WO2005068434A1 - 2-pyrimidionxy-n-carbamidophenylbenzylamine compounds and processes of the preparation thereof and the use of the same - Google Patents

Abstract

The present invention disclosed a series of 2-pyrimidionxy-N-carbamidophenylbenzylamine compounds and processes of the preparation thereof and the herbicide use of the same. The compounds represented by the following formula (I), wherein D or E is hydrogen, halogen, C1-C4 alkyl, C1-C4 akloxy, C1-C4 alkylogen or C1-C4 alkyloxygen, X is hydrogen, halogen, nitro-, cyano-, carboxyl, ester, sulfonyl, C1-C8 alkylamido, C1-C8 alkylamido halide, C1-C8 alkylacyl, C1-C8 alkyl, C1-C8 alkylogen, C1-C8 akloxy, phenyl, benzo-, substituted phenyl or heterocycle; R1R2 is hydrogen, ester, sulfonyl, C1-C8 alkyl, C1-C8 substituted alkyl, C1-C8 alkylacyl, phenyl or heterocycle; X' is H, cabamido, halogen, carboxyl, ester, C1-C8 alkylacyl, C1-C8 alkyl, C1-C8 alkyl halide, C1-C8 akloxy, phenyl, substituted phenyl or heterocycle et al; R3 is hydrogen, C1-C8 alkylacyl, C1-C8 alkylacyl halide, benzoyl, substituted benzoyl, C1-C8 alkyl.

Description

 2-pyrimidinyloxy-N-ureidophenylbenzylamine compound, preparation method and application thereof

 The present invention relates to a new class of 2-pyrimidinyloxy-N-ureidophenylbenzylamine compounds, a preparation method and uses thereof as agricultural chemical herbicides. Background technique

 Pesticides are an indispensable means of production for humans to obtain food and ensure stable and high yields in agriculture. In the past century, pesticides such as pesticides, fungicides, and herbicides have made great contributions to mankind. In recent years, with the continuous growth of the world ’s population, humans ’demand for food is also increasing, but the rate of cultivated land growth is far behind the rate of population growth. To solve this worldwide problem, we must rely on increasing the food per unit area. Yield and improvement of crop quality require various means, such as breeding, cultivation, fertilization, and the application of pesticides is also one of the essential means. However, it should be seen that, while pesticides have made great contributions to human civilization, due to cognitive limitations, highly toxic and high-residue pesticides have also negatively affected the environment on which humans depend. With the progress of society and the improvement of civilization, the development of high-efficiency, low-toxicity, easily degradable, safe and environmentally compatible green pesticides has been developed to replace those traditional pesticides with low efficiency, high toxicity, high residue and high resistance. Become the direction of new pesticide creation today.

 Pyrimidinyloxybenzene derivatives can be used as chemical herbicides, such as Agr. Biol. Chem., Vol. 30, P896 (1966); Japanese patent 79-55729; US patents 4,248,619 and 4,427,437. Recently, on the basis of pyrimidinyloxybenzene derivatives, a class of compounds having excellent herbicidal activity, a pyrimidinesalicylic acid derivative has been discovered, such as European patents 223,406, 249,708, 287,072, 287,079, 315,889, 321,846, 330,990, 335,409, 346,789, 363,040, 402,751, 435,170, 435,186, 457,505, 459,243, 468,690, 658,549, and 768034; Japanese patent 04368361; British patent 2,237,570; German patent 3,942,476, etc. Representative examples include: Pyrithiobac-sodium (KIH-2031, European Patent 315889), Bispyribac-sodium (KIH-2023, European Patent 321846), Pyriminobac-methyl , KIH-6127, Japanese Patent 04368361), Pyribenzoxim (European Patent 658549), and Cyclopsalid (Pyriftalid, European Patent 768034), their mechanism of action is the same as that of sulfonylurea herbicides, all of which are acetyl Inhibitors of lactic acid synthase (ALS) disrupt the synthesis of amino acids such as valine, leucine and isoleucine in plants. Although pyrimidinesalicylic acid compounds have high herbicidal activity, they are currently only applicable to weeding in cotton and rice fields.

1

Confirm this Lu Long et al. Reported a new class of pyrimidinyloxy benzyl substituted arylamine derivatives, preparation methods and their applications as agricultural chemical herbicides (CN 00130735.5 and CN01112689.2). However, at present, the number of new pesticides with independent intellectual property rights in China is very limited. Therefore, the development of new pesticides is still a research topic for people. Summary of invention

 The present invention provides a new compound, that is, 2-pyrimidinyloxy-N-ureidophenylamine compounds, and also provides a method for preparing the above compounds and uses as an agricultural chemical herbicide. The compound has the structural formula such as

Summary of the invention

 The problem to be solved by the present invention is to provide a new compound, that is, a 2-pyrimidinyloxy-N-ureidophenylbenzylamine compound.

 The problem to be solved by the present invention is to provide a method for preparing the aforementioned compound.

 Another problem to be solved by the present invention is to provide a use of the above compound.

 The invention provides a 2-pyrimidinyloxy-N-ureidophenylbenzylamine compound having the structural formula shown in (I):

(I) among them-

D and E may be the same or different groups, which are hydrogen, halogen, Q—C ₄ fluorenyl, —C ₄ alkoxy, Q—C ₄ haloalkyl, or Q—C ₄ halofluorenyl, It is particularly preferred that both D and E are methoxy.

X is hydrogen, halogen, nitro, cyano, carboxyl, ester, sulfonyl, Q-C ₈ fluorenyl, d-C ₈ halofluorenyl, d-C ₈ alkoxy, C plant C ₈ acyl , D—C ₈ amidamido, Q—C ₈ haloalkanoyl, phenyl, benzoyl, substituted phenyl, heterocyclyl or substituted heterocyclyl, etc., it is recommended that X be H or methoxy, X be in benzene The ring can be in any one, two, or more of the 3, 4, 5, and 6 positions.

 R2

X 'is H, ureido (H ₂ Nl' ^N , ^R1 , the substituents on the ureido are and), halogen atom, carboxyl

 0

Group, ester group, d-C ₈ alkyl group, Q-C ₈ haloalkyl group, Q-C ₈ alkoxy group, d-C ₈ alkanoyl group, phenyl group, substituted phenyl group, heterocyclic group or substituted heterocyclic group. 11 is an integer from 1 to 4. X is mono-, di- or poly-substituted on the benzene ring.

Is hydrogen, ester, sulfonyl, —C ₈ alkyl, substituted d—C ₈ fluorenyl (halogen or mono C ₈ alkoxy substituted fluorenyl may be mono-, di-, or poly-substituted, For example, CH ₂ OC¾, CH ₂ C1, CF _3, etc.), monoalkoxy, monoalkanoyl, phenyl, substituted phenyl, heterocyclyl or substituted heterocyclyl, or _Rh R _{2 is} connected as-( CH ₂ ) _m Z (CH ₂ ) _k- , where Z is CH ₂ , NH, 0 or S, and m and k are integers from 1 to 6. It is recommended that R is H, n-butyl or n-butyl, n-butyl, or, connected to-(C¾) 5-. RR ₂ is the same or different group. Wherein the ureido group (() N.ΟΝ —) can be in the ortho, meta or para position of the benzene ring, or it can contain ureido group and other substituents, such as halogen, carboxyl, ester group, —C ₈垸 group, — C halogenated alkyl with _8, a ¾-alkoxy, d-C _s alkyl group, a phenyl group, a substituted phenyl group, a heterocyclic group or substituted heterocyclic group.

R ₃ = hydrogen, d-C ₈ amidino, d-C ₈ haloalkanoyl, benzoyl, substituted benzoyl, d-C ₈ amidino.

Wherein the heterocyclic group such as pyridyl, thienyl, thiazolyl, pyrimidinyl, etc., the substituted phenyl, substituted heterocyclic group or substituted benzoyl group is preferably halogen, nitro, cyano , a carboxyl group, an ester group, a sulfonyl group, d -C ₈ alkyl, d- C _{mechanized. 8} haloalkyl group, d- embankment group, C factory _{wide. 8} C C C alkanoyl or alkanoylamino group and the _{like. 8;} the Substituted phenyl, substituted heterocyclyl or substituted benzoyl are recommended as mono-, di- or poly-substituted. The recommended compounds of the present invention have the following structural formula:

Below, we list some typical compounds of the present invention in the table.

 Table I

Compound DEX (R! R ₂ ) NC Ri R ₂ R ₃ (X ') n Material ONH-

 Location

 1- 1 OMe OMe H Para Et Et H H

1-2 OMe OMe H meta Et Et H H

1-3 OMe OMe 6-C1 meta Et Et H H

1-4 OMe OMe 6-OMe meta Et Et H H

1—5 OMe OMe H meta ⁿ Pr "Pr HH

1-6 OMe OMe 6-C1 meta ⁿ Pr ⁿ Pr HH

1-7 OMe OMe 6-MeO meta ⁿ Pr ⁿ Pr HH

1-8 OMe OMe H Para ⁿ Bu "Bu HH

1-9 OMe OMe H meta ⁿ Bu "Bu H H- 10 OMe OMe 6-C1 meta ⁿ Bu ⁿ Bu H H- 11 OMe OMe 6-MeO meta ⁿ Bu ⁿ Bu H H- 12 OMe OMe H pair Bit (CH ₂ ) ₅ (CH ₂ ) ₅ HH -13 OMe OMe H paraposition Ij ^^ OEt HHH-14 OMe OMe H paraposition HHH

 Me

-15 OMe OMe H para HHH-16 OMe OMe H meta HHH-17 OMe OMe H para HHH-18 OMe OMe H meta HHH-19 OMe OMe 6-OMe meta HHH -20 OMe OMe 6-F Bit ⁿ Bu ⁿ Bu H H-21 CI OMe H 3-position COOMe CF ₃ CH ₃ CO 4- CI-22 Me OMe COOH 3-position H MeO CICH2CO 5-NHCONH ₂ -23 CI Me H 3-position H COOMe Me 5-OMe where Me represents methyl, Et represents ethyl, ⁿ Pr represents n-propyl, and ⁿ Bu represents n-butyl. The compound 2-pyrimidinyloxy-N-ureidophenylbenzylamine compounds related to the present invention can be synthesized by the following reaction steps:

In the above reaction formula, the substituents represented by R ₂ , X, X ′, n, D, and E are as described above, and Y is halogen or methylsulfone. The starting material (II) in the reaction can be prepared by the following reaction:

 (11-3)

In the formula, R is halogen, nitro, cyano, carboxyl, ester, sulfonyl, —C ₈ alkyl, —C ₈ haloalkyl,. Broad alkoxy, Q_C ₈ alkanoyl, or -C ₈ amidamido and the like. Intermediate (Π -1) synthesis can be prepared by reducing nitrophenyl urea. It can be prepared by reducing nitrophenyl urea with hydrogen under the action of a catalyst. The catalyst can be Raney Ni, palladium carbon or For platinum black, etc., the molar ratio of substituted nitroaniline, hydrogen and catalyst is recommended to be 1: (1—1000): (0.01 -0.5). Using more hydrogen has no effect on the reaction. The reaction temperature is recommended from room temperature to 40 ° C. The reaction time is recommended from 0.5 to 10 hours. The recommended solvents can be hydrocarbon solvents such as benzene, toluene or xylene; ether solvents such as tetrahydrofuran or dioxane; methanol, ethanol Or an alcohol solvent such as isopropyl alcohol; dimethylformamide, dimethylsulfoxide, acetonitrile, and a mixture of the above solvents can also be used, and the solvent of the reaction is more preferably an alcohol. The intermediate (II-1) can also be prepared by reducing and replacing nitrophenylurea with hydrazine hydrate under the action of a catalyst. The catalyst may be Raney Ni, etc., which replaces nitroaniline, hydrazine hydrate and the catalyst. The molar ratio is recommended to be 1: (1 -1.5): (0.01-0.5), using more hydrazine hydrate has no effect on the reaction. The reaction temperature is recommended to be room temperature to 40 ° C, and the reaction time is recommended to be 0.5 to 10 hours. The recommended solvents can be hydrocarbon solvents such as benzene, toluene or xylene; ether solvents such as tetrahydrofuran or dioxane; methanol, ethanol or Alcohol solvents such as isopropyl alcohol; dimethylformamide, dimethyl sulfoxide, acetonitrile, and a mixture of the above solvents can also be used. The solvent for this reaction is further recommended as an alcohol. Nitrophenyl urea synthesis can be prepared by reacting nitrophenyl isocyanate with a substituted fatty amine, and the molar ratio is recommended to be 1: 1 to 1: 2. The recommended solvent may be a hydrocarbon solvent such as benzene, toluene or xylene; an ether solvent such as tetrahydrofuran or dioxane; and the solvent for the reaction is further recommended as benzene. The reaction temperature is preferably 5 ° C to room temperature, and the reaction time is preferably 0.5 to 12 hours. Intermediate (Π-2) synthesis can be prepared by reducing nitrophenyl to replace aryl urea. Reduction conditions can be the same as those of intermediate (Π-1) synthesis. Nitrophenyl substituted aryl synthesis can be performed by nitroaniline and substitution. Aromatic isocyanate is prepared by reaction, and the molar ratio is recommended to be 1: 1 to 1: 1.5. The recommended solvent may be a hydrocarbon solvent such as benzene, toluene, or xylene; an ether solvent such as tetrahydrofuran or dioxane; and the solvent for this reaction is further recommended as tetrahydrofuran. The reaction temperature is preferably from room temperature to reflux, and the reaction time is preferably from 8 to 48 hours. Intermediate (Π-3) synthesis can be prepared by reducing p-nitrophenyl fatty urea, and the reduction conditions can be the same as those of intermediate (Π-1). The synthesis of p-nitrophenyl fatty urea can be performed by the following method Synthesis: Dissolve p-nitroaniline in hot glacial acetic acid, add sodium cyanate, the recommended molar ratio is 1: 1 to 1: 5, and filter to obtain p-nitrophenylurea. The p-nitrophenyl urea is refluxed in dibutylamine or hexahydropyridine to obtain p-nitrophenyl fatty urea. The method for synthesizing the starting material (II) containing a (X ′) n substituent on the benzene ring is the same as the above-mentioned reaction method.

 The intermediate (III) can be synthesized by reacting ureido-substituted aniline (Π) with salicylaldehyde or substituted salicylaldehyde. The molar ratio is recommended to be 1: 0.8 ~ 2, and further recommended to be 1: 1 to 1: 2. Recommended solvents can be hydrocarbon solvents such as benzene, toluene or xylene; halogenated hydrocarbon solvents such as dichloromethane, dichloroacetamidine, or chloroform; ether solvents such as tetrahydrofuran or dioxane; acetone or methyl isobutyl Ketone solvents such as ketones; alcohol solvents such as methanol, ethanol, or isopropanol; dimethylformamide, dimethyl sulfoxide, acetonitrile, and mixtures of the above solvents can also be used, and the solvents for this reaction are further recommended as alcohols. The reaction temperature is preferably from room temperature to the boiling point of the solvent, and the reaction time is preferably from 0.5 to 12 hours. The reaction can be performed without a catalyst. The addition of a catalyst can sometimes speed up the reaction speed and increase the reaction yield. The catalyst used in the reaction can be p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, hydrochloric acid or acetic acid, etc. (Π The molar ratio of) to catalyst is recommended to be 1: 0.01-1.

The intermediate (IV) can be synthesized by reducing compound (III). The reducing agent is recommended to be sodium borohydride or potassium borohydride. The molar ratio of reactant (III) to reducing agent is recommended to be 1: 0.5-2. The reaction temperature Recommended room temperature to 40 degrees Celsius, reaction time recommended 0.5 to 10 hours, recommended solvents can be hydrocarbon solvents such as benzene, toluene or xylene; ether solvents such as tetrachlorofuran or dioxane; methanol, ethanol or Alcohol solvents such as isopropanol; dimethylformyl- A mixture of amine, dimethyl sulfoxide, acetonitrile, and the above-mentioned solvents, and the solvent of the reaction is more preferably an alcohol. In addition, the intermediate (IV) can also be prepared by reducing the compound (III) with hydrogen under the action of a catalyst. The catalyst is recommended to be Raney Ni, palladium carbon, platinum black, etc., the reactant (II), hydrogen The molar ratio to the catalyst is recommended to be 1: 1 to 1000: 0.01 -0.5. Using more hydrogen has no effect on the reaction. The reaction temperature is recommended to be room temperature to 40 ° C, and the reaction time is recommended to be 0.5 to 10 hours. The recommended solvents can be hydrocarbon solvents such as benzene, toluene or xylene; ether solvents such as tetrahydrofuran or dioxane; methanol, ethanol or Alcohol solvents such as isopropyl alcohol; dimethylformamide, dimethyl sulfoxide, acetonitrile, and a mixture of the above solvents can also be used. The solvent for this reaction is more preferably an alcohol.

Finally, the intermediate (IV) is reacted with 2-halo-4-D, 6-E-substituted pyrimidine or 2-methylsulfo-4-D, 6-E-substituted pyrimidine in the presence of a base to obtain the target. Product (I) (R ₃ = H). In this step, it is recommended that the base used is a hydride of a monovalent or divalent metal, an alkoxy metal compound or a carbonate thereof, such as sodium hydride, potassium hydride, calcium hydride ; Sodium methoxide or sodium ethoxide, potassium methoxide or potassium ethoxide; sodium carbonate, potassium carbonate, or calcium carbonate, etc .; or an organic base such as triethylamine, pyridine, or the like. Recommended reaction solvents can be hydrocarbon solvents such as benzene, toluene or xylene; halogenated hydrocarbon solvents such as dichloromethane, dichloroacetamidine or chloroform; ether solvents such as tetrahydrofuran or dioxane; acetone or methyl isobutyl Ketone solvents such as methyl ketone; alcohol solvents such as methanol, ethanol, or isopropanol; dimethylformamide, dimethylsulfoxide, acetonitrile, and mixtures of the above solvents can also be used. The best solvent for this reaction is ethers. The reaction temperature is preferably from room temperature to the boiling point of the solvent, and the reaction time is preferably from 0.5 to 20 hours. The molar ratio of intermediate (IV), 2-halo-4-D, 6-E-substituted pyrimidine or 2-methylsulfonyl-4-D, 6-E-substituted pyrimidine to base is recommended to be 1.0: 1.2 : 1-5. The final product can be further purified by silica gel column chromatography or recrystallization.

The target product (I) (R ₃ = H) is reacted with an acid chloride or a halogenated hafnium R ₃ C1 (R ₃ ≠ H) in a solvent and in the presence of a base to obtain the target product (I) (R ₃ ≠ H) at a reaction temperature At room temperature to the boiling point of the solvent, the solvent and base are as previously described.

 Unless otherwise stated, the alkyl, substituted fluorenyl, alkoxy, halofluorenyl, halofluorenyl, ester, alkanoyl, alkylamide, and haloalkylamide groups in the present invention refer to straight or branched chain. The chain group is preferably 1 to 8 carbons, and further preferably 1 to 4 carbons.

Unless otherwise stated, the ester group mentioned in the present invention is preferably an alkoxycarbonyl group, a phenoxycarbonyl group or a substituted phenoxycarbonyl group with a carbon number of 1 to 8, and further an alkoxycarbonyl group, a phenoxycarbonyl group with a carbon number of 1 to 4 Or substituted phenoxycarbonyl group; the sulfonyl group mentioned in the present invention is recommended to be an alkylsulfonyl group, a phenylsulfonyl group or a substituted phenylsulfonyl group, and further recommended to be a carbon number of 1 to 4 Alkylsulfonyl, phenylsulfonyl or substituted phenylsulfonyl; The substituted phenoxycarbonyl or substituted phenylsulfonyl is recommended to be mono-, di- or poly-substituted, and the substituents are preferably halogen, nitro , a cyano group, a carboxyl group, an ester group, a sulfonyl group, - alkyl with, d _C ₈ alkyl with halo, d-C ₈ alkoxy embankment, d alkanoyl or a C ₈ - C ₈ alkanoylamino group. The invention provides the use of the aforementioned 2-pyrimidinyloxy-N-ureidophenylbenzylamine compound, that is, it can be used as a herbicide.

 The compound of the present invention is used as an active ingredient of a pesticide chemical herbicide, and is formulated into various liquids, emulsifiable concentrates, suspensions, suspensions, microemulsions, (water) emulsions, powders, wettable powders, soluble powders, (water Dispersible) granules or capsules can be used for weed control in crops such as rice, soybean, wheat, cotton, corn and rape.

 The weight percentage of the active ingredient in the preparation is recommended to be 5 to 90%, and the rest are carriers. The carrier includes at least two kinds, at least one of which is a surfactant. The carrier can be a solid or a liquid. Suitable solid carriers include natural or synthetic clays and silicates such as natural silica and diatomaceous earth; magnesium silicates such as talc; magnesium aluminum silicates such as kaolinite, kaolin, montmorillonite, and mica; white carbon black , Calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; amine salts such as ammonium sulfate, hexamethylene diamine. Liquid carriers include water and organic solvents. When water is used as a solvent or diluent, organic solvents can also be used as adjuvants or antifreeze additives. Suitable organic solvents include aromatic hydrocarbons such as benzene, xylene, toluene, etc .; chlorinated compounds such as chlorobenzene, vinyl chloride, chloroform, dichloromethane, etc .; aliphatic hydrocarbons such as petroleum fractions, cyclohexane, light weight Mineral oils; alcohols such as isopropanol, butanol, ethylene glycol, glycerol and cyclohexanol; and their ethers and esters; and ketones such as acetone, cyclohexanone, and dimethylformamide And N-methyl-pyrrolidone.

Surfactants can be emulsifiers, dispersants or wetting agents; they can be ionic or non-ionic. Non-ionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty ammonia, and commercially available emulsifiers: agricultural milk 2201B, agricultural milk 0203B, agricultural milk 100 ^# , agricultural milk 500 ^# , Agricultural milk 600 ^# , Agricultural milk 600-2 ^# , Agricultural milk 1601, Agricultural milk 2201, Agricultural milk NP-10, Agricultural milk NP-15, Agricultural milk 507 ^# , Agricultural milk OX-635, Agricultural milk OX-622, Agricultural Milk OX-653, agricultural milk OX-667, Ning Ru 36 ^# . Dispersants include sodium ligninsulfonate, pulverized powder, calcium ligninsulfonate, methylnaphthalenesulfonic acid methyl ester condensate, and the like. Wetting agents are: sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, and the like.

 These preparations can be prepared by a general method. For example, the active substance is mixed with a liquid solvent and / or a solid carrier, and a surfactant such as an emulsifier, a dispersant, a stabilizer, a wetting agent is also added, and other auxiliary agents such as a binder, an antifoaming agent, and an oxidizing agent may be added. Wait.

 The herbicidally active compound of the present invention can be mixed with pesticides, fungicides, nematicides, plant growth regulators, fertilizers, and other herbicides or other agricultural chemicals. The compound of the present invention and its preparation have the following characteristics and advantages:

 1. It has effective herbicidal activity, and shows good post-emergent herbicidal effect at low doses of 30 to 75 gai / ha, and good pre-emergent herbicidal effect at slightly higher doses of 75 to 150 gai / ha.

2. A broad spectrum of weed control, which can not only effectively control grass weeds in farmland, but also broad-leaved weeds and sedges. 3. It has good selectivity and is safe for certain crops, such as: wheat, soybean, cotton, rice, etc.

 4. It also has very effective herbicidal activity against older sensitive weeds.

 5. The residual period in the soil is short, and it has no adverse effect on the growth of subsequent crops.

 6. It has reasonable toxicity, ecotoxicity and environmental compatibility, and is a low-toxic environment-friendly pesticide.

The compound of formula (I) provided by the present invention has not only a simple synthetic method, but also herbicidal activity and crop selectivity, and can be used as a herbicide. Its preparation can effectively control most farmland weeds, and it can effectively control sensitive grasses, broad-leaved weeds, and sedges at lower doses. CrusgalU J igitaria sanguinalis, goose grass (E

) Poa annua (Poa annua) ^ Wild oats (wfir fatua, ¾ "¾ ¾ Alopecurus aequalis) Japan watch Mai Niang (Alopecurus japonicus),

Chenopodium albu, ^^ (Br as sic a juncea) ^ portulaca okracea, Acalypha australis, Qyer s difformis ^ LeptocMoa chinemis, Operas rotundus ~), mjr z fc miliaced, stellaria (βίαΙΙατία media) ^ Stellaria alsine, Erigeron annuus, Sagittaria sagittifolia, field swirling flower (Convolvulus arvensis) and so on. detailed description

 The following examples are helpful for understanding the present invention, but the present invention is not limited to the scope of the following examples. In the embodiment where the compound of the present invention is used as an active material component to process several herbicide formulations, all "%" means weight percentages, and "g ai / ha" means per gram of active matter / ha. Example 1

 1. Synthesis of intermediate (II)

 (a) Synthesis of intermediate (II- 1)

 Step 1: Take the synthesis of 1-p-nitrophenyl-3-diethylurea as an example: Under the protection of argon, add a 0.8 mL (5 mmol) to a 100 mL three-necked flask with a thermometer and a dropping funnel. ) P-nitrophenyl isocyanate and 5 mL of anhydrous benzene, 0.57 mL (5.5 mmol) of diethylamine dissolved in 5 mL of anhydrous benzene, cooled to 0-10 ° C, added dropwise to the reaction solution, and stirred after the addition About 30min, spin-dried and purified by column chromatography with a yield of 98%.

Second step: Nitro reduction: 5 mmoll-p-nitrophenyl-3-diethylurea was dissolved in 20 mL of anhydrous methanol, 90 mg of Raney Ni was added, and 0.469 g (7.5 mmol) of 80% hydrated Add hydrazine dropwise to the reaction solution at room temperature Stir until the reaction is complete, TLC controls the end of the reaction. After filtration, the filtrate was spin-dried to obtain 1.035 g of 1-p-aminophenyl-3-diethylurea in a yield of 99%.

 (b) Synthesis of intermediate (Π-2)

 Step 1: Take the synthesis of 1-p-nitrophenyl-3- (2,4-difluorophenyl) urea as an example: Under the protection of argon, add 20 mL of anhydrous THF, 3 drops to a 50 mL Schlenck tube. Triethylamine and 1.38 g (10 mmol) of p-nitroaniline were dissolved in 1.20 mL (10 mmol) of 2,4-difluorophenyl isocyanate in 10 mL of anhydrous THF, and slowly added dropwise to the reaction solution at room temperature. Reflux until the reaction is complete, TLC controls the end of the reaction. Spin-dried and recrystallized from ethyl acetate in 52% yield.

 Second step: Nitro reduction: 5 mmoll-p-nitrophenyl-3- (2,4-difluorophenyl) urea was dissolved in 20 mL of anhydrous methanol, 90 mg of Raney Ni was added, and 0.469 g (7.5 80% of hydrazine hydrate was added dropwise to the reaction solution, and stirred at room temperature until the reaction was completed. TLC controlled the end of the reaction. After filtration, the filtrate was spin-dried to obtain 3.1 mmol of 1-p-aminophenyl-3- (2,4-difluorophenyl) urea in a yield of 62%.

 (c) Synthesis of intermediate (II-3)

 Step 1: Take the synthesis of 1-p-nitrophenyl-3-piperidinyl urea as an example: 2.5 g of p-nitroaniline is dissolved in 12.5 mL of hot glacial acetic acid, and 2 g of sodium cyanate is added to the reaction. The solution was quickly filtered while hot, poured into ice water, filtered and dried, and recrystallized from glacial acetic acid to obtain 1.554 g of p-nitrophenylurea in a yield of 47.4%. 1.554 g of p-nitrophenylurea and 15.5 mL of piperidine were heated under reflux for 8 hours, cooled to room temperature, and spin-dried. Column chromatography (petroleum ether: ethyl acetate = 1: 2) yielded 1.613 g of pure product with a yield of 75.4%.

 Second step: Nitro reduction: 5 mmoll-p-nitrophenyl-3-piperidinyl urea was dissolved in 20 mL of anhydrous methanol, 90 mg of Raney Ni was added, and 0.469 g (7.5 mmol) of 80% hydrated Hydrazine was added dropwise to the reaction solution and stirred at room temperature until the reaction was complete. TLC controlled the end of the reaction. After filtration, the filtrate was spin-dried to obtain 5 mmol of 1-p-aminophenyl-3-piperidinylurea in a yield of 99%.

2. Synthesis of 2-pyrimidinyloxy-N-arylbenzylamine compounds

Take 1 -1 synthesis as an example:

 Step 1: Condensation with salicylaldehyde: 4: 9 mmol of l-p-aminophenyl-3-diethylurea and 0.717 g (5.88 mmol) of salicylaldehyde are dissolved in 15 mL of methanol, and stirred at room temperature until the reaction Completely, TLC controls the endpoint of the reaction. Filtration gave 1.31 g of a yellow solid (III) in a yield of 86%.

Step 2: Schiff base reduction: Add 1.31 g of yellow solid (II) to 20 mL of absolute ethanol, add 0.242 g (6.18 mmol) of 97% sodium borohydride in portions, stir at room temperature for 30 min, and pour into ice Water, acetic acid The ethyl acetate was extracted three times, and the organic phases were combined, and the saturated brine and water were washed once, dried over anhydrous sodium sulfate, filtered and spin-dried to obtain the product (IV), with a yield of 99%.

 Step 3: Condensation with pyrimidine sulfone:

 Method a: 1.310 g (4.2 mmol) of imine-reduced product (IV), 0.916 g (4.2 mmol) of pyrimidine sulfone and 1.159 g (8.4 mmol) of anhydrous potassium carbonate in 50 mL of 1,4-dioxane 8-9h at reflux, TLC controls the end of the reaction. Cool to room temperature, filter, spin dry, and perform column chromatography (petroleum ether: ethyl acetate = 2: 1) to obtain pure product 1-1. The yield is 92%.

 Method b: 1.310 g (4.2 mmol) of imine-reduced product (IV), 0.916 g (4.2 mmol) of pyrimidine sulfone and 1.159 g (8.4 mmol) of anhydrous potassium carbonate in 20 mL of DMF at room temperature for 8-9 h, TLC Control the endpoint of the reaction. The reaction solution was poured into 800 mL of water, and extracted with ethyl acetate three times. The organic phases were combined, washed with saturated brine and once with water, dried over anhydrous sodium sulfate, filtered and spin-dried, and subjected to column chromatography (petroleum ether: ethyl acetate = 2). : 1) The pure product 1 -1 was obtained with a yield of 85%.

Solid

m.p .: 124.4 ± 0.5 ° C

1H NMR (300 MHz, CDC1 ₃ / TMS): δ 1.23 (6H, t, CH ₃ , J = 7.5Hz), 3.35 (4H, q, CH ₂ , J = 6.6Hz), 3.82 (6H, s, OCH ₃ ), 4.31 (2H, s, CH ₂ ), 5.78 (1H, s, CH), 6.09 (1H, s, NH), 6.54-7.47 (8H, m, CH)

 MS (EI): 245 (m / z, 100), 451 (M +., 5.41)

IR (KBr / cm ' ¹ ): 3365 (γ _Ν-Η ), 1635 (y _c = o), 1602, 1520, 1493 ( _Yc = c), 1569 (γο _Ν ), 1218 (y = _C -oc) EA for C ₂₄ H ₂₉ N ₅ 0 ₄ Calcd: C 63.84, H 6.47, N 15.51

Found: C 63.72, H 6.36, N 15.82 Example 2

 The synthesis of 1-2. The detailed experimental steps are the same as in Example 1: (1) Condensation with salicylaldehyde: 5.21 mmoll-m-aminophenyl-3-diethylurea, and 1.620 g of imide are obtained by filtration. Yield 99%. (2) Schiff base reduction: 5.21 mmol of imine was charged to obtain 1.630 g (5.21 mmol) of the product with a yield of 99%. (3) Condensation with P-pyridine sulfone: 1.630 g (5.21 mmol) of the imine-reduced product, and column chromatography (petroleum ether: ethyl acetate = 2: 1) to obtain a pure product with a yield of 85%.

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0ZZ, 000 / 1O0ZN3 / 13d 890 / S00Z ΟΛ \ There was obtained 2.639 g (7.694 mmol) of the product with a yield of 96%. (4) Condensation with pyrimidine sulfone: Synthesized by method b, with a charge of 2.637 g (7.694 mmol) of the imine-reduced product, and column chromatography (petroleum ether: ethyl acetate = 2: 1) to obtain a pure product, yield 87 %.

Solid

m.p .: 127.5 ± 0.5 ° C

1H NMR (300 MHz, CDC1 ₃ / TMS): δ 1.24 (6H, t, CH ₃ , J = 8.43Hz), 3.35 (4H, q, CH ₂ , J-7.14Hz), 3.77 (6H, s, OCH ₃ ), 3.87 (3H, s, OCH ₃ ), 4.32 (2H, s, CH ₂ ), 5.73 (1H, s, CH), 6.16-7.23 (7H, m, CH)

MS (EI): 275 (m / z, 100), 481 (M + l, 2.01)

IR (KBr / cm ' ¹ ): 3430 (γ _Ν-Η ), 3289 (γ _Ν-Η ), 1636 (γο = ο), 1612, 1572, 1520 (γα = α), 1589 (y _c = _N ) , 1222 (Y = _C -oc)

EA for C ₂₅ H ₃₁ N ₅ 0 ₄ Calcd: C 62.36, H 6.49, N 14.54

Found: C 62.55, H 6.50, N 14.65 Example 5

 For the synthesis of 1-5, the detailed experimental steps are the same as in Example 1: (1) Condensation with salicylaldehyde: 3.434 mmol of amino compound, spin-dry and go directly to the next step. (2) Schiff base reduction: 3.434 mmol of imine is charged to obtain 1.171 g (3.434 mmol) of the product with a yield of 99%. (3) Condensation with pyrimidine sulfone: Synthesized by method a. The input amount of 1.171 g (3.434 mmol) of the imine-reduced product was purified by column chromatography (petroleum ether: ethyl acetate = 2: 1), yield 76. %. Solid

m.p .: 132.5 ± 0.5 ° C

1H NMR (300 MHz, CDC1 ₃ / TMS): δ 0.96 (6H, t, CH ₃ , J = 7.2Hz), 1.58-1.70 (4H, m, CH ₂ ), 3.25 (4H, t, C¾, J = 7.5Hz), 3.82 (6H, s, OCH ₃ ), 4.33 (2H, s, CH ₂ ), 5.78 (1H, s, CH), 6.02-7.48 (8H, m, CH)

MS (EI): 245 (m / z, 100), 479 (M + ', 2.70)

IR (KBr / cm ^-1 ): 3440 (γ _Ν-Η ), 3331 (γ _Ν-Η ), 1641 (y _c = ₀ ), 1603, 1529, 1483 (y _c = c), 1569 (γοΝ), 1222 (Y = _C- OC)

EA for C ₂₆ H ₃₃ N ₅ 0 ₄ Calcd: C 65.12, H 6.94, N 14.60

Found: C 64.89, H 6.87, N 14.39 Example 6

 For the synthesis of 1-6, the detailed experimental steps are the same as those in Example 1: (1) Condensation with 6-chlorosalicylic aldehyde: Amount of 5 mmol of amino compound, spin-drying and directly into the next step, the yield is 99%. (2) Schiff base reduction: 5 mmol of imine is charged to obtain 1.887 g (5 mmol) of the product with a yield of 99%. (4) Condensation with pyrimidine sulfone: Synthesized by method b. The input amount of 1.887 g (5 mmol) of the imine-reduced product was obtained by column chromatography (petroleum ether: ethyl acetate = 5: 1). The pure product was obtained in a yield of 80. %.

Solid

m.p .: 90.1 ± 0.5 ° C

1H NMR (300 MHz, CDC13 / TMS): δ 0.94 (6H, t, CH ₃ , J = 7.5Hz), 1.57-1.70 (4H, m, CH ₂ ), 3.24 (4H, t, CH ₂ , J = 7.5Hz), 3.79 (6H, s, OCH ₃ ), 4.45 (2H, s, CH ₂ ), 5.76 (1H, s, CH), 6.23 (1H, s, NH), 6.31-7.31 (7H, m, CH)

MS (EI): 157 (m / z, 100), 513 (M "., 15.36)

IR (KBr / cm " ¹ ): 3438 (γ _Ν-Η ), 3373 (γ _Ν-Η ), 1641 (γο ₀ ), 1596, 1545, 1484 (y _c = c), 1230 (Y = _C -OC ) EA for C ₂₆ H ₃₂ C1N ₅ 0 ₄ Calcd: C 60.75, H 6.27, N 13.62

Found: C 60.58, H 6.22, N 13.58 Example 7

 For the synthesis of I-7, the detailed experimental steps are the same as in Example 1: (1) Condensation with 6-methoxysalicylic aldehyde: Amount of 5.4 mmol of amino compound, spin-drying and directly into the next step, the yield is 99%. (2) Schiff base reduction: 5.4 mmol of imine is charged to obtain 1.984 g (5.35 mmol) of the product with a yield of 99%. (4) Condensation with pyrimidine sulfone: Synthesized by method b, with a charge of 2.637 g (7.694 mmol) of the imine-reduced product, and column chromatography (petroleum ether: ethyl acetate = 2: 1) to obtain a pure product with a yield of 85. %.

Solid

m.p .: 126.0 ± 0.5 ° C

1H NMR (300 MHz, CDC1 ₃ / TMS): δ 0.87 (6H, t, CH ₃ , J = 9Hz), 1.58-1.70 (4H, m, CH ₂ ), 3.24 (4H, t, CH ₂ , J = 6.5Hz), 3.78 (6H, s, OCH ₃ ), 3.88 (3H, s, OCH ₃ ), 4.33 (2H, s, CH ₂ ), 5.74 (1H, s, CH), 6.17 (1H, s, NH ), 6.29-7.28 (7H, m, CH)

MS (EI): 275 (m / z, 100), 509 (Μ ⁺ ·, 2.70)

IR (cm- ¹ ): 3433 (γ _Ν-Η ), 3333 (γ _Ν-Η ), 1643 (γο ₀ ), 1600, 1552, 1480 (y _c = c), 1576 (γ _{α = Ν} ), 1196 (Y = coc) EA for C ₂₇ H ₃₅ N ₅ 0 ₅ Calcd: C 63.64, H 6.92, N 13.74

Found: C 63.44, H 6.90, N 13.46 Example 8

 For the synthesis of I-8, the detailed experimental steps are the same as in Example 1: (1) Condensation with salicylaldehyde: 3.35 mmol of amino compound was fed, and 1.229 g of imine was obtained by filtration, with a yield of 99%. (2) Schiff base reduction: 3.3 mmol of imide is charged to obtain 1.218 g (3.3 mmol) of the product with a yield of 99%. (3) Condensation with pyrimidine sulfone: Synthesized by method a. The amount of the imine-reduced product was 1.218 g (3.3 mmol). Column chromatography (petroleum ether: ethyl acetate = 2: 1) yielded pure product. Yield: 90. %.

Solid

m.p .: 118.0 ± 0.5 ° C

1H NMR (300 MHz, CDC13 / TMS): δ 0.95 (6H, t, CH ₃ , J = 7.2Hz), 1.28-1.41 (4H, m, CH ₂ ), 1.53-1.63 (4H, m, CH ₂ ) , 3.25 (4H, t, CH ₂ , J = 7.2Hz), 3.82 (6H, s, OCH ₃ ), 4.30 (2H, s, CH ₂ ), 5.77 (1H, s, CH), 6.01 (1H, s , NH), 6.54 (2H, d, CH, J = 8.7Hz), 7.08-7.45 (6H, m, CH) MS (EI): 275 m / z, 100), 507 CM ', 5.14)

IR (KBr / cm " ¹ ): 3354 (γ _Ν — _H ), 1631 (y _c = o), 1600, 1521, 1490 (y _c = _c ), 1572 (γ _α = _Ν ), 1220 (y = _C -oc) EA for C ₂₈ H ₃₇ N ₅ 0 ₄ Calcd: C 66.25, H 7.35, N 13.80

Found: C 66.10, H 7.29, N 13.72 Example 9

 For the synthesis of 1-9, the detailed experimental steps are the same as in Example 1: (1) Condensation with salicylaldehyde: The amount of 3 mmol of amino compound is charged, and it is spin-dried directly to the next step. (2) Schiff base reduction: 3 mmol of imine is charged to obtain 1.099 g (2.98 mmol) of the product with a yield of 99%. (3) Condensation with pyrimidine sulfone: Synthesized by method a or b. The feed amount is 1.099 g (2.98 mmol) of the imine-reduced product, and column chromatography (petroleum ether: ethyl acetate = 2: 1) is used to obtain the pure product. The yield was 75.2%. Solid

m.p .: 96.3 ± 0.5 ° C

1H NMR (300 MHz, CDC1 ₃ / TMS): δ 0.95 (6H, t, CH ₃ ), 1.30-1.39 (4H, m, CH ₂ ), 1.54-1.61 (4H, m, CH ₂ ), 2.63 (1H , s, NH), 3.27 (4H, t, CH ₂ , J = 7.5Hz), 3.77 (1H, m, NH), 3.81 (6H, s, OCH ₃ ), 4.35 (2H, s, CH ₂ ), 5.77 (1H, s, CH), 6.23-7.49 (8H, m, CH)

MS (EI): 245 (m / z, 100), 507 (Μ + ·, 21.78) IR (KBr / cm " ¹ ): 3419 (γ _Ν-Η ), 3309 (γ _Ν-Η ), 1637 (y _c = o), 1600, 1535, 1455 ( _Yc = _c ), 1569 (γ ₀ = _Ν ) EA for C ₂₈ H ₃₇ N ₅ 0 ₄ Calcd: C 66.25, H 7.35, N 13.80

Found: C 66.10, H 7.29, N 13.72 Example 10

 For the synthesis of I-10, the detailed experimental steps are the same as those in Example 1: (1) Condensation with 6-chlorosalicylic aldehyde: the amount of 3 mmol of amino compound was filtered to obtain 1.003 g of imine, with a yield of 83%. (2) Schiff base reduction: 2.5 mmol of imine is charged to obtain 0.824 g (2.042 mmol) of the product with a yield of 82%. (4) Condensation with pyrimidine sulfone: Synthesized by method b, 0.824 g (2 mmol) of imine-reduced product, and column chromatography (petroleum ether: ethyl acetate = 1: 1) to obtain pure product. Yield: 95. %.

Oil

1H NMR (300 MHz, CDC1 ₃ / TMS): δ 0.96 (6Η, t, CH ₃ , J = 7.2Hz), 1.30-1.42 (4H, m, CH ₂ ), 1.54-1.64 (4H, m, CH ₂ ), 3.27 (4H, t, CH ₂ , J = 7.5Hz), 3.79 (6H, s, OCH ₃ ), 4.43 (2H, s, CH ₂ ), 5.76 (1H, s, CH), 6.20 (1H, s, NH), 6.27-7.31 (7H, m, CH)

MS (EI): 157 (m / z, 100), 541 (M ⁺ ., 4.75)

IR (neat / cm ^-1 ): 3420 (γ _Ν-Η ), 3292 (γ _Ν-Η ), 1638 (y _c = ₀ ), 1605, 1536, 1471 (y _c = c), 1565 (y _c = _N ), 1226, 1195, 1166 (y = _c- oc)

EA for C ₂₈ H ₃₆ C1N ₅ 0 ₄ Calcd: C 62.04, H 6.69, N 12.92

Found: C 61.91, H 6.67, N 12.72 Example 11

 For the synthesis of I-11, the detailed experimental steps are the same as in Example 1: (1) Condensation with 6-methoxysalicylic aldehyde: The amount of the amino compound is 2.5 mmol, which is directly dried by spin-drying, and the yield is 99%. (2) Schiff base reduction: 2.5 mmol of imide is charged to obtain 0.913 g (2.29 mmol) of the product with a yield of 92%. (4) Condensation with pyrimidine sulfone: 釆 Synthesized by method b, 0.913 g (2.29 mmol) of imine-reduced product, and column chromatography (petroleum ether: ethyl acetate = 2: 1) to obtain pure product. Yield. 85%.

Solid

m.p .: 78.3 ± 0.5 ° C

1H NMR (300 MHz, CDC1 ₃ / TMS): δ 0.97 (6H, t, CH ₃ , J = 7.2Hz), 1.30-1.43 (4H, m, CH ₂ ), 1.54-1.64 (4H, m, CH ₂ ), 3.27 (4H, t, CH ₂ , J = 7.2Hz), 3.79 (6H, s, OC¾), 3.88 (3H, s, OCH ₃ ), 4.35 (2H, s, CH ₂ ), 5.75 (1H, s, CH), 6.20 (1H, s, NH), 6.32-7.28 (7H, m, CH) MS (EI): 275 (m / z, 100 ), 538 (Μ + ·, 4.75)

IR (KBr / cm " ¹ ): 3405 (γ _Ν-Η ), 3340 (γ _Ν - _Η ), 1645 (γ _α = ₀ ), 1600, 1544, 1469 (y _c = c), 1570 (y _c = _N ), 1220, 1196, 1166 (Y = C. _0- C)

EA for C ₂₉ H ₃₉ N ₅ 0 ₅ Calcd: C 64.78, H 7.31, N 13.03

Found: C 64.72, H 7.36, N 13.00 Example 12

 For the synthesis of 1-12, the detailed experimental steps are the same as in Example 1: (1) Condensation with salicylaldehyde: the amount of 6.48 mmol of amino compound was filtered, and 1.589 g of imine was obtained by filtration, with a yield of 76 %%. (2) Schiff base reduction: 1.92 mmol (4.51 mmol) of the product is obtained with a charge of 4.92 mmol of imine, and the yield is 92%. (3) Condensation with pyrimidine sulfone: Synthesized by method a. The input amount of 1.465 g (4.51 mmol) of the imine-reduced product was purified by column chromatography (petroleum ether: ethyl acetate = 2: 1). The yield was 89. %.

Solid

m.p .: 76.3 ± 0.5 ° C

1H NMR (300 MHz, CDC1 ₃ / TMS): δ 1.60 (6H, m, CH ₂ ), 3.40 (4H, q, CH ₂ ), 3.80 (6H, s, OCH ₃ ), 4.29 (2H, s, C¾ ,), 5.77 (1H, s, CH), 6.12 (1H, s, NH), 6.50 (2H, d, CH, J = 8.4Hz), 7.04-7.45 (6H, m, CH)

¹³ C NMR (75.5 MHz, CDC1 ₃ ): δ 24.42, 25.67, 43.62, 45.20, 54.22, 84.58, 113.26, 122.54, 122.78, 125.70, 128.06, 128.91, 129.50, 131.70, 144.46, 150.89, 155.80, 164.27. MS, 172.98 (EI): 245 (m / z, 100), 463 (Μ + ·, 5.53)

IR (KBr / cm " ¹ ): 3333 (γ _Ν-Η ), 1635 (y _c = o), 1601, 1519, 1417 (γ ₀ = ο), 1571 (γο _Ν ), 1218 (y = _C -oc ) HRMS for C ₂₅ H ₂₉ N ₅ 0 ₄ Calcd: 463.22194; Found: 463.21762 Example 13

For the synthesis of 1-13, the detailed experimental steps are the same as those in Example 1: (1) Condensation with salicylaldehyde: A feed amount of 7.18 mmol of an amino compound was filtered to obtain 1.746 g of an imine with a yield of 63.2%. (2) Schiff base reduction: 4.66 mmol of imine is charged to obtain 1.712 g (4.541 mmol) of the product with a yield of 99%. (3) Condensation with pyrimidine sulfone: (1) Synthesis by method a. The amount of the imine-reduced product was 1.712 g (4.541 mmol). Column chromatography (petroleum ether: ethyl acetate = 2: 1) The pure product was obtained with a yield of 93%.

Solid

m.p .: decomposition

1H NMR (300 MHz, CD3COCD3): δ 1.34 (3H, t, CH ₃ , J = 6.9Hz), 3.81 (6H, s, OCH ₃ ), 4.00 (2H, q, CH ₂ , J = 7.5Hz), 4.29 (2H, d, CH ₂ , J = 5.1Hz), 5.85 (1H, s, CH), 6.53-7.73 (13H, m, CH)

 MS (EI): 245 (m / z, 100), 515 (Μ + ·, 8.72)

IR (KBr / cn ¹ ): 3271 (γ _Ν-Η ), 1643 (γο.), 1615, 1514, 1474 (j _c = c), 1566 (y _c = _N ), 1224, 1197, 1172 (Y = COC)

HRMS for C ₂₈ H ₂₉ N ₅ 0 ₅ Calcd: 515.21685; Found: 515.21429 Example 14

 The synthesis of I -14. The detailed experimental steps are the same as those in Example 1: (1) Condensation with salicylaldehyde: 4.855 mmol of amino compound, which is filtered to obtain 1.654 g of imine, with a yield of 84%. (2) Schiff base reduction: 4.61 mmol of imide is charged to obtain 1.591 g (4.413 mmol) of the product with a yield of 96%. (3) Condensation with pyrimidine sulfone: Synthesized by method a. The amount of the imine-reduced product was 1.593 g (4.413 mmol). Column chromatography (petroleum ether: ethyl acetate = 2: 1) yielded pure product. Yield: 90. %.

Solid

m.p .: 190.8 ± 0.5 ° C

1H NMR (300 MHz, CDCI3 / TMS): δ 2.09 (3H, s, CH ₃ ), 2.32 (3H, s, CH ₃ ), 3.81 (6H, s, OCH3), 4.23 (1H, s, NH), 4.33 (2H, s, CH ₂ ), 5.78 (1H, s, CH), 6.11-7.47 (13H, m)

MS (EI): 275 (/ z, 100), 499 (M +., 14.74)

IR (KBr / cm " ¹ ): 3400 (γ _Ν-Η ), 3288 (γ _Ν-Η ), 1646 (γ ₀ = ο), 1602, 1520, 1491 (γ _α = ο), 1559 (γο _Ν ) , 1218, 1195 (Y = _C -OC)

Ε.Α. for C ₂₈ H ₂₉ N ₅ 0 ₄ Calcd: C 67.32, H 5.85, N 14.02

Found: C 67.19, H 6.05, N 14.00 Example 15

Synthesis of I-15, detailed experimental steps are the same as in Example 1: (1) Condensation with salicylaldehyde: 6.9 mmol ammonia The substrate was directly dried after spinning, and the yield was 99%. (2) Schiff base reduction: A feed amount of 6.9 mmol of imine yields 2.12 g (6.1 mmol) of the product with a yield of 88%. (3) Condensation with pyrimidine sulfone: 合成 Synthesized by method b. The amount of the imine-reduced product was 2.12 g (6.1 mmol). Column chromatography (petroleum ether: ethyl acetate = 2: 1) yielded pure product. 75%.

Solid

m.p .: decomposition

1H NMR (300 MHz, CDC1 ₃ / TMS): 3.80 (6H, s, OCH ₃ ), 4.29 (2H, s, CH ₂ ), 5.77 (1H, s, CH), 6.28-7.42 (14H, m)

¹⁹ F NMR (282 MHz, CD): δ -119.37 (IF, s)

MS (EI): 245 (m / z, 100), 489 (M +., 3.56)

IR (KBr / cm " ¹ ): 3275 (γ _Ν-Η ), 1668, 1647 (y _c = o), 1600, 1509, 1472 (y _c = c), 1571 (γ ₀ = _Ν ), 1217, 1166 (y = _c- oc)

EA for C ₂₆ H ₂₄ FN ₅ 0 ₄ Calcd: C 63.80, H 4.94, N 14.31

Found: C 63.70, H 4.74, N 14.21 Example 16

 For the synthesis of 1-16, the detailed experimental steps are the same as in Example 1: (1) Condensation with salicylaldehyde: 3.34 mmol of amino compound was filtered, and 1.166 g of imide was filtered, and the yield was 99%. (2) Schiff base reduction: 3.34 mmol of imide is charged to obtain 1.116 g (3.18 mmol) of the product with a yield of 95%. (3) Condensation with pyrimidine sulfone: 合成 Synthesized by method b, 1.116 g (3.18 mmol) of the imine-reduced product was charged, and column chromatography (petroleum ether: ethyl acetate = 2: 1) was obtained as a pure product in a yield. 75%.

Solid

m.p .: decomposition

1H NMR (300 MHz, CDC1 ₃ / TMS): 3.81 (6H, s, OCH ₃ ), 4.32 (2H, s, CH ₂ ), 5.78 (1H, s, CH),

6.50-7.45 (12H, m, CH)

¹⁹ F NMR (282 MHz, CD): δ -119.71 (IF, s)

MS (EI): 245 (m / z, 100), 489 (Μ ⁺ ·, 4.08)

IR (KBr / cm " ¹ ): 3400 (γ _Ν . _Η ), 3301 (γ _Ν-Η ), 1643 (γ _α = ο), 1602, 1521, 1510 (j _c = c), 1568 (γ _α = _Ν ), 1197 ( _T = coc)

EA for C ₂₆ H ₂₄ FN ₅ 0 ₄ Calcd: C 63.80, H 4.94, N 14.31 Found: C 63.76, H 4.67, N 14.32 Example 17

 For the synthesis of 1-17, the detailed experimental steps are the same as those in Example 1: (1) Condensation with salicylaldehyde: 3.18 mmol of amino compound, and 1.167 g of imine were obtained by filtration, with a yield of 99%. (2) Schiff base reduction: 3.18 mmol of imide is charged to obtain 1.125 g (3.05 mmol) of the product with a yield of 96%. (3) Condensation with pyrimidine sulfone: It was synthesized by method a. The amount of the imine-reduced product was 1.125 g (3.05 mmol). Column chromatography (petroleum ether: ethyl acetate = 2: 1) was used to obtain the pure product. Yield. 40%.

Solid

m.p .: decomposition

1H NMR (300 MHz, CD ₃ COCD ₃ ): 3.80 (6H, s, OCH ₃ ), 4.29 (2H, d, CH ₂ , J = 5.4Hz), 4.35

(1H, s, NH), 5.30 (1H, s, NH), 5.85 (1H, s, CH), 6.54-8.28 (12H, m, CH)

¹⁹ F NMR (282 MHz, CD ₃ COCD ₃ ): δ -120.89 (IF, t, J = 14.66Hz), -128.62 (IF, t, J =

11.56Hz)

 MS (EI): 108 (m / z, 100), 507 (Μ "*" ·, 9.60)

IR (KBr / cm- ¹ ): 3396 (γ _Ν-Η ), 3288 (γ _Ν-Η ), 1639 (y _c = o), 1602, 1519, 1467 (y _c = c), 1535 (γ _α = _Ν ), 1195 (Y = COC)

EA for C ₂₆ H2 ₃ F ₂ N ₅ 0 ₄ Calcd: C 61.53, H 4.57, N 13.80

Found: C 61.83, H 4.58, N 13.70 Example 18

 The synthesis of I-18. The detailed experimental steps are the same as in Example 1: (1) Condensation with salicylaldehyde: 7.12 mmol of amino compound was filtered, and 1.649 g of imine was obtained by filtration. The theoretical yield was 63%. (2) Schiff base reduction: 1.49 g (4.44 mmol) of the imide is charged in an amount of 4.49 mmol, and the yield is 99%. (3) Condensation with pyrimidine sulfone: Synthesized by method b, 1.639 g (4.44 mmol) of the imine-reduced product was charged, and column chromatography (petroleum ether: ethyl acetate = 2: 1) was obtained in pure form, yield 75 %.

Solid

m.p .: 173.8 ± 0.5 ° C

'H NMR (300 MHz, CDCI3 / TMS): δ 3.81 (6H, s, OCH ₃ ), 4.30 (2H, s, CH ₂ ), 5.78 (1H, s, CH), 6.30-7.43 (11H, m) , 8.01 (2H, m, NH) ¹⁹ FNMR (282 MHz, CDC1 ₃ ): δ -116.91 (IF, s), -126.46 (IF, s)

MS (EI): 151 in / z, 100), 474 (Μ ⁺ ·, 22.71)

IR KBr / cm— ¹ ): 3375 (γ _Ν-Η ), 3294 (γ _Ν-Η ), 1611, 1573, 1526 (j _c = c), 1236, 1219 (y = _C -oc) EA for C ₂₆ H ₂₃ F ₂ N ₅ 0 ₄ Calcd: C 61.53, H 4.57, N 13.80

Found: C 61.61, H 4.67, N 13.82 Example 19

 The synthesis of I-19, the detailed experimental steps are the same as in Example 1: (1) Condensation with 6-methoxysalicylic aldehyde: Amount of 5 mmol of amino compound, spin-drying, and directly into the next step, the yield is 99%. (2) Schiff base reduction: Feed 5 mmol of imine to obtain 1.715 g (4.5 mmol) of the product with a yield of 90%. (3) Condensation with pyrimidine sulfone: Synthesized by method b. The input product is 0.758 g (1.99 mmol) of imine-reduced product. Column chromatography (petroleum ether: ethyl acetate = 2: 1) yields pure product. Yield: 75. %.

Solid

m.p .: 221.8 ± 0.5 ° C

1H NMR (300 MHz, CDCI3 / TMS): δ 3.78 (6H, s, OCH ₃ ), 3.88 (3H, s, OC¾), 4.33 (2H, s, CH ₂ ), 5.75 (1H, s, CH), 6.34-7.34 (12H, m)

1 ⁹ FNMR (282M, CDC1 ₃ ): -119.66 (IF, s)

MS (EI): 275 (m / z, 100), 519 (M ⁺ , 33.19)

IR (KBr / cm " ¹ ): 3384 (γ _Ν — _H ), 3323 (γ _Ν-Η ), 1643 (y _c = o), 1598, 1555, 1511 (yc = c), 1573 (y _c = _N ), 1220, 1197, 1113 (Y = _C-0 -C)

EA for C ₂₇ H ₂₆ FN ₅ 0 ₅ Calcd: C 62.42, H 5.04, N 13.48

Found: C 62.20, H 4.73, N 13.57 Example 20

 For the synthesis of I-20, the detailed experimental steps are the same as those in Example 1: (1) Condensation with 6-fluorosalicylic aldehyde: The feed amount is 3.8 mmol of amino, which is directly dried after spinning to the next step with a yield of 99%. (2) Schiff base reduction: 3.8 mmol of imine is charged to obtain 1.397 g (3.61 mmol) of the product with a yield of 95%. (3) Condensation with pyrimidine sulfone: Synthesized by method b, 0.929 g (2.4 mmol) of imine-reduced product, column chromatography (petroleum ether: ethyl acetate = 2: 1) to obtain pure product, yield 85 %.

Oil 1H NMR (300 MHz, CDC1 ₃ / TMS): δ 0.97 (6H, t, CH ₃ , J = 7.5Hz), 1.33-1.43 (4H, m, CH ₂ ): 1.55-1.65 (4H, m, CH ₂ ), 3.27 (4H, t, CH ₂ , J = 7.5Hz), 3.79 (6H, s, OC¾), 4.35 (2H, s, CH ₂ ): 5.78 (1H, s, CH), 6.15-7.31 (8H , m)

MS (EI): 245 (m / z, 100), 525 (M + ', 10.24)

IR (KBr / cm- ¹ ): 3356 (γ _Ν-Η ), 1645 (γ ₀ = _ο ), 1604, 1540, 1470 (γ ₀ = ο) ₅ 1571 (γ _€ = _Ν ), 1222, 1197, 1168 ( _{T = c-} oc)

Ε.Α. for C ₂₈ H ₃₇ N ₅ 0 ₄ Calcd: C 63.98, H 6.90, N 13.32

Found: C 64.36, H 7.14, N 13.06 Example 21.

 The following Examples 21 to 25 give practical examples of processing and formulating several herbicide formulations using the compound of the present invention as an active material component. It should be noted that the present invention is not limited to the scope of the following examples.

Wettable powder (WP) formula: 15% compound (I-1) (Table 1), 5% lignin sulfonate ( _Mq ), 1% lauryl alcohol polyoxyethylene ether (JFC), 40 % Diatomaceous earth and 44% light calcium carbonate are evenly mixed and crushed to obtain a wettable powder. Example 22

 EC formula: 10% compound (1 ~ 1) (Table 1), 5% agricultural milk 500 (calcium salt), 5% agricultural milk 602, 5% N-methyl-2 -Pyrrolidone and 75% xylene are heated and stirred to obtain 10% emulsifiable concentrate. Example 23

 Granule (GR) formulation: 5% compound (I-1) (Table 1), 1% polyvinyl alcohol (PVA), 4% sodium naphthalenesulfonate formaldehyde condensate (NMO) and 90% clay are uniform It was mixed and pulverized, and then 20 parts of water was added to the 100 parts of the mixture, kneaded, and granulated by an extruder to obtain 14-32 mesh granules, and dried to obtain 5% granules. Example 24

Water emulsion (EW) formula: 15% of compound (I-1) (Table 1), 8% alkylaryl formaldehyde resin polyoxyethylene ether, 10% calcium dodecylbenzenesulfonate, 3% fourteen Methanol, 10% dimethylformamide, 5% propylene glycol, and the balance is water. According to the properties of each component, an oil phase and an aqueous phase are respectively prepared, and then the two are mixed under high speed stirring to form 15% water emulsion with good dispersibility. Example 25

 Water suspension (SC) formula: 15% of the compound (1-1) (Table 1), 5% calcium lignosulfonate, 0.5% white carbon black, 4% ethylene glycol, 1% defoamer, The balance is water. Add it to a sand mill and grind to a certain fineness to make 15% suspension. Example 26

 The following examples give examples of biological activity determination using the compounds of the present invention. It should be noted that the present invention is not limited to the scope of the following examples.

 The herbicidal activity evaluation test was performed according to the following methods:

 The test soil was a prepared sandy loam soil. The diameter of the pot bowl for the herbicidal activity test was 9.5 cm, and the diameter of the pot bowl for the safety test was 12.0 cm.

 The pre-emergence test pot was sprayed with soil surface one day after sowing. The treated liquid was the compound dissolved with organic solvents such as acetone and DMF, and 0.5% Tween-80 laboratory preparation was added, and then diluted with water as needed. dose.

 The post-emergence test pot was placed in the greenhouse for 7-9 days after sowing, and then foliar sprayed. The treated liquid was a compound dissolved with organic solvents such as acetone and DMF, and 0.5% Tween-80 was added. Chamber preparation, and diluted with water to the required dose.

 The compound treatment concentration in the first activity determination test was 300 gai / ha or 150 gai / ha, and the compound treatment concentration in the second activity determination test was 75, 150, and 300 gai / ha or 37.5, 75, 150 gai / ha. The treated pots were allowed to stand for 1 day, then placed in a greenhouse, and watered regularly. After 14 to 21 days, the herbicidal activity of the recorded compounds was observed visually.

 The herbicidal activity of the compound was visually measured by the degree of plant damage symptoms (inhibition, malformation, yellowing, albinism). 0 means no herbicidal effect or safety to the crop, and 100% means complete weed or crop killing.

 The evaluation criteria of herbicidal activity and crop safety visual method are as follows:

 Phytotoxicity Herbicidal activity reviews Crop safety reviews

 (%) (Suppression, deformity, whitening, etc.) (Suppression, deformity, whitening, etc.)

0 Same control, resistant, eliminated Same control, resistant, normal

10-20 light, slightly affected, eliminated light, slightly affected, can be considered

30-40 light, influential, elimination, sensitive, influential, elimination 50-60 Sensitive and influential

70-80 is more sensitive, it can be considered extremely sensitive, serious drug damage, eliminated

90-100 is extremely sensitive, very sensitive, and severely harmful. The results of the first herbicidal activity test for eliminating the first high-dose treatment are shown in Table 1 and Table 2. Crop safety test results are shown in Table 5.

 The types of weeds and crops selected for the biological activity test are as follows:

Chinese name English name Scientific name abbreviation barnyardgrass Echinochloa crusgalli ECHCG Crabgrass Digitaria sanguinalis DIGSA Bullgrass Eleusine indica ELEIN Mustard Leaf mustard Brassicajuncea BRAJU Portion Amaranth pigweed AcornORa coma mays ZEAMX Soybean Glycine max GLXMA Cotton Cotton Gossypium hispitum GOSHI Wheat Wheat Triticum aestivum TRZAW Rice Rice Oryza sativa ORYSD Rape Brassica napus BRSNW

Table 1.Results of the first herbicidal activity test on post-emergence stem and leaf treatments.

 稗 草 Matang Goosegrass Anti-branch Purslane Number (g ai / ha)

 1- 1 300 85 80 80 100 100 100

1-2 300 100 85 100 90 100 100

1-3 300 100 100 100 100 100 100

1-4 300 100 100 100 100 100 90

1-5 300 100 85 100 95 100 95

1-6 300 100 100 100 100 100 100

1-7 300 100 100 100 100 100 95

1-8 150 0 60 70 70 80 0

1-9 300 90 80 40 80 100 0 I one 10 150 85 95 80 100 100 100

I one 11 150 90 100 90 100 100 80

1-12 300 85 60 80 85 85 0

1-13 300 80 70 60 80 80 80

1-14 300 85 70 60 90 90 80

1-15 150 85 90 100 95 98 70

1-16 150 85 90 100 95 100 70

1-17 150 85 90 100 95 100 60

1-18 150 98 95 90 70 100 85

1-19 150 90 95 100 100 100 85

Table 2: Results of the first herbicidal activity test on pre-emergent soil treatment

 Potamogeton spp.Easygrass Reeds Purslane Number (g ai / ha)

 1-1 300 80 60 80 70 60 70

1-2 300 90 90 80 90 90 90

1-3 300 90 95 85 95 95 90

1-4 300 90 90 85 98 90 90

1-5 300 100 80 80 90 90 90

1-6 300 100 80 80 95 95 90

1-7 300 90 85 80 90 95 90

1-8 150 0 0 40 80 70 0

1-9 300 0 0 ― 60 0 0

1-10 150 95 90 80 80 85 80

1-11 150 95 90 80 80 85 90

1-12 300-50 ― 70 60 0

1-13 300 50 70 ― 70 0 ―

1-14 300 50 50 50 60 50 0

1-15 150 ― ― ― 80 90 80

1-16 150 ― ―-85 90 80

1-17 150 80 85 85 80 95 80

1-18 150 85 85 85 80 90 85

1-19 150 50 80 80 90 90 80 Results of the second evaluation of the herbicidal activity after the shoot and stem treatment

 Potamogeton crispus gluten, mustard grass, mustard, reverse branch, purslane number g ai / ha

 75 80 50 85 80 100 80

1-1 150 90 85 100 85 100 85

 300 95 90 100 100 100 100

75 100 80 85 70 100 40

1-2 150 100 90 100 75 100 60

 300 100 98 100 80 100 60

75 70 80 80 100 100 100

1-3 150 100 85 80 100 100 50

 300 100 100 80 100 100 100

75 100 85 90 95 100 85

1-4 150 100 95 95 95 100 90

 300 100 95 95 100 100 100

75 60 70 70 70 100 60

1-5 150 100 80 100 70 100 60

 300 100 85 100 75 100 75

75 90 95 100 100 100 95

1-6 150 100 100 100 100 100 100

 300 100 100 100 100 100 100

75 95 95 95 75 90 50

1 ~ 7 150 95 95 95 80 90 60

 300 100 95 95 90 100 90

37.5 0 0 60 60 60 40

1-8 75 20 0 80 60 60 40

 150 30 40 100 60 80 40

75 90 80 70 60 85 80

1-9 150 95 85 80 100 100 100

 300 100 85 80 100 100 100

1- 12 75 90 60 100 60 90 50

150 90 90 100 85 100 80 300 100 100 100 90 100 80

75 80 60 95 90 95 90

1- 13 150 90 80 100 90 100 90

 300 98 95 100 100 100 100

75 90 80 100 90 100 70

1- 14 150 90 80 100 90 100 40

 300 100 100 100 100 100 80

37.5 60 70 60 30 60 0

1- 15 75 70 70 80 40 '80 30

 150 85 75 90 50 80 30

37.5 70 60 80 30 80 0

1- 16 75 90 80 100 40 100 0

 150 95 85 100 60 100 30

37.5 50 50 80 50 65 0

1- 17 75 70 60 100 70 80 30

 150 80 80 100 80 80 40

37.5 75 60 70 20 80 0

1- 18 75 80 75 80 30 90 0

 150 85 80 90 50 100 70

37.5 80 75 100 60 80 0

1- 19 75 100 90 100 70 80 60

 150 100 100 100 75 80 75

Table 4: Evaluation results of the second herbicidal activity in pre-emergent soil treatment

 Echinochloa crusgalli, Tendon serrata, rice branch width, purslane number g ai / ha

 75 40 40 40 80 90 90

1- 1 150 80 70 60 80 90 80

 300 95 90 90 90 95 95

75 60 60 60 60 85 70

1-2 150 60 70 60 60 85 80

 300 80 80 80 70 95 85

1-3 75 60 90 70 95 90 90 6c

Z.000 / l700ZN3 / X3d 890 / S00Z OAV 37.5 40 70 70 70 85 70

1- 16 75 80 85 80 85 90 80

 150 85 90 90 90 95 85

37.5 ― ―-50 20 0

1- 17 75 ― ―-70 80 80

 150 85 90 80 75 90 80

37.5 50 60 60 75 80 60

1- 18 75 80 70 75 80 90 70

 150 85 80 75 80 95 80

37.5 0 60 60 90 95 60

1- 19 75 60 70 70 90 95 75

 150 70 90 75 95 100 80

Table 5: Crop safety test results of post-emergence foliar treatment

Compound dose corn soybean cotton rapeseed rice

 (g ai / ha)

 37.5 20 10 10 20 20 0

1-5 75 40 30 10 30 20 20

 150 40 50 50 50 20 30

37.5 60 10 20 0 30 20

1-7 75 60 10 20 30 30 30

 150 90 20 50 30 30 40

37.5 20 30 10 20 10 20

1-9 75 30 30 50 30 10 20

 150 40 70 80 40 70 60

37.5 50 0 0 0 ― 10

1- 12

 75 50 40 30 20 ― 30

37.5 0 0 20 30 50 20

1- 14

 75 30 0 40 40 50 60

Claims

Rights request

1. A compound whose structure is as follows (I):

Where: D or E = hydrogen, halogen, —C ₄ alkyl, d—C ₄ alkoxy, —C ₄ haloalkyl, or —C ^ halofluorenoxy;

X = hydrogen, halogen, nitro, cyano, carboxyl, ester group, a sulfonyl group, wide C C ₈ alkyl, C "embankment C ₈ haloalkyl group, a C _s embankment group, - embankment acyl, d-C ₈ alkanoylamino, d-C ₈ haloalkanoylamino, phenyl, benzoyl, substituted phenyl, heterocyclyl or substituted heterocyclyl;

Ri, R ₂ = hydrogen, ester group, sulfonyl, —C ₈ alkyl, substituted d—C ₈ substituted alkyl, d—C ₈ alkoxy, ¾ acyl, phenyl, heterocyclic or substituted A heterocyclic group, or,-(CH ₂ ) _m Z (CH ₂ ) _k- , wherein Z is CH ₂ , NH, O, or S, and m and k are integers of 1 to 6;

X 'is H,, halogen atom, carboxyl, ester, —alkanoyl, d—C ₈ alkyl, d

A C ₈ haloalkyl, d-C ₈ alkoxy, phenyl, substituted phenyl, heterocyclyl or substituted heterocyclyl;

n is an integer from 1 to 4;

R ₃ = hydrogen, alkanoyl, —C ₈ haloalkanoyl, benzoyl, substituted benzoyl, d-Csfluorenyl.

2. The compound according to claim 1, wherein its structural formula is as follows −

Wherein D, E, X, and are as described in claim 1.

 3. The compound according to claim 1 or 2, wherein in the structural formula, both D and E are methoxy groups.

4. The compound according to claim 1, wherein in the structural formula, the heterocyclic group is pyridyl, thienyl, thiazolyl, or pyrimidinyl; the substituent on the substituted fluorenyl is Halogenated or Q ~ C ₈ alkoxy; said substituted phenyl, substituted heterocyclyl or substituted benzoyl are mono-, di- or poly-substituted, said substituents are halogen, nitro, Cyano, carboxyl, ester, sulfonyl, d-C ₈ fluorenyl, d-C ₈ haloalkyl, mono-alkoxy, mono-alkanoyl or 6 _1- ¾-alkanoylamino.

 5. A method for preparing a compound according to claim 1, characterized in that it is prepared by the following method:

 Compounds of the general formula (IV)

 (IV)

 Where χ, χ ′, η, and as described in claim 1,

In the presence of a base, in or without a solvent, reacts with a pyrimidine having the general structure

 Wherein D and E are as described in claim 1, and Y represents halogen or methylsulfone.

6. The preparation method according to claim 5, wherein the reaction is that the compound (IV) is reacted with 2-halo-4-D, 6-E-substituted pyrimidine or 2-methylsulfone in an organic solvent. -4-D, 6-E-substituted pyrimidine is reacted in the presence of a base for 0.5 to 20 hours. Compound (IV), 2-halo-4-D, 6-E-substituted pyrimidine or 2-methylsulfanyl-4 -D, 6-E-Substituted pyrimidine and base The molar ratio is 1: (1.0-1.2): (1-5), the base is a hydride of a monovalent or divalent metal, an alkoxy metal compound or a carbonate thereof, triethylamine, pyridine, and a reaction temperature. The temperature is from room temperature to the boiling point of the solvent, wherein compounds (IV), D, and E are as shown in claim 5.

 7. The preparation method according to claim 5 or 6, further comprising the following steps (2) or the following steps (1) and (2):

 (1) In a solvent, with or without the catalyst, 1-aminophenyl-3-substituted urea (11) and substituted salicylaldehyde are reacted with the catalyst to obtain an intermediate (111). The catalyst is Toluenesulfonic acid, methanesulfonic acid, sulfuric acid, hydrochloric acid or acetic acid;

 (2) reacting the reactant (III) with a reducing agent to obtain a compound (IV), the reducing agent is sodium borohydride or potassium borohydride;

 Or the reactant (in) is reduced by a hydrogen to produce the compound αν) under the action of a catalyst, and the catalyst is Raney Ni, palladium carbon or platinum black;

 The structural formulas of the aforementioned N-amidoaniline (11), intermediate (III) and compound (IV) are as follows respectively.

 (IV)

Wherein, D, E, X, X ', n,, R ₂ or the 2-pyrimidinyloxy-N-ureidophenylbenzylamine compound is as shown in claim 1.

 8. The preparation method according to claim 7, wherein the steps (1) and (2) are as follows:

(1) In a solvent, the reaction temperature is from room temperature to the boiling point of the solvent, and 1-aminophenyl-3-substituted urea (II) is reacted with salicylaldehyde or substituted salicylaldehyde with or without a catalyst, and the molar ratio is 1 : (0.8— 2), Intermediate απ) is obtained by reacting for 0.5 to 12 hours, and the catalyst is p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, hydrochloric acid or acetic acid;

 (2) The molar ratio of the reactant (II) to the reducing agent is 1: 0.5-2, the reaction temperature is from room temperature to 40 degrees Celsius, and the intermediate (IV) is prepared by reacting for 0.5 to 10 hours, and the reducing agent is boron Sodium hydride or potassium borohydride;

Or, the reactant (II) is reduced to compound (111) with hydrogen under the action of a catalyst, and reacted at room temperature to 40 degrees Celsius for 0.5 to 10 hours to obtain an intermediate (IV). The catalyst is Ra _ne y Ni , Palladium on carbon or platinum black, the molar ratio of reactant (111), hydrogen to catalyst is 1: (1-1000): (0.01 -0.5);

The N-amidoaniline (11), the intermediate (III) and the intermediate (IV) have the structural formulas as described in claim 7.

 9. The preparation method according to claim 5, characterized in that the final product is purified by silica gel column chromatography or recrystallization.

 10. A pesticide composition for use as an agricultural chemical herbicide, comprising the compound of claim 1 and an acceptable carrier for herbicide control.

 11. Use of a compound according to claim 1, characterized in that it is used in agricultural chemical herbicides.