A compound containing a triazolinone structure and application thereof and a herbicide

Abstract

The present application relates to the technical field of new pesticide compounds, and discloses a compound containing a triazolinone structure, application of the compound, and a herbicide.The compound has a structure shown in formula (I). The compound provided by the present application has high herbicidal activity, a wide weed killing spectrum, and good safety for PPO transgenic soybeans, and is of great significance for creating a novel-structure super-high-efficiency PPO inhibitor herbicide and preventing resistant weeds.

Description

Technical Field

[0001] This invention relates to the field of new pesticide compounds, specifically to a compound containing a triazolinone structure and its application, as well as a herbicide. Background Technology

[0002] Protoporphyrinogen oxidase (PPO, EC 1.3.3.4) is an important herbicide target. It is the final common enzyme in the biosynthesis of chlorophyll and heme, widely found in various organisms, and catalyzes the oxidation of protoporphyrinogen IX to protoporphyrin IX.

[0003] In plants, protoporphyrin IX is an important substance for the synthesis of chlorophyll. If PPO enzymes in plants are inhibited, the substrate protoporphyrin IX will accumulate rapidly and permeate into the cytoplasm to be oxidized, producing high concentrations of protoporphyrin IX. Under the action of light and oxygen, singlet oxygen is generated. Under the action of singlet oxygen, the cell membrane undergoes a peroxidation reaction and is damaged, thereby causing cell death, ultimately leading to leaf whitening and death of the plant.

[0004] Herbicides targeting PPO have a unique mechanism of action, develop resistance slowly, and have broad-spectrum herbicidal activity, enabling them to control a variety of weeds and resistant weeds.

[0005] PPO inhibitor herbicides have become the most important class of herbicides and are a hot research topic for major pesticide companies.

[0006] To date, 30 PPO inhibitor herbicides across nine categories have been successfully launched on the market.

[0007] In the past fifty years of widespread use of PPO inhibitors, researchers have found that herbicides targeting PPO have the characteristics of broad spectrum, high efficiency, low toxicity, low residue, environmental friendliness, and high crop safety. More encouragingly, these herbicides have excellent specific control effects on a variety of resistant weeds and can be used to control weeds that have developed resistance to glyphosate and ALS inhibitor herbicides.

[0008] In 1990, WO9002120A1 disclosed a triazolinone PPO inhibitor, the structural formula of which is shown below. This substance (trade name: triazolinone) is mainly used to control broadleaf weeds in cereal fields, etc.

[0009]

[0010] However, this substance requires high doses to achieve relatively good efficacy, which significantly reduces its safety.

[0011] Therefore, creating new green and highly efficient PPO inhibitor herbicides with higher activity and better safety has become one of the research hotspots for major pesticide companies and research institutes. Summary of the Invention

[0012] The purpose of this invention is to provide a novel triazoline compound with high herbicidal activity.

[0013] To achieve the above objectives, a first aspect of the present invention provides a compound containing a triazolinone structure, or an agriculturally chemically acceptable salt, hydrate, solvate, or an enantiomer or optically active derivative thereof, having the structure shown in formula (I).

[0014] Formula (I):

[0015] In equation (I), R is selected from H and C. 1-6 Alkyl, substituted or unsubstituted C 2-6 alkenyl, substituted or unsubstituted C 2-6 The acetylin group.

[0016] The second aspect of the present invention provides the use of compounds containing a triazolinone structure as described in the first aspect, or their agriculturally chemically acceptable salts, hydrates, solvates, or their enantiomers or optically active derivatives, as PPO inhibitors.

[0017] The third aspect of the present invention provides the use of the compounds containing the triazolinone structure described in the first aspect, or their agriculturally chemically acceptable salts, hydrates, solvates, or their enantiomers or optically active derivatives, in the control of weeds.

[0018] A fourth aspect of the present invention provides a herbicide comprising an active ingredient and excipients, wherein the active ingredient comprises at least one of the compounds described in the first aspect thereof, or an agriculturally chemically acceptable salt, hydrate, solvate thereof, or an enantiomer or optically active derivative thereof. Detailed Implementation

[0019] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0020] The following explanations of the terms used in this document shall apply to all identical or similar terms in this document unless otherwise stated.

[0021] “C 1-6 "alkyl" refers to a straight-chain or branched alkyl group with a total of 1-6 carbon atoms. For example, the number of carbon atoms can be 1, 2, 3, 4, 5, or 6, including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and n-hexyl. 1-4 "alkyl" has a similar definition.

[0022] “C 2-6 "Alkenyl" refers to a straight-chain or branched alkenyl group with a total of 2-6 carbon atoms. For example, the number of carbon atoms can be 2, 3, 4, 5, or 6, including but not limited to allyl, propenyl, 1-butenyl, and 2-butenyl. 2-4 "Alkenyl" has a similar definition.

[0023] “C 2-6 "Alynyl" refers to a straight-chain or branched alkynyl group with a total of 2-6 carbon atoms. For example, the number of carbon atoms can be 2, 3, 4, 5, or 6, including but not limited to propynyl, propynyl, 1-butynyl, and 2-butynyl. 2-4 The "alkynyl group" has a similar definition.

[0024] HATU is 2-(7-azabenzotriazole)-N,N,N′,N′-tetramethylurea hexafluorophosphate;

[0025] HBTU is O-benzotriazole-tetramethylurea hexafluorophosphate;

[0026] EDCI is 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride;

[0027] CDI is N,N′-carbonyldiimidazole;

[0028] HOBt is 1-hydroxybenzotriazole;

[0029] DCC stands for dicyclohexylcarbodiimide;

[0030] DIC is N,N′-diisopropylcarbodiimide;

[0031] PyBOP is benzotriazol-1-yl-oxytripyrrolidinyl hexafluorophosphate;

[0032] POCl3 is phosphorus oxychloride;

[0033] T3P is 1-propyl phosphate cyclic anhydride;

[0034] DIPEA is N,N-diisopropylethylamine;

[0035] DMAP is 4-dimethylaminopyridine;

[0036] DBU is 1,8-diazabicycloundec-7-ene.

[0037] As previously described, a first aspect of the present invention provides a compound containing a triazolinone structure or an agriculturally chemically acceptable salt, hydrate, solvate, or an enantiomer or optically active derivative thereof, having the structure shown in formula (I).

[0038] Formula (I):

[0039] In equation (I), R is selected from H and C. 1-6 Alkyl, substituted or unsubstituted C 2-6 alkenyl, substituted or unsubstituted C 2-6 The acetylin group.

[0040] According to a preferred embodiment, in formula (I), R is selected from H and C. 1-4 Alkyl, substituted or unsubstituted C 2-4 alkenyl, substituted or unsubstituted C 2-4 The acetylin group.

[0041] More preferably, the compound represented by formula (I) is selected from any one of the following:

[0042] Compound 1: Compound 2: Compound 3: Compound 4: Compound 5: Compound 6:

[0043] Particularly preferably, the compound represented by formula (I) is compound 1, compound 4, or compound 6. The inventors of this invention have discovered in their research that the compound under these preferred conditions exhibits superior herbicidal activity.

[0044] This invention does not impose any particular requirements on the method for preparing the compounds described in the first aspect. Those skilled in the art can determine a suitable synthetic route based on the structural formulas provided by this invention and known knowledge in the field of organic synthesis to obtain the compounds described in the first aspect of this invention. However, in order to achieve significantly higher yields and purity, this invention provides a preferred method for preparing the compounds described in the first aspect of this invention.

[0045] According to a preferred embodiment, a method for preparing the compound containing the triazolinone structure or its agriculturally chemically acceptable salt, hydrate, solvate, or its enantiomer or optically active derivative comprises: subjecting the compound of formula (II) to a compound of formula (III) or a hydrochloride salt of the compound of formula (III) in the presence of a solvent and a condensing agent.

[0046] NH2-(CH2)2-C(O)-O-Q1 (Formula III)

[0047] Q1 is selected from H and C. 1-6 Alkyl groups.

[0048] According to another preferred embodiment, a method for preparing the compound containing the triazolinone structure or its agriculturally chemically acceptable salt, hydrate, solvate, or its enantiomer or optically active derivative comprises: subjecting compound 4 to a condensation reaction with the compound of formula (IV) in the presence of a solvent and a condensing agent.

[0049] Q2-OH formula (IV)

[0050] Q2 is selected from substituted or unsubstituted C. 2-6 alkenyl, substituted or unsubstituted C 2-6 The acetylin group.

[0051] In a preferred embodiment, the condensing agent is selected from at least one of HATU, HBTU, EDCI, CDI, HOBt, DCC, DIC, PyBOP, POCl3, and T3P.

[0052] Preferably, the condensation reaction is carried out in the presence of an alkaline substance selected from at least one of triethylamine, DIPEA, DMAP, DBU, potassium carbonate, sodium carbonate, cesium carbonate, and pyridine.

[0053] Preferably, the solvent is selected from at least one of dichloromethane, trichloromethane, dichloroethane, acetonitrile, toluene, tetrahydrofuran, and benzene.

[0054] In the preparation method described in this invention, the intermediates and various reagents used can be commercially available or prepared using known reactions in the art.

[0055] The following is an exemplary method for preparing the compound shown in formula (II):

[0056]

[0057] Specifically, the process includes: reacting the product of diazotization of compound A-1 with pyruvate to obtain compound A-2, and further obtaining the cyclically closed triazolone compound A-3, then difluoromethylating to obtain compound A-4, nitrifying compound A-4 to obtain nitrated product A-5, then nitroreduction to obtain compound A-6, diazotizing compound A-6 to obtain diazonium salt A-7, and then reacting it with acrylic acid and cuprous chloride to obtain the compound shown in formula (II).

[0058] As previously stated, the second aspect of the present invention provides the use of compounds containing a triazolinone structure as described in the first aspect, or their agriculturally chemically acceptable salts, hydrates, solvates, or their enantiomers or optically active derivatives, as PPO inhibitors.

[0059] As previously stated, the third aspect of the present invention provides the use of compounds containing a triazolinone structure as described in the first aspect, or their agriculturally chemically acceptable salts, hydrates, solvates, or their enantiomers or optically active derivatives, in the control of weeds.

[0060] The compounds provided by this invention have excellent herbicidal activity. Therefore, the compounds provided by this invention are expected to become excellent ultra-efficient herbicides that can be effective against plants growing in places that are harmful to human survival and activities, including non-cultivated wild plants or plants that are useless to humans; for example, they can have a good weeding effect on various wild plants in crop fields.

[0061] For example, it can be used to control at least one weed in cotton fields, wheat fields, rice fields, corn fields, soybean fields, and PPO genetically modified soybean fields.

[0062] In a preferred embodiment, the weeds are selected from at least one of broadleaf weeds, grass weeds, and sedge weeds.

[0063] Preferably, the broadleaf weeds are selected from at least one of the following: Polygonum hydropiper, Amaranth, Rumex japonicus, Duckweed, Artemisia annua, Capsella bursa-pastoris, Chenopodium album, Abutilon theophrasti, Galium aparine, Veronica persica, Stellaria media, Amaranth, Amaranthus chinensis, Solanum nigrum, Solanum lyratum, Portulaca oleracea, Amaranthus retroflexus, Amaranthus spinosa, Celosia argentea, Bindweed, Carp's intestines, Zinnia elegans, and Erigeron annuus.

[0064] Preferably, the grassy weeds are selected from at least one of the following: barnyard grass, wild millet, wild sorghum, goosegrass, golden foxtail grass, foxtail grass, tiger tail grass, crabgrass, wild oat, Japanese wild oat, jointed barley, wild oat, wild oat, barnyard grass, and double-spike barnyard grass.

[0065] Preferably, the Cyperaceae family is selected from at least one of Cyperus rotundus, Cyperus ferrugineus, and Cyperus divaricata.

[0066] As previously stated, a fourth aspect of the present invention provides a herbicide comprising an active ingredient and excipients, wherein the active ingredient comprises at least one of the compounds described in the first aspect thereof, or their agriculturally chemically acceptable salts, hydrates, solvates, or their enantiomers or optically active derivatives thereof.

[0067] Preferably, the content of the active ingredient is 1-99.9999% by weight. For example, it can be 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt%, etc.

[0068] More preferably, the content of the active ingredient is 5-99.9999% by weight.

[0069] Particularly preferably, the content of the active ingredient is 5-99% by weight.

[0070] The present invention does not impose any particular limitation on the selection of excipients. Those skilled in the art can select excipients based on those known in the art. For example, the excipients are selected from at least one of surfactants, protective colloids, adhesives, thickeners, thixotropic agents, penetrants, chelating agents, colorants, and polymers. Further details are omitted here, and should not be construed as limiting the present invention.

[0071] Preferably, the formulation of the herbicide of the present invention is selected from at least one of emulsifiable concentrate, suspension concentrate, wettable powder, powder, granule, aqueous solution, poison bait, mother liquor and mother powder.

[0072] In a preferred embodiment, the herbicide is applied via soil treatment.

[0073] The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, all raw materials used are commercially available and of analytical purity. Room temperature below refers to 25 ± 1 °C.

[0074] Preparation Example 1: Preparation of Compound 1

[0075]

[0076]

[0077] (1) Synthesis of compound A-2

[0078] In a 1L three-necked flask, 100g of compound A-1 was dissolved in 500mL of 2N HCl aqueous solution and stirred at -5°C. 1.5 equivalents of NaNO₂ were dissolved in 100mL of water and slowly added to the reaction system. After stirring at -5°C for 2 hours, a concentrated hydrochloric acid solution containing 2 equivalents of SnCl₂ was slowly added dropwise. After stirring at -5°C for 30 minutes, the mixture was brought to room temperature and stirred for 2 hours. 50mL of water was added to the reaction system, followed by 50mL of an aqueous solution containing 1.5 equivalents of pyruvate. Stirring continued for 30 minutes. The reaction was monitored by TLC until complete. The mixture was filtered, and the filter cake was washed with a small amount of water and dried to obtain compound A-2, with a yield of 91%.

[0079] (2) Synthesis of compound A-3

[0080] Compound A-2 prepared above was added to a 500 mL two-necked flask, along with 200 mL of toluene and an equimolar amount of triethylamine. While stirring, 1.5 equimolar amounts of (PhO)₂PON₃ were added to the reaction system. The reaction mixture was heated to reflux, and the reaction was monitored by TLC. After the reaction was complete, the toluene was removed, and the solid was recrystallized from ethanol. The solid was filtered, dried, and compound A-3 was obtained, with a yield of 71%.

[0081] (3) Synthesis of compound A-4

[0082] Compound A-3 synthesized above was added to a 500 mL single-necked flask, along with 2 equivalents of KOH, 5 equivalents of tetrabutylammonium bromide, and 200 mL of tetrahydrofuran. The mixture was heated to reflux. Difluorochloromethane gas was slowly bubbled in until the reactants reacted completely. The reaction mixture was concentrated under reduced pressure, and 200 mL of water was added. The mixture was extracted three times with 100 mL of dichloromethane. The combined organic layers were dried over anhydrous sodium sulfate and purified by column chromatography to obtain compound A-4 in 96% yield.

[0083] (4) Synthesis of compound A-5

[0084] The synthesized compound A-4 was placed in a 500 mL single-necked flask, and 100 mL of concentrated sulfuric acid was added. The mixture was stirred at -5 °C until homogeneous. 1.5 equivalents of concentrated nitric acid were dissolved in 50 mL of concentrated sulfuric acid and slowly added dropwise to the reaction system. The reaction was carried out at -5 °C until the reactants were completely reacted. The system was then slowly poured into 1 L of ice water, and a large amount of solid precipitated. After stirring to room temperature, the mixture was filtered, washed with water, and dried to obtain compound A-5 with a yield of 89%.

[0085] (5) Synthesis of compound A-6

[0086] Compound A1-5 prepared above was placed in a 1L single-necked flask, and 2 equivalents of NH4Cl and 3 equivalents of reduced iron powder were added. 500 mL of ethanol and 100 mL of water were added, and the mixture was refluxed until the starting material was completely eliminated. The mixture was filtered through diatomaceous earth, washed with ethanol, and the filtrate was desolvated. The resulting solid dissolved in water, extracted with ethyl acetate, and the organic layer was washed with saturated brine. After drying with anhydrous sodium sulfate, compound A-6 was obtained with a yield of 90%.

[0087] (6) Synthesis of the compound shown in formula (II)

[0088] Compound A-6 was added to a 500 mL single-necked flask, followed by 200 mL of water. The reaction system was stirred at -5 °C. 1.5 equivalents of NaNO2 were dissolved in 100 mL of water and slowly added dropwise to the reaction system. After stirring at -5 °C for 2 hours, the system was added to a solution of 1.5 equivalents of acrylic acid, 2 equivalents of cuprous chloride, and hydrochloric acid. The mixture was stirred at room temperature until the reaction was complete as monitored by TLC. The compound represented by formula (II) was obtained by filtration, with a yield of 78%.

[0089] (7) Synthesis of Compound 1

[0090]

[0091] 1 mmol of the compound represented by formula (II) was added to a 50 mL single-necked flask, followed by 20 mL of dichloromethane and 1.5 mmol of CDI. The mixture was stirred at room temperature for 2 hours. Then, 1.5 mmol of methyl 3-aminopropionate hydrochloride and 2 mmol of DBU were added, and the mixture was stirred at room temperature for 30 minutes. The reaction was monitored by TLC. Once the reaction was complete, the mixture was acidified with 20 mL of 1N HCl solution. The aqueous phase was extracted with 20 mL of dichloromethane, and the organic phase was dried over anhydrous sodium sulfate and concentrated. The resulting product was purified by column chromatography to give compound 1 in 87% yield.

[0092] Preparation Example 2: Preparation of Compound 2

[0093] This preparation example uses a similar process to preparation example 1, except that methyl 3-aminopropionate hydrochloride in step (7) is replaced with an equimolar amount of isopropyl 3-aminopropionate hydrochloride.

[0094] The rest were the same as in Preparation Example 1, and Compound 2 was prepared with a yield of 65%.

[0095] Preparation Example 3: Preparation of Compound 3

[0096] This preparation example uses a similar process to preparation example 1, except that methyl 3-aminopropionate hydrochloride in step (7) is replaced with an equimolar amount of tert-butyl 3-aminopropionate hydrochloride.

[0097] The rest were the same as in Preparation Example 1, and compound 3 was prepared with a yield of 73%.

[0098] Preparation Example 4: Preparation of Compound 4

[0099]

[0100] This preparation example uses a similar process to Preparation Example 1, except that methyl 3-aminopropionate hydrochloride in step (7) is replaced with an equimolar amount of β-alanine.

[0101] The rest were the same as in Preparation Example 1, and compound 4 was prepared with a yield of 71%.

[0102] Preparation Example 5: Preparation of Compound 5

[0103]

[0104] 1 mmol of compound 4 was added to a 50 mL single-necked flask, followed by 20 mL of dichloromethane and 1.5 mmol of CDI. The mixture was stirred at room temperature for 2 hours. Then, 1.5 mmol of allyl alcohol and 2 mmol of DBU were added, and the mixture was stirred at room temperature for 30 minutes. The reaction was monitored by TLC. Once the reaction was complete, the mixture was acidified with 20 mL of 1N HCl solution. The aqueous phase was extracted with 20 mL of dichloromethane, and the organic phase was dried over anhydrous sodium sulfate and concentrated. The resulting product was purified by column chromatography to give compound 5 in 75% yield.

[0105] Preparation Example 6: Preparation of Compound 6

[0106] This preparation example uses a similar process to preparation example 5, except that allyl alcohol in preparation example 5 is replaced with an equimolar amount of propargyl alcohol.

[0107] The rest were the same as in Preparation Example 5, and compound 6 was prepared with a yield of 79%.

[0108] Characterization data for the specific compounds of this invention are shown in Table 1.

[0109] Table 1

[0110]

[0111] Test Example 1: Inhibitory Activity of Protoporphyrinogen Oxidase

[0112] Protoporphyrinogen oxidase: The protoporphyrinogen oxidase used in the experiment was purified from tobacco PPO expression. It was prepared according to the method described in Chinese Patent CN110093325A. Enzyme activity was tested according to the method described in the literature "J. Agric. Food Chem. 2016, 64, 3, 552–562", and the inhibitory activity (inhibition constant K) of the triazoline-containing compound and the control compound oxadiazon against protoporphyrinogen oxidase was determined. i ).

[0113] The results are shown in Table 2.

[0114] Table 2

[0115] 1 3.6 3 4.2 4 4.1 5 3.2 6 3.4 cyclohexane 5.6

[0116] As can be seen from Table 2, the compounds provided by this invention have strong inhibitory activity against tobacco PPO, which is significantly better than that of the commercial herbicide oxychloride.

[0117] Test Example 2: Greenhouse Wide-Range Screening Experiment

[0118] Weigh a certain amount of the original drug using an analytical balance (0.0001g), dissolve it in N,N-dimethylformamide (DMF) containing 1wt% Tween-80 emulsifier to prepare a 0.5-1wt% stock solution, and then dilute it with distilled water to different concentrations of stock solution for later use.

[0119] Two treatment methods were used: foliar spraying and soil spraying.

[0120] Post-emergence foliar spraying: Take a 7cm inner diameter paper cup, fill it with composite soil (garden soil: seedling substrate, 1:2, v / v) to 3 / 4 full, directly sow the test target seeds, cover with 0.2cm of soil, and wait until the seedlings reach the 3-leaf stage for later use. Both the comparative compound oxychloride and the compound provided in this invention were applied at a dosage of 10g ai / mu in an automatic spray tower. After the foliar spray dried, the plants were transferred to a greenhouse for cultivation (temperature maintained at 25-28℃, humidity maintained at 70%). Results were investigated after 20 days.

[0121] Soil spraying: Take a 15cm*70cm lunchbox, fill it with composite soil (garden soil: seedling substrate, 1:2, v / v) to 3 / 4 full, directly sow weeds, and cover with 0.2cm of soil. Both the comparative compound oxychloride and the compound provided in this invention were sprayed into the soil at a dosage of 10g ai / mu, and the results were investigated after 20 days.

[0122] Investigation method: After 20 days of experimental treatment, the symptoms of damage and growth inhibition of the target were visually observed, and the fresh weight of the aboveground parts was measured. The fresh weight inhibition rate (%) was calculated and expressed as the growth inhibition rate (%).

[0123] Fresh weight inhibition rate (%) = (Control fresh weight - Treatment fresh weight) / Control fresh weight × 100%

[0124] The ratings were determined based on the information shown in Table 3, and the test results are shown in Table 4.

[0125] Table 3

[0126] Level 0 (same as control) It has no effect on the growth of weeds or crops, and there are no symptoms of pesticide efficacy. 0 Level 1 It has a slight impact on the growth of weeds or crops, with no obvious symptoms of efficacy. 1-19 Level 2 It affects the growth of weeds or crops and has obvious medicinal effects. 20-49 Level 3 Weeds or crops are severely inhibited in growth 50-79 Level 4 Weeds or crops are basically dead 80-99 Level 5 Weeds or crops completely dead 100

[0127] Table 4

[0128]

[0129] The above herbicidal activity test results show that the compound provided by the present invention has excellent control effects on broadleaf weeds, grass weeds and sedge weeds.

[0130] In particular, as can be seen from the efficacy data obtained by foliar and soil treatments in Table 4, compounds 1, 4, and 6 provided by this invention exhibited excellent herbicidal activity against all tested weeds, with a grade of 5 for all of them. In particular, their efficacy against grass weeds such as barnyard grass, barnyard grass, and sedge was significantly better than that against oxadiazon.

[0131] At the same dosage, compounds 2 and 3 provided by this invention have a control efficacy level of 5 against amaranth, shepherd's purse, black nightshade, and sedge, which is comparable to the herbicidal activity of the commercial herbicide oxychloride.

[0132] Compounds 2, 3, and 5 provided by this invention achieve a control efficacy level of 4 or 5 against barnyard grass, sedge, and sedge, while the efficacy level of chlorpyrifos at the same dosage is only 2 or 3. The compounds of this invention have a significantly better control effect on the tested weeds than the commercially available chlorpyrifos.

[0133] Furthermore, the results above show that when active esters or amino acid / ester fragments are introduced into the molecule, the resulting new compounds significantly enhance the control effect against barnyard grass and other grassy weeds. This indicates that, for compounds with the structure shown in formula (I) provided by this invention, the active esters or amino acid / ester fragments specifically discovered by the inventors of this invention have a significant promoting effect on improving the herbicidal activity of PPO inhibitors.

[0134] Comprehensive analysis shows that active esters or amino acid / ester fragments play an important role in improving the herbicidal activity of the triazolone PPO inhibitors of this invention.

[0135] Test Example 3: Greenhouse Initial Screening Experiment

[0136] Weigh a certain amount of the original drug using an analytical balance (0.0001g), dissolve it in DMF containing 1wt% Tween-80 emulsifier to prepare a 0.5-1wt% stock solution, and then dilute it with distilled water to different concentrations of stock solution for later use.

[0137] The pot method was used: 6cm inner diameter flowerpots were filled with composite soil (garden soil: seedling substrate, 1:2, v / v) to 3 / 4 full. Weed targets (germination rate ≥85%) were directly sown, covered with 0.2cm of soil, and left to grow to the 4-leaf stage. The control compound oxychloride and the compound provided in this invention were applied at the dosages shown in the table below using an automatic sprayer. After the pesticide solution on the weed leaves dried, the plants were transferred to a greenhouse for cultivation. Results were collected after 20 days.

[0138] Soil spraying: Take a 15cm*70cm lunchbox, fill it with composite soil (garden soil: seedling substrate, 1:2, v / v) to 3 / 4 full, directly sow weeds, and cover with 0.2cm of soil. Apply each compound at the dosage shown in the table below using an automatic spray tower, and investigate the results after 20 days.

[0139] The survey method was the same as in Test Example 2, and the test results are shown in Table 5.

[0140] Table 5

[0141]

[0142]

[0143] Note: " / " indicates that it has not been tested.

[0144] The preliminary screening results above indicate that the efficacy of the compound of the present invention against the tested weeds decreases with decreasing dosage. However, the test results show that when the dosage is reduced to 2.5 g ai / mu, the compound of the present invention still maintains a high level of efficacy against weeds, regardless of whether foliar or soil treatment is used. The compound of the present invention has a superior control effect compared to the commercially available herbicide oxychloride.

[0145] In particular, at doses of 5 g ai / mu and 2.5 g ai / mu, compounds 1, 4, and 6 provided by this invention also exhibited extremely excellent herbicidal activity against older weeds, especially against grass weeds, with significantly better control efficacy than the commercially available herbicide acetamiprid.

[0146] Test Example 4: Field Trial of PPO Genetically Modified Soybean Safety

[0147] Weigh a certain amount of the original drug using an analytical balance (0.0001g), dissolve it in DMF containing 1wt% Tween-80 emulsifier to prepare a 0.5-1wt% stock solution, and then dilute it with distilled water to different concentrations of stock solution for later use.

[0148] Crop testing: PPO genetically modified soybean (LT32) was tested.

[0149] Test method: at 36m 2 Each treatment was repeated three times in one plot. Foliar spraying was performed when the target plant reached approximately three leaves. In the treatment plot, compound 1 and oxychloride were sprayed at the dosages shown in the table below. In the control plot, a reagent without the active ingredient, i.e., DMF containing 1 wt% Tween-80 emulsifier, was used for spraying. The treatment and control plots were observed and the results were investigated 14 days after treatment.

[0150] The safety of PPO genetically modified soybeans was investigated using the same survey method as in Test Example 2. The test results are shown in Table 6.

[0151] Table 6

[0152]

[0153] Field trials on the safety of PPO genetically modified soybeans showed that compound 1 of the present invention has very good safety for PPO genetically modified soybeans (LT32) at the test dose. When the test dose reached 20 g ai / mu, compound 1 had virtually no effect on the growth of PPO genetically modified soybeans (LT32); while after treatment with the same dose of oxychloride, PPO genetically modified soybeans (LT32) were essentially killed.

[0154] It is evident that compound 1 exhibits significantly better safety against PPO genetically modified soybean (LT32) than the commercially available herbicide oxychloride. Therefore, the compound provided by this invention can be used to control at least one weed in PPO genetically modified soybean fields.

[0155] Based on the current experimental data, it is fully demonstrated that the compounds of this invention have excellent application value and can serve as candidate drug molecules for PPO-type herbicides. The compounds containing triazolinone structural fragments provided by this invention are of great significance for the creation of ultra-efficient herbicides and their use in weed control.

[0156] In this invention, the active ester or amino acid / ester fragment enhances both the herbicidal activity of the inhibitor molecule and its crop safety. Further development of the compounds of this invention holds promise for application in the control of various field weeds, offering significant economic and social benefits.

[0157] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A compound containing a triazolinone structure or an agriculturally chemically acceptable salt thereof, or an enantiomer thereof, characterized in that, The compound has the structure shown in compound 4: Compound 4: .

2. The use of the compound containing the triazolinone structure as described in claim 1, or its agriculturally acceptable salt, or its enantiomer, as a PPO inhibitor in weed control.

3. The application according to claim 2, wherein, The weeds are selected from at least one of broadleaf weeds, grass weeds, and sedge weeds.

4. The application according to claim 3, wherein, The broadleaf weeds are selected from at least one of the following: *Polygonum hydropiper*, *Amaranthus praecox*, *Gnaphalium affine*, *Monochoria vaginalis*, *Dictamnus dasycarpus*, *Capsella bursa-pastoris*, *Amaranthus verniciflua*, *Gnaphalium affine*, *Stellaria media*, *Amaranthus urinaria*, *Solanum nigrum*, *Phyllostachys edulis*, *Portulaca oleracea*, *Amaranthus retroflexus*, *Amaranthus spinosa*, *Celosia argentea*, *Caesalpinia serratifolia*, *Zinnia elegans*, and *Erigeron annuus*; and / or, The grassy weeds mentioned are selected from at least one of the following: barnyard grass, wild millet, wild foxtail, goosegrass, golden foxtail, foxtail grass, tiger tail grass, crabgrass, wild oat, Japanese wild oat, jointed barley, wild oat, wild oat, barnyard grass, and double-spike paspalum; and / or, The sedges are selected from at least one of Cyperus rotundus, Cyperus rotundus, and Cyperus divaricata.

5. A herbicide, characterized in that, The herbicide comprises an active ingredient and excipients, wherein the active ingredient includes at least one of the compounds of claim 1 or an agriculturally chemically acceptable salt thereof, or an enantiomer thereof.

6. The herbicide according to claim 5, wherein, The content of the active ingredient is 1-99.9999 by weight.

7. The herbicide according to claim 6, wherein, The content of the active ingredient is 5-99.9999 by weight.

8. The herbicide according to any one of claims 5-7, wherein, The herbicide formulation is selected from at least one of emulsifiable concentrates, suspension concentrates, wettable powders, granules, aqueous solutions, poison baits, mother liquors, and mother powders; and / or, The herbicide is applied via soil treatment.

9. The herbicide according to any one of claims 5-7, wherein, The herbicide is in powder form.

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