Substituted oximido aromatic compound as well as preparation method, weeding composition and application thereof

Abstract

The invention relates to the technical field of pesticides, and particularly discloses a substituted oximido aromatic compound, a preparation method thereof, a weeding composition and application of the substituted oximido aromatic compound, and the substituted oximido aromatic compound is shown as a formula I: # imgabs0 # I; the variables in the formula I are defined as follows: R1 is selected from CF3; r2 is selected from C1-C4 alkyl groups, C1-C4 halogenated alkyl groups, allyl groups, propargyl groups and cyclopropyl groups; r3, R4, R5, R6, R7, R8, R9, R10 and R11 are respectively and independently selected from one of hydrogen, fluorine, chlorine, bromine, iodine, C1-C4 alkyl, C1-C4 halogenated alkyl, allyl, propargyl, cyclopropyl, C1-C3 alkoxy C1-C3 alkyl, C1-C4 alkyl carbonyloxy C2-C3 alkyl, benzyl, furfuryl or tetrahydrofurfuryl. The compound disclosed by the invention is high in herbicidal activity, simple in preparation process and capable of being applied on a large scale, and the herbicidal composition containing the compound is high in compatibility and stability of components, is slightly influenced by the environment, has excellent herbicidal effect on various weeds at a low application rate, and has high selectivity on crops.

Description

Technical Field

[0001] The invention relates to the technical field of pesticides, and specifically discloses a substituted oxime aromatic compound, a preparation method thereof, a herbicidal composition and application thereof. Background Art

[0002] Chemical weed control is the most economical and effective means of weed control in farmland, but long-term continuous high-dose use of a single variety or a single mode of action of chemical herbicides can easily cause problems such as weed resistance and resistance evolution. Therefore, the market is in urgent need of developing chemical herbicides with advantages such as expanding the weed spectrum, improving control effects, delaying the occurrence and development of weed resistance and resistance, and having better weed control effects.

[0003] The invention patent with application number 202011226390.6 discloses a ternary herbicidal composition comprising an oxyiminoaryl compound substituted with a carboxylic acid derivative and its application, wherein the ternary herbicidal composition comprises an active ingredient A, an active ingredient B and an active ingredient C in a herbicidally effective amount, wherein the active ingredient A is an oxyiminoaryl compound substituted with a carboxylic acid derivative, and the active ingredients B and C are respectively selected from any one of the following types of compounds and another compound of a different type: VLCFA inhibitors, microtubule assembly inhibitors, EPSPS inhibitors, etc. The composition can effectively prevent and control various weed problems such as grasses or broad-leaved plants, and has the characteristics of expanding the weed control spectrum, reducing the application amount, being able to produce synergistic effects and solving resistant weeds. However, the oxyiminoaryl compound substituted with a carboxylic acid derivative may require strict control of the reaction and production conditions, and large-scale production and application may be limited. At the same time, its stability under specific environments (such as light, high temperature and humidity conditions, etc.) is poor. Summary of the invention

[0004] In view of the defects of the prior art, the present invention discloses a substituted oxime aromatic compound and a preparation method thereof, a herbicidal composition and application. The compound disclosed in the present invention is an oxime aromatic compound containing a new structure, has high herbicidal activity, a simple preparation process, and can be applied on a large scale. The herbicidal composition containing the compound has high compatibility and stability of each component, is less affected by the environment, has excellent herbicidal efficacy against various weeds at a low application rate, and has high selectivity for crops.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0006] The first aspect of the present invention provides a substituted oxime aromatic compound, wherein the substituted oxime aromatic compound is as shown in Formula I:

[0007]

[0008] The variables in Formula I are defined as follows:

[0009] R1 is selected from CF3;

[0010] R2 is selected from C1-C4 alkyl, C1-C4 haloalkyl, allyl, propargyl, cyclopropyl;

[0011] R3, R4, R5, R6, R7, R8, R9, R10, and R11 are independently selected from one of hydrogen, fluorine, chlorine, bromine, iodine, C1-C4 alkyl, C1-C4 haloalkyl, allyl, propargyl, cyclopropyl, C1-C3 alkoxy C1-C3 alkyl, C1-C4 alkylcarbonyloxy C2-C3 alkyl, benzyl, furanyl, or tetrahydrofuranyl.

[0012] In some embodiments of the present invention, the variables in Formula I are defined as follows:

[0013] R1 is selected from CF3;

[0014] R2 is selected from CH3;

[0015] R3, R4, R5, R6, R7, R8, R9, R10, and R11 are each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, and C1-C4 alkyl.

[0016] In some embodiments of the present invention, the variables in Formula I are defined as follows:

[0017] R1 is selected from CF3;

[0018] R2 is selected from CH3;

[0019] R3 and R4 are independently selected from one of hydrogen, fluorine or chlorine;

[0020] R5 and R6 are each selected from hydrogen;

[0021] R7 is selected from hydrogen or methyl;

[0022] R8 is selected from hydrogen or methyl;

[0023] R9 is selected from hydrogen or methyl;

[0024] R10 is selected from hydrogen, fluorine, chlorine, and bromine;

[0025] R11 is selected from hydrogen, fluorine, chlorine and bromine.

[0026] In some embodiments of the present invention, the variables in Formula I are defined as follows:

[0027] R1 is selected from CF3;

[0028] R2 is selected from CH3;

[0029] R3 and R4 are independently selected from one of hydrogen, fluorine or chlorine;

[0030] R5, R6, R7, R8, and R9 are each selected from hydrogen;

[0031] R10 and R11 are selected from hydrogen and chlorine.

[0032] Another aspect of the present invention provides a method for preparing a substituted oxime aromatic compound. The substituted oxime aromatic compound shown in formula I is obtained by an amino compound, and the amino compound is shown in formula II:

[0033]

[0034] In some embodiments of the present invention, the substituted oxime aromatic compound represented by formula I is synthesized by the amino compound represented by formula II by the following route using the method described in the literature, such as US5336663, US6992044 or WO2001083459:

[0035]

[0036] In some embodiments of the present invention, the amino compound can be obtained from the nitro compound by conventional methods using a reducing agent such as iron, zinc, palladium carbon, stannous chloride, etc., for details, see EP2044006; US20070155738; European Journal of Medicinal Chemistry, 2013, 65, 32-40; Synlett, 2010, (20), 3019-3022; Heterocycles, 2008, 75 (1): 57-64.

[0037] In some embodiments of the present invention, the nitro compound can be synthesized from aldehyde according to the description in existing literature: such as J. Agric. Food Chem. 2005, 53, 8639-8643 or WO2006090234.

[0038] Another aspect of the present invention provides a method for preparing another substituted oxime aromatic compound. The substituted oxime aromatic compound represented by formula I is obtained by using a compound represented by formula III. The compound represented by formula III is as follows:

[0039]

[0040] In some embodiments of the present invention, the substituted oxime aromatic compound of formula I is obtained by synthesizing the compound of formula III by the following route:

[0041]

[0042] The present invention prepares a new oxime aromatic compound having a structure shown in formula I through a specific synthetic route. Compared with the oxime aromatic compounds commonly used in the prior art, the herbicidal activity of the oxime aromatic compound is further improved on the basis of the phenyl heterocyclic molecular skeleton as the pharmacophore. This may be because the angle between the phenyl heterocyclic rings of the substituted oxime aromatic compound is increased, thereby improving the activity.

[0043] In some embodiments of the present invention, the present reaction is carried out in a suitable solvent.

[0044] Preferably, the suitable solvent is at least one of benzene, toluene, xylene, acetone, tetrahydrofuran, petroleum ether, acetonitrile, N,N-dimethylformamide, N-methylpyrrolidone, dichloromethane, chloroform, dichloroethane or ethyl acetate.

[0045] In some embodiments of the present invention, the reaction of the present invention can be carried out in the presence of a base or in the absence of a base. When the reaction is carried out in the presence of a base, the reaction can be accelerated.

[0046] In some embodiments of the present invention, the base is one of an alkali metal hydride, an alkali metal hydroxide, an alkali metal carbonate and an organic base.

[0047] Preferably, the alkali metal hydride is one of sodium hydride, lithium hydride and sodium amide.

[0048] Preferably, the alkali metal hydroxide is sodium hydroxide or potassium hydroxide.

[0049] Preferably, the alkali metal carbonate is sodium carbonate or potassium carbonate.

[0050] Preferably, the organic base is one of pyridine, 4-dimethylaminopyridine, triethylamine, N-methylpyrrole or diisopropylethylamine.

[0051] In some embodiments of the present invention, the reaction temperature may be between -10°C and the boiling point of the appropriate solvent selected in the reaction.

[0052] Preferably, the reaction temperature is 0-100°C.

[0053] In some embodiments of the present invention, the reaction time is 30 min to 20 h.

[0054] Preferably, the reaction time is 1 to 10 hours.

[0055] In another aspect, the present invention provides a herbicidal composition, which comprises the following raw materials, calculated as 100% by mass: 30-60% of substituted oxime aromatic compounds and the remainder as auxiliary agents; wherein the substituted oxime aromatic compounds are obtained by the above scheme.

[0056] In some embodiments of the present invention, the auxiliary agent is a modified stabilizer; the preparation steps of the modified stabilizer are as follows:

[0057] Sodium p-styrene sulfonate and deionized water are added to the reactor, the pH is adjusted to be weakly alkaline, N,N-dimethylacrylamide, vinyl pyrrolidone and allyl polyoxyethylene ether are added, an inert atmosphere is introduced, the temperature is raised to 60-80° C., an initiator is added, the reaction is carried out for 3-7 hours, and the modified stabilizer is obtained after washing and drying.

[0058] In some embodiments of the present invention, the mass ratio of sodium p-styrene sulfonate, N,N-dimethylacrylamide, vinyl pyrrolidone and allyl polyoxyethylene ether is (0.5-2):(1-4):(0.1-2):10.

[0059] Preferably, the mass ratio of sodium p-styrene sulfonate, N,N-dimethylacrylamide, vinyl pyrrolidone and allyl polyoxyethylene ether is 1.2:2.5:1:10.

[0060] Preferably, the preparation steps of the herbicidal composition are as follows:

[0061] The substituted oxime aromatic compound and the modified stabilizer are stirred and mixed to obtain the herbicidal composition.

[0062] Stabilizers are often added to herbicidal compositions to improve the stability of the system in the environment. However, common stabilizers in the prior art are prone to floating when used in this system, and are prone to causing phytotoxicity when environmental conditions change. In addition, they have weak compatibility with the herbicidal composition and poor stabilization effect.

[0063] The present invention adds specific monomers to sodium styrene sulfonate, N,N-dimethylacrylamide, vinyl pyrrolidone and allyl polyoxyethylene ether for copolymerization in specific steps to obtain a modified stabilizer. The modified stabilizer has good dispersibility and stability to other components of the herbicidal composition, solves the problem that chlorinated olefin-substituted oxime aromatic compounds are prone to drift damage, and also solves the problem that the stabilizer in the prior art is not compatible with the substituted oxime aromatic compounds prepared by the present invention, which is not conducive to the weed control effect.

[0064] The possible reason is that the introduction of benzene ring groups and dimethyl groups on N,N-dimethylacrylamide increases the steric hindrance effect of the modified stabilizer, prevents the degradation of other copolymer monomers, improves the adaptability of the modified stabilizer in various environments, and ensures the anchoring and dispersion-promoting effects of the copolymerization of long side chains and highly adsorbed polyether monomers on other components of the herbicide composition. In addition, the introduction of sulfonic acid groups further assists the long side chains and highly adsorbed polyether monomers to exert stronger aggregation stability, so that the herbicide composition can still withstand environmental shocks such as rain washing when precipitation occurs shortly after application.

[0065] The present invention also provides an application of the above-mentioned herbicidal composition, wherein the herbicidal composition is used to control weeds in useful crops; the useful crops include transgenic crops or crops treated with genome editing technology; and the weeds include herbicide-resistant or -tolerant weed species.

[0066] It should be noted that the terms used in the definitions of Formula I, Formula II and Formula III given above are generally defined as follows:

[0067] Halogen: refers to fluorine, chlorine, bromine or iodine.

[0068] Alkyl: a straight-chain or branched alkyl group, for example, methyl, ethyl, propyl, isopropyl, n-butyl or tert-butyl.

[0069] Cycloalkyl: a substituted or unsubstituted cyclic alkyl group, for example, cyclopropyl, cyclopentyl or cyclohexyl.

[0070] Substituents include methyl, halogen, etc.

[0071] Haloalkyl: a straight-chain or branched alkyl group, in which the hydrogen atoms may be partially or completely replaced by halogen atoms, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, etc.

[0072] Alkoxy: A straight or branched chain alkyl group attached to the structure via an oxygen atom.

[0073] Haloalkoxy: a straight or branched alkoxy group, in which the hydrogen atoms may be partially or completely replaced by halogen atoms, for example, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, etc.

[0074] Compared with the prior art, the present invention has the following beneficial effects:

[0075] (1) The present invention prepares a substituted oxime aromatic compound with a new structure and a modified stabilizer as a herbicidal composition. The obtained substituted oxime aromatic compound has high herbicidal activity, a simple preparation process, and can be applied on a large scale. The herbicidal composition containing the compound has high compatibility and stability of each component, is less affected by the environment, has excellent herbicidal efficacy against various weeds at a low application rate, and has high selectivity for crops.

[0076] (2) The present invention adds specific monomers to sodium styrene sulfonate, N,N-dimethylacrylamide, vinyl pyrrolidone and allyl polyoxyethylene ether and copolymerizes them in specific steps to obtain a modified stabilizer. The modified stabilizer has good dispersibility and stability to other components of the herbicidal composition, solves the problem that chlorinated olefin-substituted oxime aromatic compounds are prone to drift damage, and also solves the problem that the stabilizer in the prior art is not compatible with the substituted oxime aromatic compounds prepared by the present invention, which is not conducive to the weed control effect. DETAILED DESCRIPTION

[0077] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0078] Unless otherwise specified, the reagents used below can be easily obtained from commercial companies, wherein the model of the allyl polyoxyethylene ether used is APEG-500.

[0079] Preparation Example 1

[0080] The preparation method of substituted oxime aromatic compounds, the synthetic route is as follows:

[0081]

[0082] The following steps are involved:

[0083] 1) Preparation of 2-chloro-4-fluoro-5-nitrobenzaldehyde oxime: 21 g (0.103 mol) of 2-chloro-4-fluoro-5-nitrobenzaldehyde was dissolved in 100 mL of ethanol, cooled to 0°C, and 8.7 g (0.125 mol) of hydroxylamine hydrochloride was added under stirring, followed by slow addition of 10 g of sodium hydroxide to react under stirring. After 2 h, the reaction was complete as monitored by TLC, and the mixture was poured into water and filtered to obtain 19 g of a white solid, namely 2-chloro-4-fluoro-5-nitrobenzaldehyde oxime;

[0084] 2) Preparation of O-3'-chloroallyl-2-chloro-4-fluoro-5-nitrobenzaldehyde oxime: 43.7 g (0.2 mol) of 2-chloro-4-fluoro-5-nitrobenzaldehyde oxime was dissolved in 150 mL of N,N-dimethylformamide, and the temperature was raised to 30°C. 55 g of potassium carbonate was added at this temperature, and 27.8 g of E-1,3-dichloropropylene was added dropwise at 35°C to react for 1 h, and the temperature was lowered to room temperature, and 800 mL of ice water was added. 54 g of white solid was obtained by filtration, which is O-3'-chloroallyl-2-chloro-4-fluoro-5-nitrobenzaldehyde oxime;

[0085] 3) Preparation of O-3'-chloroallyl-2-chloro-4-fluoro-5-aminobenzaldehyde oxime: 52.7 g (0.18 mol) of O-3'-chloroallyl-2-chloro-4-fluoro-5-nitrobenzaldehyde oxime was dissolved in 300 mL of ethyl acetate, 163 g (0.72 mol) of stannous chloride dihydrate was added in batches under heating, and then reacted under reflux for 8 h. The reaction was monitored by TLC to be complete, cooled to room temperature, added to ice water, and the pH was adjusted to 8 with sodium hydroxide. The product was extracted with ethyl acetate, washed with saturated brine, dried over anhydrous magnesium sulfate, and then distilled under reduced pressure to obtain 43 g of an oily substance, namely O-3'-chloroallyl-2-chloro-4-fluoro-5-aminobenzaldehyde oxime;

[0086] 4) Preparation of 2-dimethylamino-4-trifluoromethyl-6H-1,3-oxazin-6-one: 25 g (0.15 mol) of dichloromethylenedimethylammonium chloride was added to 100 mL of chloroform, the temperature was raised to 60°C, and a mixture of 25 g (0.14 mol) of ethyl 3-amino-4,4,4-trifluorocrotonate and 15 mL of chloroform was added dropwise. The reflux reaction was continued, and the solution gradually changed from light yellow turbidity to clarity. After 4 h, the reaction was complete as monitored by TLC. The mixture was cooled to room temperature, saturated aqueous sodium bicarbonate solution was added, and the organic phase was separated and washed with saturated brine. The organic phase was dried over anhydrous magnesium sulfate and distilled under reduced pressure to obtain 30.8 g of a light yellow solid, which was 2-dimethylamino-4-trifluoromethyl-6H-1,3-oxazin-6-one.

[0087] 5) Preparation of O-3'-chloroallyl-2-chloro-5-(2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)-4-fluorobenzaldehyde oxime: 12.1 g (0.046 mol) of O-3'-chloroallyl-2-chloro-4-fluoro-5-aminobenzaldehyde oxime and 9.8 g (0.047 mol) of 2-dimethylamino-4-trifluoromethyl-6H-1,3-oxazin-6-one were added to a 100 mL ethanol solution. The reaction flask of the acid was heated to reflux to form a dark solution, which was kept at this temperature for 6 hours, and the solvent was evaporated under reduced pressure. An aqueous sodium bicarbonate solution was added to adjust the pH to 7, and the product was extracted with ethyl acetate. After drying over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure to obtain a crude product, which was recrystallized from ethanol to obtain 14.5 g of a white solid, which was O-3'-chloroallyl 2-chloro-5-(2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)-4-fluorobenzaldehyde oxime.

[0088] 6) Preparation of substituted oxime aromatic compounds: 13.1 g (0.031 mol) O-3'-chloroallyl 2-chloro-5-(2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)-4-fluorobenzaldehyde oxime and 12.9 g (0.094 mol) potassium carbonate were added to a reaction bottle containing 150 mL N,N-dimethylformamide in sequence, cooled to 0°C, 8.9 g (0.062 mol) iodomethane was added dropwise, and then the temperature was raised to room temperature and stirred for 6 h. The reaction was completed by TLC monitoring, poured into water, extracted with ethyl acetate, washed with saturated brine, the organic phase was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and recrystallized from ethanol to obtain 12.8 g of the product, which is a substituted oxime aromatic compound, with the following structural formula:

[0089]

[0090] Preparation Example 2

[0091] The preparation method of substituted oxime aromatic compounds, the synthetic route is as follows:

[0092]

[0093] The following steps are involved:

[0094] 1) Preparation of 2-chloro-4-fluoro-5-aminobenzaldehyde: 21 g (0.02 mol) of 2-chloro-4-fluoro-5-nitrobenzaldehyde was dissolved in 200 ml of methanol, 0.1 g of palladium carbon was added, the temperature was raised to 50°C, and hydrogenated at 0.4 MPa for 2 h. The reaction was monitored by TLC. After filtration, the solvent was evaporated under reduced pressure to obtain 16 g of an oily substance, which was 2-chloro-4-fluoro-5-aminobenzaldehyde;

[0095] 2) Preparation of 2-chloro-5-(2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)-4-fluorobenzaldehyde: 8.1 g (0.047 mol) of 2-chloro-4-fluoro-5-aminobenzaldehyde and 9.8 g (0.047 mol) of 2-dimethylamino-4-trifluoromethyl-6H-1,3-oxazin-6-one were added to a reaction bottle containing 100 mL of acetic acid, and the temperature was raised to reflux to form a dark solution, which was kept at this temperature for 6 h, and the solvent was evaporated under reduced pressure. A sodium bicarbonate aqueous solution was added to adjust the pH to 7, and the product was extracted with ethyl acetate, dried over anhydrous magnesium sulfate, and then the solvent was removed under reduced pressure to obtain a crude product, which was recrystallized from ethanol to obtain 12.3 g of a white solid, namely 2-chloro-5-(2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)-4-fluorobenzaldehyde;

[0096] 3) Preparation of 2-chloro-5-(N-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)-4-fluorobenzaldehyde: 10.0 g (0.031 mol) of 2-chloro-5-(2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)-4-fluorobenzaldehyde and 12.9 g (0.094 mol) of potassium carbonate were added in sequence to a reaction bottle containing 150 ml of N,N-dimethylformamide, cooled to 0°C, 8.9 g (0.062 mol) of iodomethane was added dropwise, and then the temperature was raised to room temperature and stirred for reaction for 6 hours. The reaction was complete after TLC monitoring, poured into water, extracted with ethyl acetate, washed with saturated brine, and the organic phase was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and recrystallized from ethanol to obtain 9.8 g of 2-chloro-5-(N-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)-4-fluorobenzaldehyde;

[0097] 4) Preparation of substituted oxime aromatic compounds: 15 g (0.044 mol) of 2-chloro-5-(N-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)-4-fluorobenzaldehyde was added to 50 mL of methanol at room temperature, and then 5.7 g (0.0527 mol) of O-3-chloro-2-propenylhydroxylamine was added. The temperature was raised to reflux for 2 h, and the temperature was lowered to 3° C. A white solid was precipitated, and 13.5 g of a substituted oxime aromatic compound was obtained by filtration. The structural formula is as follows:

[0098]

[0099] Preparation Example 3

[0100] The preparation steps of the modified stabilizer are as follows:

[0101] Add 1.2 g of sodium p-styrene sulfonate and 50 mL of deionized water to reactor 3, adjust the pH to 7, then add 2.5 g of N,N-dimethylacrylamide, 1 g of vinyl pyrrolidone and 10 g of allyl polyoxyethylene ether, introduce nitrogen atmosphere, raise the temperature to 70°C, add 0.02 g of dibenzoyl peroxide, react for 5 h, wash and dry to obtain the modified stabilizer.

[0102] Preparation Example 4

[0103] The preparation steps of the modified stabilizer are the same as those of Preparation Example 3, except that the amount of N,N-dimethylacrylamide added is 5 g.

[0104] Preparation Example 5

[0105] The preparation steps of the modified stabilizer are the same as those of Preparation Example 3, except that the amount of vinyl pyrrolidone added is 2.2 g.

[0106] Preparation Example 6

[0107] The preparation steps of the modified stabilizer are the same as those of Preparation Example 3, except that the amount of sodium p-styrene sulfonate added is 2.2 g.

[0108] Example 1

[0109] Based on 100% by mass, the preparation steps of a herbicidal composition are as follows:

[0110] 45% of the substituted oxime aromatic compound and the remaining amount of the modified stabilizer are stirred and mixed to obtain a herbicidal composition.

[0111] The substituted oxime aromatic compound is obtained from Preparation Example 1, and the modified stabilizer is obtained from Preparation Example 3.

[0112] Example 2

[0113] Based on 100% by mass, the preparation steps of a herbicidal composition are as follows:

[0114] 60% of the substituted oxime aromatic compound and the remaining amount of the modified stabilizer are stirred and mixed to obtain a herbicidal composition.

[0115] The substituted oxime aromatic compound is obtained from Preparation Example 1, and the modified stabilizer is obtained from Preparation Example 3.

[0116] Example 3

[0117] Based on 100% by mass, the preparation steps of a herbicidal composition are as follows:

[0118] 30% of the substituted oxime aromatic compound and the remaining amount of the modified stabilizer are stirred and mixed to obtain a herbicidal composition.

[0119] The substituted oxime aromatic compound is obtained from Preparation Example 1, and the modified stabilizer is obtained from Preparation Example 3.

[0120] Example 4

[0121] A herbicidal composition, the specific implementation manner is the same as that of Example 1, except that the substituted oxime aromatic compound used is obtained from Preparation Example 2.

[0122] Example 5

[0123] A herbicidal composition, the specific implementation manner is the same as that of Example 1, except that the modified stabilizer used is obtained from Preparation Example 4.

[0124] Example 6

[0125] A herbicidal composition, the specific implementation manner is the same as Example 1, except that the modified stabilizer used is obtained from Preparation Example 5.

[0126] Example 7

[0127] A herbicidal composition, the specific implementation manner is the same as Example 1, except that the modified stabilizer used is obtained from Preparation Example 6.

[0128] Example 8

[0129] A herbicidal composition, the specific implementation manner is the same as that of Example 1, except that an equal amount of a commercially available pesticide stabilizer (model 500LQ, purchased from Yixing Jiateng Chemical Co., Ltd.) is used to replace the modified stabilizer prepared by the present invention.

[0130] Example 9

[0131] A herbicidal composition, the specific implementation manner is the same as that of Example 1, except that an equal amount of a commercially available herbicide (the active ingredient is 5 wt% cycloazinone, purchased from Shandong Jiaduobao Biotechnology Co., Ltd.) is substituted for the substituted oxime aromatic compound prepared in the present invention.

[0132] Performance Test:

[0133] The herbicidal composition prepared in Examples 1-9 was stored in a cool and dry place for 30 days, dissolved in acetone, and then Tween 80 was added at a concentration of 1.5 L / hm2. 2 The emulsifiable concentrate of methyl oleate was used as a synergist, and water was added to prepare a 0.3 g / L test solution, and the following performance tests were performed:

[0134] Weed control test: Take each test solution to carry out weed control test experiment. The experimental objects are annual grass weeds, perennial broadleaf weeds and sedge weeds in rice fields. Leptochloa chinensis, Cyperus rotundus and Stachys truncatula are mainly selected as experimental objects. The indoor bioassay method is adopted. Four parallel experiments are carried out for each embodiment to take the average value. The number of weeds is 30 each time. The conventional spray method is adopted. The weeds are in the 1-1.5 leaf stage when the pesticide is applied. The application rate is 150g / hm 2 The control group was a blank sample without the test solution, and the fresh weight inhibition rate of each treatment was calculated by the following formula:

[0135] Fresh weight inhibition rate = (fresh weight of control group - fresh weight of treatment group) / fresh weight of control group × 100%.

[0136] Table 1

[0137]

[0138]

[0139] As shown in Table 1, the herbicidal compositions disclosed in Examples 1 to 4 of the present invention have a good inhibitory effect on weeds and a wide weed control range, and have good weed control effects on Leptochloa chinensis, Cyperus rotundus and Stachys sphaerocephala;

[0140] By comparing Examples 5, 6 and 7 with Example 1, it can be seen that when the amounts of the comonomers N,N-dimethylacrylamide, vinyl pyrrolidone and sodium p-styrene sulfonate added in the preparation of the modified stabilizer are changed respectively, the inhibitory effect of the herbicidal composition on weeds will be deteriorated. This may be because the effect of the herbicidal composition is hindered by the impact of the environment when it is applied;

[0141] From the comparison between Example 8 and Example 1, it can be seen that when the modified stabilizer prepared by the present invention is replaced by an equal amount of a commercially available polycarboxylic acid stabilizer, the inhibitory effect of the herbicidal composition on weeds may be poor due to its poor stability matching with the substituted oxime aromatic compound prepared by the present invention;

[0142] From the comparison between Example 9 and Example 1, it can be seen that when the substituted oxime aromatic compound prepared by the present invention is replaced by an equal amount of commercially available herbicides, its herbicidal activity and dispersibility are reduced, which together will lead to a worse fresh weight inhibition rate of weeds.

[0143] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technician familiar with this profession can make some changes or modifications to equivalent embodiments of equivalent changes using the technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A substituted oxime aromatic compound, characterized in that: The substituted oxime aromatic compound is shown in Formula I: The variables in Formula I are defined as follows: R1 is selected from CF3; R2 is selected from C1-C4 alkyl, C1-C4 haloalkyl, allyl, propargyl, cyclopropyl; R3, R4, R5, R6, R7, R8, R9, R10, and R11 are each independently selected from one of hydrogen, fluorine, chlorine, bromine, iodine, C1-C4 alkyl, C1-C4 haloalkyl, allyl, propargyl, cyclopropyl, C1-C3 alkoxy C1-C3 alkyl, C1-C4 alkylcarbonyloxy C2-C3 alkyl, benzyl, furanyl, or tetrahydrofuranyl.

2. The substituted oxime aromatic compound according to claim 1, characterized in that: The variables in Formula I are defined as follows: R1 is selected from CF3; R2 is selected from CH3; R3, R4, R5, R6, R7, R8, R9, R10, and R11 are each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, and C1-C4 alkyl.

3. The substituted oxime aromatic compound according to claim 2, characterized in that: The variables in Formula I are defined as follows: R1 is selected from CF3; R2 is selected from CH3; R3 and R4 are independently selected from one of hydrogen, fluorine or chlorine; R5 and R6 are each selected from hydrogen; R7 is selected from hydrogen or methyl; R8 is selected from hydrogen or methyl; R9 is selected from hydrogen or methyl; R10 is selected from hydrogen, fluorine, chlorine, and bromine; R11 is selected from hydrogen, fluorine, chlorine and bromine.

4. The substituted oxime aromatic compound according to claim 3, characterized in that: The variables in Formula I are defined as follows: R1 is selected from CF3; R2 is selected from CH3; R3 and R4 are independently selected from one of hydrogen, fluorine or chlorine; R5, R6, R7, R8, and R9 are each selected from hydrogen; R10 and R11 are selected from hydrogen and chlorine.

5. A method for preparing a substituted oxime aromatic compound according to any one of claims 1 to 4, characterized in that: The substituted oxime aromatic compound shown in formula I is obtained through an amino compound, and the amino compound is shown in formula II:

6. A method for preparing a substituted oxime aromatic compound according to any one of claims 1 to 4, characterized in that: The substituted oxime aromatic compound represented by formula I is obtained by the compound represented by formula III, and the compound represented by formula III is as follows:

7. A herbicidal composition, characterized in that: The herbicidal composition comprises the following raw materials, calculated as 100% by mass: 30-60% of a substituted oxime aromatic compound and the remainder being an auxiliary agent; wherein the substituted oxime aromatic compound is a substituted oxime aromatic compound according to any one of claims 1 to 4 or a substituted oxime aromatic compound obtained by the preparation method according to claim 5 or claim 6.

8. The herbicidal composition according to claim 7, characterized in that The auxiliary agent is a modified stabilizer, and the preparation steps of the modified stabilizer are as follows: Sodium p-styrene sulfonate and deionized water are added to the reactor, the pH is adjusted to be weakly alkaline, N,N-dimethylacrylamide, vinyl pyrrolidone and allyl polyoxyethylene ether are added, an inert atmosphere is introduced, the temperature is raised to 60-80° C., an initiator is added, the reaction is carried out for 3-7 hours, and the modified stabilizer is obtained after washing and drying.

9. The herbicidal composition according to claim 8, characterized in that The mass ratio of sodium p-styrene sulfonate, N,N-dimethylacrylamide, vinyl pyrrolidone and allyl polyoxyethylene ether is (0.5-2):(1-4):(0.1-2):

10.

10. Use of the herbicidal composition according to any one of claims 7 to 9, characterized in that: The herbicidal composition is used for controlling weeds in useful crops; the useful crops include transgenic crops or crops treated with genome editing technology; the weeds include herbicide-resistant or -tolerant weed species.

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