An n-phenylthio triazone derivative, and a preparation method and application thereof

Abstract

This invention relates to the fields of compound synthesis technology and pesticide technology, specifically to N-phenylthiotriazinone derivatives, their preparation methods, and applications. The N-phenylthiotriazinone derivatives are either N-phenylthiotriazinone derivatives containing oxime ester groups or N-phenylthiotriazinone derivatives containing oxime ether groups. The N-phenylthiotriazinone derivatives of this invention exhibit 100% control efficacy against six weeds at doses of 37.5-150 a.g. / ha. These compounds achieve good weed control effects at low doses and have relatively good safety profiles for crops such as corn, wheat, peanuts, soybeans, and cotton. They can be used as selective herbicides in agriculture. The compounds described in this invention can be developed and used as potential PPO inhibitors and post-emergence herbicides for broadleaf weeds. The derivatives have simple structures and preparation processes, low production costs, and broad application prospects.

Description

Technical Field

[0001] This invention belongs to the field of compound pesticides, specifically relating to an N-phenylthiotriazinone derivative and its preparation method and application, as well as N-thiotriazinone oxime ethers or oxime esters and protoporphyrinogen oxidase herbicides. Background Technology

[0002] Weeds are an important component of the farmland ecosystem, alongside diseases and pests, causing serious harm to agricultural production. Weeds compete with crops for sunlight, space, water, and nutrients, leading to reduced crop yields and lower quality. Therefore, weed control is a major challenge for farmers. The use of herbicides can effectively increase crop yields, providing an opportunity for herbicide development. Continuously developing new, highly effective, and environmentally friendly herbicides is an urgent need in current agricultural production.

[0003] Protoporphyrinogen oxidase (PPO) catalyzes the oxidation of protoporphyrinogen IX to protoporphyrin IX, and is one of the most important targets discovered in herbicide research. Protoporphyrinogen oxidase is the penultimate enzyme in the biosynthesis of chlorophyll and heme, belonging to a large family of enzymes containing flavonoid adenine dinucleotides (FAD). It catalyzes the conversion of protoporphyrinogen IX to protoporphyrin IX, and plant inhibition of PPO can lead to the toxic accumulation of protoporphyrin IX in the cytoplasm. Under light, protoporphyrin IX reacts with oxygen to produce numerous reactive oxygen species, damaging cell membranes and causing rapid burn symptoms in plants. On the other hand, PPO inhibitors have many advantages, including broad-spectrum weed control, strong resistance, environmental friendliness, low toxicity, and low usage rates. N-phenylimide PPO herbicides, due to their different hydrophobic groups, are more easily absorbed by leaves and translocated throughout the plant, and also have increased binding affinity to plant PPO. N-Phenylacethiazineone is a relatively new PPO inhibitor structure with a novel mechanism of action. Oxime ethers and oxime esters are considered important groups in new drug development, possessing broad biological activities and attracting widespread attention in medicinal chemistry, pesticide chemistry, and other fields. Therefore, designing and synthesizing small herbicides based on N-phenylthiotriazineone units is highly consistent with current trends in new pesticide development.

[0004] Trifludimoxazin is the first PPO inhibitor herbicide containing triazine, featuring a novel mechanism of action. It exhibits rapid scorching and wilting effects on weed leaves within a day. Trifludimoxazin is unique in that it acts as both a PPO inhibitor and a control for PPO-resistant weeds, including even resistant weeds such as Amaranthus spp. and Ambrosia spp.

[0005]

[0006] Application number 201910419966.1 discloses a "thiotriazinone isoxazoline compound, its preparation method and application, protoporphyrinogen oxidase inhibitor and herbicide".

[0007]

[0008] Application number 201911038131.8 discloses "a triazinone compound and its uses".

[0009]

[0010] These compounds have a broad spectrum of weed control and exhibit highly effective and long-lasting weed control activity, especially against broadleaf weeds. However, these compounds also cause severe damage to broadleaf crops, and their safety profile needs improvement. Furthermore, they suffer from high production costs, lengthy synthesis steps, and low overall yield.

[0011] Furthermore, most existing herbicides (including the herbicide with the structure disclosed in CN105753853A) not only suppress weeds but also have a strong inhibitory effect on crops. This makes these herbicides unsuitable for use during crop growth. However, in actual production, there is a high demand for weed control during crop growth. Therefore, developing a herbicide with high crop safety is essential.

[0012] Although the compounds disclosed in the prior art have some similarities with the compounds of the present invention, the compounds represented by the general formula of the present invention are significantly different from those in the prior art. They have a novel structure, good herbicidal activity, readily available raw materials, high overall yield, and relatively high safety for broadleaf crops. Summary of the Invention

[0013] To address the shortcomings of existing technologies, this invention proposes an N-phenylthiotriazinone derivative, its preparation method, and its applications.

[0014] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0015] An N-phenylthiotriazinone derivative is an N-phenylthiotriazinone derivative containing an oxime ether group or an N-phenylthiotriazinone derivative containing an oxime ester group, wherein the general structural formula of the N-phenylthiotriazinone derivative is as shown in formula (I):

[0016] In equation (I) or equation (II), Het is:

[0017]

[0018] In formula (I):

[0019] X 1 X 2 X 3 They are selected from O, S, NCH3, N(CH3)2, NCN, or NOCH3, respectively;

[0020] R 1 R 2 Selected from C1-C6 alkyl or C1-C6 haloalkyl;

[0021] R 3 R 4 They are selected from H, halogen, -CN, C1-C6 alkyl, (C1-C6 haloalkyl)-O- or (C1-C6 alkyl)-SO2-, respectively;

[0022] R 5 Selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, and C1-C6 alkylCR, respectively. 6 NOR 7 NCR 8 R 9 ;

[0023] R 6 They are selected from H, halogens, -CN, C1-C6 alkyl groups, or C1-C6 haloalkyl groups, respectively;

[0024] R 7 Selected from H, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 alkenyl, C3-C6 alkynyl, C1-C6 alkoxy, C1-C6 alkyl, C1-C6 alkylcarbonyloxy, C2-C4 alkyl, C1-C6 alkyl, CO2, CH3, CO2, respectively. CH3, CH2OCH3, CH2SCH3, CON(CH3)2, CONHSO2N(CH3)2, unsubstituted or substituted by 1-4 independently selected groups, C1-C6 alkylcarbonyloxy-C2-C4 alkyl, unsubstituted or substituted by 1-4 independently selected groups, benzyl, furanylene, thiazolemethylene, tetrahydrofuranylene or pyridinylene, halogen, CN, NO2, C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 alkoxy, C1-C8 haloalkoxy, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl;

[0025] R 8 They are selected from H, halogens, -CN, C1-C6 alkyl groups, or C1-C6 haloalkyl groups, respectively;

[0026] R 9Selected from H, C1-C6 alkyl or C1-C6 haloalkyl, C3-C6 alkenyl, C3-C6 alkoxy, C1-C6 alkyl, C1-C6 alkylcarbonyloxy, C2-C4 alkyl, C1-C6 alkyl, CO2, CH3, CO2, respectively. CH3, CH2OCH3, CH2SCH3, CON(CH3)2, CONHSO2N(CH3)2, unsubstituted or substituted by 1-4 independently selected groups, C1-C6 alkylcarbonyloxy-C2-C4 alkyl, unsubstituted or substituted by 1-4 independently selected groups, benzyl, furanylene, thiazolemethylene, tetrahydrofuranylene or pyridinylene, halogen, CN, NO2, C1-C8 alkyl, C1-C8 haloalkyl, C1-C8 alkoxy, C1-C8 haloalkoxy, C1-C8 alkoxycarbonyl, C1-C8 alkylthio, C1-C8 alkylsulfonyl.

[0027] The N-phenylthiotriazinone derivative is characterized by comprising the following compounds:

[0028] Compound A1: 2-((allyloxy)imino)propyl 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate

[0029] Compound A2: 2-((benzyloxy)imino)propyl 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate

[0030] Compound A3: 2-((allyloxy)imino)propyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate

[0031] Compound A4: 2-((benzyloxy)imino)propyl-2-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate

[0032] Compound A5: 2-((allyloxy)imino)propyl 2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate

[0033] Compound A6: 2-((benzyloxy)imino)propyl 2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate

[0034] Compound A7: 2-((allyloxy)imino)propyl 4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate

[0035] Compound A8: 2-((benzyloxy)imino)propyl 4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate

[0036] Compound A9: 2-((allyloxy)imino)propyl 2,4-difluoro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate

[0037] Compound A10: 2-((benzyloxy)imino)propyl 2,4-difluoro5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate

[0038] Compound A11: 2-((allyloxy)imino)propyl-2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate

[0039] Compound A12: 2-((benzyloxy)imino)propyl-2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate

[0040] Compound A13: 2-((allyloxy)imino)propyl-2-chloro-5-(3,5-diethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate

[0041] Compound A14: 2-((benzyloxy)imino)propyl-2-chloro-5-(3,5-diethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate

[0042] Compound A15: 2-((allyloxy)imino)propyl-2-chloro-5-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)-4-fluorobenzoate

[0043] Compound A16: 2-((benzyloxy)imino)propyl-2-chloro-5-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)-4-fluorobenzoate

[0044] Compound A17: 2-((allyloxy)imino)propyl-2-chloro-5-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)-4-fluorobenzoate

[0045] Compound A18: 2-((benzyloxy)imino)propyl-2-chloro-5-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)-4-fluorobenzoate

[0046] Compound A19: 2-(hydroxyimino)propyl 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate

[0047] Compound A20: 2-(hydroxyimino)propyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazine-1-yl)benzoate

[0048] Compound A21: 2-(hydroxyimino)propyl 2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate

[0049] Compound A22: 2-(hydroxyimino)propyl-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate

[0050] Compound A23: 2-(hydroxyimino)propyl-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-2,4-difluorobenzoate

[0051] Compound A24: 2-(hydroxyimino)propyl-2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate

[0052] Compound A25: 2-(hydroxyimino)propyl-2-chloro-5-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)-4-fluorobenzoate

[0053] Compound A26: 2-(hydroxyimino)propyl-2-chloro-5-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)-4-fluorobenzoate

[0054] Compound A27: N-((4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazine-1-yl)benzoyl)oxy)ethyl acetate

[0055] Compound A28: N-((2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazine-1-yl)benzoyl)oxy)ethyl acetate

[0056] Compound A29: N-((2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoyl)oxy)ethyl acetate

[0057] Compound A30: N-((3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)ethyl acetate

[0058] Compound A31: N-((5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-2,4-difluorobenzoyl)oxy)ethyl acetate

[0059] Compound A32: N-((2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)ethyl acetate

[0060] Compound A33: 3-(4-chloro-2-fluoro-5-(propane-2-imideamino)oxycarbonyl)phenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione

[0061] Compound A34: Isobutyraldehyde O-(2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl) oxime

[0062] Compound A35: 3-(((but-2-imino)oxycarbonyl)-4-chloro-2-fluorophenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione

[0063] Compound A36: Butyraldehyde O-(2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl) oxime

[0064] Compound A37: 3-(4-chloro-5-((cyclopentylamino)oxycarbonyl)-2-fluorophenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione

[0065] Compound A38: 3-(4-chloro-5-((cyclohexylamino)oxycarbonyl)-2-fluorophenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione

[0066] Compound A39: 3-(4-chloro-2-fluoro-5-((1-(furan-2-yl)ethyleneamino)oxycarbonyl)phenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione

[0067] Compound A40: 3-(4-chloro-2-fluoro-5-((1-(thiophen-2-yl)ethyleneamino)oxycarbonyl)phenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione

[0068] Compound A41: Ethyl (2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)iminopropionate

[0069] Compound A42: 2-chloro-2-(2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)imino)ethyl acetate

[0070] Compound A43: (2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)ethyl iminobutyrate

[0071] Compound A44: Ethyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)imino)valerate

[0072] Compound A45: (2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)imino)ethyl hexanoate)

[0073] Compound A46: 3-(4-chloro-2-fluoro-5-((3-oxobutane-2-imino)oxocarbonyl)phenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione

[0074] Compound A47: 2-Oxopropanal O-(2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl) oxime

[0075] Compound A48: N-((2-chloro-5-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)ethyl acetate

[0076] Compound A49: N-((2-chloro-5-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)ethyl acetate

[0077] Compound A50: Ethyl (2-chloro-5-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)iminopropionate

[0078] Another object of the present invention is to provide a method for preparing the N-phenylthiotriazinone derivative, using polysubstituted nitrobenzoic acid and substituted thiourea as main raw materials, and synthesizing N-phenylthiotriazinone derivatives containing oxime ethers and oxime esters through esterification, reduction, ring closure, hydrolysis, condensation or substitution reactions, respectively.

[0079] The preparation method of the N-phenylthiotriazinone derivative includes the following steps:

[0080] (1) Preparation of methyl 5-nitropolysubstituted benzoate (intermediates 1a-1f):

[0081] Take 5-nitropolysubstituted benzoic acid, dissolve it in methanol, slowly add concentrated sulfuric acid dropwise, after the addition is complete, heat to 80℃ to react, after the reaction is complete, concentrate the reaction system under reduced pressure, add water, extract with ethyl acetate, dry and column chromatography to obtain solid methyl 2-chloro-4-fluoro-5-nitrobenzoate, which is intermediate 1a-1f.

[0082] (2) Preparation of methyl 5-aminopolysubstituted benzoate (intermediates 2a-2f):

[0083] After mixing and stirring intermediate 1a-1f, ammonium chloride and 90% ethanol solution, the temperature was raised to 80℃, and then iron powder was slowly added. The reaction system was allowed to react at 80℃ for 4 hours. After the reaction was complete, the remaining iron powder was removed by filtration, and then water was added. After extraction with ethyl acetate, drying and column chromatography were performed to obtain methyl 5-aminopolysubstituted benzoate, which is intermediate 2a-2f.

[0084] (3) Preparation of methyl 5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl) polysubstituted benzoate (intermediates 3a-3f):

[0085] Triphosgene and toluene were added to a round-bottom flask and cooled to 0°C. A solution of intermediates 2a-2f and triethylamine in toluene was added dropwise over 10 minutes, and the mixture was then slowly heated to reflux. After 10 hours, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation. Toluene and N,N-dimethylthiourea were added to the residue, and the solution was stirred at room temperature for 30 minutes. Finally, CDI was added to the solution, and the solution was slowly heated to 85°C and reacted for 10 hours. After the reaction was complete, the reaction solution was cooled to room temperature, the system was concentrated under reduced pressure, and then extracted with ethyl acetate and water. The organic layer was separated, washed with saturated brine, dried, concentrated, and subjected to column chromatography to obtain methyl 5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl) polysubstituted benzoate (intermediate 3a-3f).

[0086] (4) Preparation of 5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl) polysubstituted benzoic acid (intermediates 4a-4f):

[0087] Intermediates 3a-3f were dissolved in glacial acetic acid. Then, H₂O and H₂SO₄ were added to the solution with stirring, and the reaction solution was heated to 100°C and reacted for 10 hours. After the reaction was complete, the reaction solution was cooled to room temperature and poured into ice, and stirred vigorously for 30 minutes. The resulting solid was filtered, washed with H₂O, and dried under vacuum to obtain compounds 4a-4f.

[0088] (5) Preparation of methyl 2-chloro-4-fluoro-5-(phenoxycarbonylthioamide)benzoate (intermediate 6):

[0089] Intermediate 5 and phenyl thiochloroformate were dissolved in 1,4-dioxane. The reaction solution was then heated to reflux and stirred for 2 hours. After the reaction was complete, the solution was cooled to room temperature, and the solvent was removed by rotary evaporation. The residue was purified by rapid chromatography to obtain intermediate 6.

[0090] (6) Preparation of phenylmethyl (methylaminothio) carbamate / thiocarbamate (intermediates 8a-8b):

[0091] K₂CO₃ was added to 1,3-dimethylthiourea in ethyl acetate under a nitrogen atmosphere at room temperature. Then, phenyl chloroformate / phenyl thiochloroformate was added dropwise to the mixture, and the mixture was stirred for 2 hours. After the reaction was complete, the mixture was filtered, and the resulting solvent was concentrated and evaporated by rotary evaporation to give intermediates 8a-8b.

[0092] (7) Preparation of methyl 2-chloro-5-(3,5-dimethyl-2,4,6-polythio-1,3,5-triazin-1-yl)-4-fluorobenzoate (intermediates 9a-9b):

[0093] Intermediates 6 and 8a-8b were dissolved in DMF with NaOAc and then heated to 60°C for 3 hours. After the reaction was complete, the mixture was cooled to room temperature; the organic layers were extracted with water and ethyl acetate, and washed with ethyl acetate. The combined organic layers were washed with saturated brine and concentrated by rotary evaporation. The residue was purified by rapid chromatography to obtain intermediates 9a-9b.

[0094] (8) Preparation of methyl 2-chloro-5-(3,5-dimethyl-2,4,6-polythio-1,3,5-triazinyl-1-yl)-4-fluorobenzoate (intermediates 10a-10b):

[0095] Intermediate 10a-10f was dissolved in glacial acetic acid. Then, H₂O and H₂SO₄ were added to the solution with stirring, and the reaction solution was heated to 100°C and reacted for 10 hours. After the reaction was complete, the reaction solution was cooled to room temperature and poured into ice, and stirred vigorously for 30 minutes. The resulting solid was filtered, washed with H₂O, and dried under vacuum to obtain compound 10a-10f.

[0096] (9) Preparation of N-phenylthiotriazinone derivatives of the target compound containing an oxime ether group:

[0097] Intermediate 4a-4f / 10a-10b and potassium carbonate were mixed in acetone solution. Various corresponding 1-chloropropane-2-ketooximes and potassium iodide were added at room temperature. The reaction system was heated to 50°C and refluxed. After the reaction was complete, the system was concentrated under reduced pressure, extracted and purified by column chromatography to obtain N-phenylthiotriazinone derivatives containing oxime ether groups.

[0098] (10) Preparation of N-phenylthiotriazinone derivatives of the target compound containing an oxime ester group:

[0099] Intermediate 4a-4f / 10a-10b was mixed with dichloromethane, and EDCI and DMAP were added at room temperature. After stirring for a period of time, various substituted oximes were added. The reaction system was carried out at room temperature. After the reaction was complete, the system was washed with saturated sodium chloride solution, dried, concentrated under reduced pressure, and purified by column chromatography to obtain N-phenylthiotriazinone derivatives containing oxime ester groups.

[0100] In step (1), the amounts of 5-nitropolysubstituted benzoic acid and concentrated sulfuric acid are calculated in the following molar ratio: 5-nitropolysubstituted benzoic acid: concentrated sulfuric acid = 1:1.1;

[0101] In step (1), the amount of methanol used is controlled by adding 1 mL of methanol per millimol of 5-nitropolysubstituted benzoic acid.

[0102] In step (2), the amounts of intermediate 1a-1f, ammonium chloride, and iron powder are calculated in the following molar ratio: intermediate 1: ammonium chloride: iron powder = 1:3:3;

[0103] In step (2), the amount of 90% ethanol used is controlled by adding 1 mL of 90% ethanol per millimol of intermediate 1.

[0104] In step (3), the amounts of intermediate 2a-2f, triphosgene, triethylamine, N,N-dimethylthiourea, and CDI are in the following molar ratio: intermediate 2a-2f: triphosgene: triethylamine, N,N-dimethylthiourea: CDI = 1:0.5:0.2:2:2;

[0105] In step (3), the amount of toluene is controlled by adding 1 mL of toluene per millimole of intermediate 2a-2f.

[0106] In step (4), the amount of acetic acid used is controlled by adding 2 mL of acetic acid per millimol of intermediate 3a-3f;

[0107] In step (4), the amount of water used is controlled by adding 1 mL of water per millimole of intermediate 3a-3f;

[0108] In step (4), the amount of sulfuric acid used is controlled by adding 1 mL of sulfuric acid per millimole of intermediate 3a-3f;

[0109] In step (5), the amount of 1,4-dioxane is controlled by adding 1 mL of 1,4-dioxane per millimole of intermediate 5.

[0110] In step (5), the amounts of intermediate 5 and phenyl thiochloroformate, calculated by molar ratio, are: intermediate 5 : phenyl thiochloroformate = 1 : 1.1

[0111] In step (6), the amounts of intermediate 7, phenyl thiochloroformate / phenyl chloroformate, and K2CO3, calculated by molar ratio, are: intermediate 7 : phenyl thiochloroformate / phenyl chloroformate : K2CO3 = 1 : 1.4 : 1.5

[0112] In step (6), the amount of ethyl acetate is controlled by adding 1 mL of ethyl acetate per millimol of intermediate 7.

[0113] In step (7), the amounts of intermediate 6, intermediates 8a-8b, and NaOAc are in the following molar ratio: intermediate 6 : intermediates 8a-8b : NaOAc = 1 : 1.2 : 0.5

[0114] In step (7), the amount of DMF is controlled by adding 1 mL of DMF per millimole of intermediate 6.

[0115] In step (8), the amount of acetic acid used is controlled by adding 2 mL of acetic acid per millimol of intermediate 8a-8b.

[0116] In step (8), the amount of water used is controlled by adding 1 mL of water per millimole of intermediate 8a-8b.

[0117] In step (8), the amount of sulfuric acid used is controlled by adding 1 mL of sulfuric acid per millimole of intermediate 8a-8b.

[0118] In step (9), the amounts of intermediate 4a-4f, substituted 1-chloropropane-2-one oxime, potassium carbonate, and potassium iodide are in the following molar ratio: intermediate 4a-4f: substituted 1-chloropropane-2-one oxime: potassium carbonate: potassium iodide = 1:1.2:1.5:0.1;

[0119] In step (9), the amount of acetone used is controlled by adding 1 mL of acetone per millimole of intermediate 4a-4f.

[0120] In step (10), the amounts of intermediate 4a-4f, EDCI, DMAP, and various substituted oximes are calculated in the following molar ratio: intermediate 4a-4f: EDCI: DMAP: various substituted oximes = 1: 1.1: 0.2: 1.2;

[0121] In step (10), the amount of dichloromethane used is controlled by adding 1 mL of dichloromethane per millimole of intermediate 4a-4f.

[0122] The preparation route of the N-phenylthiotriazinone derivative is as follows:

[0123] Route 1:

[0124]

[0125] Route 2:

[0126]

[0127] Another object of the present invention is the use of the N-phenylthiotriazinone derivative in the preparation of herbicides and weed growth enzyme inhibitors.

[0128] Specifically, the weeds are barnyard grass, barnyard grass, velvetleaf, amaranth retroflexus, lambsquarters, ryegrass, purslane, bermudagrass, rapeseed, speedwell, amaranth, black nightshade, bitter lettuce, dandelion, sage, clover, chickweed, goosegrass, goosegrass, and foxtail grass.

[0129] Beneficial effects:

[0130] This invention is based on the structure of N-phenylthiotriazinone and introduces herbicidal active pharmacophores such as oxime ethers and oxime esters, thus creating small molecules of N-phenylthiotriazinone herbicides containing oxime ethers or oxime esters with relatively stable physicochemical properties and excellent drug-like properties. These derivatives have particularly significant post-emergence inhibitory effects on barnyard grass, crabgrass, foxtail grass, velvetleaf, amaranth retroflexus, and purslane, and show relatively good crop safety for broadleaf crops.

[0131] Post-emergence herbicidal activity tests showed that most N-phenylthiotriazinone compounds exhibited good herbicidal activity against *Abutilon theophrasti*, *Amaranthus retroflexus*, and *Portulaca oleracea* at a dosage of 150 g ai / ha, with inhibition rates all exceeding 100%. Compounds A34, A36, A42, and A43 demonstrated excellent herbicidal activity against *Barnyardgrass*, *Digitaria sanguinalis*, and *Setaria viridis*, achieving 100% inhibition rates at 75-150 g ai / ha. Some compounds showed herbicidal activity comparable to the positive control trifluralin, causing complete wilting and severe inhibition of weed growth.

[0132] The N-phenylthiotriazine ketone derivatives containing oxime ether or oxime ester groups of the present invention have simple structures, simple preparation processes, low production costs, high yields, low toxicity, are easily degradable, have good environmental compatibility, high safety in use, and are non-toxic and harmless in the preparation process. Detailed Implementation

[0133] The specific embodiments of the present invention will be described in further detail below, but the present invention is not limited to these embodiments. Any improvements or substitutions based on the basic spirit of these embodiments shall still fall within the scope of protection claimed by the claims of the present invention.

[0134] The preparation routes for the N-phenylthiotriazinone derivatives provided in Examples 1-50 are as follows:

[0135] Route 1:

[0136]

[0137] Route 2:

[0138]

[0139] Example 1: A method for preparing 2-((allyloxy)imino)propyl 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate (i.e., compound A1), comprising the following steps:

[0140] (1) Preparation of methyl 4-chloro-3-nitrobenzene:

[0141] 30.00 g (148.84 mmol) of 4-chloro-3-nitrobenzoic acid was dissolved in 300 mL of methanol. Concentrated sulfuric acid (16.06 g (163.72 mmol) was slowly added dropwise at room temperature. After the addition was complete, the mixture was heated to reflux at 65 °C for 4 hours. After the reaction was completed, the reaction system was concentrated under reduced pressure, extracted with water and ethyl acetate, and dried to obtain 30.02 g of solid methyl 4-chloro-3-nitrobenzoate intermediate, with a yield of 93.56%.

[0142] (2) Preparation of methyl 3-amino-4-chlorobenzoate:

[0143] Methyl 4-chloro-3-nitrobenzoate (30.02 g, 139.25 mmol), NH4Cl (23.33 g, 417.74 mmol), and EtOH (90%, 300 mL) were added to a flask, and the mixture was heated to reflux. Iron powder (22.34 g, 417.74 mmol) was then added in portions to the solution, and the reaction mixture was refluxed for another 4 hours. After the reaction was complete, the hot reaction mixture was filtered through a diatomaceous earth mat, and the residue was washed with ethyl acetate (100 mL). H2O (200 mL) was added to the filtrate, followed by extraction with 200 mL of ethyl acetate. The combined organic layers were concentrated by rotary evaporation over anhydrous Na2SO4 to give 22.31 g of methyl 3-amino-4-chlorobenzoate intermediate, in 86.32% yield.

[0144] (3) Preparation of methyl 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate:

[0145] Dissolve methyl 3-amino-4-chlorobenzoate (22.31 g, 120.20 mmol) and Et3N (2.43 g, 24.04 mmol) in 100 mL of toluene. Add triphosgene (17.83 g, 60.10 mmol) dissolved in 100 mL of toluene to a 500 mL round-bottom flask and cool to 0 °C. Add the solution of methyl 3-amino-4-chlorobenzoate (22.31 g, 120.20 mmol) and Et3N (2.43 g, 24.04 mmol) dissolved in 100 mL of toluene dropwise over 10 minutes, then slowly heat the mixture to reflux. After 10 hours, cool the mixture to room temperature and remove the solvent by rotary evaporation. Add toluene (200 mL) and CS(NHCH3)2 (25.04 g, 240.40 mmol) sequentially to the residue and stir the solution at room temperature for 30 minutes. Then, CDI (38.98 g, 240.40 mmol) was added to the solution, and the solution was slowly heated to 85 °C for 12 hours. After the reaction was complete, the reaction solution was cooled to room temperature, and ethyl acetate (200 mL) and H2O (200 mL) were added to the solution. The organic layer was separated, washed with H2O (200 mL) and saturated NaCl solution (200 mL), dried over anhydrous Na2SO4, concentrated under reduced pressure, and column chromatography was performed to give 24.65 g of methyl 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate intermediate, with a yield of 60.00%.

[0146] (4) Preparation of 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid:

[0147] 24.65 g (75.21 mmol) of methyl 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate was added to 100 mL of HOAc. Then, with stirring, 50 mL of H₂O and 50 mL of H₂SO₄ were added to the solution, and the reaction solution was heated to 100 °C for 10 hours. After the reaction was complete, the reaction solution was cooled to room temperature and poured into 500 g of ice, and stirred vigorously for 30 minutes. The resulting solid was filtered and washed with 50 mL of H₂O, then dried under vacuum to give 17.37 g of 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid intermediate. Yield: 73.48%.

[0148] (5) Preparation of 2-((allyloxy)imino)propyl 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate:

[0149] Dissolve 250 mg (0.76 mmol) of 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid in 15 mL of acetone, add potassium carbonate (114.48 mg, 0.92 mmol) and potassium iodide (11.46 mg, 0.08 mmol), and add 1-chloropropane-2-one O-allyl oxime (122.26 mg, 0.92 mmol) under stirring at room temperature. Then, reflux the mixture at 60 °C for 6 hours. After the reaction was complete, excess potassium carbonate and potassium iodide were removed by filtration, the mixture was concentrated under reduced pressure, and column chromatography was performed to obtain 0.29 g of 2-((allyloxy)imino)propyl 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate, with a yield of 86.62%.

[0150] Example 2: A method for preparing 2-((benzyloxy)imino)propyl 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate (i.e., compound A2), comprising the following steps:

[0151] Steps (1)-(4): Refer to steps (1)-(4) of Example 1;

[0152] (5) Preparation of 2-((benzyloxy)imino)propyl 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazine-1-yl)benzoate:

[0153] Dissolve 250 mg (0.76 mmol) of 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid in 15 mL of acetone, add potassium carbonate (114.48 mg, 0.92 mmol) and potassium iodide (11.46 mg, 0.08 mmol), and add 1-chloropropane-2-one O-allyl oxime (180.93 mg, 0.92 mmol) under stirring at room temperature. Then, reflux the mixture at 60 °C for 6 hours. After the reaction was complete, excess potassium carbonate and potassium iodide were removed by filtration, the mixture was concentrated under reduced pressure, and column chromatography was used to obtain 0.30 g of 2-((benzyloxy)imino)propyl 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate, with a yield of 80.44%.

[0154] Example 3: A method for preparing 2-((allyloxy)imino)propyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate (i.e., compound A3), comprising the following steps:

[0155] Step (1): Referring to step (1) of Example 1, 4-chloro-3-nitrobenzoic acid is replaced with 2-chloro-5-nitrobenzoic acid;

[0156] Step (2): Refer to step (2) of Example 1; replace methyl 4-chloro-5-nitrobenzoate with methyl 2-chloro-5-nitrobenzoate;

[0157] Step (3): Refer to step (3) of Example 1; methyl 5-amino-4-chlorobenzoate is replaced with methyl 5-amino-2-chlorobenzoate.

[0158] Step (4): Refer to step (4) of Example 1; 2-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid;

[0159] (5) Preparation of 2-((allyloxy)imino)propyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate:

[0160] Dissolve 2-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.76 mmol) in 15 mL of acetone, add potassium carbonate (114.48 mg, 0.92 mmol) and potassium iodide (11.46 mg, 0.08 mmol), and add 1-chloropropane-2-one O-allyl oxime (122.26 mg, 0.92 mmol) under stirring at room temperature. Then, reflux the mixture at 60 °C for 6 hours. After the reaction was complete, excess potassium carbonate and potassium iodide were removed by filtration, the mixture was concentrated under reduced pressure, and column chromatography was performed to obtain 0.28 g of 2-((allyloxy)imino)propyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate, with a yield of 83.64%.

[0161] Example 4: A method for preparing 2-((benzyloxy)imino)propyl 2-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate (i.e., compound A4), comprising the following steps:

[0162] Step (1): Referring to step (1) of Example 1, 4-chloro-3-nitrobenzoic acid is replaced with 2-chloro-5-nitrobenzoic acid;

[0163] Step (2): Refer to step (2) of Example 1; replace methyl 4-chloro-5-nitrobenzoate with methyl 2-chloro-5-nitrobenzoate;

[0164] Step (3): Refer to step (3) of Example 1; methyl 5-amino-4-chlorobenzoate is replaced with methyl 5-amino-2-chlorobenzoate.

[0165] Step (4): Refer to step (4) of Example 1; 2-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid;

[0166] (5) Preparation of 2-((benzyloxy)imino)propyl 2-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate:

[0167] Dissolve 2-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.76 mmol) in 15 mL of acetone, add potassium carbonate (114.48 mg, 0.92 mmol) and potassium iodide (11.46 mg, 0.08 mmol), and then add 1-chloropropane-2-one O-benzyl oxime (122.26 mg, 0.92 mmol) under stirring at room temperature. The mixture is then refluxed at 60 °C for 6 hours. After the reaction is complete, excess potassium carbonate and potassium iodide are removed by filtration, and the mixture is concentrated under reduced pressure. Column chromatography yields 0.28 g of 2-((benzyloxy)imino)propyl 2-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thiooxy-1,3,5-triazin-1-yl)benzoate, with a yield of 85.80%.

[0168] Example 5: A method for preparing 2-((allyloxy)imino)propyl 2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate (i.e., compound A5), comprising the following steps:

[0169] Step (1): Referring to step (1) of Example 1, 4-chloro-3-nitrobenzoic acid is replaced with 2,4-dichloro-5-nitrobenzoic acid;

[0170] Step (2): Refer to step (2) of Example 1; methyl 4-chloro-3-nitrobenzoate is replaced with methyl 2,4-dichloro-5-nitrobenzoate;

[0171] Step (3): Refer to step (3) of Example 1; methyl 3-amino-4-chlorobenzoate is replaced with methyl 5-amino-2,4-dichloro-5-nitrobenzene;

[0172] Step (4): Refer to step (4) of Example 1; 2,4-dichloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid;

[0173] (5) Preparation of 2-((allyloxy)imino)propyl 2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate:

[0174] Dissolve 2,4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.69 mmol) in 15 mL of acetone, add potassium carbonate (114.48 mg, 0.83 mmol) and potassium iodide (11.46 mg, 0.07 mmol), and add 1-chloropropane-2-one O-allyl oxime (122.26 mg, 0.83 mmol) under stirring at room temperature. Then, reflux the mixture at 60 °C for 6 hours. After the reaction was complete, excess potassium carbonate and potassium iodide were removed by filtration, the mixture was concentrated under reduced pressure, and column chromatography was performed to obtain 0.28 g of 2-((allyloxy)imino)propyl 2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate, with a yield of 85.70%.

[0175] Example 6: A method for preparing 2-((benzyloxy)imino)propyl 2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate (i.e., compound A6), comprising the following steps:

[0176] Step (1): Referring to step (1) of Example 1, 4-chloro-3-nitrobenzoic acid is replaced with 2,4-dichloro-5-nitrobenzoic acid;

[0177] Step (2): Refer to step (2) of Example 1; methyl 4-chloro-3-nitrobenzoate is replaced with methyl 2,4-dichloro-5-nitrobenzoate;

[0178] Step (3): Refer to step (3) of Example 1; methyl 3-amino-4-chlorobenzoate is replaced with methyl 5-amino-2,4-dichloro-5-nitrobenzene;

[0179] Step (4): Refer to step (4) of Example 1; 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid is replaced with 2,4-dichloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid;

[0180] (5) Preparation of 2-((benzyloxy)imino)propyl 2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate:

[0181] Dissolve 2,4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.69 mmol) in 15 mL of acetone, add potassium carbonate (114.48 mg, 0.83 mmol) and potassium iodide (11.46 mg, 0.07 mmol), and add 1-chloropropane-2-one O-allyl oxime (163.73 mg, 0.83 mmol) under stirring at room temperature. Then, reflux the mixture at 60 °C for 6 hours. After the reaction was complete, excess potassium carbonate and potassium iodide were removed by filtration, and the mixture was concentrated under reduced pressure and subjected to column chromatography to obtain 0.32 g of 2-((benzyloxy)imino)propyl 2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate, with a yield of 88.58%.

[0182] Example 7: A method for preparing 2-((allyloxy)imino)propyl 4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate (i.e., compound A7), comprising the following steps:

[0183] Step (1): Referring to step (1) of Example 1, 4-chloro-3-nitrobenzoic acid is replaced with 4-fluoro-5-nitrobenzoic acid;

[0184] Step (2): Refer to step (2) of Example 1; methyl 4-chloro-3-nitrobenzoate is replaced with methyl 4-fluoro-5-nitrobenzoate;

[0185] Step (3): Refer to step (3) of Example 1; methyl 3-amino-4-chlorobenzoate is replaced with methyl 3-amino-4-fluorobenzoate;

[0186] Step (4): Refer to step (4) of Example 1; 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid is replaced with 4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid;

[0187] (5) Preparation of 2-((allyloxy)imino)propyl 4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate:

[0188] Dissolve 250 mg (0.80 mmol) of 4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid in 15 mL of acetone, add potassium carbonate (133.19 mg, 0.96 mmol) and potassium iodide (13.33 mg, 0.08 mmol), and then add 1-chloropropane-2-one O-allyl oxime (142.25 mg, 0.96 mmol) under stirring at room temperature. Then, reflux the mixture at 60 °C for 6 hours. After the reaction was complete, excess potassium carbonate and potassium iodide were removed by filtration, the mixture was concentrated under reduced pressure, and column chromatography was performed to obtain 0.30 g of 2-((allyloxy)imino)propyl 4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate, with a yield of 88.43%.

[0189] Example 8: A method for preparing 2-((benzyloxy)imino)propyl 4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate (i.e., compound A8), comprising the following steps:

[0190] Step (1): Referring to step (1) of Example 1, 4-chloro-3-nitrobenzoic acid is replaced with 4-fluoro-5-nitrobenzoic acid;

[0191] Step (2): Refer to step (2) of Example 1; methyl 4-chloro-3-nitrobenzoate is replaced with methyl 4-fluoro-5-nitrobenzoate;

[0192] Step (3): Refer to step (3) of Example 1; methyl 3-amino-4-chlorobenzoate is replaced with methyl 3-amino-4-fluorobenzoate;

[0193] Step (4): Refer to step (4) of Example 1; 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid is replaced with 4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid;

[0194] (5) Preparation of 2-((benzyloxy)imino)propyl 4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate:

[0195] Dissolve 250 mg (0.80 mmol) of 4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid in 15 mL of acetone, add potassium carbonate (133.19 mg, 0.96 mmol) and potassium iodide (13.33 mg, 0.08 mmol), and then add 1-chloropropane-2-one O-benzyl oxime (190.49 mg, 0.96 mmol) under stirring at room temperature. Then, reflux the mixture at 60 °C for 6 hours. After the reaction was complete, excess potassium carbonate and potassium iodide were removed by filtration, and the mixture was concentrated under reduced pressure and subjected to column chromatography to obtain 0.33 g of 2-((benzyloxy)imino)propyl 2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate, with a yield of 86.96%.

[0196] Example 9: A method for preparing 2-((allyloxy)imino)propyl 2,4-difluoro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate (i.e., compound A9), comprising the following steps:

[0197] Step (1): Referring to step (1) of Example 1, 4-chloro-3-nitrobenzoic acid is replaced with 2,4-difluoro-5-nitrobenzoic acid;

[0198] Step (2): Refer to step (2) of Example 1; methyl 4-chloro-3-nitrobenzoate is replaced with methyl 2,4-difluoro-5-nitrobenzoate;

[0199] Step (3): Refer to step (3) of Example 1; methyl 3-amino-4-chlorobenzoate is replaced with methyl 5-amino-2,4-difluoro-5-nitrobenzoate;

[0200] Step (4): Refer to step (4) of Example 1; 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid is replaced with 2,4-difluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid;

[0201] (5) Preparation of 2-((allyloxy)imino)propyl 2,4-difluoro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazine-1-yl)benzoate:

[0202] Dissolve 2,4-difluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.76 mmol) in 15 mL of acetone, add potassium carbonate (125.92 mg, 0.91 mmol) and potassium iodide (12.60 mg, 0.08 mmol), and add 1-chloropropane-2-one O-allyl oxime (134.48 mg, 0.92 mmol) with stirring at room temperature. Then, reflux the mixture at 60 °C for 6 hours. After the reaction was complete, excess potassium carbonate and potassium iodide were removed by filtration, and the mixture was concentrated under reduced pressure and subjected to column chromatography to obtain 0.27 g of 2-((allyloxy)imino)propyl 2,4-difluoro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate, with a yield of 80.75%.

[0203] Example 10: A method for preparing 2-((benzyloxy)imino)propyl 2,4-difluoro5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate (i.e., compound A10), comprising the following steps:

[0204] Step (1): Referring to step (1) of Example 1, 4-chloro-3-nitrobenzoic acid is replaced with 2,4-difluoro-5-nitrobenzoic acid;

[0205] Step (2): Refer to step (2) of Example 1; methyl 4-chloro-3-nitrobenzoate is replaced with methyl 2,4-difluoro-5-nitrobenzoate;

[0206] Step (3): Refer to step (3) of Example 1; methyl 3-amino-4-chlorobenzoate is replaced with methyl 5-amino-2,4-difluoro-5-nitrobenzoate;

[0207] Step (4): Refer to step (4) of Example 1; 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid is replaced with 2,4-difluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid;

[0208] (5) Preparation of 2-((benzyloxy)imino)propyl 2,4-difluoro5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate:

[0209] Dissolve 2,4-difluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.76 mmol) in 15 mL of acetone, add potassium carbonate (125.92 mg, 0.91 mmol) and potassium iodide (12.60 mg, 0.08 mmol), and add 1-chloropropane-2-one O-benzyl oxime (180.09 mg, 0.92 mmol) under stirring at room temperature. Then, reflux the mixture at 60 °C for 6 hours. After the reaction was complete, excess potassium carbonate and potassium iodide were removed by filtration, and the mixture was concentrated under reduced pressure and subjected to column chromatography to obtain 0.29 g of 2-((benzyloxy)imino)propyl 2,4-difluoro5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate, with a yield of 77.87%.

[0210] Example 11: A method for preparing 2-((allyloxy)imino)propyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate (i.e., compound A11), comprising the following steps:

[0211] Step (1): Referring to step (1) of Example 1, 4-chloro-3-nitrobenzoic acid is replaced with 2-chloro-4-fluoro-5-nitrobenzoic acid;

[0212] Step (2): Refer to step (2) of Example 1; methyl 4-chloro-3-nitrobenzoate is replaced with methyl 2-chloro-4-fluoro-5-nitrobenzoate;

[0213] Step (3): Refer to step (3) of Example 1; methyl 3-amino-4-chlorobenzoate is replaced with methyl 5-amino-2-chloro-4-fluorobenzoate;

[0214] Step (4): Refer to step (4) of Example 1; 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid is replaced with 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid;

[0215] (5) Preparation of 2-((allyloxy)imino)propyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate:

[0216] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.72 mmol) in 15 mL of acetone, add potassium carbonate (119.92 mg, 0.87 mmol) and potassium iodide (12.00 mg, 0.07 mmol), and add 1-chloropropane-2-one O-allyl oxime (128.08 mg, 0.87 mmol) under stirring at room temperature. Then, reflux the mixture at 60 °C for 6 hours. After the reaction was complete, excess potassium carbonate and potassium iodide were removed by filtration, the mixture was concentrated under reduced pressure, and column chromatography was performed to obtain 0.29 g of 2-((allyloxy)imino)propyl-2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate, with a yield of 87.78%.

[0217] Example 12: A method for preparing 2-((benzyloxy)imino)propyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate (i.e., compound A12), comprising the following steps:

[0218] Step (1): Referring to step (1) of Example 1, 4-chloro-3-nitrobenzoic acid is replaced with 2-chloro-4-fluoro-5-nitrobenzoic acid;

[0219] Step (2): Refer to step (2) of Example 1; methyl 4-chloro-3-nitrobenzoate is replaced with methyl 2-chloro-4-fluoro-5-nitrobenzoate;

[0220] Step (3): Refer to step (3) of Example 1; methyl 3-amino-4-chlorobenzoate is replaced with methyl 5-amino-2-chloro-4-fluorobenzoate;

[0221] Step (4): Refer to step (4) of Example 1; 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid is replaced with 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid;

[0222] (5) Preparation of 2-((benzyloxy)imino)propyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate:

[0223] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.72 mmol) in 15 mL of acetone, add potassium carbonate (119.92 mg, 0.87 mmol) and potassium iodide (12.00 mg, 0.07 mmol), and add 1-chloropropane-2-one O-benzyl oxime (119.92 mg, 0.87 mmol) under stirring at room temperature. Then, reflux the mixture at 60 °C for 6 hours. After the reaction was complete, excess potassium carbonate and potassium iodide were removed by filtration, the mixture was concentrated under reduced pressure, and column chromatography was performed to obtain 0.28 g of 2-((benzyloxy)imino)propyl-2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate, with a yield of 76.38%.

[0224] Example 13: A method for preparing 2-((allyloxy)imino)propyl 2-chloro-5-(3,5-diethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate (i.e., compound A13), comprising the following steps:

[0225] Step (1): Referring to step (1) of Example 1, 4-chloro-3-nitrobenzoic acid is replaced with 2-chloro-4-fluoro-5-nitrobenzoic acid;

[0226] Step (2): Refer to step (2) of Example 1; methyl 4-chloro-3-nitrobenzoate is replaced with methyl 2-chloro-4-fluoro-5-nitrobenzoate;

[0227] Step (3): Refer to step (3) of Example 1; methyl 3-amino-4-chlorobenzoate is replaced with methyl 5-amino-2-chloro-4-fluorobenzoate, and CS(NHCH3)2 is replaced with CS(NHCH2CH3)2;

[0228] Step (4): Refer to step (4) of Example 1; 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid is replaced with 2-chloro-4-fluoro-3-(3,5-diethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid;

[0229] (5) Preparation of 2-((allyloxy)imino)propyl 2-chloro-5-(3,5-diethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate:

[0230] Dissolve 2-chloro-4-fluoro-3-(3,5-diethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.67 mmol) in 15 mL of acetone, add potassium carbonate (110.92 mg, 0.80 mmol) and potassium iodide (11.00 mg, 0.07 mmol), and add 1-chloropropane-2-one O-benzyl oxime (110.92 mg, 0.87 mmol) under stirring at room temperature. Then, reflux the mixture at 60 °C for 6 hours. After the reaction was complete, excess potassium carbonate and potassium iodide were removed by filtration, the mixture was concentrated under reduced pressure, and column chromatography was performed to obtain 0.26 g of 2-((benzyloxy)imino)propyl-2-chloro-5-(3,5-diethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate, with a yield of 80.16%.

[0231] Example 14: A method for preparing 2-((benzyloxy)imino)propyl 2-chloro-5-(3,5-diethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate (i.e., compound A14), comprising the following steps:

[0232] Step (1): Referring to step (1) of Example 1, 4-chloro-3-nitrobenzoic acid is replaced with 2-chloro-4-fluoro-5-nitrobenzoic acid;

[0233] Step (2): Refer to step (2) of Example 1; methyl 4-chloro-3-nitrobenzoate is replaced with methyl 2-chloro-4-fluoro-5-nitrobenzoate;

[0234] Step (3): Refer to step (3) of Example 1; methyl 3-amino-4-chlorobenzoate is replaced with methyl 5-amino-2-chloro-4-fluorobenzoate, and CS(NHCH3)2 is replaced with CS(NHCH2CH3)2;

[0235] Step (4): Refer to step (4) of Example 1; 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid is replaced with 2-chloro-4-fluoro-3-(3,5-diethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid;

[0236] (5) Preparation of 2-((benzyloxy)imino)propyl 2-chloro-4-fluoro-5-(3,5-diethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate:

[0237] Dissolve 2-chloro-4-fluoro-(3,5-diethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.67 mmol) in 15 mL of acetone, add potassium carbonate (110.92 mg, 0.80 mmol) and potassium iodide (11.00 mg, 0.07 mmol), and add 1-chloropropane-2-one O-benzyl oxime (110.92 mg, 0.87 mmol) under stirring at room temperature. Then, reflux the mixture at 60 °C for 6 hours. After the reaction was complete, excess potassium carbonate and potassium iodide were removed by filtration, the mixture was concentrated under reduced pressure, and column chromatography was performed to obtain 0.26 g of 2-((benzyloxy)imino)propyl-2-chloro-5-(3,5-diethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate, with a yield of 80.16%.

[0238] Example 15: A method for preparing 2-(allyloxy)imino)propyl 2-chloro-5-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)-4-fluorobenzoate (i.e., compound A15), comprising the following steps:

[0239] (1) Preparation of methyl 2-chloro-4-fluoro-5-(phenoxycarbonylthioamide)benzoate (intermediate 6):

[0240] Intermediate 5 (10 g, 49.12 mmol) and phenyl thiochloroformate (9.33 g, 54.03 mmol) were dissolved in 100 mL of 1,4-dioxane. The reaction solution was then heated to reflux and stirred for 2 hours. After the reaction was complete, the solution was cooled to room temperature, and the solvent was removed by rotary evaporation. The residue was purified by rapid chromatography to give intermediate 6, 13.4 g. Yield: 80.3%.

[0241] (2) Preparation of phenylmethyl (methylaminomethylthio)carbamate (intermediate 8a)

[0242] K₂CO₃ (13.24 g, 95.81 mmol) was added to 1,3-dimethylthiourea (9.31 g, 89.42 mmol) in 100 mL of ethyl acetate under a nitrogen atmosphere at room temperature. Then, phenyl chloroformate (10 g, 63.87 mmol) was added to the mixture, and the mixture was stirred for 2 hours. After the reaction was complete, the mixture was filtered, and the resulting solvent was evaporated by rotary evaporation to give intermediate 8a, 10.31 g. Yield: 71.97%.

[0243] (3) Preparation of methyl 2-chloro-5-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)-4-fluorobenzoate (intermediate 9a):

[0244] Intermediate 6 (17.27 g, 50.83 mmol) and intermediate 8a (9.50 g, 42.36 mmol), along with NaOAc (1.74 g, 21.18 mmol), were dissolved in 100 mL of LDM. The mixture was then heated to 60 °C and reacted for 3 hours. After the reaction was complete, the mixture was cooled to room temperature. The organic layers were extracted with 200 mL of water and 200 mL of ethyl acetate, and washed with ethyl acetate. The combined organic layers were washed with saturated brine (100 mL × 2) and concentrated by rotary evaporation. The residue was purified by rapid chromatography to give intermediate 9a, 11.83 g. Yield: 74.31%.

[0245] (4) Preparation of methyl 2-chloro-5-(3,5-dimethyl-2,4,6-polythio-1,3,5-triazin-1-yl)-4-fluorobenzoate (intermediate 10a):

[0246] Intermediate 9a (11.83 g, 31.48 mmol) was dissolved in 100 mL of glacial acetic acid. Then, 50 mL of H₂O and 50 mL of H₂SO₄ were added to the solution with stirring, and the reaction solution was heated to 100 °C and reacted for 10 hours. After the reaction was complete, the reaction solution was cooled to room temperature and poured into 300 g of ice, and stirred vigorously for 30 minutes. The resulting solid was filtered, washed with H₂O, and dried under vacuum to give compound 10a, 8.07 g. Yield: 70.86%.

[0247] (5) Preparation of 2-(allyloxy)imino)propyl 2-chloro-5-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)-4-fluorobenzoate:

[0248] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.69 mmol) in 15 mL of acetone, add potassium carbonate (114.60 mg, 0.83 mmol) and potassium iodide (11.47 mg, 0.07 mmol), and add 1-chloropropane-2-one O-allyl oxime (122.39 mg, 0.83 mmol) under stirring at room temperature. Then, reflux the mixture at 60 °C for 6 hours. After the reaction was complete, excess potassium carbonate and potassium iodide were removed by filtration, the mixture was concentrated under reduced pressure, and column chromatography was performed to obtain 0.26 g of 2-(allyloxy)imino)propyl 2-chloro-5-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)-4-fluorobenzoate, with a yield of 79.56%.

[0249] Example 16: A method for preparing 2-((benzyloxy)imino)propyl 2-chloro-5-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)-4-fluorobenzoate (i.e., compound A16), comprising the following steps:

[0250] Steps (1)-(4): Refer to steps (1)-(4) of Example 15;

[0251] (5) Preparation of 2-((benzyloxy)imino)propyl 2-chloro-5-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)-4-fluorobenzoate:

[0252] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.69 mmol) in 15 mL of acetone, add potassium carbonate (114.60 mg, 0.83 mmol) and potassium iodide (11.47 mg, 0.07 mmol), and add 1-chloropropane-2-one O-benzyl oxime (163.90 mg, 0.83 mmol) under stirring at room temperature. Then, reflux the mixture at 60 °C for 6 hours. After the reaction was complete, excess potassium carbonate and potassium iodide were removed by filtration, the mixture was concentrated under reduced pressure, and column chromatography was performed to obtain 0.29 g of 2-((benzyloxy)imino)propyl-2-chloro-5-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)-4-fluorobenzoate, with a yield of 80.25%.

[0253] Example 17: A method for preparing 2-((allyloxy)imino)propyl 2-chloro-5-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)-4-fluorobenzoate (i.e., compound A17), comprising the following steps:

[0254] Step (1): Refer to step (1) of Example 15;

[0255] Step (2): Refer to step (2) of Example 15; replace phenyl chloroformate with phenyl thiochloroformate. Step (3): Refer to step (3) of Example 15; replace 8a with 8b.

[0256] Step (4): Refer to step (4) of Example 15; 9a is replaced with 9b;

[0257] (5) Preparation of 2-((allyloxy)imino)propyl 2-chloro-5-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)-4-fluorobenzoate:

[0258] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.66 mmol) in 15 mL of acetone, add potassium carbonate (109.73 mg, 0.80 mmol) and potassium iodide (10.98 mg, 0.07 mmol), and add 1-chloropropane-2-one O-allyl oxime (117.19 mg, 0.80 mmol) under stirring at room temperature. Then, reflux the mixture at 60 °C for 6 hours. After the reaction was complete, excess potassium carbonate and potassium iodide were removed by filtration, the mixture was concentrated under reduced pressure, and column chromatography was performed to obtain 0.26 g of 2-((allyloxy)imino)propyl-2-chloro-5-(3,5-diethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate, with a yield of 80.36%.

[0259] Example 18: A method for preparing 2-((benzyloxy)imino)propyl 2-chloro-5-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)-4-fluorobenzoate (i.e., compound A18), comprising the following steps:

[0260] Step (1): Refer to step (1) of Example 15;

[0261] Step (2): Refer to step (2) of Example 15; replace phenyl chloroformate with phenyl thiochloroformate. Step (3): Refer to step (3) of Example 15; replace 8a with 8b.

[0262] Step (4): Refer to step (4) of Example 15; 9a is replaced with 9b.

[0263] (5) Preparation of 2-((benzyloxy)imino)propyl 2-chloro-5-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)-4-fluorobenzoate:

[0264] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.66 mmol) in 15 mL of acetone, add potassium carbonate (109.73 mg, 0.80 mmol) and potassium iodide (10.98 mg, 0.07 mmol), and add 1-chloropropane-2-one O-benzyl oxime (156.94 mg, 0.80 mmol) under stirring at room temperature. Then, reflux the mixture at 60 °C for 6 hours. After the reaction was complete, excess potassium carbonate and potassium iodide were removed by filtration, the mixture was concentrated under reduced pressure, and column chromatography was performed to obtain 0.31 g of 2-((benzyloxy)imino)propyl-2-chloro-5-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)-4-fluorobenzoate, with a yield of 86.92%.

[0265] Example 19: A method for preparing 2-(hydroxyimino)propyl 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate (i.e., compound A19), comprising the following steps:

[0266] Steps (1)-(4): Refer to steps (1)-(4) of Example 1;

[0267] (5) Preparation of 2-(hydroxyimino)propyl 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate:

[0268] Dissolve 250 mg (0.76 mmol) of 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid in 15 mL of acetone. Add potassium carbonate (114.48 mg, 0.92 mmol) and potassium iodide (11.46 mg, 0.08 mmol). Add 1-chloropropane-2-one oxime (98.44 mg, 0.92 mmol) with stirring at room temperature. Then, reflux at 60 °C for 6 hours. After the reaction is complete, filter to remove excess potassium carbonate and potassium iodide, concentrate under reduced pressure, and obtain 0.24 g of 2-(hydroxyimino)propyl 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate by column chromatography, yield 78.89%.

[0269] Example 20: A method for preparing 2-(hydroxyimino)propyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate (i.e., compound A20), comprising the following steps:

[0270] Steps (1)-(4): Refer to steps (1)-(4) of Example 3;

[0271] (5) Preparation of 2-(hydroxyimino)propyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate:

[0272] Dissolve 2-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.76 mmol) in 15 mL of acetone, add potassium carbonate (114.48 mg, 0.92 mmol) and potassium iodide (11.46 mg, 0.08 mmol), and add 1-chloropropane-2-one oxime (98.44 mg, 0.92 mmol) with stirring at room temperature. Then, reflux at 60 °C for 6 hours. After the reaction is complete, filter to remove excess potassium carbonate and potassium iodide, concentrate under reduced pressure, and obtain 0.25 g of 2-(hydroxyimino)propyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate by column chromatography, yield 82.18%.

[0273] Example 21: A method for preparing 2-(hydroxyimino)propyl 2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate (i.e., compound A21), comprising the following steps:

[0274] Steps (1)-(4): Refer to steps (1)-(4) of Example 5;

[0275] (5) Preparation of 2-(hydroxyimino)propyl 2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate:

[0276] 2,4-Dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.69 mmol) was dissolved in 15 mL of acetone. Potassium carbonate (114.48 mg, 0.83 mmol) and potassium iodide (11.46 mg, 0.07 mmol) were added. 1-Chloropropane-2-ketooxime (89.07 mg, 0.83 mmol) was added with stirring at room temperature. The mixture was then refluxed at 60 °C for 6 hours. After the reaction was complete, excess potassium carbonate and potassium iodide were removed by filtration. The mixture was concentrated under reduced pressure and column chromatography yielded 0.23 g of 2-(hydroxyimino)propyl 2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoate, with a yield of 76.91%.

[0277] Example 22: A method for preparing 2-(hydroxyimino)propyl-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate (i.e., compound A22), comprising the following steps:

[0278] Steps (1)-(4): Refer to steps (1)-(4) of Example 7;

[0279] (5) Preparation of 2-(hydroxyimino)propyl-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate:

[0280] Dissolve 250 mg (0.80 mmol) of 4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid in 15 mL of acetone. Add potassium carbonate (133.19 mg, 0.96 mmol) and potassium iodide (13.33 mg, 0.08 mmol). Add 1-chloropropane-2-one oxime (103.64 mg, 0.96 mmol) with stirring at room temperature. Then, reflux at 60 °C for 6 hours. After the reaction is complete, filter to remove excess potassium carbonate and potassium iodide, concentrate under reduced pressure, and obtain 0.23 g of 2-(hydroxyimino)propyl-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate by column chromatography, yield 74.90%.

[0281] Example 23: A method for preparing 2-(hydroxyimino)propyl-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-2,4-difluorobenzoate (i.e., compound A23), comprising the following steps:

[0282] Steps (1)-(4): Refer to steps (1)-(4) of Example 9;

[0283] (5) Preparation of 2-(hydroxyimino)propyl-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-2,4-difluorobenzoate:

[0284] Dissolve 2,4-difluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.76 mmol) in 15 mL of acetone, add potassium carbonate (125.92 mg, 0.91 mmol) and potassium iodide (12.60 mg, 0.08 mmol), and add 1-chloropropane-2-one oxime (97.98 mg, 0.92 mmol) with stirring at room temperature. Then, reflux at 60 °C for 6 hours. After the reaction is complete, filter to remove excess potassium carbonate and potassium iodide, concentrate under reduced pressure, and obtain 0.23 g of 2-(hydroxyimino)propyl-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-2,4-difluorobenzoate by column chromatography, yield 75.67%.

[0285] Example 24: A method for preparing 2-(hydroxyimino)propyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate (i.e., compound A24), comprising the following steps:

[0286] Steps (1)-(4): Refer to steps (1)-(4) of Example 11;

[0287] (5) Preparation of 2-(hydroxyimino)propyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate:

[0288] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.72 mmol) in 15 mL of acetone, add potassium carbonate (119.92 mg, 0.87 mmol) and potassium iodide (12.00 mg, 0.07 mmol), and add 1-chloropropane-2-one oxime (93.31 mg, 0.87 mmol) with stirring at room temperature. Then, reflux at 60 °C for 6 hours. After the reaction is complete, filter to remove excess potassium carbonate and potassium iodide, concentrate under reduced pressure, and obtain 0.22 g of 2-(hydroxyimino)propyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoate by column chromatography, yield 72.99%.

[0289] Example 25: A method for preparing 2-(hydroxyimino)propyl-2-chloro-5-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)-4-fluorobenzoate (i.e., compound A25), comprising the following steps:

[0290] Steps (1)-(4): Refer to steps (1)-(4) of Example 15;

[0291] (5) Preparation of 2-(hydroxyimino)propyl-2-chloro-5-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)-4-fluorobenzoate:

[0292] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.72 mmol) in 15 mL of acetone, add potassium carbonate (114.60 mg, 0.83 mmol) and potassium iodide (11.47 mg, 0.07 mmol), and add 1-chloropropane-2-one oxime (89.17 mg, 0.83 mmol) with stirring at room temperature. Then, reflux at 60 °C for 6 hours. After the reaction is complete, filter to remove excess potassium carbonate and potassium iodide, concentrate under reduced pressure, and obtain 0.22 g of 2-(hydroxyimino)propyl-2-chloro-5-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)-4-fluorobenzoate by column chromatography, yield 73.55%.

[0293] Example 26: A method for preparing 2-(hydroxyimino)propyl 2-chloro-5-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)-4-fluorobenzoate (i.e., compound A26), comprising the following steps:

[0294] Steps (1)-(4): Refer to steps (1)-(4) of Example 17;

[0295] (5) Preparation of 2-(hydroxyimino)propyl 2-chloro-5-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)-4-fluorobenzoate:

[0296] Dissolve 250 mg (0.76 mmol) of 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid in 15 mL of CH2Cl2. Add potassium carbonate (109.73 mg, 0.79 mmol) and potassium iodide (10.98 mg, 0.07 mmol). Add 1-chloropropane-2-one oxime (85.38 mg, 0.79 mmol) with stirring at room temperature. Then, reflux at 60 °C for 6 hours. After the reaction is complete, filter to remove excess potassium carbonate and potassium iodide, concentrate under reduced pressure, and obtain 0.21 g of 2-(hydroxyimino)propyl 2-chloro-5-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)-4-fluorobenzoate by column chromatography, yield 70.70%.

[0297] Example 27: A method for preparing N-((4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoyl)oxy)ethyl acetate (i.e., compound A27), comprising the following steps:

[0298] Steps (1)-(4): Refer to steps (1)-(4) of Example 1;

[0299] (5) Preparation of N-((4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoyl)oxy)ethyl acetate:

[0300] Dissolve 250 mg (0.76 mmol) of 4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid in 15 mL of CH2Cl2, add EDCI (160.85 mg, 0.84 mmol) and DMAP (18.64 mg, 0.15 mmol), stir at room temperature for 30 min, then add ethyl N-hydroxyacetylimine (94.39 mg, 0.92 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.23 g of N-((4-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoyl)oxy)ethyl acetate, yield 73.03%.

[0301] Example 28: A method for preparing N-((2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoyl)oxy)ethyl acetate (i.e., compound A28), comprising the following steps:

[0302] Steps (1)-(4): Refer to steps (1)-(4) of Example 3;

[0303] (5) Preparation of ethyl acetate N-((2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoyl)oxy)ethyl acetate:

[0304] Dissolve 2-chloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.76 mmol) in 15 mL of CH2Cl2, add EDCI (160.85 mg, 0.84 mmol) and DMAP (18.64 mg, 0.15 mmol), stir at room temperature for 30 min, then add ethyl N-hydroxyacetylimine (94.39 mg, 0.92 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, and the organic layer was collected. The organic layer was dried over anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.24 g of ethyl N-((2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazine-1-yl)benzoyl)oxy)ethyl acetate, with a yield of 76.21%.

[0305] Example 29: A method for preparing N-((2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoyl)oxy)ethyl acetate (i.e., compound A29), comprising the following steps:

[0306] Steps (1)-(4): Refer to steps (1)-(4) of Example 5;

[0307] (5) Preparation of N-((2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazine-1-yl)benzoyl)oxy)ethyl acetate:

[0308] Dissolve 2,4-dichloro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.69 mmol) in 15 mL of CH2Cl2, add EDCI (145.56 mg, 0.76 mmol) and DMAP (16.87 mg, 0.14 mmol), stir at room temperature for 30 min, then add ethyl N-hydroxyacetylimine (85.42 mg, 0.83 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.22 g of N-((2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoyl)oxy)ethyl acetate, yield 71.26%.

[0309] Example 30: A method for preparing N-((3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)ethyl acetate (i.e., compound A30), comprising the following steps:

[0310] Steps (1)-(4): Refer to steps (1)-(4) of Example 7;

[0311] (5) Preparation of N-((3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)ethyl acetate:

[0312] Dissolve 250 mg (0.80 mmol) of 4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid in 15 mL of CH2Cl2, add EDCI (169.36 mg, 0.88 mmol) and DMAP (19.62 mg, 0.16 mmol), stir at room temperature for 30 min, then add ethyl N-hydroxyacetylimine (85.42 mg, 0.83 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.19 g of N-((3-(3,5-dimethyl-2,6-dioxo-4-thiooxy-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)ethyl acetate, yield 59.68%.

[0313] Example 31: A method for preparing N-((5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-2,4-difluorobenzoyl)oxy)ethyl acetate (i.e., compound A31), comprising the following steps:

[0314] Steps (1)-(4): Refer to steps (1)-(4) of Example 9;

[0315] (5) Preparation of N-((5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-2,4-difluorobenzoyl)oxy)ethyl acetate:

[0316] Dissolve 2,4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.76 mmol) in 15 mL of CH2Cl2, add EDCI (160.10 mg, 0.84 mmol) and DMAP (18.55 mg, 0.15 mmol), stir at room temperature for 30 min, then add ethyl N-hydroxyacetylimine (93.95 mg, 0.91 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.20 g of N-((5-(3,5-dimethyl-2,6-dioxo-4-thiooxy-1,3,5-triazin-1-yl)-2,4-difluorobenzoyl)oxy)ethyl acetate, yield 63.57%.

[0317] Example 32: A method for preparing N-((2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)ethyl acetate (i.e., compound A32), comprising the following steps:

[0318] Steps (1)-(4): Refer to steps (1)-(4) of Example 11;

[0319] (5) Preparation of N-((2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)ethyl acetate:

[0320] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.72 mmol) in 15 mL of CH2Cl2, add EDCI (152.48 mg, 0.80 mmol) and DMAP (17.67 mg, 0.14 mmol), stir at room temperature for 30 min, then add ethyl N-hydroxyacetylimine (89.48 mg, 0.87 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.21 g of ethyl N-((2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thiooxy-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)ethyl acetate, yield 67.41%.

[0321] Example 33: A method for preparing 3-(4-chloro-2-fluoro-5-(propane-2-imideamino)oxycarbonyl)phenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione (i.e., compound A33), comprising the following steps:

[0322] Steps (1)-(4): Refer to steps (1)-(4) of Example 11;

[0323] (5) Preparation of 3-(4-chloro-2-fluoro-5-(prop-2-imideamino)oxycarbonyl)phenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione:

[0324] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.72 mmol) in 15 mL of CH2Cl2, add EDCI (152.48 mg, 0.80 mmol) and DMAP (17.67 mg, 0.14 mmol), stir at room temperature for 30 min, then add acetone oxime (63.43 mg, 0.87 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.18 g of 3-(4-chloro-2-fluoro-5-(propane-2-imideamino)oxycarbonyl)phenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione, with a yield of 62.11%.

[0325] Example 34: Preparation method of isobutyraldehyde O-(2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl) oxime (i.e., compound A34), including the following steps:

[0326] Steps (1)-(4): Refer to steps (1)-(4) of Example 11;

[0327] (5) Preparation of isobutyraldehyde O-(2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl) oxime:

[0328] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.72 mmol) in 15 mL of CH2Cl2, add EDCI (152.48 mg, 0.80 mmol) and DMAP (17.67 mg, 0.14 mmol), stir at room temperature for 30 min, then add isobutyraldehyde oxime (75.60 mg, 0.87 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.18 g of isobutyraldehyde O-(2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl) oxime, with a yield of 60.01%.

[0329] Example 35: Preparation method of 3-(((but-2-imino)oxycarbonyl)-4-chloro-2-fluorophenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione (i.e., compound A35), including the following steps:

[0330] Steps (1)-(4): Refer to steps (1)-(4) of Example 11;

[0331] (5) Preparation of 3-(((but-2-imino)oxycarbonyl)-4-chloro-2-fluorophenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione:

[0332] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.72 mmol) in 15 mL of CH2Cl2, add EDCI (152.48 mg, 0.80 mmol) and DMAP (17.67 mg, 0.14 mmol), stir at room temperature for 30 min, then add but-2-one oxime (75.60 mg, 0.87 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.17 g of 3-(((but-2-imino)oxycarbonyl)-4-chloro-2-fluorophenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione, with a yield of 56.67%.

[0333] Example 36: Preparation method of butyraldehyde O-(2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl) oxime (i.e., compound A36), including the following steps:

[0334] Steps (1)-(4): Refer to steps (1)-(4) of Example 11;

[0335] (5) Preparation of butyraldehyde O-(2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl) oxime:

[0336] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.72 mmol) in 15 mL of CH2Cl2, add EDCI (152.48 mg, 0.80 mmol) and DMAP (17.67 mg, 0.14 mmol), stir at room temperature for 30 min, then add butyraldehyde oxime (75.60 mg, 0.87 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.18 g of butyraldehyde O-(2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl) oxime, with a yield of 60.01%.

[0337] Example 37: Preparation method of 3-(4-chloro-5-((cyclopentylamino)oxycarbonyl)-2-fluorophenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione (i.e., compound A37), including the following steps:

[0338] Steps (1)-(4): Refer to steps (1)-(4) of Example 11;

[0339] (5) Preparation of 3-(4-chloro-5-((cyclopentylamino)oxycarbonyl)-2-fluorophenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione:

[0340] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.72 mmol) in 15 mL of CH2Cl2, add EDCI (152.48 mg, 0.80 mmol) and DMAP (17.67 mg, 0.14 mmol), stir at room temperature for 30 min, then add cyclopentanone oxime (86.02 mg, 0.87 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.18 g of 3-(4-chloro-5-((cyclopentylamino)oxycarbonyl)-2-fluorophenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione, with a yield of 58.32%.

[0341] Example 38: Preparation method of 3-(4-chloro-5-((cyclohexylamino)oxycarbonyl)-2-fluorophenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione (i.e., compound A38), including the following steps:

[0342] Steps (1)-(4): Refer to steps (1)-(4) of Example 11;

[0343] (5) Preparation of 3-(4-chloro-5-((cyclohexylamino)oxycarbonyl)-2-fluorophenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione:

[0344] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.72 mmol) in 15 mL of CH2Cl2, add EDCI (152.48 mg, 0.80 mmol) and DMAP (17.67 mg, 0.14 mmol), stir at room temperature for 30 min, then add cyclohexanone oxime (98.19 mg, 0.87 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.18 g of 3-(4-chloro-5-((cyclohexylamino)oxycarbonyl)-2-fluorophenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione, with a yield of 56.46%.

[0345] Example 39: Preparation method of 3-(4-chloro-2-fluoro-5-((1-(furan-2-yl)ethyleneamino)oxycarbonyl)phenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione (i.e., compound A39), including the following steps:

[0346] Steps (1)-(4): Refer to steps (1)-(4) of Example 11;

[0347] (5) Preparation of 3-(4-chloro-2-fluoro-5-((1-(furan-2-yl)ethyleneamino)oxycarbonyl)phenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione:

[0348] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.72 mmol) in 15 mL of CH2Cl2, add EDCI (152.48 mg, 0.80 mmol) and DMAP (17.67 mg, 0.14 mmol), stir at room temperature for 30 min, then add 1-furan-2-yl)ethane-1-one oxime (108.58 mg, 0.87 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.17 g of 3-(4-chloro-2-fluoro-5-((1-(furan-2-yl)ethyleneamino)oxycarbonyl)phenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione, with a yield of 51.92%.

[0349] Example 40: Preparation method of 3-(4-chloro-2-fluoro-5-((1-(thiophen-2-yl)ethyleneamino)oxycarbonyl)phenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione (i.e., compound A40), including the following steps:

[0350] Steps (1)-(4): Refer to steps (1)-(4) of Example 11;

[0351] (5) Preparation of 3-(4-chloro-2-fluoro-5-((1-(thiophen-2-yl)ethyleneamino)oxycarbonyl)phenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione:

[0352] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.72 mmol) in 15 mL of CH2Cl2, add EDCI (152.48 mg, 0.80 mmol) and DMAP (17.67 mg, 0.14 mmol), stir at room temperature for 30 min, then add 1-thiophen-2-yl)ethane-1-one oxime (108.58 mg, 0.87 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.16 g of 3-(4-chloro-2-fluoro-5-((1-(thiophene-2-yl)ethyleneamino)oxycarbonyl)phenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione, with a yield of 47.19%.

[0353] Example 41: A method for preparing ethyl 2-(((2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)imino)propionate (i.e., compound A41), comprising the following steps:

[0354] Steps (1)-(4): Refer to steps (1)-(4) of Example 11;

[0355] (5) Preparation of ethyl 2-(((2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)imino)propionate:

[0356] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.72 mmol) in 15 mL of CH2Cl2, add EDCI (152.48 mg, 0.80 mmol) and DMAP (17.67 mg, 0.14 mmol), stir at room temperature for 30 min, then add ethyl 2-hydroxyiminopropionate (113.79 mg, 0.87 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.20 g of ethyl 2-(((2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)imino)propionate, yield 60.28%).

[0357] Example 42: A method for preparing ethyl acetate 2-chloro-2-(2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)imino)ethyl acetate (i.e., compound A42) includes the following steps:

[0358] Steps (1)-(4): Refer to steps (1)-(4) of Example 11;

[0359] (5) Preparation of ethyl acetate 2-chloro-2-(2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)imino):

[0360] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.72 mmol) in 15 mL of CH2Cl2, add EDCI (152.48 mg, 0.80 mmol) and DMAP (17.67 mg, 0.14 mmol), stir at room temperature for 30 min, then add ethyl 4-(hydroxyimino)valerate (138.13 mg, 0.87 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.18 g of ethyl acetate 2-chloro-2-(2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)imino)ethyl acetate, yield 51.12%.

[0361] Example 43: A method for preparing ethyl (2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)iminobutyrate (i.e., compound A43), comprising the following steps:

[0362] Steps (1)-(4): Refer to steps (1)-(4) of Example 11;

[0363] (5) Preparation of ethyl (2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)iminobutyrate:

[0364] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.72 mmol) in 15 mL of CH2Cl2, add EDCI (152.48 mg, 0.80 mmol) and DMAP (17.67 mg, 0.14 mmol), stir at room temperature for 30 min, then add ethyl 5-(hydroxyimino)hexanoate (138.13 mg, 0.87 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.21 g of ethyl (2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)iminobutyrate, yield 57.89%.

[0365] Example 44: A method for preparing ethyl valerate (2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazinyl-1-yl)-4-fluorobenzoyl)oxy)imino)valerate (i.e., compound A44), comprising the following steps:

[0366] Steps (1)-(4): Refer to steps (1)-(4) of Example 11;

[0367] (5) Preparation of ethyl 2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazinyl-1-yl)-4-fluorobenzoyl)oxy)imino)valerate:

[0368] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.72 mmol) in 15 mL of CH2Cl2, add EDCI (152.48 mg, 0.80 mmol) and DMAP (17.67 mg, 0.14 mmol), stir at room temperature for 30 min, then add 3-hydroxyiminobutane-2-one (87.73 mg, 0.87 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.17 g of ethyl (2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)imino)valerate, yield 56.81%).

[0369] Example 45: A method for preparing ethyl hexanoate (2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)imino)hexanoate (i.e., compound A45), comprising the following steps:

[0370] Steps (1)-(4): Refer to steps (1)-(4) of Example 11;

[0371] (5) Preparation of ethyl hexanoate of (2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazinyl-1-yl)-4-fluorobenzoyl)oxy)imino)hexanoate:

[0372] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.72 mmol) in 15 mL of CH2Cl2, add EDCI (152.48 mg, 0.80 mmol) and DMAP (17.67 mg, 0.14 mmol), stir at room temperature for 30 min, then add ethyl (E)-5-(hydroxyimino)hexanoate (150.30 mg, 0.87 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.19 g of ethyl (2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)imino)hexanoate, yield 51.02%).

[0373] Example 46: A method for preparing 3-(4-chloro-2-fluoro-5-((3-oxobutane-2-imino)oxocarbonyl)phenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione (i.e., compound A46), comprising the following steps:

[0374] Steps (1)-(4): Refer to steps (1)-(4) of Example 11;

[0375] (5) Preparation of 3-(4-chloro-2-fluoro-5-((3-oxobutane-2-imino)oxocarbonyl)phenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione:

[0376] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.72 mmol) in 15 mL of CH2Cl2, add EDCI (152.48 mg, 0.80 mmol) and DMAP (17.67 mg, 0.14 mmol), stir at room temperature for 30 min, then add 3-hydroxyiminobutane-2-one (87.73 mg, 0.87 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.20 g of 3-(4-chloro-2-fluoro-5-((3-oxobutane-2-imino)oxocarbonyl)phenyl)-1,5-dimethyl-6-thio-1,3,5-triazine-2,4-dione, with a yield of 64.50%.

[0377] Example 47: A method for preparing 2-oxopropanal O-(2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazinyl-1-yl)-4-fluorobenzoyl) oxime (i.e., compound A47), comprising the following steps:

[0378] Steps (1)-(4): Refer to steps (1)-(4) of Example 11;

[0379] (5) Preparation of 2-oxopropanal O-(2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl) oxime:

[0380] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.72 mmol) in 15 mL of CH2Cl2, add EDCI (152.48 mg, 0.80 mmol) and DMAP (17.67 mg, 0.14 mmol), stir at room temperature for 30 min, then add (E)-2-oxopropanal oxime (75.56 mg, 0.87 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.20 g of 2-oxopropanal O-(2-chloro-5-(3,5-dimethyl-2,6-dioxo-4-thio-1,3,5-triazin-1-yl)-4-fluorobenzoyl) oxime, with a yield of 63.35%.

[0381] Example 48: A method for preparing N-((2-chloro-5-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)ethyl acetate (i.e., compound A48), comprising the following steps:

[0382] Steps (1)-(4): Refer to steps (1)-(4) of Example 15;

[0383] (5) Preparation of N-((2-chloro-5-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)ethyl acetate:

[0384] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.69 mmol) in 15 mL of CH2Cl2, add EDCI (145.72 mg, 0.76 mmol) and DMAP (16.88 mg, 0.14 mmol), stir at room temperature for 30 min, then add ethyl N-hydroxyacetylimine (85.51 mg, 0.83 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, and the organic layer was collected. The organic layer was dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.18 g of ethyl acetate N-((2-chloro-5-(3,5-dimethyl-2-oxo-4,6-dithio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)ethyl acetate, yield 58.29%.

[0385] Example 49: A method for preparing N-((2-chloro-5-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)ethyl acetate (i.e., compound A49), comprising the following steps:

[0386] Steps (1)-(4): Refer to steps (1)-(4) of Example 17;

[0387] (5) Preparation of N-((2-chloro-5-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)ethyl acetate:

[0388] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.66 mmol) in 15 mL of CH2Cl2, add EDCI (139.52 mg, 0.73 mmol) and DMAP (16.17 mg, 0.13 mmol), stir at room temperature for 30 min, then add ethyl N-hydroxyacetylimine (81.87 mg, 0.79 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.17 g of ethyl N-((2-chloro-5-(3,5-dimethyl-2,4,6-trisulfoxy-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)ethyl acetate, yield 57.49%.

[0389] Example 50: A method for preparing ethyl (2-chloro-5-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)iminopropionate (i.e., compound A50), comprising the following steps:

[0390] Steps (1)-(4): Refer to steps (1)-(4) of Example 17;

[0391] (5) Preparation of ethyl (2-chloro-5-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazinyl-1-yl)-4-fluorobenzoyl)oxy)iminopropionic acid:

[0392] Dissolve 2-chloro-4-fluoro-3-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)benzoic acid (250 mg, 0.66 mmol) in 15 mL of CH2Cl2, add EDCI (139.52 mg, 0.73 mmol) and DMAP (16.17 mg, 0.13 mmol), stir at room temperature for 30 min, then add ethyl 2-hydroxyiminopropionate (104.11 mg, 0.79 mmol), and react at room temperature for 6 hours. After the reaction was complete, the mixture was poured into 20 mL of water, extracted with 20 mL of CH2Cl2, the organic layer was collected, dried with anhydrous Na2SO4, concentrated under reduced pressure, and the residue was subjected to column chromatography to obtain 0.17 g of ethyl (2-chloro-5-(3,5-dimethyl-2,4,6-trithio-1,3,5-triazin-1-yl)-4-fluorobenzoyl)oxy)iminopropionate, yield 54.10%.

[0393] The structural and molecular formulas of the target compounds obtained in the above examples are shown in Table 1, and their physicochemical properties and spectral information are also shown in Table 1.

[0394] Table 1. Molecular formulas and structural formulas of the target compounds obtained in Examples 1-50

[0395]

[0396]

[0397]

[0398]

[0399]

[0400]

[0401]

[0402] Table 2. Physicochemical properties and spectroscopic data of the target compounds obtained in Examples 1-50

[0403]

[0404]

[0405]

[0406]

[0407]

[0408]

[0409]

[0410]

[0411]

[0412] Post-seeding activity test of target compound:

[0413] This experiment employed a spraying method, using various weeds as test targets. Weed seeds were directly sown and evenly scattered in 8x8cm plastic pots filled two-thirds with organic substrate, and then grown in a greenhouse. Both grasses and broadleaf weeds were ready for testing when they reached the two- to three-leaf stage. The compound was dissolved in 100 μL DMF and diluted with 0.1% Tween-80 to a dosage of 37.5–150 g ai / ha. Trifluralin was used as a positive control and the target compound to spray all weeds. After 15 days in the greenhouse, the herbicidal activity of the treated weeds was evaluated visually as a control (CK) group, repeated three times.

[0414] Table 3. Post-emergence herbicidal activity of target compounds in Examples 1-50

[0415]

[0416]

[0417]

[0418] Crop safety testing of target compounds:

[0419] This experiment used a spraying method with various crops as test subjects. Crop seeds were directly sown and evenly scattered in 8x8cm plastic pots filled with two-thirds organic substrate soil, and then grown in a greenhouse. The compound was dissolved in 100 μL DMF and diluted with 0.1% Tween-80 to a dose of 150 g ai / ha. Trifluralin was used as a positive control and the target compound to spray all weeds. After the treated crops were placed in the greenhouse for 30 days, the crop safety was evaluated visually as a control (CK) group, and the experiment was repeated three times.

[0420] Table 4. Crop safety of target compounds in Examples 34 and 43 at a dose of 150 g ai / ha.

[0421]

[0422] Table 3 shows that at a dose of 150 g ai / ha, compounds A24, A33, A34, A36, A42, A43, A44, A46, and A47 exhibited excellent herbicidal activity against barnyard grass, crabgrass, foxtail, velvetleaf, amaranth, and purslane. The weeds completely withered, and their growth was severely inhibited, with inhibition rates reaching 100%, comparable to the positive control trifluralin. Among these, compounds A34, A36, and A43, as target compounds, showed significant herbicidal activity at 37.5 g ai / ha. Barnyard grass, crabgrass, foxtail grass, velvetleaf, amaranth, and purslane still exhibit excellent herbicidal activity, comparable to the positive control trifluralin. As shown in Table 4, trifluralin causes very serious damage to broadleaf crops, even leading to complete plant death. In contrast, compounds A34 and A43 show superior crop safety to trifluralin in crops such as rice, corn, wheat, peanuts, soybeans, and cotton, with relatively better safety in broadleaf crops.

[0423] In summary, this series of N-phenylthiotriazinone derivatives possesses novel structures, simple structures and preparation processes, low production costs, and excellent post-emergence herbicidal activity. Therefore, this series of compounds can be used as novel PPO inhibitors and post-emergence herbicides, and further development of novel selective herbicides will enable their application in a wider range of farmlands.

[0424] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. An N-phenylthiotriazinone derivative, characterized in that, Selected from the following compounds: Compound A1: ; Compound A2: ; Compound A3: ; Compound A4: ; Compound A5: ; Compound A6: ; Compound A7: ; Compound A8: ; Compound A9: ; Compound A10: ; Compound A11: ; Compound A12: ; Compound A13: ; Compound A14: ; Compound A15: ; Compound A16: ; Compound A17: ; Compound A18: ; Compound A19: ; Compound A20: ; Compound A21: ; Compound A22: ; Compound A23: ; Compound A24: ; Compound A25: ; Compound A26: ; Compound A27: ; Compound A28: ; Compound A29: ; Compound A30: ; Compound A31: ; Compound A32: ; Compound A33: ; Compound A34: ; Compound A35: ; Compound A36: ; Compound A37: ; Compound A38: ; Compound A39: ; Compound A40: ; Compound A41: ; Compound A42: ; Compound A43: ; Compound A44: ; Compound A45: ; Compound A46: ; Compound A47: ; Compound A48: ; Compound A49: ; Compound A50: .

2. As described in claim 1 N Application of phenylthiotriazinone derivatives in the preparation of weed growth enzyme inhibitors, wherein the weeds are barnyard grass, velvetleaf, amaranth, purslane, amaranth, and foxtail grass.

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