WO2024012537A1

WO2024012537A1 - Compound containing triazolinone structure, and use thereof and herbicide

Info

Publication number: WO2024012537A1
Application number: PCT/CN2023/107276
Authority: WO
Inventors: 杨光富; 郑佰峰
Original assignee: 武汉智汇农耀科技有限公司
Priority date: 2022-07-14
Filing date: 2023-07-13
Publication date: 2024-01-18
Also published as: CN117402121A; CN117069667A

Abstract

The present invention relates to the technical field of new pesticide compounds, and disclosed are a compound containing a triazolinone structure, and the use thereof and an herbicide. The compound has the structure as represented by formula (I). The compound provided in the present invention has high herbicidal activity and broad herbicide controlling spectra, is highly safe for PPO transgenic soybeans, and has great significance for the creation of an ultra-highly efficient PPO inhibitor herbicide with a new structure, and in the control of resistant weeds.

Description

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

Cross-references to related applications

This application claims the rights and interests of Chinese patent application 202210834562.0 submitted on July 14, 2022. The contents of this application are incorporated herein by reference.

Technical field

The invention relates to the technical field of new pesticide compounds, and specifically to a compound containing a triazolinone structure and its application as well as a herbicide.

Background technique

Protoporphyrinogen oxidase (PPO, EC 1.3.3.4) is an important herbicide target. It is the last common enzyme in the biosynthetic steps of chlorophyll and heme. It is widely present in various organisms and can catalyze the oxidation of protoporphyrinogen IX to produce protoporphyrin IX.

In plants, protoporphyrin IX is an important substance for the synthesis of chlorophyll. If the PPO enzyme in plants is inhibited, the substrate protoporphyrin IX will rapidly accumulate and penetrate into the cytoplasm to be oxidized, resulting in high concentrations. Protoporphyrin IX generates singlet oxygen under the action of light and oxygen. Under the action of singlet oxygen, the cell membrane undergoes a peroxidation reaction and is destroyed, causing cell death and eventually causing plant leaves to turn white and die.

Herbicides targeting PPO have a unique mechanism of action and are slow to develop resistance. At the same time, they have broad-spectrum herbicidal activity and can control a variety of weeds and resistant weeds.

PPO inhibitor herbicides have become the most important type of herbicide quality currently and are a hot research topic for major pesticide companies.

Up to now, a total of 30 PPO inhibitor herbicides in nine categories have been successfully launched on the market.

In the past fifty years of widespread use of PPO inhibitors, researchers have found that herbicides targeting PPO have the characteristics of broad spectrum and high efficiency, low toxicity, low residue, environmental friendliness, and high crop safety. What is even more gratifying is that Yes, this type of herbicide has excellent control effect on a variety of resistant weeds specifically and can be used to control weeds that have developed resistance to glyphosate and ALS inhibitor herbicides.

In 1990, WO9002120A1 disclosed a triazolinone-based PPO inhibitor. The structural formula of its representative substance is as follows. This substance (trade name: mesotrione) is mainly used to control broadleaf weeds in grain fields and the like.

However, the substance must be used in high doses to be relatively effective, which results in a significant reduction in its safety.

Therefore, the creation of green, super-efficient new PPO inhibitor herbicides with higher activity and better safety has become one of the research hotspots of major pesticide companies and scientific research institutes.

Contents of the invention

The object of the present invention is to provide a novel triazolinone compound with high herbicidal activity.

In order to achieve the above object, the first aspect of the present invention provides a compound containing a triazolinone structure or an agrochemically acceptable salt, hydrate, solvate thereof, or an enantiomer or optically active form thereof. Derivatives, the compound has the structure shown in formula (I),

Wherein, in formula (I), R is selected from H, a C _1-6 alkyl group, a substituted or unsubstituted C _2-6 alkenyl group, and a substituted or unsubstituted C _2-6 alkynyl group.

The second aspect of the present invention provides the triazolinone structure-containing compound described in the first aspect or its agrochemically acceptable salt, hydrate, solvate, or its enantiomer or optically active form. Application of derivatives as PPO inhibitors.

The third aspect of the present invention provides the triazolinone structure-containing compound described in the first aspect or its agrochemically acceptable salt, hydrate, solvate, or its enantiomer or optically active form. Application of derivatives in weed control.

The fourth aspect of the present invention provides a herbicide, which is composed of active ingredients and auxiliary materials. The active ingredients include the compound described in the first aspect or its agrochemically acceptable salt, hydrated At least one of its enantiomers, solvates, or derivatives in its optically active form.

Detailed ways

The endpoints of ranges and any values disclosed herein are not limited to the precise range or value, but these ranges or values are to be understood to include values approaching such ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range and individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges. These values The scope shall be deemed to be specifically disclosed herein.

The terms involved in this article are explained below. Unless otherwise stated, the following terminology explanations apply the same interpretation to all the same or similar terms in this article.

"C _1-6 alkyl" means a straight-chain or branched alkyl group with a total number of carbon atoms of 1-6, for example, the number of carbon atoms can be 1, 2, 3, 4, 5, 6, including but not limited to methyl , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, etc. "C _1-4 alkyl" has a similar definition.

"C _2-6 alkenyl" means a linear or branched alkenyl group with a total number of carbon atoms of 2-6. For example, the number of carbon atoms can be 2, 3, 4, 5, or 6, including but not limited to allyl, Pronyl, 1-butenyl, 2-butenyl. "C _2-4 alkenyl" has a similar definition.

"C _2-6 alkynyl group" means a straight-chain or branched-chain alkynyl group with a total number of carbon atoms of 2-6. For example, the number of carbon atoms can be 2, 3, 4, 5, or 6, including but not limited to propargyl, Proparnyl, 1-butynyl, 2-butynyl. "C _2-4 alkynyl" has a similar definition.

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

HBTU is O-benzotriazole-tetramethylurea hexafluorophosphate;

EDCI is 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride;

CDI is N, N′-carbonyldiimidazole;

HOBt is 1-hydroxybenzotriazole;

DCC is dicyclohexylcarbodiimide;

DIC is N, N′-diisopropylcarbodiimide;

PyBOP is benzotriazol-1-yl-oxytripyrrolidinyl hexafluorophosphate;

POCl ₃ is phosphorus oxychloride;

T ₃ P is 1-propyl phosphoric acid cyclic anhydride;

DIPEA is N, N-diisopropylethylamine;

DMAP is 4-dimethylaminopyridine;

DBU is 1,8-diazabicycloundec-7-ene.

As mentioned above, the first aspect of the present invention provides a compound containing a triazolinone structure or its agrochemically acceptable salt, hydrate, solvate, or its enantiomer, optically active form A derivative of a compound having a structure represented by formula (I),

According to a preferred embodiment, in formula (I), R is selected from H, C _1-4 alkyl, substituted or unsubstituted C _2-4 alkenyl, substituted or unsubstituted C _{2- 4} alkynyl group.

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

Particularly preferably, the compound represented by formula (I) is compound 1, compound 4 or compound 6. The inventor of the present invention found during research that the compound under this preferred condition has more excellent herbicidal activity.

The present invention has no special requirements on the method for preparing the compound described in the first aspect. Those skilled in the art can determine a suitable synthetic route based on the structural formula provided by the present invention and the known knowledge in the field of organic synthesis to obtain the second aspect of the present invention. The compound described in one aspect. However, in order to achieve significantly higher yields and purities, the present invention provides a preferred method for preparing the compounds described in the first aspect of the invention.

According to a preferred embodiment, the compound containing a triazolinone structure or its agrochemically acceptable salt, hydrate, solvate, or its enantiomers, derivatives of optically active forms are prepared The method includes: in the presence of a solvent and a condensing agent, the compound described in formula (II) and the compound described in formula (III) or the hydrochloride of the compound described in formula (III) are subjected to a condensation reaction,

NH ₂ -(CH ₂ ) ₂ -C(O)-OQ _1Formula (III)

Among them, Q1 is selected from H and C _1-6 alkyl group.

According to another preferred embodiment, the compound containing a triazolinone structure or its agrochemically acceptable salt, hydrate, solvate, or its enantiomer or optically active form is prepared. The method of derivatives includes: performing a condensation reaction on compound 4 and the compound described in formula (IV) in the presence of a solvent and a condensing agent,
Q ₂ -OH Formula (IV)

Wherein, Q ₂ is selected from substituted or unsubstituted C _2-6 alkenyl group, substituted or unsubstituted C _2-6 alkynyl group.

Preferably, the condensing agent is selected from at least one of HATU, HBTU, EDCI, CDI, HOBt, DCC, DIC, PyBOP, POCl ₃ and T ₃ P.

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

Preferably, the solvent is selected from at least one of dichloromethane, chloroform, dichloroethane, acetonitrile, toluene, tetrahydrofuran and benzene.

In the preparation method of the present invention, the intermediates and various reagents used are commercially available or can be prepared using known reactions in the art.

The following exemplarily provides a method for preparing the compound represented by formula (II):

Specifically, it includes: reacting the product of the diazotization reaction of compound A-1 with pyruvic acid to obtain compound A-2, and further obtaining the ring-closed triazolinone compound A-3, and then undergoing difluoromethylation to obtain Compound A-4. Compound A-4 obtains the nitration product A-5 through nitration reaction, and then undergoes nitro reduction reaction to obtain compound A-6. Compound A-6 is diazotized to obtain diazonium salt A-7, which is then mixed with acrylic acid. React with cuprous chloride to obtain the compound represented by formula (II).

As mentioned above, the second aspect of the present invention provides the triazolinone structure-containing compound described in the first aspect or its agrochemically acceptable salt, hydrate, solvate, or its enantiomers. Application of derivatives in bulk and optically active form as PPO inhibitors.

As mentioned above, the third aspect of the present invention provides the triazolinone structure-containing compound described in the first aspect or its agrochemically acceptable salt, hydrate, solvate, or its enantiomers. Application of derivatives in bulk and optically active forms in weed control.

The aforementioned compounds provided by the present invention have excellent herbicidal activity. Therefore, the aforementioned compounds provided by the present invention are expected to become excellent super-efficient herbicides for plants growing in sites that are harmful to human survival and activities, and can be used for non-cultivated wild plants. Or plants that are useless to humans; for example, they have a good weeding effect on various wild plants in crop fields.

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 transgenic soybean fields.

Preferably, the weeds are selected from at least one of broadleaf weeds, grassy weeds and sedge weeds.

Preferably, the broad-leaf weeds are selected from the group consisting of Polygonum lilac, Amaranth, Mosaic grass, Common duckweed, Artemisia barbadensis, Shepherd's purse, Chenopodium quinoa, Amaranthus miltiorrhiza, Pork root, Granny's weed, Chickweed, Amaranth, Iron At least one of amaranth, nightshade, lantern, purslane, amaranth retroflexus, spiny amaranth, amaranth, cypress, carp intestine, zinnia, and annual canopy.

Preferably, the grass weeds are selected from the group consisting of barnyard grass, wild millet, wild millet, oxgrass, golden setaria, setaria, tigertail grass, crabgrass, wheatgrass, Japanese wheatgrass, buckwheat, and wild oats. , bromus, stephanotis, and at least one species of paspalum.

Preferably, the Cyperaceae is selected from at least one selected from the group consisting of Cyperus spp., Cyperus spp., and Cyperus heterophylla.

As mentioned above, the fourth aspect of the present invention provides a herbicide, which is composed of active ingredients and auxiliary materials. The active ingredients include the compounds described in the first aspect or their agrochemically acceptable salts. , hydrates, solvates, or at least one of its enantiomers and optically active derivatives.

Preferably, the active ingredient is present in an amount of 1 to 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.

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

Particularly preferably, the active ingredient content is from 5 to 99% by weight.

The present invention has no special restrictions on the selection of the auxiliary materials. Those skilled in the art can select according to the auxiliary materials known in the art. For example, the auxiliary materials are selected from the group consisting of surfactants, protective colloids, adhesives, and additives. At least one of thickening agent, thixotropic agent, penetrating agent, chelating agent, colorant and polymer. The present invention will not be described in detail here, and those skilled in the art should not understand it as a limitation of the present invention.

Preferably, the dosage form of the herbicide of the present invention is selected from at least one of emulsifiable concentrate, suspension, wettable powder, dust, granule, aqueous formulation, poisonous bait, mother liquor and mother powder.

Preferably, the herbicide is applied by soil treatment.

The present invention will be described in detail below through examples. In the following examples, unless otherwise specified, all raw materials used in this example are commercially available, and their purity levels are all analytically pure. The following room temperature indicates 25±1°C.

Preparation Example 1: Preparation of Compound 1

(1) Synthesis of compound A-2

Dissolve 100g of compound A-1 in 500mL of 2N HCl aqueous solution in a 1L three-neck flask, stir at -5°C, dissolve 1.5 equivalents of _NaNO2 in 100mL of water, and slowly add it to the reaction system, at -5°C After stirring for 2 hours, slowly add a concentrated hydrochloric acid solution containing 2 equivalents of SnCl ₂ dropwise, stir at -5°C for 30 minutes, then move to room temperature and stir for 2 hours, add 50mL of water to the reaction system, and add 50mL of aqueous solution containing 1.5 equivalents of pyruvic acid. Continue stirring for 30 minutes. TLC followed until the reaction was complete, filtered with suction, and then rinsed the filter cake with a small amount of water and dried to obtain compound A-2 with a yield of 91%.

(2) Synthesis of compound A-3

Add the compound A-2 prepared above into a 500 mL two-necked flask, add 200 mL of toluene, add an equivalent of triethylamine, and add 1.5 equivalents of (PhO) ₂ PON ₃ to the reaction system while stirring. The reaction solution was heated to reflux, and the reaction process was followed by TLC. After the reaction was completed, the toluene was removed, and the solid obtained by ethanol recrystallization was suction filtered and dried to obtain compound A-3, with a yield of 71%.

(3) Synthesis of compound A-4

Add the compound A-3 synthesized above into a 500 mL single-neck bottle, add 2 equivalents of KOH, 5 equivalents of tetrabutylammonium bromide and 200 mL of tetrahydrofuran, and heat to reflux. Slowly bubble difluorochloromethane gas until the raw material reaction is complete. Concentrate the reaction solution under reduced pressure. Add 200 mL of water and extract 3 times with 100 mL of dichloromethane. The organic layers are combined and dried over anhydrous sodium sulfate. Purify by column chromatography to obtain Compound A-4, the yield was 96%.

(4) Synthesis of Compound A-5

Place the above synthesized compound A-4 into a 500mL single-neck bottle, add 100mL concentrated sulfuric acid, stir evenly at -5°C, dissolve 1.5 equivalents of concentrated nitric acid in 50mL concentrated sulfuric acid, and slowly drop it into the reaction system, - React at 5°C until the raw material reaction is complete. The system is slowly poured into 1 L of ice water to precipitate a large amount of solid. Stir to room temperature and then filter with suction. Wash with water and dry to obtain compound A-5 with a yield of 89%.

(5) Synthesis of compound A-6

Place the compound A1-5 prepared above into a 1L single-neck bottle, add 2 equivalents of NH ₄ Cl and 3 equivalents of reduced iron powder, add 500 mL of ethanol and 100 mL of water, and reflux until the raw materials disappear completely. Filter, wash with ethanol, and remove the filtrate. The solid obtained was dissolved in water, extracted with ethyl acetate, and then The organic layer was washed with brine, dried over anhydrous sodium sulfate and desolvated to obtain compound A-6, with a yield of 90%.

(6) Synthesis of compounds represented by formula (II)

Add compound A-6 to a 500mL single-neck bottle, add 200mL of water, and stir the reaction system at -5°C. Dissolve 1.5 equivalents of NaNO ₂ in 100mL of water and slowly add it dropwise to the reaction system at -5°C. After stirring for 2 hours, the system was added to 1.5 equivalents of acrylic acid, 2 equivalents of cuprous chloride and hydrochloric acid solution, stirred at room temperature until the reaction was completed as monitored by TLC, and filtered to obtain the compound represented by formula (II), with a yield of 78 %.

(7) Synthesis of Compound 1

Add 1 mmol of the compound represented by formula (II) into a 50 mL single-neck bottle, add 20 mL of methylene chloride, add 1.5 mmol of CDI, and stir at room temperature for 2 hours. Add 1.5 mmol of 3-aminopropionic acid methyl ester hydrochloride and 2 mmol of DBU, stir at room temperature for 30 minutes, monitor the reaction progress with TLC, until the reaction is complete, acidify with 20 mL of 1N HCl solution, and use 20 mL of dichloromethane for the aqueous phase. After extraction, the organic phase was dried over anhydrous sodium sulfate, concentrated, and purified by column chromatography to obtain compound 1 with a yield of 87%.

Preparation Example 2: Preparation of Compound 2

This preparation example is carried out using a process similar to preparation example 1, except that the 3-aminopropionic acid methyl ester hydrochloride in step (7) is replaced with an equal molar amount of 3-aminopropionic acid isopropyl ester salt. acid salt;

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

Preparation Example 3: Preparation of Compound 3

This preparation example is carried out using a process similar to preparation example 1, except that the 3-aminopropionic acid methyl ester hydrochloride in step (7) is replaced with an equal molar amount of 3-aminopropionic acid tert-butyl ester salt. acid salt;

The rest were the same as Preparation Example 1, and Compound 3 was prepared with a yield of 73%.

Preparation Example 4: Preparation of Compound 4

This preparation example is carried out using a process similar to preparation example 1, except that the 3-aminopropionic acid methyl ester hydrochloride in step (7) is replaced with an equimolar amount of β-alanine;

The rest were the same as Preparation Example 1, and Compound 4 was prepared with a yield of 71%.

Preparation Example 5: Preparation of Compound 5

Add 1 mmol of compound 4 to a 50 mL single-neck bottle, add 20 mL of dichloromethane, add 1.5 mmol of CDI, and stir at room temperature for 2 hours. Add 1.5 mmol of allyl alcohol and 2 mmol of DBU, stir at room temperature for 30 minutes, monitor the reaction progress with TLC, until the reaction is complete, acidify with 20 mL of 1N HCl solution, extract the aqueous phase with 20 mL of methylene chloride, and use anhydrous sulfuric acid for the organic phase. After drying over sodium, it was concentrated and purified by column chromatography to obtain compound 5 with a yield of 75%.

Preparation Example 6: Preparation of Compound 6

This preparation example is carried out using a process similar to preparation example 5, except that the allyl alcohol in preparation example 5 is replaced with an equal molar amount of propargyl alcohol;

The rest were the same as Preparation Example 5, and Compound 6 was prepared with a yield of 79%.

Characterization data for specific compounds of the invention are shown in Table 1.

Table 1

Test Example 1: Protoporphyrinogen oxidase inhibitory activity

Protoporphyrinogen oxidase: The protoporphyrinogen oxidase used in the experiment was expressed and purified from tobacco PPO. It was prepared according to the method in Chinese patent CN110093325A. The enzyme activity test was carried out according to the method described in the document "J. Agric. Food Chem. 2016, 64, 3, 552-562", and it was concluded that the compound containing a triazolinone structure of the present invention and the reference compound pentrazofen had no effect on the original Inhibitory activity of porphyrinogen oxidase (inhibition constant K _i of the inhibitor).

The results are shown in Table 2.

Table 2

As can be seen from Table 2, the compound provided by the present invention has strong inhibitory activity on tobacco PPO, which is significantly better than the commercial herbicide pentrazone.

Test Example 2: Greenhouse General Screening Experiment

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

Two treatment methods are used: stem and leaf spray and soil spray.

Post-emergence stem and leaf spray: Take a paper cup with an inner diameter of 7cm, fill it with compound soil (garden soil: seedling cultivation medium, 1:2, v/v) to 3/4 of the position, directly sow the test target seeds, cover with 0.2cm of soil, and wait until it grows to 3 leaves. Reserved for a period of time. After the comparative compound pentramethadil and the compounds provided by the present invention are applied in the automatic spray tower at a dose of 10g a.i./mu, the leaf surface liquid is dried and then moved into a greenhouse for cultivation (the temperature is maintained at 25-28°C and the humidity is maintained at 70 %), survey results after 20 days.

Soil spray: Take a 15cm*70cm lunch box, fill it with compound soil (vegetable garden soil: seedling cultivation substrate, 1:2, v/v) to 3/4, sow weeds directly, and cover with 0.2cm of soil. Comparative compound pyrazopend and the compound provided by the invention were sprayed on the soil at a dose of 10g a.i./mu, and the results were investigated after 20 days.

Investigation method: After 20 days of experimental treatment, the target damage symptoms and growth inhibition were visually observed, and the fresh weight of the above-ground parts was weighed. The fresh weight inhibition rate (%) was calculated, and the fresh weight inhibition rate was used to express the growth inhibition rate (%).
Fresh weight inhibition rate (%) = (Control fresh weight – Treatment fresh weight)/Control fresh weight × 100%

The rating is specifically based on the conditions shown in Table 3, and the test results are shown in Table 4.

table 3

Table 4

The above herbicidal activity test results show that the compounds provided by the invention have excellent control effects on broadleaf weeds, grass weeds and sedge weeds.

In particular, it can be seen from the control effect data obtained by stem and leaf treatment and soil treatment in Table 4 that Compound 1, Compound 4, and Compound 6 provided by the present invention show excellent herbicidal activity against all tested weeds. The grades are all 5, especially the control effect on crabgrass, barnyardgrass, stephanotis and other grassy weeds is significantly better than that of pentramethadil.

At the same dosage, the control effect level of Compound 2 and Compound 3 provided by the present invention on amaranth, shepherd's purse, nightshade, and rice sedge are all 5, and they have comparable herbicidal activity to the commercial drug trimethrin.

The control effect level of Compound 2, Compound 3 and Compound 5 provided by the present invention on crabgrass, barnyardgrass and Stephania chinensis reaches 4 or 5, while the control effect level of the compound 2, compound 3 and compound 5 at the same dosage is only 2 or 3. The control effect of the tested weeds was significantly better than that of the commercial drug pentramethadil.

In addition, it can be seen from the above results that when active esters or amino acids/ester fragments are introduced into the molecule, the new compounds obtained can significantly enhance the control effect on grass weeds such as barnyard grass. This shows that for the compound represented by formula (I) provided by the present invention, the active ester or amino acid/ester fragment specially discovered by the inventor of the present invention has a significant promoting effect on improving the herbicidal activity of PPO inhibitors.

Comprehensive analysis shows that active esters or amino acids/ester fragments play an important role in improving the herbicidal activity of the triazolinone PPO inhibitor of the present invention.

Test Example 3: Greenhouse preliminary screening experiment

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

Adopt the potting method: take a flower pot with an inner diameter of 6cm, fill it with compound soil (garden soil: seedling cultivation medium, 1:2, v/v) to 3/4, directly sow the weed target (bud rate ≥ 85%), and cover it with 0.2cm soil , the target to be tested grows to the 4-leaf stage for later use. After applying the comparative compound pentramethadil and the compounds provided by the present invention in the automatic spray tower according to the dosage shown in the following table, wait for the weed leaf surface liquid to dry and then move it to the greenhouse for cultivation. The investigation results will be obtained after 20 days. fruit.

Soil spray: Take a 15cm*70cm lunch box, fill it with compound soil (vegetable garden soil: seedling cultivation substrate, 1:2, v/v) to 3/4, sow weeds directly, and cover with 0.2cm of soil. Each compound was applied in an automatic spray tower at the dosage shown in the table below, and the results were observed after 20 days.

The investigation method is the same as in Test Example 2, and the test results are shown in Table 5.

table 5

Note: "/" means not tested.

The above preliminary screening experiment results show that as the dosage decreases, the control effect of the compound of the present invention on the tested weeds also decreases. However, judging from the test results, when the dosage is reduced to 2.5g a.i./mu, whether it is stem and leaf treatment or soil treatment, the compound of the present invention can still maintain a high level of weed control effect. The compound of the present invention has a better control effect than the commercial drug pentramethadil.

In particular, at the doses of 5g ai/mu and 2.5g ai/mu, Compound 1, Compound 4, and Compound 6 provided by the present invention also showed extremely excellent herbicidal activity against older weeds, especially against grassy weeds. The control effect is significantly better than that of the commercial herbicide pentrazone.

Test Example 4: Field trial on the safety of PPO genetically modified soybeans

Crop testing: PPO transgenic soybeans (LT32) were tested.

Test method: Take ^36m2 as a plot, repeat each treatment three times, and spray the stems and leaves of the target to be tested when it reaches about the 3-leaf stage. In the treatment area, compound 1 and mefenacetate are dosed as shown in the table below. Carry out spray application; in the control area, use a reagent that does not contain the original drug, that is, use DMF containing 1wt% Tween-80 emulsifier for spraying. Observe the treated area and control area after 14 days of treatment and investigate the results.

The safety of PPO transgenic soybeans was calculated according to the same investigation method as Test Example 2. The test results are shown in Table 6.

Table 6

Field trials on the safety of PPO transgenic soybeans show that compound 1 of the present invention has very good safety on PPO transgenic soybeans (LT32) at the tested dose. When the test dose reached 20g a.i./mu, Compound 1 had basically no effect on the growth of PPO transgenic soybeans (LT32); while after treatment with mefenacetate at the same dose, PPO transgenic soybeans (LT32) basically died.

It can be seen that the safety effect of Compound 1 on PPO transgenic soybeans (LT32) is significantly better than that of the commercial herbicide pentramethadil. Therefore, the compounds provided by the present invention can be used to control at least one weed in PPO transgenic soybean fields.

Combined with the current experimental data, it is fully demonstrated that the compound of the present invention has very good application value and can be used as a candidate drug molecule for PPO herbicides. The compounds containing triazolinone structural fragments provided by the present invention are of great significance for creating super-efficient herbicides and for controlling weeds.

In the present invention, the active ester or amino acid/ester fragment improves the herbicidal activity of the inhibitor molecule on the one hand, On the other hand, the crop safety of inhibitor molecules is improved. The subsequent development of the compound of the present invention is expected to be applied to the control of various field weeds, and has very good economic value and social benefits.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner. These simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.

Claims

A compound containing a triazolinone structure or its agrochemically acceptable salt, hydrate, solvate, or its enantiomer, optically active form derivatives, characterized in that the compound has the formula ( I) the structure shown,

Wherein, in formula (I), R is selected from H, a C 1-6 alkyl group, a substituted or unsubstituted C 2-6 alkenyl group, and a substituted or unsubstituted C 2-6 alkynyl group.
The compound according to claim 1, wherein, in formula (I), R is selected from H, C 1-4 alkyl, substituted or unsubstituted C 2-4 alkenyl, substituted or unsubstituted C 2-4 alkynyl groups.
The compound according to claim 1 or 2, wherein the compound represented by formula (I) is selected from any one of the following:
The compound containing a triazolinone structure according to any one of claims 1 to 3 or its agrochemically acceptable salt, hydrate, solvate, or its enantiomers, optically active derivatives Application as PPO inhibitor.
The compound containing triazolinone structure according to any one of claims 1-3 or its agricultural chemistry Use of above-accepted salts, hydrates, solvates, or derivatives thereof in enantiomeric or optically active forms for the control of weeds.
The application according to claim 5, wherein the weeds are selected from at least one of broadleaf weeds, grassy weeds and sedge weeds.
The application according to claim 5 or 6, wherein the broad-leaf weeds are selected from the group consisting of polygonum lilac, water amaranth, mossicae, duckweed, wormwood, shepherd's purse, pigweed, amaranth, and pigweed, Mother-in-law, chickweed, amaranth, amaranth, nightshade, lanternweed, purslane, amaranthus retroflexus, spiny amaranth, amaranth, bowl flower, carp intestine, zinnia, at least one of the annual canopies species; and/or,

Described gramineous weeds are selected from barnyard grass, wild millet, wild millet, goosegrass, golden foxtail, foxtail grass, tigertail grass, crabgrass, sedge, Japanese sage, Aesthesia, wild oats, bromegrass , Stephanotis , at least one species of Paspalum bitachyon; and/or,

The Cyperaceae is selected from at least one type selected from the group consisting of Cyperus cyperum, Cyperus spp., and Cyperus heterophylla.
A herbicide, characterized in that the herbicide is composed of active ingredients and auxiliary materials, and the active ingredients include the compound described in any one of claims 1-3 or its agrochemically acceptable salt or hydrate , solvate, or at least one of its enantiomers and optically active derivatives.
The herbicide according to claim 8, wherein the content of the active ingredient is 1-99.9999% by weight, preferably 5-99.9999% by weight.
The herbicide according to claim 8 or 9, wherein the dosage form of the herbicide is selected from at least one of emulsifiable concentrate, suspension, wettable powder, powder, granule, aqueous preparation, poisonous bait, mother liquor and mother powder; and / or,

The herbicide is applied through soil treatment.