterized in that: The general formula of the derivative is as follows: Wherein: R is N-(4,6-dimethylpyrimidin-2-yl)benzenesulfonamide, N-(pyrimidin-2-yl)benzenesulfonamide, N-(3,4-dimethylisoxazol-5-yl)benzenesulfonamide, N-(3-methoxypyrazin-2-yl)benzenesulfonamide, N-(6-methoxypyrimidin-4-yl)benzenesulfonamide, 3-amino-N-phenylbenzenesulfonamide, N-((4-aminophenyl)sulfonyl)benzamide, N-(5,6-dimethoxypyrimidin-4-yl)benzenesulfonamide, N-(6-chloropyridazine-3-yl)benzenesulfonamide, N-(6-methoxypyridazine-3-yl)benzenesulfonamide, 1-(4-methylpyrimidin-2-yl)benzenesulfonamide, 4-(morpholinesulfonyl)aniline, N-(4-aminophenyl)-4-methylbenzenesulfonamide, 6-amino-N-methylnaphthalene-2-sulfonamide or a disubstituted form of any combination of the above substituents.

2. The rosin acid derivative containing sulfonamide according to claim 1, characterized in that: R is N-(4,6-dimethylpyrimidin-2-yl)benzenesulfonamide, N-(pyrimidin-2-yl)benzenesulfonamide, N-(3,4-dimethylisoxazol-5-yl)benzenesulfonamide, N-(3-methoxypyrazin-2-yl)benzenesulfonamide, N-(6-methoxypyrimidin-4-yl)benzenesulfonamide, 3-amino-N-phenylbenzenesulfonamide, N-((4-aminophenyl)sulfonyl)benzamide, N-(5,6-dimethoxypyrimidin-4-yl)benzenesulfonamide, N-(6-chloropyridazin-3-yl)benzenesulfonamide, N-(6-methoxy benzenesulfonamide, N-(4-methylpyrimidin-2-yl)benzenesulfonamide, N-(2,6-dimethoxypyrimidin-4-yl)benzenesulfonamide, N-(pyridin-2-yl)benzenesulfonamide, N-(5-methoxypyrimidin-2-yl)benzenesulfonamide, N-methylbenzenesulfonamide, N,N-dimethylbenzenesulfonamide, N-cyclopropylbenzenesulfonamide, N-(thiazol-2-yl)benzenesulfonamide, N-(4-methylpyrimidin-2-yl)benzenesulfonamide, 4-(morpholinesulfonyl)aniline, N-(4-aminophenyl)-4-methylbenzenesulfonamide, 6-amino-N-methylnaphthalene-2-sulfonamide.

3. The method for preparing a rosin acid derivative containing sulfonamide as claimed in claim 1, characterized in that: The following steps are involved:

4. The method for preparing a sulfonamide-containing abietic acid derivative according to claim 3, characterized in that: The synthesis steps and process conditions are as follows: add abietic acid: thionyl chloride in a molar ratio of 1:3, heat under reflux for 1-3 hours, wait for the reaction to be completed, reduce the temperature to room temperature, evaporate under reduced pressure to obtain 1-formyl chloride abietic acid; add 1-formyl chloride abietic acid: substituted sulfonamide: triethylamine in a ratio of 1:1 to 1.2:0.5, add dichloromethane, stir in an ice bath, wait for the reaction to be completed, pour the reaction system into saturated brine, extract with dichloromethane, collect the organic layer, separate and purify by column chromatography (petroleum ether: ethyl acetate = 3:1 to 1:1) to obtain the target compound.

5. Use of a rosin acid derivative containing sulfonamide as claimed in claim 1 or 2 in the preparation of drugs and medicaments for preventing and controlling rice streak pathogen, tobacco bacterial wilt, potato late blight and tobacco mosaic disease.

6. A compound pesticide composition, characterized in that: The composition comprises the derivative according to claim 1 and kasugamycin.

7. The composition according to claim 6, characterized in that: The mass ratio of the derivative to kasugamycin is 1:2-2:

1.

8. Use of the composition as claimed in claim 6 in the preparation of drugs for preventing and treating plant bacterial diseases.

9. The composition according to claim 6, characterized in that: The derivative is (1S, 4S, 10S)-N-(4-(N-(3,4-dimethylisoxazol-5-yl)aminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide.

10. A novel plant growth regulator, characterized in that: The regulator is a derivative (1S, 4S, 10S)-N-(4-(N-(3,4-dimethylisoxazol-5-yl)aminosulfonyl)phenyl)-7-isopropyl-1,4-dimethyl-1,2,3,4,5,6,10-decahydrophenanthrene-1-carboxamide.

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