A compound containing a triazolinone structure, and a preparation method and application thereof

Abstract

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

Description

Technical Field

[0001] This invention relates to the field of novel pesticide compounds, specifically to a compound containing a triazolinone structure, its preparation method, and its application. 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 grain 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]

[0015] In equation (I),

[0016] X and Y are each independently selected from halogens;

[0017] M is either O or NH;

[0018] R is selected from -(CH2) n -R 1 -(CH2) n -C(CH2)-R 2 -(CH2) n -OC(O)-C(CH2)-R 2 -S(O2)-R 2 -S(O2)-N(R) 2 R 3 -(CH2) n -C(O)-OR 2 -CH(R) 3 )-C(O)-OR 2 -C(R) 3 R 4 )-C(O)-OR 2 ;

[0019] R 1 Selected from C containing at least one unsaturated carbon-carbon double bond 2-10 Hydrocarbon group, C containing at least one unsaturated carbon-carbon triple bond 2-10 hydrocarbon group, C 3-8 cycloalkyl, C 5-10 Alkyl, halogen, or at least one halogen-substituted C 1-10 Alkyl groups, C groups substituted with trimethylsilyl groups containing at least one unsaturated carbon-carbon triple bond 2-10 Hydrocarbon group, -SO3H;

[0020] Each R2 Each is independently selected from H and C. 1-10 alkyl, C 3-8 cycloalkyl groups;

[0021] Each R 3 Each was independently selected from C 1-10 alkyl, phenyl substituted C 1-6 Alkyl group, -(CH2) n -C(O)-OR 5 ;R 4 Selected from C 1-10 Alkyl groups; or R 3 and R 4 Together they form a ring to form C 3-6 cycloalkyl groups;

[0022] R 5 Selected from C 1-10 Alkyl groups;

[0023] Each n is independently selected from an integer between 0 and 10.

[0024] A second aspect of the present invention provides a method for preparing the compound containing a triazolinone structure as described in the first aspect, or its agriculturally chemically acceptable salt, hydrate, solvate, or its enantiomer or optically active derivative, comprising: condensing the compound of formula (II) with the compound of formula (III) or with the hydrochloride salt of the compound of formula (III) in the presence of a solvent and a condensing agent.

[0025]

[0026] Wherein, X, Y, M and R are the same as those defined in the first aspect of the present invention.

[0027] 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, as PPO inhibitors.

[0028] The fourth 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.

[0029] The compounds containing triazoline ketone structures provided by this invention are of great significance for creating novel, highly efficient PPO inhibitor herbicides and controlling resistant weeds.

[0030] The compounds containing triazoline ketone structures provided by this invention have higher herbicidal activity and a broader spectrum of weed control compared to oxadiazon.

[0031] The compounds containing triazolinone structures provided by this invention have good safety for PPO genetically modified soybeans compared with oxychloride. Therefore, the compounds provided by this invention can be used as a complementary herbicide for PPO genetically modified soybeans. Detailed Implementation

[0032] 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.

[0033] The following explanations of the terms used in this document shall apply to all identical or similar terms in this document unless otherwise stated.

[0034] C containing at least one unsaturated carbon-carbon double bond 2-10 The hydrocarbon group refers to a hydrocarbon group with a total number of carbon atoms of 2-10, including straight-chain hydrocarbon groups and branched hydrocarbon groups, and the C2-C... 10 The hydrocarbon group contains at least one carbon-carbon double bond, for example, the C2-C 10 The hydrocarbon group contains 1, 2, 3, 4, or 5 carbon-carbon double bonds. A C-type hydrocarbon containing at least one unsaturated carbon-carbon double bond... 2-10 The hydrocarbon group can be, for example, vinyl, propenyl, allyl, butadienyl, isoprene, 1,3,5-hextrienyl, etc.

[0035] C containing at least one unsaturated carbon-carbon triple bond 2-10 The hydrocarbon group refers to a hydrocarbon group with a total number of carbon atoms of 2-10, including straight-chain hydrocarbon groups and branched hydrocarbon groups, and the C2-C... 10 The hydrocarbon group contains at least one carbon-carbon triple bond. A C-type hydrocarbon containing at least one unsaturated carbon-carbon triple bond... 2-10 Hydrocarbon groups, such as the C2-C 10 The hydrocarbon group has 1, 2, 3, 4, or 5 carbon-carbon triple bonds, such as ethynyl, propynyl, propynyl, butyrynyl, 1,3-pentadiynyl, 1,3,5-hexanetriynyl, etc.

[0036] C 3-8 The cycloalkyl group refers to a cycloalkyl group with a total number of carbon atoms of 3-8. For example, it can be a cycloalkyl group with a total number of carbon atoms of 3, 4, 5, 6, 7, or 8, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl.

[0037] C 5-10Alkyl groups refer to alkyl groups with a total number of carbon atoms of 5-10, including straight-chain alkyl groups and branched alkyl groups. For example, they can be straight-chain alkyl groups or branched alkyl groups with a total number of carbon atoms of 5, 6, 7, 8, 9, or 10, such as n-pentyl, isopentyl, n-hexyl, etc.

[0038] Halogens are fluorine, chlorine, bromine, and iodine.

[0039] At least one halogen-substituted C 1-10 Alkyl groups, representing alkyl groups with a total number of carbon atoms of 1-10, include straight-chain alkyl groups and branched-chain alkyl groups, and the C1-C... 10 At least one H in the alkyl group is replaced by a halogen atom selected from halogens. For example, the 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 H in the C1-C6 alkyl group are replaced by any one or more halogen atoms selected from fluorine, chlorine, bromine, and iodine. For example, they can be trifluoromethyl, difluoromethyl, monofluoromethyl, monofluoroethyl, difluoroethyl, trifluoroethyl, etc.

[0040] C atoms containing at least one unsaturated carbon-carbon triple bond are replaced by trimethylsilyl groups. 2-10 The hydrocarbon group indicates that the aforementioned C contains at least one unsaturated carbon-carbon triple bond. 2-10 Based on the definition of a hydrocarbon group, at least one H is replaced by a trimethylsilyl group.

[0041] HATU is 2-(7-azabenzotriazole)-N,N,N',N'-tetramethylurea hexafluorophosphate;

[0042] HBTU is O-benzotriazole-tetramethylurea hexafluorophosphate;

[0043] EDCI is 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride;

[0044] CDI is N,N'-carbonyldiimidazole;

[0045] HOBt is 1-hydroxybenzotriazole;

[0046] DCC stands for dicyclohexylcarbodiimide;

[0047] DIC stands for N,N'-diisopropylcarbodiimide;

[0048] PyBOP is benzotriazol-1-yl-oxytripyrrolidinyl hexafluorophosphate;

[0049] POCl3 is phosphorus oxychloride;

[0050] T3P is 1-propyl phosphate cyclic anhydride;

[0051] DIPEA is N,N-diisopropylethylamine;

[0052] DMAP is 4-dimethylaminopyridine;

[0053] DBU is 1,8-diazabicycloundec-7-ene.

[0054] 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).

[0055]

[0056] In equation (I),

[0057] X and Y are each independently selected from halogens;

[0058] M is either O or NH;

[0059] R is selected from -(CH2) n -R 1 -(CH2) n -C(CH2)-R 2 -(CH2) n -OC(O)-C(CH2)-R 2 -S(O2)-R 2 -S(O2)-N(R) 2 R 3 -(CH2) n -C(O)-OR 2 -CH(R) 3 )-C(O)-OR 2 -C(R) 3 R 4 )-C(O)-OR 2 ;

[0060] R 1 Selected from C containing at least one unsaturated carbon-carbon double bond 2-10 Hydrocarbon group, C containing at least one unsaturated carbon-carbon triple bond 2-10 hydrocarbon group, C 3-8 cycloalkyl, C 5-10 Alkyl, halogen, or at least one halogen-substituted C 1-10 Alkyl groups, C groups substituted with trimethylsilyl groups containing at least one unsaturated carbon-carbon triple bond 2-10 Hydrocarbon group, -SO3H;

[0061] Each R 2 Each is independently selected from H and C. 1-10 alkyl, C 3-8 cycloalkyl groups;

[0062] Each R 3 Each was independently selected from C 1-10 alkyl, phenyl substituted C 1-6 Alkyl group, -(CH2) n -C(O)-OR 5 ;R 4 Selected from C 1-10 Alkyl groups; or R 3 and R 4 Together they form a ring to form C 3-6 cycloalkyl groups;

[0063] R 5 Selected from C 1-10 Alkyl groups;

[0064] Each n is independently selected from an integer between 0 and 10.

[0065] In the preferred case, in equation (I),

[0066] X and Y are each independently selected from F and Cl;

[0067] M is either O or NH;

[0068] R is selected from -(CH2) n -R 1 -(CH2) n -C(CH2)-R 2 -(CH2) n -OC(O)-C(CH2)-R 2 -S(O2)-R 2 -S(O2)-N(R) 2 R 3 -(CH2) n -C(O)-OR 2 -CH(R) 3 )-C(O)-OR 2 -C(R) 3 R 4 )-C(O)-OR 2 ;

[0069] R 1 Selected from C containing at least one unsaturated carbon-carbon double bond 2-8 Hydrocarbon group, C containing at least one unsaturated carbon-carbon triple bond 2-8 hydrocarbon group, C 3-6 cycloalkyl, C 5-8 Alkyl, halogen, or at least one halogen-substituted C 1-8 Alkyl groups, C groups substituted with trimethylsilyl groups containing at least one unsaturated carbon-carbon triple bond 2-8 Hydrocarbon group, -SO3H;

[0070] Each R 2 Each is independently selected from H and C. 1-8 alkyl, C 3-6 cycloalkyl groups;

[0071] Each R 3 Each was independently selected from C 1-8 alkyl, phenyl substituted C 1-4 Alkyl group, -(CH2) n -C(O)-OR 5 ;R 4 Selected from C 1-8 Alkyl groups; or R 3 and R 4 Together they form a ring to form C 3-6 cycloalkyl groups;

[0072] R 5 Selected from C 1-8 Alkyl groups;

[0073] Each n is independently selected from an integer between 0 and 8.

[0074] More preferably, in equation (I),

[0075] X and Y are each independently selected from F and Cl;

[0076] M is either O or NH;

[0077] R is selected from -(CH2) n -R 1 -(CH2) n -C(CH2)-R 2 -(CH2) n -OC(O)-C(CH2)-R 2 -S(O2)-R 2 -S(O2)-N(R) 2 R 3 -(CH2) n -C(O)-OR 2 -CH(R) 3 )-C(O)-OR 2 -C(R) 3 R 4 )-C(O)-OR 2 ;

[0078] R 1 Selected from C containing at least one unsaturated carbon-carbon double bond 2-8 Hydrocarbon group, C containing at least one unsaturated carbon-carbon triple bond 2-8 hydrocarbon group, C 3-6cycloalkyl, C 5-6 Alkyl, halogen, or at least one halogen-substituted C 1-6 Alkyl groups, C groups substituted with trimethylsilyl groups containing at least one unsaturated carbon-carbon triple bond 2-6 Hydrocarbon group, -SO3H;

[0079] Each R 2 Each is independently selected from H and C. 1-6 alkyl, C 3-6 cycloalkyl groups;

[0080] Each R 3 Each was independently selected from C 1-6 alkyl, phenyl substituted C 1-3 Alkyl group, -(CH2) n -C(O)-OR 5 ;R 4 Selected from C 1-6 Alkyl groups; or R 3 and R 4 They cyclize together to form a cyclopropyl group;

[0081] R 5 Selected from C 1-6 Alkyl groups;

[0082] Each n is independently selected from 0, 1, 2, 3, 4, 5, 6.

[0083] According to a preferred embodiment 1, in formula (I),

[0084] X and Y are each independently selected from F and Cl;

[0085] M is O;

[0086] R is selected from -(CH2) n -R 1 -(CH2) n -C(CH2)-R 2 -(CH2) n -OC(O)-C(CH2)-R 2 -S(O2)-R 2 -S(O2)-N(R) 2 R 3 -(CH2) n -C(O)-OR 2 -CH(R) 3 )-C(O)-OR 2 -C(R) 3 R 4 )-C(O)-OR 2 ;

[0087] R 1 Selected from C containing at least one unsaturated carbon-carbon double bond 2-8 Hydrocarbon group, C containing at least one unsaturated carbon-carbon triple bond 2-8 hydrocarbon group, C 3-6 cycloalkyl, C 5-6 Alkyl, halogen, or at least one halogen-substituted C 1-6 Alkyl groups, C groups substituted with trimethylsilyl groups containing at least one unsaturated carbon-carbon triple bond 2-6 hydrocarbon group;

[0088] Each R 2 Each is independently selected from H and C. 1-6 alkyl, C 3-6 cycloalkyl groups;

[0089] Each R 3 Each was independently selected from C 1-6 alkyl, phenyl substituted C 1-3 Alkyl group, -(CH2) n -C(O)-OR 5 ;R 4 Selected from C 1-6 Alkyl groups; or R 3 and R 4 They cyclize together to form a cyclopropyl group;

[0090] R 5 Selected from C 1-6 Alkyl groups;

[0091] Each n is independently selected from 0, 1, 2, 3, 4, 5, 6.

[0092] According to the aforementioned preferred embodiment 1, more preferably, the compound represented by formula (I) is selected from any one of the following:

[0093]

[0094]

[0095] According to a preferred embodiment 2, in formula (I),

[0096] X and Y are each independently selected from F and Cl;

[0097] M is NH;

[0098] R is selected from -(CH2) n -R 1 -S(O2)-R 2 -S(O2)-N(R) 2 R 3 -(CH2)n -C(O)-OR 2 -CH(R) 3 )-C(O)-OR 2 -C(R) 3 R 4 )-C(O)-OR 2 ;

[0099] R 1 Selected from C containing at least one unsaturated carbon-carbon double bond 2-8 Hydrocarbon group, C containing at least one unsaturated carbon-carbon triple bond 2-8 hydrocarbon group, C 3-6 cycloalkyl, C 5-6 Alkyl, halogen, or at least one halogen-substituted C 1-6 Alkyl groups, C groups substituted with trimethylsilyl groups containing at least one unsaturated carbon-carbon triple bond 2-6 Hydrocarbon group, -SO3H;

[0100] Each R 2 Each is independently selected from H and C. 1-6 alkyl, C 3-6 cycloalkyl groups;

[0101] Each R 3 Each was independently selected from C 1-6 alkyl, phenyl substituted C 1-3 Alkyl group, -(CH2) n -C(O)-OR 5 ;R 4 Selected from C 1-6 Alkyl groups; or R 3 and R 4 They cyclize together to form a cyclopropyl group;

[0102] R 5 Selected from C 1-6 Alkyl groups;

[0103] Each n is independently selected from 0, 1, 2, 3, 4, 5, 6.

[0104] According to the aforementioned preferred embodiment 2, more preferably, the compound represented by formula (I) is selected from any one of the following:

[0105] According to a preferred embodiment 3, the compound represented by formula (I) is selected from any one of the following:

[0106]

[0107]

[0108]

[0109] 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. However, in order to achieve significantly higher yields and purity, this invention provides the preferred method described in the second aspect for preparing the compounds described in the first aspect.

[0110] As previously stated, a second aspect of the present invention provides a method for preparing the compound containing the triazolinone structure described in the first aspect, or its agriculturally chemically acceptable salt, hydrate, solvate, or its enantiomer or optically active derivative, comprising: condensing the compound of formula (II) with the compound of formula (III) or with the hydrochloride salt of the compound of formula (III) in the presence of a solvent and a condensing agent.

[0111]

[0112] Wherein, X, Y, M and R are the same as those defined in the first aspect of the present invention.

[0113] 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.

[0114] 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.

[0115] Preferably, the solvent is selected from at least one of dichloromethane, trichloromethane, dichloroethane, acetonitrile, toluene, tetrahydrofuran, and benzene.

[0116] 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.

[0117] The following is an exemplary method for preparing the compound shown in formula (II):

[0118]

[0119]

[0120] 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).

[0121] 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, as PPO inhibitors.

[0122] As previously stated, the fourth 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.

[0123] 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.

[0124] For example, it can be used to control at least one weed in cotton fields, wheat fields, rice fields, corn fields, and soybean fields.

[0125] Preferably, the weeds are selected from at least one of broadleaf weeds, grass weeds, and sedge weeds.

[0126] More preferably, the broadleaf weeds are selected from at least one of the following: shepherd's purse, shepherd's purse, lambsquarters, velvetleaf, cleavers, speedwell, chickweed, amaranth, black nightshade, lantern grass, purslane, amaranth retroflexus, and carp intestines.

[0127] More preferably, the grass weeds are selected from at least one of barnyard grass, goosegrass, golden foxtail grass, foxtail grass, crabgrass, barnyard grass, Japanese barnyard grass, jointed barnyard grass, wild oat, wild oat, barnyard grass, and double-spike barnyard grass.

[0128] More preferably, the Cyperaceae family is selected from at least one of Cyperus rotundus, Cyperus ferrugineus, and Cyperus divaricata.

[0129] 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.

[0130] Preparation Example 1: Preparation of Compound 11

[0131]

[0132] Preparation of compound A1-2

[0133] In a 1L three-necked flask, 100g of compound A1-1 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. The mixture was stirred at -5°C for 30 minutes, then cooled 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 A1-2, with a yield of 91%.

[0134] Preparation of compound A1-3

[0135] Compound A1-2 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 A1-3 was obtained, with a yield of 71%.

[0136] Synthesis of compound A1-4

[0137] The synthesized compound A1-3 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 A1-4 in 96% yield.

[0138] Synthesis of compound A1-5

[0139] The synthesized compound A1-4 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 A1-5 with a yield of 89%.

[0140] Synthesis of compound A1-6

[0141] 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 A1-6 was obtained with a yield of 90%.

[0142] Synthesis of compound A1-8

[0143] Compound A1-6 was added to a 500 mL single-necked flask, along with 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 mixture was then filtered to obtain compound A1-8, with a yield of 78%.

[0144] Synthesis of Compound 11

[0145]

[0146] 1 mmol of compound A1-8 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 11 in 87% yield.

[0147] Preparation Example 2: Preparation of Compound 34

[0148]

[0149] 1 mmol of compound A1-8 was added to a 50 mL single-necked flask, followed by 20 mL of dichloromethane and 2 mmol of EDCI. The mixture was stirred at room temperature for 2 hours. Then, 1.5 mmol of glycine methyl ester hydrochloride and 2 mmol of DMAP were added to the reaction mixture, and the mixture was stirred at room temperature for 30 minutes. The reaction was monitored by TLC until complete. The solution was acidified with 20 mL of 1N HCl solution. The aqueous phase was extracted with 20 mL of dichloromethane. The organic phase was dried over anhydrous sodium sulfate and concentrated. The solution was purified by column chromatography to give compound 34 in 85% yield.

[0150] The preparation methods of the other compounds of the present invention are the same as those described in the preparation examples above. Table 1 lists the characterization data of some specific compounds of the present invention.

[0151] Table 1

[0152]

[0153]

[0154]

[0155]

[0156] Test Example 1: Greenhouse Wide-Range Screening Experiment

[0157] 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.

[0158] Two treatment methods were used: foliar spraying and soil spraying.

[0159] 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 it grows to the 4-5 leaf stage for 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%), and the results were investigated after 20 days.

[0160] 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.

[0161] 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 (%).

[0162] Fresh weight inhibition rate (%) = (Control fresh weight - Treatment fresh weight) / Control fresh weight × 100%

[0163] The ratings were determined based on the information shown in Table 2, and the test results are shown in Tables 3-12.

[0164] Table 2

[0165]

[0166]

[0167] Table 3

[0168]

[0169] Table 4

[0170]

[0171] Table 5

[0172]

[0173]

[0174] Table 6

[0175]

[0176]

[0177] Table 7

[0178]

[0179]

[0180] Table 8

[0181]

[0182]

[0183] Table 9

[0184]

[0185] Table 10

[0186]

[0187]

[0188] Table 11

[0189]

[0190]

[0191] Table 12

[0192]

[0193]

[0194] The above herbicidal activity test results show that the compound of the present invention has excellent control efficacy against the tested weeds. Moreover, at the same dosage, the compound of the present invention is more effective than the commercially available herbicide oxychloride in controlling the tested weeds.

[0195] Furthermore, the results above show that introducing active esters or amino acid / ester fragments into the molecule significantly enhances 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.

[0196] 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.

[0197] Test Example 2: Greenhouse Initial Screening Experiment

[0198] 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.

[0199] 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 until the targets reached approximately 3 leaves. Each compound was 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.

[0200] 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.

[0201] The survey method was the same as in Test Example 1, and the test results are shown in Tables 13-17.

[0202] Table 13

[0203]

[0204] Table 14

[0205]

[0206] Table 15

[0207]

[0208] Table 16

[0209]

[0210]

[0211] Table 17

[0212]

[0213] The preliminary screening results showed that the efficacy of the compound of the present invention against the tested weeds decreased with decreasing dosage. However, the test results showed that when the dosage was reduced to 2.5 g ai / mu, the compound of the present invention still maintained a high level of efficacy against weeds, and the compound of the present invention had a superior control effect compared to the commercially available herbicide oxychloride.

[0214] Test Example 3: Crop Safety Test

[0215] 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.

[0216] 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. Seeds of the tested crops (germination rate ≥85%) were directly sown, covered with 0.2cm of soil, and left to grow until the target plants reached approximately 3 leaves. Each compound was applied at a dosage of 10g ai / mu 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. The test results are shown in Tables 18-21.

[0217] 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. The test results are shown in Tables 22-26.

[0218] Table 18

[0219] 26 2 39 2 cyclohexane 2

[0220] Table 19

[0221] 26 1 42 2 46 2 cyclohexane 2

[0222] Table 20

[0223] 26 2 39 2 42 2 43 2 44 2 46 2 cyclohexane 2

[0224] Table 21

[0225] 26 1 39 1 42 2 43 2 44 2 46 2 cyclohexane 2

[0226] Table 22

[0227] 26 0 42 0 43 0 44 0 46 0 cyclohexane 0

[0228] Table 23

[0229] 39 1 42 0 43 0 46 0 cyclohexane 5

[0230] Table 24

[0231] 26 0 39 0 42 1 43 0 46 0 cyclohexane 1

[0232] Table 25

[0233] 39 1 42 0 43 0 44 2 46 1 cyclohexane 4

[0234] Table 26

[0235] 26 2 42 2 46 2 cyclohexane 3

[0236] Crop safety tests on stem and leaf treatments showed that, at the test dosages provided by this invention, the compounds of this invention exhibit good crop safety in maize, wheat, indica rice, and japonica rice.

[0237] Soil treatment crop safety tests showed that, at the test dosage provided by this invention, the compounds of this invention have good crop safety for corn, soybeans, wheat, cotton and japonica rice.

[0238] Therefore, the compounds of the present invention can be used to control at least one weed in corn fields, soybean fields, wheat fields, cotton fields, indica rice fields and japonica rice fields.

[0239] 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.

[0240] 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.

[0241] 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 combinations of 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, the compound having the structure shown in formula (I) and selected from any of the following compounds; in formula (I), the definitions of X, Y, M, and R correspond to the corresponding positions in the following compounds; Equation (I), Compound 11: Compound 12: Compound 13: Compound 14: Compound 15: Compound 16: Compound 17: Compound 18: Compound 19: Compound 20: Compound 21: Compound 22: Compound 23: Compound 24: Compound 25: Compound 26: Compound 27: Compound 28: Compound 29: Compound 30: Compound 31: Compound 32: Compound 33: Compound 34: Compound 39: Compound 41: Compound 42: Compound 43: Compound 44: Compound 45: Compound 46: Compound 47: Compound 48: Compound 49: Compound 50: Compound 51: Compound 52: Compound 53: Compound 54: Compound 55: Compound 56: Compound 57: Compound 58: .

2. The compound according to claim 1, characterized in that, The compound is selected from any one of the following: Compound 11: Compound 12: Compound 13: Compound 14: Compound 15: Compound 16: Compound 17: Compound 18: Compound 19: Compound 20: Compound 21: Compound 22: Compound 23: Compound 24: Compound 25: Compound 26: Compound 27: Compound 28: Compound 50: Compound 51: Compound 52: Compound 53: Compound 54: Compound 55: Compound 56: Compound 57: Compound 58: .

3. The compound according to claim 1, characterized in that, The compound is selected from any one of the following: Compound 29: Compound 30: Compound 31: Compound 32: Compound 33: Compound 34: Compound 39: Compound 41: Compound 42: Compound 43: Compound 44: Compound 45: Compound 46: Compound 47: Compound 48: Compound 49: .

4. A method for preparing the compound containing a triazolinone structure as described in any one of claims 1-3, or an agriculturally chemically acceptable salt thereof, characterized in that, include: In the presence of a solvent and a condensing agent, the compound of formula (II) is subjected to a condensation reaction with the compound of formula (III) or with the hydrochloride salt of the compound of formula (III). Formula (II), RMH, Formula (III); Wherein, X, Y, M and R are the same as those defined in any one of claims 1-3.

5. The method according to claim 4, wherein, The condensing agent is selected from at least one of HATU, HBTU, EDCI, CDI, HOBt, DCC, DIC, PyBOP, POCl3, and T3P.

6. The method according to claim 4, wherein, The solvent is selected from at least one of dichloromethane, trichloromethane, dichloroethane, acetonitrile, toluene, tetrahydrofuran, and benzene.

7. The use of the compound containing a triazolinone structure as described in any one of claims 1-3, or an agriculturally chemically acceptable salt thereof, as a PPO inhibitor.

8. The use of the triazolinone-containing compound or its agriculturally chemically acceptable salt as described in any one of claims 1-3 in the control of weeds.

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