Tetra-substituted phenyl ether (thioether) compound containing alkoxyacetate substituent and application of tetra-substituted phenyl ether (thioether) compound

Abstract

The invention discloses a tetra-substituted phenyl ether (thioether) compound containing an alkoxyacetate substituent group and application thereof, the tetra-substituted phenyl ether (thioether) compound has a structure as shown in a formula I, and the definition of each substituent group in the compound as shown in the specification. The compound shown in the formula I has excellent herbicidal activity and crop safety, and can be used for preventing and treating agricultural weeds. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the field of herbicides, and in particular relates to a tetrasubstituted phenyl ether (thioether) compound containing an alkoxyacetate substituent and application thereof. Background Art

[0002] Weeds cause huge economic losses worldwide by reducing crop yield and quality. Crops around the world must contend with hundreds of weed species. Due to the succession and changes in weed populations, the emergence and rapid development of resistance to chemical pesticides, and the increasing awareness of chemical pesticide pollution and ecological environmental protection, there is still a need for research and development of more effective and / or more selective herbicides.

[0003] Patent EP83055A2 and patent WO2016120116A1 respectively disclose tetrasubstituted benzene compounds with alkoxyacetate substituents and their use as herbicides, and specifically disclose that the following compounds KC1 (compound No. 57 in Table 1 of patent EP83055A2) and KC2 (compound of Example 1 in patent WO2016120116A1) have high herbicidal activity. However, the herbicidal activity and / or safety of these compounds to crops are not completely satisfactory.

[0004]

[0005] With the gradual reduction of the world's arable land area, the continuous growth of population and the increase in demand for food, people are forced to rapidly develop agricultural production technology, improve and perfect the farming system, and continuously invent new and improved herbicidal compounds and compositions. Summary of the invention

[0006] The object of the present invention is to provide a novel tetrasubstituted phenyl ether (thioether) compound containing an alkoxyacetate substituent, and a herbicidal composition containing the compound as an active ingredient. The compound not only has excellent herbicidal activity at a lower application dose, but also has higher safety to crops at a higher application dose. The object of the present invention can also be extended to provide a novel compound used as a desiccant or defoliant.

[0007] The technical solution adopted by the present invention is as follows:

[0008] The present invention provides a novel tetrasubstituted phenyl ether (thioether) compound containing an alkoxyacetate substituent, having a structure as shown in Formula I:

[0009]

[0010] in:

[0011] X is selected from hydrogen, halogen, C1-C6 alkyl or C1-C6 alkoxy;

[0012] Y is selected from halogen, cyano, nitro, C1-C6 alkyl, C1-C6 alkoxy, CONH2 or CSNH2;

[0013] Z is selected from oxygen or sulfur;

[0014] R and Ak are each independently selected from C1-C6 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkylthio C1-C6 alkyl, C1-C6 alkylamino C1-C6 alkyl, C3-C8 cycloalkyl C1-C6 alkyl, C2-C8 oxacycloalkyl C1-C6 alkyl, C1-C6 alkoxycarbonyl C1-C6 alkyl, phenyl or benzyl, and the above groups may be further substituted by any combination of one or more halogens, cyano, nitro, C1-C6 alkoxy, C1-C6 haloalkyl or C1-C6 haloalkoxy, or R and Ak together with the atoms to which they are attached form a 5- to 7-membered heterocyclic ring;

[0015] Het is selected from

[0016]

[0017] in,

[0018] W1, W2 and W3 are each independently oxygen or sulfur;

[0019] R1 and R2 are each independently selected from hydrogen, cyano, amino, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 haloalkoxy, C3-C7 cycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, benzyl, C1-C6 cyanoalkyl, OR7, or R1 and R2 together with the atoms to which they are attached form a 3-membered to 7-membered ring system, and the ring system may be further substituted by any combination of one to more halogens, nitro, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino or C1-C4 alkylthio;

[0020] R3 and R4 are each independently selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 haloalkoxy, C3-C7 cycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, OR7, S(O) nR7, OSO2R7, NR7R8, or R3 and R4 together with the atoms to which they are attached form a 3- to 7-membered ring system, and the ring system may be further substituted by any combination of one to more halogen, nitro, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino or C1-C4 alkylthio, wherein n is 0, 1 or 2;

[0021] R5 is selected from hydrogen, halogen or C1-C6 alkyl;

[0022] R6 is selected from hydrogen, halogen, C1-C6 alkyl, OR7, SR7, S(O) n R7, OSO2R7 or NR7R8;

[0023] R7 and R8 are each independently selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, phenyl or benzyl, and the above groups may be further substituted by any combination of one to more halogen, nitro, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino or C1-C4 alkylthio.

[0024] The preferred compounds of the present invention are those in formula I:

[0025] X is selected from hydrogen or halogen;

[0026] Y is selected from halogen or cyano;

[0027] Z is selected from oxygen or sulfur;

[0028] R and Ak are each independently selected from C1-C6 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkylthio C1-C6 alkyl, C1-C6 alkylamino C1-C6 alkyl, C3-C8 cycloalkyl C1-C6 alkyl, C2-C8 oxacycloalkyl C1-C6 alkyl, C1-C6 alkoxycarbonyl C1-C6 alkyl, phenyl or benzyl, and the above groups may be further substituted by any combination of one or more halogens, cyano, nitro, C1-C6 alkoxy, C1-C6 haloalkyl or C1-C6 haloalkoxy;

[0029] Het is selected from Het1, Het2, Het3, Het4, Het6, Het7, Het8 or Het 10 .

[0030] The preferred compounds of the present invention are, wherein:

[0031] X is selected from hydrogen, fluorine or chlorine;

[0032] Y is selected from fluorine, chlorine, bromine or cyano;

[0033] Z is selected from oxygen or sulfur;

[0034] R and Ak are each independently selected from C1-C6 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkylthio C1-C6 alkyl, C1-C6 alkylamino C1-C6 alkyl, C3-C8 cycloalkyl C1-C6 alkyl, C2-C8 oxacycloalkyl C1-C6 alkyl, C1-C6 alkoxycarbonyl C1-C6 alkyl, phenyl or benzyl, and the above groups may be further substituted by any combination of one or more halogens, cyano, nitro, C1-C6 alkoxy, C1-C6 haloalkyl or C1-C6 haloalkoxy;

[0035] Het is selected from Het1, Het3, Het6, Het8 or Het 10 .

[0036] The more preferred compounds of the present invention are, wherein:

[0037] X is selected from hydrogen, fluorine or chlorine;

[0038] Y is selected from fluorine or chlorine;

[0039] Z is selected from oxygen or sulfur;

[0040] Ak is selected from methyl, ethyl, n-propyl, isopropyl, phenyl or 2,4-dichlorophenyl;

[0041] R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, allyl, 2-buten-1-yl, propargyl, 2-butyn-1-yl, cyclopropyl, cyclopentyl, trifluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, methylthiomethyl, 2-methylthioethyl, cyclopropylmethyl, 2-cyclopropylethyl, cyclo Butyl methyl, cyclopentyl methyl, cyclohexyl methyl, oxirane methyl, tetrahydrofuran-2-methyl, tetrahydrofuran-3-methyl, 2,2-dimethyl-1,3-dioxolane-4-methyl, methoxycarbonyl methyl, ethoxycarbonyl methyl, 1-ethoxycarbonyl ethyl, 2-ethoxycarbonyl ethyl, cyanomethyl, 2-nitroethyl, 2-(2-methoxyethoxy)ethyl, 2-(trifluoroethoxy)ethyl, 2-(2-chloroethoxy)ethyl, 2-(cyanomethoxy)ethyl, etc.;

[0042] When Het is selected from Het1 or Het3, wherein R1 and R2 together with the atoms to which they are attached form a 6-membered ring system, W1 and W2 are selected from oxygen; when Het is selected from Het6, wherein R1 and R2 are selected from methyl, W1 and W2 are selected from oxygen, and W3 is selected from sulfur; when Het is selected from Het8, wherein R1 is selected from methyl, R3 is selected from trifluoromethyl, R4 is selected from hydrogen, and W1 and W2 are selected from oxygen; when Het is selected from Het 10 When R3 is selected from trifluoromethyl, R4 and R6 are selected from hydrogen or methyl, and W1 is selected from oxygen.

[0043] The particularly preferred compound of the present invention is a tetrasubstituted phenyl ether (thioether) compound containing an alkoxyacetate substituent as described in Formula I, selected from any one of the following compounds:

[0044] 2-methoxy-2-(2-chloro-4-fluoro-5-(1,3-dioxohexahydroimidazo[1,5-a]pyridin-2(3H)-yl)phenoxy)acetic acid n-pentyl ester (Compound 1-31);

[0045] 2-ethoxy-2-(2-chloro-4-fluoro-5-(1,3-dioxotetrahydro-1H-[1,2,4]triazolo[1,2-a]pyridazin-2(3H)-yl)phenoxy)acetic acid methyl ester (Compound 2-51);

[0046] 2-methoxy-(2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazin-1-yl)phenoxy)acetic acid ethyl ester (Compound 3-152);

[0047] 2-methoxy-(2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazin-1-yl)phenoxy)acetate (Compound 3-153);

[0048] 2-methoxy-(2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazin-1-yl)phenoxy)acetate isopentyl ester (Compound 3-157);

[0049] 2-methoxy-(2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazin-1-yl)phenoxy)acetate (Compound 3-158);

[0050] 2-isopropoxy-(2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazin-1-yl)phenoxy)acetic acid ethyl ester (Compound 3-202);

[0051] 2-methoxy-(2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazin-1-yl)phenoxy)acetic acid ethyl ester (Compound 3-301);

[0052] 2-methoxy-2-(2-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenoxy)acetic acid ethyl ester (Compound 4-2);

[0053] 2-methoxy-2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenoxy)acetate (Compound 4-101);

[0054] 2-methoxy-2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenoxy)acetic acid n-butyl ester (Compound 4-105);

[0055] 2-methoxy-2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenoxy)acetate (Compound 4-106);

[0056] 2-methoxy-2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenoxy)acetate (Compound 4-108);

[0057] 2-methoxy-2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenoxy)acetate (2-methoxyethanol) (Compound 4-116);

[0058] 2-ethoxy-2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenoxy)acetic acid ethyl ester (Compound 4-127);

[0059] Ethyl 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenoxy)-2-phenoxyacetate (Compound 4-176);

[0060] 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenoxy)-ethyl 2-(2,4-dichlorophenoxy)acetate (Compound 4-205);

[0061] 2-methoxy-2-(2-fluoro-4-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenylthio)acetate (Compound 4-276);

[0062] 2-methoxy-2-(2-chloro-4-fluoro-5-(5-methyl-6-oxo-4-trifluoromethylpyridazin-1(6H)-yl)phenoxy)acetic acid methyl ester (Compound 5-76);

[0063] 2-Methoxy-2-(2-chloro-4-fluoro-5-(5-methyl-6-oxo-4-trifluoromethylpyridazin-1(6H)-yl)phenoxy)acetate (2-chloroethanol) (Compound 5-88);

[0064] 2-methoxy-2-(2-chloro-4-fluoro-5-(5-methyl-6-oxo-4-trifluoromethylpyridazin-1(6H)-yl)phenoxy)acetic acid cyclopropylmethyl ester (Compound 5-93);

[0065] Methyl 2-ethoxy-2-(2-chloro-4-fluoro-5-(5-methyl-6-oxo-4-trifluoromethylpyridazin-1(6H)-yl)phenoxy)acetate (Compound 5-101).

[0066] The groups mentioned for the substituents Ak, R and R1 to R8 in Formula I, or the groups on the phenyl, benzyl or heterocyclic rings, when collectively referred to, have the following meanings:

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

[0068] All carbon chains, i.e., the alkyl moieties in all alkyl, haloalkyl, alkenyl and alkynyl groups, may be straight or branched. For example, C1-C6 alkyl groups may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, 2-methylbutyl, tert-pentyl, neopentyl, 1,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, isohexyl, sec-hexyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2-methylpentyl, 3-methylpentyl, tert-hexyl, 1,3-dimethylbutyl, neohexyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-methyl-1-ethylpropyl or 2-methyl-1-ethylpropyl, etc. Similarly, C2-C8 alkenyl can be vinyl, propenyl, allyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methylpropenyl, 2-methylpropenyl, 1-methylallyl, 2-methylallyl, 2,2-dimethylvinyl, etc. C2-C8 alkynyl can be ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpropargyl, etc. The multiple bonds of alkenyl or alkynyl can be at any position of each unsaturated group. C3-C8 cycloalkyl refers to a carbocyclic saturated ring system with 3 to 8 carbon atoms, which can be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

[0069] The haloalkyl group, haloalkoxy group or haloalkenyl group refers to an alkyl group, alkoxy group or alkenyl group respectively substituted with one or more halogen atoms, wherein the substituted halogen atoms may be the same or different.

[0070] If a group is substituted by another group, it is understood that the group is substituted by one or more identical or different groups selected from those mentioned. In addition, the identical or different substitution characters contained in the identical or different substituents can be selected independently. This also applies to ring systems formed by different atoms and units.

[0071] In addition, depending on the nature of the substituents and the way they are connected, Formula I and its derivatives may exist as stereoisomers. For example, if there are one or more asymmetric carbon atoms, enantiomers and diastereomers may occur. Stereoisomers can be obtained from the preparation mixture by conventional separation methods, such as by chromatographic separation (such as chiral HPLC separation), or by using stereoselective reactions, using optically active raw materials, intermediates and (or) auxiliary agents, catalysts, etc. to selectively prepare stereoisomers.

[0072] The compound of formula I of the present invention can be prepared by the following method. Unless otherwise noted in the reaction formula, the definitions of other groups are the same as above:

[0073]

[0074] The compound of formula I can be prepared by the corresponding compound of formula II and a substituted alkoxy carboxylic acid ester III (commercially available) with an easy leaving group. In a suitable solvent, the temperature is from -30°C to the boiling point of the solvent for 0.5 to 48 hours to obtain the obtained compound. The solvent can be selected from dichloromethane, chloroform, carbon tetrachloride, acetonitrile, n-hexane, cyclohexane, benzene, toluene, ethyl acetate, DMF, DMA, ether, methyl tert-butyl ether, THF, DMSO or dioxane. Adding alkaline substances such as triethylamine, DIEA, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium phosphate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide or potassium tert-butoxide is beneficial to the reaction. In the substituted alkoxy carboxylic acid ester (III) with an easy leaving group, L is a leaving group, such as chlorine, bromine, iodine, methyl sulfonate, p-methylbenzenesulfonate, etc.

[0075] The compound of formula II can be prepared by different synthetic methods depending on whether Z is oxygen or sulfur.

[0076] When Z is oxygen, Formula II a The compound can be represented by formula IV a The compound is prepared by removing the protecting group P.

[0077]

[0078] Formula IV a The compound is reacted with a suitable reducing agent at a temperature ranging from -30°C to the boiling point of the solvent for 0.5 to 48 hours to obtain a product of formula II a Compound. The solvent can be selected from alcohols such as methanol, ethanol, isopropanol, etc., and ethers such as diethyl ether, tetrahydrofuran, dioxane, etc. The reducing agent is selected from hydrogen, a catalytic amount of a transition metal or a catalytic amount of a transition metal compound; wherein the transition metal can be selected from Group VIII compounds in the periodic table, preferably Ni, Pd, Pt, etc. (directly used or loaded via activated carbon, aluminum oxide, silicon dioxide, etc.); hydrogen can be provided by a hydrogen storage cylinder, or by an active metal (such as reduced iron powder, reduced zinc powder, etc.) in situ under acidic conditions (such as hydrochloric acid, sulfuric acid) and participate in the reduction reaction. Suitable reducing agents also include metal hydrides, semi-metal hydrides and their derivatives, such as lithium aluminum hydride, diisobutylaluminum hydride, sodium borohydride, borane, etc.

[0079] Formula IV a The compound can also be reacted under the catalysis of a suitable Lewis acid at a temperature of -30°C to the boiling point of the solvent for 0.5 to 48 hours to obtain the compound of formula II aCompound. The solvent can be selected from dichloromethane, chloroform, carbon tetrachloride, acetonitrile, n-hexane, cyclohexane, benzene, toluene, ethyl acetate, DMF, DMA, ether, methyl tert-butyl ether, THF, DMSO or dioxane, etc. Suitable Lewis acid can be selected from sulfuric acid, hydrochloric acid, phosphoric acid, anhydrous zinc chloride, anhydrous aluminum chloride, boron trifluoride, boron tribromide, sulfur trioxide, iron bromide, titanium tetrachloride, trimethylchlorosilane or trimethyliodosilane, etc.

[0080] When Z is sulfur, Formula II b The compound can be represented by formula IV b The compound undergoes chlorosulfonation reaction with chlorosulfonic acid (commercially available) to obtain a compound of formula V b Intermediate compound, formula V b The intermediate compound undergoes reduction reaction with an appropriate reducing agent to obtain a compound of formula II b Compound.

[0081]

[0082] Formula IV b The compound and chlorosulfonic acid are reacted in the absence of solvent or with an appropriate solvent at a temperature of -30°C to the boiling point of the solvent for 0.5 to 48 hours to obtain the product of formula V b Intermediate compound. Suitable solvents can be selected from dichloromethane, chloroform, carbon tetrachloride, n-hexane, cyclohexane, diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane.

[0083] Formula V b The intermediate compound is reacted with a suitable reducing agent at a temperature ranging from -30°C to the boiling point of the solvent for 0.5 to 48 hours to obtain a product of formula II b Compound. The solvent can be selected from alcohols such as methanol, ethanol, isopropanol, etc., ethers such as ether, tetrahydrofuran, dioxane, etc., acids such as formic acid, acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, etc. The reducing agent is selected from hydrogen, a catalytic amount of a transition metal or a catalytic amount of a transition metal compound; wherein the transition metal can be a Group VIII compound, preferably Ni, Pd, Pt, etc. (directly used or loaded via activated carbon, aluminum oxide, silicon dioxide, etc.); hydrogen can be provided by a hydrogen storage cylinder, or by an active metal (such as reduced iron powder, reduced zinc powder, etc.) in situ under acidic conditions (such as hydrochloric acid, sulfuric acid) and participate in the reduction reaction. Suitable reducing agents also include salts formed by certain low-valent ions, such as stannous chloride, ferrous sulfate, sodium nitrite, sodium bisulfite, etc.

[0084] For Formula IV a Compound or Formula IV b The compounds need to be prepared separately according to the different Het.

[0085] Wherein, when Het is selected from Het1, W1 and W2 are oxygen, X is fluorine, Y is chlorine, and R1 and R2 together with the atoms to which they are attached form a ring of formula V a Compound or formula V b Compounds, such as 2-chloro-4-fluoro-5-(1,3-dioxohexahydroimidazo[1,5-a]pyridin-2-yl)phenyl isopropyl ether (CAS No. 85113-26-4), can be synthesized with reference to JP57209290A.

[0086] When Het is selected from Het2, W1 is oxygen, R1 is difluoromethyl, R2 is methyl, X is fluorine, and Y is chlorine, the formula V a Compounds such as 2-chloro-4-fluoro-5-(4-difluoromethyl-2,4-dihydro-5-methyl-3H-3-oxo-1,2,4-triazol-2-yl)anisole (CAS No. 97986-18-0) can be synthesized with reference to WO8501637A1 and WO8700730A1; or formula V b Compounds, such as 2-(2-fluoro-2-chlorophenyl)-4-difluoromethyl-2,4-dihydro-5-methyl-3H-1,2,4-triazol-3-one (CAS No.111992-05-3), can be synthesized with reference to CN103965124A; in addition, when Het is selected from Het2, W1 is oxygen, X and Y are both chlorine, and R1 and R2 together with the atoms to which they are connected form a ring of formula V a Compound or formula V b Compounds, such as 2,4-dichloro-5-(5,6,7,8-tetrahydro-3-oxo-1,2,4-triazolo[4,3-a]pyridin-2-yl)anisole (CAS No.68049-73-0) or 2-chloro-4-fluoro-5-(5,6,7,8-tetrahydro-3-oxo-1,2,4-triazolo[4,3-a]pyridin-2-yl)benzene (CAS No.68049-30-9), can be synthesized with reference to US4213773A.

[0087] When Het is selected from Het3, W1 and W2 are both oxygen, X is fluorine, Y is chlorine, and R1 and R2 together with the atoms to which they are attached form a ring of formula V a Compounds such as 2-chloro-4-fluoro-5-(tetrahydro-1H-[1,2,4]triazolo[1,2-a]pyridazine-1,3(2H)-dione-2-yl)phenyl isopropyl ether (CAS No.86798-18-7) can be prepared by synthesis with reference to EP75267A1; or Formula V bCompounds, such as 2-(2-fluoro-4-chlorophenyl)tetrahydro-1H-[1,2,4]triazolo[1,2-a]pyridazine-1,3(2H)-dione (CAS No. 68017-42-5), can be synthesized with reference to JP S3044587A.

[0088] When Het is selected from Het6, W1 and W2 are both oxygen, W3 is sulfur, R1 and R2 are both methyl, X is fluorine, and Y is chlorine, the formula V a Compounds, such as 2-chloro-4-fluoro-5-(1,5-dimethyl-6-thio-1,3,5-triazine-2,4(1H,3H)-dione-3-yl)phenyl isopropyl ether (CAS No.289882-55-9), can be synthesized with reference to WO2000050409A1; when Het is selected from Het6, W1 and W2 are both oxygen, W3 is sulfur, R1 and R2 are both methyl, X is hydrogen, and Y is chlorine, formula V b Compounds, such as 3-(4-chlorophenyl)-1,5-dimethyl-6-thioxo-1,3,5-triazine-2,4(1H,3H)-dione (CAS No. 289882-75-3), can also be synthesized with reference to WO2000050409A1.

[0089] When Het is selected from Het8, W1 and W2 are both oxygen, R1 is methyl, R2 is trifluoromethyl, R4 is hydrogen, X is fluorine, and Y is chlorine, the formula V a Compounds such as 2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione-3-yl)phenyl isopropyl ether (CAS No.114168-55-7); or a compound of formula V b Compounds, such as 3-(2-fluoro-4-chlorophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione (CAS No. 114136-66-2), can be synthesized with reference to EP255047A1 and WO9314073A1.

[0090] When Het is selected from Het 10 , W1 is oxygen, X is fluorine, Y is chlorine, R3 is trifluoromethyl, R4 is methyl, and R6 is hydrogen of formula V a Compound or formula V b Compounds, such as 2-chloro-4-fluoro-5-(5-methyl-6-oxo-4-trifluoromethyl-1(6H)-pyridazinyl)phenyl isopropyl ether (CAS No. 188489-04-5), can be synthesized with reference to WO9707104A1.

[0091] The compound of formula I and its salt, whether in the form of isomer mixture or pure isomer form, can be used as a herbicide. The herbicidal composition containing the compound of formula I can well control plants in non-crops, especially at high application rates. The compound of formula I of the present invention has good herbicidal activity for many important monocotyledonous weeds and dicotyledonous weeds. Although the compound of formula of the present invention has excellent herbicidal activity for monocotyledonous weeds and dicotyledonous weeds, it has no damage or minimal damage to important economic crops, such as wheat, barley, rye, rice, corn, soybeans and cotton, and does not cause significant impact on crops. This effect can be observed especially at low application rates. Therefore, the technical solution of the present invention also includes the use of the compound of formula I for controlling weeds in economic crops.

[0092] The present invention also includes a herbicidal composition with the compound of formula I as an active component. The weight percentage of the active component in the herbicidal composition is 1-99%. The herbicidal composition also includes an agriculturally acceptable carrier.

[0093] The herbicidal composition of the present invention can be applied in the form of a variety of formulations. The compound of the present invention is usually dissolved or dispersed in a carrier to prepare a formulation so that it is easier to disperse when used as a herbicide. For example, these chemical formulations can be made into wettable powders or emulsifiable concentrates. Therefore, in these compositions, at least one liquid or solid carrier is added, and it is usually necessary to add a suitable surfactant.

[0094] Another embodiment of the present invention is a method for controlling weeds, which comprises applying a herbicidal effective amount of the herbicidal composition of the present invention to the weeds or the surface of the site where the weeds grow or the growth medium thereof. The more suitable effective amount is usually selected to be 1 gram to 500 grams per hectare, and the preferred effective amount is 2 grams to 250 grams per hectare. For some applications, one or more other herbicides can be added to the herbicidal composition of the present invention, thereby producing additional advantages and effects.

[0095] The compounds of the present invention can be used alone or in admixture with other known insecticides, fungicides, plant growth regulators or fertilizers.

[0096] It should be understood that various changes and modifications can be made within the scope of the present invention as defined by the claims. Specific implementation methods

[0097] The following synthesis examples and biological test results are used to further illustrate the present invention, but are not intended to limit the present invention. For those skilled in the art, it should not be understood that the scope of the above subject matter of the present invention is limited to the following compounds and / or biological test results.

[0098] Synthesis Example

[0099] Example 1: Preparation of 2-methoxy-2-(2-chloro-4-fluoro-5-(1,3-dioxohexahydroimidazo[1,5-a]pyridin-2(3H)-yl)phenoxy)acetic acid n-pentyl ester (Compound 1-31)

[0100]

[0101] Step a) Synthesis of intermediate 2-chloro-4-fluoro-5-nitrophenyl benzyl ether

[0102]

[0103] 2-Chloro-4-fluoro-5-nitrophenol (3.83 g, 20.0 mmol), dichloromethane (40 mL) and triethylamine (2.45 g, 24.2 mmol) were added to a 250 mL reaction bottle to form a solution, and benzyl bromide (3.76 g, 22.0 mmol) was added dropwise at room temperature and the reaction was stirred at room temperature for 2 h. The reaction solution was poured into 50 mL of water and extracted with 50 mL of dichloromethane. The combined organic layer was washed with 30 mL of saturated brine, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 5.40 g of yellow liquid with a crude yield of 96%. The obtained 2-chloro-4-fluoro-5-nitrophenyl benzyl ether was directly used in the next step of synthesis without further purification.

[0104] Step b) Synthesis of intermediate 2-fluoro-4-chloro-5-benzyloxyaniline

[0105]

[0106] In a 250mL reaction bottle, 2-chloro-4-fluoro-5-nitrophenyl benzyl ether (5.40g, 19.2mmol) was mixed with 20mL ethanol and 20mL tetrahydrofuran to form a solution, and reduced iron powder (3.75g, 67.0mmol) was added. Concentrated hydrochloric acid (13.5mL, about 158mmol) was added dropwise under an ice-water bath. After the addition was completed, the mixture was returned to room temperature and reacted for 1h. The solvent was evaporated under reduced pressure, 50mL water was added to the residue, and it was extracted with ethyl acetate (30mL×3). The combined organic layer was washed with 50mL saturated brine, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 3.50g of yellow liquid with a crude yield of 72%. The obtained 2-fluoro-4-chloro-5-benzyloxyaniline was directly used in the next step of synthesis without further purification.

[0107] Step c) Synthesis of intermediate 2-chloro-4-fluoro-5-(1,3-dioxohexahydroimidazo[1,5-a]pyridin-2(3H)-yl)phenyl benzyl ether

[0108]

[0109] In a 250 mL reaction bottle, 2-fluoro-4-chloro-5-benzyloxyaniline (5.00 g, 20.0 mmol) and triphosgene (2.97 g, 10.0 mmol) were dissolved in 100 mL toluene to form a solution, heated to reflux, and reacted for 4 h. After stopping the reaction, the reaction system was cooled, the toluene was evaporated, and the residue was directly used in the next step.

[0110] In a 250 mL reaction bottle, the residue from the previous step, ethyl piperidine-2-carboxylate (3.10 g, 22.0 mmol) and triethylamine (2.23 g, 22.0 mmol) were dissolved in 100 mL of ethyl acetate to form a solution, heated to 60 ° C, and reacted for 4 hours. After the reaction was completed, 60 mL of ethyl acetate was added, washed with saturated brine (60 mL × 2), dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a brown viscous liquid. Column chromatography (SiO2, EtOAc: PE = 1:9, then 1:3) was used to obtain the intermediate compound 2-chloro-4-fluoro-5-(1,3-dioxohexahydroimidazo[1,5-a]pyridine-2(3H)-yl)phenylbenzyl ether 6.0 g, yellow liquid, yield 80%.

[0111] Step d) Synthesis of the intermediate 2-chloro-4-fluoro-5-(1,3-dioxohexahydroimidazo[1,5-a]pyridin-2(3H)-yl)phenol

[0112]

[0113] In a 100 mL reaction bottle, 2-chloro-4-fluoro-5-(1,3-dioxohexahydroimidazo[1,5-a]pyridin-2(3H)-yl)phenyl benzyl ether (3.89 g, 10.0 mmol) was dissolved in 40 mL of acetonitrile to form a solution, and trimethylsilyl iodide (10.00 g, 50.0 mmol) was added thereto at room temperature and reacted overnight. After the reaction was completed, an appropriate amount of silica gel was added thereto and the mixture was concentrated under reduced pressure. Column chromatography (SiO2, EtOAc:PE=1:5, then 1:1) was performed to obtain 2.39 g of the intermediate compound 2-chloro-4-fluoro-5-(1,3-dioxohexahydroimidazo[1,5-a]pyridin-2(3H)-yl)phenol as a yellow solid with a yield of 80%.

[0114] Step e) Synthesis of Compound 1-31

[0115]

[0116] In a 50 mL reaction bottle, 2-chloro-4-fluoro-5-(1,3-dioxohexahydroimidazo[1,5-a]pyridin-2(3H)-yl)phenol (300 mg, 1.0 mmol) was dissolved in 10 mL of dichloromethane, triethylamine (120 mg, 1.2 mmol) was added at room temperature, and 2-bromo-2-methoxyacetic acid n-pentyl ester (287 mg, 1.2 mmol) was added dropwise thereto, and the reaction was kept at room temperature for 0.5 h. After the reaction was completed, an appropriate amount of silica gel was added thereto, and the mixture was concentrated under reduced pressure. Column chromatography (SiO2, EtOAc:PE=1:3) was used to obtain 250 mg of compound 1-31 as a yellow oil with a yield of 54%.

[0117] Example 2: Preparation of methyl 2-ethoxy-2-(2-chloro-4-fluoro-5-(1,3-dioxotetrahydro-1H-[1,2,4]triazolo[1,2-a]pyridazin-2(3H)-yl)phenoxy)acetate (Compound 2-51)

[0118]

[0119] Step a) Synthesis of intermediate 2-chloro-4-fluoro-5-(1,3-dioxotetrahydro-1H-[1,2,4]triazolo[1,2-a]pyridazin-2(3H)-yl)phenyl benzyl ether

[0120]

[0121] In a 250 mL reaction bottle, 2-fluoro-4-chloro-5-benzyloxyaniline (5.00 g, 20.0 mmol) and triphosgene (2.97 g, 10.0 mmol) were dissolved in 100 mL toluene to form a solution, heated to reflux, and reacted for 4 h. After stopping the reaction, the reaction system was cooled, the toluene was evaporated, and the residue was directly used in the next step.

[0122] In a 250 mL reaction bottle, the residue from the previous step, hexahydropyridazine dihydrochloride (3.50 g, 22.0 mmol) and triethylamine (2.23 g, 22.0 mmol) were dissolved in 100 mL of dichloromethane to form a solution, and the solution was reacted at room temperature for 4 h. After the reaction was completed, 60 mL of dichloromethane was added, and the solution was washed with saturated brine (100 mL × 2), dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a brown solid.

[0123] In a 250 mL reaction bottle, the brown solid from the previous step, triphosgene (2.97 g, 10.0 mmol), and pyridine (3.16 g, 40.0 mmol) were dissolved in 100 mL of dichloroethane to form a solution, which was heated to reflux for 4 h. After the reaction was completed, 60 mL of dichloroethane was added, washed with saturated brine (100 mL × 2), dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a brown solid. Column chromatography (SiO2, EtOAc: PE = 1:3, then 1:1) gave 4.67 g of 2-chloro-4-fluoro-5-(1,3-dioxotetrahydro-1H-[1,2,4]triazolo[1,2-a]pyridazine-2(3H)-yl)phenyl benzyl ether as a brown solid with a yield of 60%.

[0124] Step b) Synthesis of the intermediate 2-chloro-4-fluoro-5-(1,3-dioxotetrahydro-1H-[1,2,4]triazolo[1,2-a]pyridazin-2(3H)-yl)phenol

[0125]

[0126] In a 100 mL reaction bottle, 2-chloro-4-fluoro-5-(1,3-dioxotetrahydro-1H-[1,2,4]triazolo[1,2-a]pyridazine-2(3H)-yl)phenyl benzyl ether (3.89 g, 10.0 mmol) was dissolved in 40 mL of acetonitrile to form a solution, and trimethylsilyl iodide (10.00 g, 50.0 mmol) was added thereto at room temperature and reacted overnight. After the reaction was completed, an appropriate amount of silica gel was added thereto and the mixture was concentrated under reduced pressure. Column chromatography (SiO2, EtOAc:PE=1:3, then 1:1) was performed to obtain 2.88 g of 2-chloro-4-fluoro-5-(1,3-dioxotetrahydro-1H-[1,2,4]triazolo[1,2-a]pyridazine-2(3H)-yl)phenol as a brown solid with a yield of 80%.

[0127] Step c) Synthesis of Compound 2-51

[0128]

[0129] In a 50 mL reaction bottle, 2-chloro-4-fluoro-5-(1,3-dioxotetrahydro-1H-[1,2,4]triazolo[1,2-a]pyridazine-2(3H)-yl)phenol (300 mg, 1.0 mmol) was dissolved in 10 mL of dichloromethane, triethylamine (120 mg, 1.2 mmol) was added at room temperature, and 2-bromo-2-ethoxyacetic acid methyl ester (236 mg, 1.2 mmol) was added dropwise thereto, and the reaction was kept at room temperature for 0.5 h. After the reaction was completed, an appropriate amount of silica gel was added thereto, and the mixture was concentrated under reduced pressure. Column chromatography (SiO2, EtOAc:PE=1:3) was used to obtain 300 mg of compound 2-51 as a yellow oil with a yield of 72%.

[0130] Example 3: Preparation of ethyl 2-methoxy-2-(2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazin-1-yl)phenoxy)acetate (Compound 3-152)

[0131]

[0132] Step a) Synthesis of intermediate 2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazin-1-yl)phenyl benzyl ether

[0133]

[0134] Add 30 mL of ethyl acetate to a 250 mL reaction bottle, then add 2-fluoro-4-chloro-5-benzyloxyaniline (3.50 g, 13.9 mmol), triethylamine (2.5 mL, 18.0 mmol) and carbonyldiimidazole (DCI, 5.60 g, 34.5 mmol) in sequence to form a solution, heat to 50 ° C, and react for 30 min. Then add 1,3-dimethylthiourea (1.75 g, 16.8 mmol), then heat to reflux and react for 2 h. After the reaction is completed, add 60 mL of ethyl acetate, wash with saturated brine (30 mL × 2), dry with anhydrous magnesium sulfate, filter, and concentrate under reduced pressure to obtain a brown viscous liquid. Column chromatography (SiO2, EtOAc:PE=1:9, then 1:4) gave 3.85 g of the intermediate compound 2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazin-1-yl)phenyl benzyl ether as a yellow liquid. After cooling, a light yellow solid was precipitated. The yield was 68%.

[0135] Step b) Synthesis of intermediate 2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazine-1-yl)phenol

[0136]

[0137] In a 100 mL reaction bottle, 2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazine-1-yl)phenyl benzyl ether (2.04 g, 5.0 mmol) was dissolved in 20 mL of acetonitrile, trimethylsilyl iodide (5.00 g, 25.0 mmol) was added thereto at room temperature and the reaction was kept overnight. After the reaction was completed, an appropriate amount of silica gel was added thereto and the reaction was concentrated under reduced pressure. Column chromatography (SiO2, EtOAc:PE=1:9, then 1:4) was performed to obtain 1.45 g of the intermediate compound 2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazine-1-yl)phenol as an orange-yellow solid with a yield of 91%.

[0138] Step c) Synthesis of Compound 3-152

[0139]

[0140] In a 50 mL reaction bottle, 2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazine-1-yl)phenol (318 mg, 1.0 mmol) was dissolved in 10 mL of dichloromethane, triethylamine (0.5 mL, 3.6 mmol) was added at room temperature, and ethyl 2-bromo-2-methoxyacetate (217 mg, 1.1 mmol) was added dropwise thereto, and the reaction was kept at room temperature overnight. After the reaction was completed, an appropriate amount of silica gel was added thereto, and the mixture was concentrated under reduced pressure. Column chromatography (SiO2, EtOAc:PE=1:9) was used to obtain 312 mg of compound 3-152 as a yellow oil with a yield of 72%.

[0141] Example 4: Preparation of ethyl 2-methoxy-2-(2-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenoxy)acetate (Compound 4-2)

[0142]

[0143] Step a) Synthesis of intermediate 2-chloro-5-nitrophenyl benzyl ether

[0144]

[0145] 2-Chloro-5-nitrophenol (3.47 g, 20.0 mmol), potassium carbonate (3.04 g, 22.0 mmol) and DMF 100 mL were added to a 250 mL reaction bottle to form a solution, and benzyl bromide (3.76 g, 22.0 mmol) was added dropwise at room temperature and the reaction was stirred overnight at room temperature. The reaction solution was poured into 100 mL of ice water and extracted with 100 × 2 mL of ethyl acetate. The combined organic layer was washed with 100 mL × 2 saturated brine, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 5.20 g of yellow liquid with a crude yield of 99%. The obtained 2-chloro-5-nitrophenyl benzyl ether was directly used in the next step of synthesis without further purification.

[0146] Step b) Synthesis of intermediate 2-chloro-5-benzyloxyaniline

[0147]

[0148] In a 250mL reaction bottle, 2-chloro-5-nitrophenyl benzyl ether (5.20g, 19.7mmol) was mixed with 20mL ethanol and 20mL tetrahydrofuran to form a solution, and reduced iron powder (3.75g, 67.0mmol) was added. Concentrated hydrochloric acid (13.5mL, about 158mmol) was added dropwise under an ice-water bath. After the addition was completed, the mixture was returned to room temperature and reacted for 1h. The solvent was evaporated under reduced pressure, 50mL water was added to the residue, and it was extracted with ethyl acetate (30mL×3). The combined organic layer was washed with 50mL saturated brine, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 3.30g brown solid, with a crude yield of 71%. The obtained 2-chloro-5-benzyloxyaniline was directly used in the next step of synthesis without further purification.

[0149] Step c) Synthesis of intermediate 2-chloro-5-(4-trifluoromethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-1-yl)phenyl benzyl ether

[0150]

[0151] In a 250 mL reaction bottle, 2-chloro-5-benzyloxyaniline (7.01 g, 30.0 mmol) and (Z)-3-(3,3-dimethylureido)-4,4,4-trifluoro-2-butenoic acid ethyl ester (8.40 g, 33.0 mmol) were dissolved in 50 mL of acetic acid to form a solution, which was heated to reflux and reacted for 4 h. After stopping the reaction, the reaction mixture was poured into a 200 mL ice-water mixture to precipitate 2-chloro-5-(4-trifluoromethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-1-yl)phenyl benzyl ether 9.52 g was precipitated as a yellow solid with a yield of 80%.

[0152] Step d) Synthesis of intermediate 2-chloro-5-(3-methyl-4-trifluoromethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-1-yl)phenyl benzyl ether

[0153]

[0154] In a 250 mL reaction bottle, 2-chloro-5-(4-trifluoromethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-1-yl)phenyl benzyl ether (10.0 g, 25.2 mmol) was dissolved in 100 mL of DMF to form a solution, potassium carbonate (4.15 g, 30.0 mmol) was added at room temperature and reacted for 30 min, and then iodomethane (3.90 g, 27.5 mmol) was added and reacted overnight. After the reaction was completed, 100 mL of ethyl acetate was added, washed with saturated brine (100 mL × 2), dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a brown viscous liquid. Column chromatography (SiO2, EtOAc:PE=1:9, then 1:4) gave 9.32 g of 2-chloro-5-(3-methyl-4-trifluoromethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-1-yl)phenyl benzyl ether as a yellow liquid with a yield of 90%.

[0155] Step e) Synthesis of intermediate 2-chloro-5-(3-methyl-4-trifluoromethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-1-yl)phenol

[0156]

[0157] In a 100 mL reaction bottle, 2-chloro-5-(3-methyl-4-trifluoromethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-1-yl)phenyl benzyl ether (4.11 g, 10.0 mmol) was dissolved in 40 mL of acetonitrile to form a solution, and trimethylsilyl iodide (10.00 g, 50.0 mmol) was added thereto at room temperature and reacted overnight. After the reaction was completed, an appropriate amount of silica gel was added thereto and the mixture was concentrated under reduced pressure. Column chromatography (SiO2, EtOAc:PE=1:9, then 1:3) was performed to obtain 2.56 g of 2-chloro-5-(3-methyl-4-trifluoromethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-1-yl)phenol as a yellow solid with a yield of 83%.

[0158] Step f) Synthesis of Compound 4-2

[0159]

[0160] In a 50 mL reaction bottle, 2-chloro-5-(3-methyl-4-trifluoromethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-1-yl)phenol (300 mg, 0.94 mmol) was dissolved in 10 mL of dichloromethane, triethylamine (110 mg, 1.1 mmol) was added at room temperature, and ethyl 2-bromo-2-methoxyacetate (236 mg, 1.2 mmol) was added dropwise thereto, and the reaction was kept at room temperature for 0.5 h. After the reaction was completed, an appropriate amount of silica gel was added thereto, and the mixture was concentrated under reduced pressure. Column chromatography (SiO2, EtOAc:PE=1:3) was used to obtain 300 mg of compound 4-2 as a yellow oil with a yield of 73%.

[0161] Example 5: Preparation of methyl 2-methoxy-2-(2-chloro-4-fluoro-5-(3-methyl-4-trifluoromethyl-2,6-dioxo-3,6-dihydropyrimidin-1-yl)phenoxy)acetate (Compound 4-101)

[0162]

[0163] Step a) Synthesis of intermediate 2-chloro-4-fluoro-5-(4-trifluoromethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-1-yl)phenyl benzyl ether

[0164]

[0165] In a 250 mL reaction bottle, 2-fluoro-4-chloro-5-benzyloxyaniline (7.55 g, 30.0 mmol) and (Z)-3-(3,3-dimethylureido)-4,4,4-trifluoro-2-butenoic acid ethyl ester (8.40 g, 33.0 mmol) were dissolved in 30 mL of acetic acid to form a solution, which was heated to reflux and reacted for 4 h. After stopping the reaction, the reaction mixture was poured into 200 mL of ice-water mixture, and 10.00 g of 2-chloro-4-fluoro-5-(4-trifluoromethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-1-yl)phenyl benzyl ether was precipitated as a yellow solid with a yield of 80%.

[0166] Step b) Synthesis of intermediate 2-chloro-4-fluoro-5-(3-methyl-4-trifluoromethyl-2,6-dioxo-3,6-tetrahydropyrimidin-1-yl)phenyl benzyl ether

[0167]

[0168] In a 250 mL reaction bottle, 2-chloro-4-fluoro-5-(4-trifluoromethyl-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-1-yl)phenyl benzyl ether (10.00 g, 24.1 mmol) was dissolved in 25 mL of DMF to form a solution, potassium carbonate (4.15 g, 30.0 mmol) was added at room temperature to react for 30 min, and then iodomethane (3.90 g, 27.5 mmol) was added to react overnight. After the reaction was completed, 60 mL of ethyl acetate was added to it, washed with saturated brine (30 mL × 2), dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a brown viscous liquid. Column chromatography (SiO2, EtOAc:PE=1:9, then 1:4) was used to obtain 9.00 g of 2-chloro-4-fluoro-5-(3-methyl-4-trifluoromethyl-2,6-dioxo-3,6-tetrahydropyrimidin-1-yl)phenyl benzyl ether as a yellow liquid with a yield of 87%.

[0169] Step e) Synthesis of intermediate 2-chloro-4-fluoro-5-(3-methyl-4-trifluoromethyl-2,6-dioxo-3,6-dihydropyrimidin-1-yl)phenol

[0170]

[0171] In a 100 mL reaction bottle, 2-chloro-4-fluoro-5-(3-methyl-4-trifluoromethyl-2,6-dioxo-3,6-tetrahydropyrimidin-1-yl)phenyl benzyl ether (4.29 g, 10.0 mmol) was dissolved in 20 mL of acetonitrile to form a solution, and trimethylsilyl iodide (5.00 g, 25.0 mmol) was added thereto at room temperature and reacted overnight. After the reaction was completed, an appropriate amount of silica gel was added thereto and the mixture was concentrated under reduced pressure. Column chromatography (SiO2, EtOAc:PE=1:9, then 1:4) was performed to obtain 2.80 g of 2-chloro-4-fluoro-5-(3-methyl-4-trifluoromethyl-2,6-dioxo-3,6-dihydropyrimidin-1-yl)phenol as a yellow solid with a yield of 83%.

[0172] Step f) Synthesis of Compound 4-101

[0173]

[0174] In a 50 mL reaction bottle, 2-chloro-4-fluoro-5-(3-methyl-4-trifluoromethyl-2,6-dioxo-3,6-dihydropyrimidin-1-yl)phenol (339 mg, 1.0 mmol) was dissolved in 10 mL of dichloromethane, triethylamine (0.5 mL, 3.6 mmol) was added at room temperature, and 2-bromo-2-methoxyacetic acid methyl ester (201 mg, 1.1 mmol) was added dropwise, and the reaction was kept at room temperature overnight. After the reaction was completed, an appropriate amount of silica gel was added and concentrated under reduced pressure. Column chromatography (SiO2, EtOAc: PE = 1: 9) was used to obtain 300 mg of compound 4-101 as a yellow oil with a yield of 68%.

[0175] Example 6: Preparation of methyl 2-methoxy-2-(2-fluoro-4-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenylthio)acetate (Compound 4-276)

[0176]

[0177] Step a) Synthesis of the intermediate 3-(2-chloro-4-fluorophenyl)-6-trifluoromethylpyrimidine-2,4(1H,3H)-dione

[0178]

[0179] In a 250 mL reaction bottle, 2-chloro-4-fluoroaniline (4.37 g, 30.0 mmol) and (Z)-3-(3,3-dimethylureido)-4,4,4-trifluoro-2-butenoic acid ethyl ester (8.40 g, 33.0 mmol) were dissolved in 50 mL of acetic acid to form a solution, which was heated to reflux and reacted for 4 h. After stopping the reaction, the reaction mixture was poured into 200 mL of ice-water mixture, and 7.40 g of 3-(2-chloro-4-fluorophenyl)-6-trifluoromethylpyrimidine-2,4(1H,3H)-dione was precipitated as a yellow solid with a yield of 80%.

[0180] Step b) Synthesis of intermediate 3-(2-chloro-4-fluorophenyl)-1-methyl-6-trifluoromethylpyrimidine-2,4(1H,3H)-dione

[0181]

[0182] In a 250mL reaction bottle, 3-(2-chloro-4-fluorophenyl)-6-trifluoromethylpyrimidine-2,4(1H,3H)-dione (10.00g, 32.4mmol) was dissolved in 50mL of DMF to form a solution, potassium carbonate (5.38g, 38.9mmol) was added at room temperature and reacted for 30min, and then iodomethane (5.06g, 35.6mmol) was added and reacted overnight. After the reaction was completed, 100mL of ethyl acetate was added, washed with saturated brine (50mL×2), dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a brown viscous liquid. Column chromatography separation (SiO2, EtOAc:PE=1:9, then 1:4) gave 3-(2-chloro-4-fluorophenyl)-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione 9.40g, yellow liquid, yield 90%.

[0183] Step c) Synthesis of intermediate 2-fluoro-4-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)benzenesulfonyl chloride

[0184]

[0185] In a 250 mL reaction bottle, 3-(2-chloro-4-fluorophenyl)-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione (9.40 g, 29.2 mmol) and 20 mL of chlorosulfonic acid were stirred at 130 ° C for 2.5 h. After the reaction was completed, the reaction system was cooled to room temperature and then slowly added dropwise to crushed ice. After the suspension was filtered, the filter cake was washed with water and dried to obtain 11.8 g of 2-fluoro-4-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidine-1(2H)-yl)benzenesulfonyl chloride as a gray solid with a yield of 99%.

[0186] Step d) Synthesis of intermediate 2-fluoro-4-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)thiophenol

[0187]

[0188] In a 250 mL reaction bottle, 2-fluoro-4-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)benzenesulfonyl chloride (10.0 g, 23.7 mmol), 75 mL of acetic acid and 35 mL of hydrochloric acid were mixed, and then stannous chloride dihydrate (26.8 g, 119 mmol) was added to the reaction system, and the temperature was raised to 80°C and stirred for 1.5 h. After the reaction was completed, the reaction system was cooled to room temperature, and 100 mL of ethyl acetate was added thereto, washed with saturated brine (100 mL×2), dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 5.88 g of 2-fluoro-4-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)thiophenol as a gray solid with a yield of 70%.

[0189] Step e) Preparation of Compound 4-276

[0190]

[0191] In a 50 mL reaction bottle, 2-fluoro-4-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)thiophenol (300 mg, 0.85 mmol) was dissolved in 10 mL of dichloromethane, triethylamine (100 mg, 1.0 mmol) was added at room temperature, and 2-bromo-2-methoxyacetic acid methyl ester (183 mg, 1.0 mmol) was added dropwise thereto, and the reaction was kept at room temperature for 0.5 h. After the reaction was completed, an appropriate amount of silica gel was added thereto, and the mixture was concentrated under reduced pressure. Column chromatography (SiO2, EtOAc:PE=1:3) was used to obtain 350 mg of compound 4-276 as a light yellow oil with a yield of 90%.

[0192] Example 7: Preparation of 2-methoxy-2-(2-chloro-4-fluoro-5-(5-methyl-6-oxo-4-trifluoromethylpyridazin-1(6H)-yl)phenoxy)acetic acid cyclopropylmethyl ester (Compound 5-93)

[0193]

[0194] Step a) Synthesis of intermediate 1-chloro-5-fluoro-2-isopropoxy-4-nitrobenzene

[0195]

[0196] In a 250 mL reaction bottle, 2-chloro-4-fluoro-5-nitrophenol (5.74 g, 30 mmol), isopropyl bromide (4.06 g, 33 mmol), potassium carbonate (4.56 g, 33 mmol) and 100 mL of DMF were added to form a solution, and the reaction system was stirred overnight. After the reaction was completed, 100 mL of ethyl acetate was added to the reaction system, washed with saturated brine (100 mL × 2), dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 6.94 g of 1-chloro-5-fluoro-2-isopropoxy-4-nitrobenzene as a yellow solid with a yield of 98%.

[0197] Step b) Synthesis of intermediate 4-chloro-2-fluoro-5-isopropoxyaniline

[0198]

[0199] In a 250 mL reaction bottle, 1-chloro-5-fluoro-2-isopropoxy-4-nitrobenzene (5.74 g, 30 mmol), dihydrated stannous chloride (23.7 g, 10.5 mmol) and 100 mL of DMF were added to form a solution, and the reaction system was heated to 60°C and reacted for 4 hours. After the reaction was completed, the reaction system was poured into 200 mL of water, and after adjusting the pH to >7, ethyl acetate was added to the reaction system for extraction (100 mL×2), washed with saturated brine (100 mL×2), dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 5.38 g of 4-chloro-2-fluoro-5-isopropoxyaniline as a brown solid with a yield of 88%.

[0200] Step c) Synthesis of intermediate 4-chloro-2-fluoro-5-isopropoxyphenylhydrazine

[0201]

[0202] After adding 4-chloro-2-fluoro-5-isopropoxyaniline (5.00 g, 24.5 mmol) and 30 mL of sulfuric acid to a 250 mL reaction bottle to form a solution, the reaction system was stirred in an ice bath for 10 min. 50 mL of an aqueous solution of NaNO2 (1.69 g, 24.5 mmol) was slowly added dropwise to the reaction system and reacted for 30 min after the addition was complete.

[0203] Add stannous chloride dihydrate (16.6 g, 73.5 mmol) and 50 mL of hydrochloric acid to a 250 mL reaction bottle to form a solution, and place in an ice bath. Slowly add the reaction solution from the previous step to the hydrochloric acid solution of stannous chloride and react for 2 h. After the reaction is completed, pour the reaction system into 100 mL of water, adjust the pH to strong alkalinity, add methyl tert-butyl ether for extraction (100 mL × 2), dry over anhydrous magnesium sulfate, filter, and concentrate under reduced pressure to obtain 2.68 g of 4-chloro-2-fluoro-5-isopropoxyphenylhydrazine as a black solid with a yield of 50%.

[0204] Step d) Synthesis of the intermediate 3-(2-(4-chloro-2-fluoro-5-isopropoxyphenyl)hydrazone)-1,1,1-trifluoropropane-2-one

[0205]

[0206] After adding 3,3-dibromo-1,1,1-trifluoropropane-2-one (3.24 g, 12 mmol), sodium acetate (1.64 g, 20 mmol) and 50 mL of water to a 250 mL reaction bottle to form a solution, the reaction solution was stirred, slowly heated to 80 ° C, and reacted for 0.5 h. After the reaction was completed, 50 mL of 4-chloro-2-fluoro-5-isopropoxyphenylhydrazine (2.19 g, 10 mmol) dichloromethane solution was added to the reaction system, and the reaction was continued overnight. After the reaction was completed, dichloromethane was added to the reaction system for extraction (100 mL × 2), washed with saturated brine (100 mL × 2), dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a yellow liquid. Column chromatography (SiO2, EtOAc:PE=1:9, then 1:5) afforded 2.29 g of 3-(2-(4-chloro-2-fluoro-5-isopropoxyphenyl)hydrazone)-1,1,1-trifluoropropane-2-one as a yellow solid in a yield of 70%.

[0207] Step e) Synthesis of intermediate 2-(4-chloro-2-fluoro-5-isopropoxyphenyl)-4-methyl-5-trifluoromethylpyridazin-3(2H)-one

[0208]

[0209] In a 100mL reaction bottle, 3-(2-(4-chloro-2-fluoro-5-isopropoxyphenyl)hydrazone)-1,1,1-trifluoropropane-2-one (2.29g, 7.0mmol), ethoxycarbonylethylidenetriphenylphosphine (2.79g, 7.7mmol) and 50mL tetrahydrofuran were added to form a solution, and the reaction solution was stirred, slowly heated to reflux, and reacted for 2h. After the reaction was completed, ethyl acetate was added to the reaction system for extraction (100mL×2), washed with saturated brine (100mL×2), dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a brown liquid. Column chromatography separation (SiO2, EtOAc:PE=1:9, then 1:5) gave 2-(4-chloro-2-fluoro-5-isopropoxyphenyl)-4-methyl-5-trifluoromethylpyridazine-3(2H)-one 1.79g, brown liquid, yield 70%.

[0210] Step f) Synthesis of intermediate 2-chloro-4-fluoro-5-(5-methyl-6-oxo-4-trifluoromethylpyridazin-1(6H)-yl)phenol

[0211]

[0212] After adding 2-(4-chloro-2-fluoro-5-isopropoxyphenyl)-4-methyl-5-trifluoromethylpyridazine-3(2H)-one (1.79 g, 4.9 mmol) and 50 mL of dichloromethane to a 100 mL reaction bottle to form a solution, the reaction solution was stirred, and boron tribromide (1.35 g, 5.4 mmol) was slowly added dropwise, and the reaction was allowed to proceed overnight. After the reaction was completed, 100 mL of dichloromethane was added to the reaction system for dilution, and the mixture was washed with saturated brine (100 mL × 2), dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a yellow solid. Column chromatography (SiO2, EtOAc:PE=1:9, then 1:3) was performed to obtain 1.13 g of 2-chloro-4-fluoro-5-(5-methyl-6-oxo-4-trifluoromethylpyridazine-1(6H)-yl)phenol as a yellow solid with a yield of 70%.

[0213] Step g) Preparation of Compound 5-93

[0214]

[0215] In a 50 mL reaction bottle, 2-chloro-4-fluoro-5-(5-methyl-6-oxo-4-trifluoromethylpyridazine-1(6H)-yl)phenol (300 mg, 0.93 mmol) was dissolved in 10 mL of dichloromethane, triethylamine (110 mg, 1.1 mmol) was added at room temperature, and 2-bromo-2-methoxyacetic acid cyclopropylmethyl ester (260 mg, 1.1 mmol) was added dropwise thereto, and the reaction was kept at room temperature for 0.5 h. After the reaction was completed, an appropriate amount of silica gel was added thereto, and the mixture was concentrated under reduced pressure. Column chromatography (SiO2, EtOAc:PE=1:5) was used to obtain 300 mg of compound 5-93 as a red oil with a yield of 70%.

[0216] By replacing the starting materials according to the above-described method, other compounds represented by the compound of formula I can be obtained. The structures and physical properties of some compounds of formula I are shown in Tables 1 to 5.

[0217]

[0218] Table 1

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226]

[0227] Table 2

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236] Table 3

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261] Table 4

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284]

[0285]

[0286] Table 5

[0287]

[0288]

[0289]

[0290]

[0291]

[0292]

[0293]

[0294]

[0295]

[0296] Bioassay Example

[0297] Example 8: Testing of herbicidal activity

[0298] Stem and leaf activity test: Sow the seeds of broadleaf weeds (Amaranth, Shepherd's Purse, Solanum nigrum), Gramineae weeds (Digitaria, Echinochloa crusgalli, Leptochloa chinensis) or Cyperus weeds (Cyperus rotundus) in plastic cups with a diameter of 5 cm filled with nutrient soil. Cover with 0.1-0.5 cm of soil after sowing, flatten it, absorb enough water from the bottom of the plastic cup, place it in a greenhouse and cultivate it according to the conventional method. Spray the stems and leaves after the weeds have 2-3 leaves.

[0299] Soil activity test: The sowing method is the same as the stem and leaf activity determination, and the soil is sprayed 24 hours after sowing.

[0300] Test and efficacy evaluation method: After the original drug is dissolved in N, N-dimethylformamide solvent, 0.1% Tween 80 water is used to prepare the required concentration of the test solution according to the test requirements. According to the designed test dose, spray treatment is carried out in a 3WP-2000 walking spray tower (manufactured by Nanjing Agricultural Machinery Research Institute) (spray pressure 0.3MPa, spray volume 45mL / m 2 , nozzle model TP6501E, spray height 300mm, nozzle travel speed 320mm / s), the test was repeated 3 times. After the test materials were treated with the agent, the solution was naturally dried in the shade, and then transferred to the greenhouse for cultivation according to the conventional method. The weed reaction symptoms were regularly observed and recorded. The control effect of the test agent on weeds was investigated 14 days after the application, and it was expressed as 0-100%, "0" means no control effect, and "100%" means that the weeds were completely killed.

[0301] The Chinese, English and Latin names of the weeds used in the experiment are as follows:

[0302] Amaranth (three-colored amaranth, Amaranthus tricolor);

[0303] shepherd's purse (Capsella bursa-pastoris);

[0304] Black nightshade (Solanum nigrum);

[0305] Crabgrass (large crabgrass, Digitaria sanguinalis);

[0306] Barnyard grass (Echinocloa crus-galli);

[0307] Chinese sprangletop, Leptochloa chinensis;

[0308] Rice flatsedge (Cyperus iria).

[0309] The results of the herbicidal activity test on stems and leaves showed that the compounds of formula I generally had good control effects on broad-leaved weeds. Some of the tested compounds had good control effects on broad-leaved weeds at an application dose of 75 g ai / hm 2The compounds have excellent control effect on amaranth, with a control effect of not less than 80%. They are: compounds 2-26, 3-2, 3-38, 3-151, 3-152, 3-153, 3-154, 3-155, 3-156, 3-157, 3-158, 3-163, 3-164, 3-165, 3-168, 3-176, 3-177, 3-188, 3-189, 3-193, 3-201, 3-308, 4-2, 4-26, 4-27, 4-101, 4-102, 4-103, 4-104, 4-105, 4-106, 4-107, 4-108, 4-113, 4-114, 4-116, 4-126 , 4-127, 4-138, 4-139, 4-140, 4-143, 4-151, 4-152, 4-205, 4-226, 4-227, 4-230, 4-231, 4-233, 4-243, 4-251, 4-252, 4-253, 4-255, 4-256, 4-258, 4-268, 5-1, 5-8, 5-13, 5-18, 5-26, 5-30, 5-31, 5-76, 5-77, 5-78, 5-80, 5-81, 5-83, 5-88, 5-89, 5-93, 5-101, 5-102, 5-103, 5-113, 5-115 and 5-118.

[0310] The results of the herbicidal activity test on stems and leaves showed that the compounds of formula I generally had good control effects on broad-leaved weeds. Some of the tested compounds had good control effects on broad-leaved weeds at an application dose of 75 g ai / hm 2The compounds have excellent control effect on shepherd's purse, with a control effect of not less than 80%. They are: compounds 2-30, 3-14, 3-152, 3-153, 3-154, 3-155, 3-156, 3-157, 3-158, 3-163, 3-164, 3-165, 3-168, 3-193, 4-1, 4-2, 4-26, 4-101, 4-102, 4-103, 4-104, 4-105, 4-106, 4-107, 4-108, 4-113, 4-114, 4-116, 4-118, 4-126, 4-127, 4-138, 4-139 , 4-140, 4-143, 4-151, 4-152, 4-226, 4-227, 4-230, 4-231, 4-233, 4-243, 4-251, 4-252, 4-253, 4-255, 4-256, 4-258, 4-268, 5-1, 5-8, 5-13, 5-18, 5-26, 5-30, 5-31, 5-76, 5-77, 5-78, 5-80, 5-81, 5-83, 5-88, 5-89, 5-93, 5-101, 5-102, 5-103, 5-113, 5-115 and 5-118.

[0311] The results of the herbicidal activity test on stems and leaves showed that the compounds of formula I generally had good control effects on broad-leaved weeds. Some of the tested compounds had good control effects on broad-leaved weeds at an application dose of 75 g ai / hm 2 It has excellent control effect on Solanum nigrum, with a control effect of not less than 90%. Such as compounds 3-151, 3-152, 3-153, 3-154, 3-155, 3-156, 3-157, 3-158, 3-163, 3-164, 3-165, 3-168, 3-177, 4-1, 4-2, 4-4, 4-27, 4-101, 4-102, 4-103, 4-104, 4-105, 4-106, 4-107, 4-108, 4-113, 4-114, 4-116, 4-118, 4-126, 4-127, 4-138, 4-139, 4-140, 4-143 , 4-151, 4-152, 4-176, 4-205, 4-226, 4-227, 4-230, 4-231, 4-233, 4-243, 4-251, 4-252, 4-253, 4-255, 4-256, 4-258, 4-268, 5-1, 5-8, 5-13, 5-18, 5-26, 5-76, 5-77, 5-78, 5-80, 5-81, 5-83, 5-88, 5-89, 5-93, 5-101, 5-102, 5-103, 5-113, 5-115 and 5-118.

[0312] The results of the herbicidal activity test on stems and leaves showed that the compounds of formula I generally had good control effects on grass weeds. Some of the tested compounds had good control effects on grass weeds at an application dose of 75 g ai / hm 2 Under the condition of high temperature, it has good control effect on crabgrass, with a control effect of not less than 60%. They are: compounds 3-15, 3-151, 3-152, 3-153, 3-155, 3-156, 3-157, 3-158, 3-177, 4-1, 4-2, 4-27, 4-101, 4-102, 4-103, 4-104, 4-1054-106, 4-107, 4-108, 4-113, 4-114, 4-116, 4-126, 4-127, 4-138, 4-151, 4-152, 4-153 -176, 4-205, 4-226, 4-227, 4-230, 4-231, 4-233, 4-243, 4-253, 4-255, 4-256, 4-258, 4-268, 5-1, 5-8, 5-13, 5-18, 5-26, 5-30, 5-31, 5-76, 5-77, 5-78, 5-80, 5-81, 5-83, 5-88, 5-89, 5-93, 5-101, 5-102, 5-103, 5-113, 5-115 and 5-118.

[0313] The results of the herbicidal activity test on stems and leaves showed that the compounds of formula I generally had good control effects on grass weeds. Some of the tested compounds had good control effects on grass weeds at an application dose of 75 g ai / hm 2 Under the condition, it has a good control effect on barnyard grass, with a control effect of not less than 60%. They are: 3-151, 3-152, 3-153, 3-155, 3-156, 3-157, 3-158, 4-2, 4-101, 4-102, 4-103, 4-104, 4-105, 4-106, 4-107, 4-108, 4-116, 4-126, 4- 127, 4-151, 4-152, 4-226, 4-227, 4-230, 4-231, 4-233, 4-243, 4-251, 4-252, 4-253, 4-255, 4-268, 5-76, 5-77, 5-78, 5-80, 5-81, 5-88, 5-89, 5-93, 5-102 and 5-113.

[0314] The results of the herbicidal activity test on stems and leaves showed that the compounds of formula I generally had good control effects on grass weeds. Some of the tested compounds had good control effects on grass weeds at an application dose of 75 g ai / hm 2Under the condition of high temperature, it has excellent control effect on Leptochloa chinensis, with a control effect of not less than 60%. They are: compounds 3-4, 3-26, 3-52, 3-105, 3-151, 3-152, 3-153, 3-154, 3-155, 3-156, 3-157, 3-158, 3-176, 3-177, 3-201, 3-202, 3-302, 3-327, 4-1, 4-2, 4-4, 4-26, 4-27, 4-55, 4-101, 4-102, 4-103, 4-104, 4-105, 4-106, 4-107, 4-108, 4-113 , 4-114, 4-116, 4-118, 4-126, 4-127, 4-138, 4-140, 4-151, 4-152, 4-176, 4-205, 4-226, 4-227, 4-230, 4-231, 4-233, 4-243, 4-253, 4-255, 4-256, 4-258, 4-268, 5-76, 5-77, 5-78, 5-80, 5-81, 5-83, 5-88, 5-89, 5-93, 5-101, 5-102, 5-103, 5-113, 5-115 and 5-118.

[0315] The results of the herbicidal activity test on stems and leaves showed that the compounds of formula I generally had good control effects on sedge weeds. Some of the tested compounds had good control effects on sedge weeds at an application dose of 75 g ai / hm 2 The compounds 3-15, 3-52, 3-151, 3-152, 3-153, 3-154, 3-156, 3-157, 3-158, 3-177, 3-201, 3-202, 3-226, 4-1, 4-2, 4-4, 4-27, 4-101, 4-102, 4-103, 4-104, 4-105, 4-106, 4-107, 4-108, 4-113, 4-114, 4-116, 4-118, 4-126, 4-127, 4-138, 4-139 9, 4-140, 4-143, 4-151, 4-152, 4-176, 4-226, 4-227, 4-230, 4-231, 4-233, 4-243, 4-252, 4-253, 4-255, 4-256, 4-258, 4-268, 5-1, 5-8, 5-13, 5-18, 5-26, 5-30, 5-31, 5-76, 5-77, 5-78, 5-80, 5-81, 5-83, 5-88, 5-89, 5-93, 5-101, 5-102, 5-103, 5-113, 5-115 and 5-118.

[0316] The results of the soil treatment herbicidal activity test showed that the compounds of formula I generally have good control effects on broad-leaved weeds. Some of the tested compounds had good control effects on broad-leaved weeds at an application dose of 75 g ai / hm 2 The compounds 2-30, 2-31, 2-33, 2-53, 2-63, 2-67, 3-4, 3-15, 3-18, 3-26, 3-27, 3-151, 3-152, 3-153, 3-154, 3-155, 3-157, 3-158, 3-16 3, 3-164, 3-165, 3-168, 3-176, 3-188, 3-189, 3-190, 3-193, 3-201, 3-202, 3-226, 3-301, 4-1, 4-2, 4-27, 4-101, 4-102, 4-103, 4-104, 4-105, 4-107, 4-113 , 4-114, 4-116, 4-126, 4-127, 4-138, 4-139, 4-140, 4-143, 4-151, 4-152, 4-176, 4-205, 4-226, 4-227, 4-230, 4-231, 4-233, 4-243, 4-251, 4-252, 4-253, 4 -255, 4-256, 4-258, 4-268, 5-1, 5-13, 5-18, 5-26, 5-30, 5-76, 5-77, 5-78, 5-80, 5-81, 5-83, 5-88, 5-89, 5-93, 5-101, 5-102, 5-103, 5-113, 5-115 and 5-118.

[0317] The results of the soil treatment herbicidal activity test showed that the compounds of formula I generally have good control effects on broad-leaved weeds. Some of the tested compounds had good control effects on broad-leaved weeds at an application dose of 75 g ai / hm 2The compounds have excellent control effect on shepherd's purse, with a control effect of not less than 80%. They are: compounds 1-28, 1-31, 1-43, 2-26, 2-67, 3-1, 3-2, 3-3, 3-4, 3-5, 3-6, 3-7, 3-8, 3-14, 3-15, 3-18, 3-26, 3-27, 3-38, 3-52, 3-76, 3-105, 3-153, 3-154, 3-155, 3-156, 3-157 7, 3-158, 3-163, 3-164, 3-165, 3-168, 3-176, 3-188, 3-189, 3-190, 3-193, 3-201, 3-202, 3-226, 3-255, 3-301, 3-302, 3-305, 3-327, 3-351, 3-380, 4-1, 4-2, 4-4, 4-26, 4-27, 4-55, 4-103, 4-104, 4-105, 4-106, 4-107, 4-108, 4-113, 4-114, 4-116, 4-118, 4-126, 4-127, 4-138, 4-139, 4-140, 4-143, 4-151, 4-152, 4-176, 4-205, 4-226, 4-227, 4-230, 4-231, 4-233, 4-243, 4-251, 4-252, 4-253 , 4-255, 4-256, 4-258, 4-268, 4-276, 4-301, 4-327, 5-1, 5-5, 5-8, 5-13, 5-18, 5-26, 5-30, 5-31, 5-76, 5-77, 5-78, 5-80, 5-81, 5-83, 5-88, 5-89, 5-93, 5-101, 5-102, 5-103, 5-113, 5-115 and 5-118.

[0318] The results of the soil treatment herbicidal activity test showed that the compounds of formula I generally have good control effects on broad-leaved weeds. Some of the tested compounds had good control effects on broad-leaved weeds at an application dose of 75 g ai / hm 2Under the condition of excellent control effect on Solanum nigrum, the control effect is not less than 80%. They are: compounds 3-4, 3-15, 3-151, 3-152, 3-153, 3-154, 3-155, 3-156, 3-157, 3-158, 3-163, 3-164, 3-165, 3-168, 3-176, 3-189, 3-193, 3-201, 3-202, 3-226, 3-301, 4-1, 4-2, 4-4, 4-27, 4-55, 4-101, 4-102, 4-103, 4-104, 4-105, 4-106, 4-107, 4-108, 4-113, 4-114, 4-116, 4-118, 4-119 26, 4-127, 4-138, 4-139, 4-140, 4-143, 4-151, 4-152, 4-226, 4-227, 4-230, 4-231, 4-233, 4-243, 4-251, 4-252, 4-253, 4-255, 4-256, 4-258, 4-268, 4 -301, 4-327, 5-1, 5-8, 5-13, 5-18, 5-26, 5-30, 5-31, 5-76, 5-77, 5-78, 5-80, 5-81, 5-83, 5-88, 5-89, 5-93, 5-101, 5-102, 5-103, 5-113, 5-115 and 5-118.

[0319] The results of the soil treatment herbicidal activity test showed that the compounds of formula I generally have good control effects on grass weeds. Some of the tested compounds had good control effects on grass weeds at an application dose of 75 g ai / hm 2Under the condition of high temperature, the control effect on crabgrass is good, and the control effect is not less than 60%. They are: compounds 3-52, 3-76, 3-151, 3-152, 3-153, 3-155, 3-156, 3-157, 3-163, 3-164, 3-165, 3-168, 3-177, 3-188, 3-190, 3-202, 3-255, 4-1, 4-2, 4-27, 4-101, 4-102, 4-103, 4-104, 4-105, 4-106, 4-107, 4-108, 4-113, 4-114, 4-116, 4-117 8, 4-126, 4-127, 4-138, 4-139, 4-140, 4-143, 4-151, 4-152, 4-176, 4-205, 4-226, 4-227, 4-230, 4-231, 4-233, 4-243, 4-251, 4-253, 5-1, 5-8, 5-13, 5-18, 5-26, 5-30, 5-31, 5-76, 5-77, 5-78, 5-80, 5-81, 5-83, 5-88, 5-89, 5-93, 5-101, 5-102, 5-115 and 5-118.

[0320] The results of the soil treatment herbicidal activity test showed that the compounds of formula I generally have good control effects on grass weeds. Some of the tested compounds had good control effects on grass weeds at an application dose of 75 g ai / hm 2 Under the condition of low temperature, it has good control effect on barnyard grass, with a control effect of not less than 60%. They are: compounds 3-151, 3-152, 3-157, 3-163, 3-164, 3-165, 3-177, 4-1, 4-2, 4-27, 4-101, 4-102, 4-105, 4-106, 4-107, 4-108, 4-113, 4-114, 4-116, 4-127, 4-138, 4-140, 4-152, 4-233, 5-80, 5-81, 5-88, 5-89 and 5-93.

[0321] The results of the soil treatment herbicidal activity test showed that the compounds of formula I generally have good control effects on grass weeds. Some of the tested compounds had good control effects on grass weeds at an application dose of 75 g ai / hm 2Under the condition of high temperature, the compounds have good control effect on Leptochloa chinensis, with a control effect of not less than 60%. They are: compounds 2-51, 2-67, 3-52, 3-151, 3-152, 3-153, 3-154, 3-155, 3-156, 3-157, 3-158, 3-163, 3-164, 3-165, 3-168, 3-176, 3-1 77, 3-188, 3-189, 3-190, 3-193, 3-201, 3-202, 3-306, 4-1, 4-2, 4-4, 4-27, 4-101, 4-102, 4-103, 4-104, 4-105, 4-106, 4-107, 4-108, 4-113, 4-114, 4-116 , 4-118, 4-126, 4-127, 4-138, 4-139, 4-140, 4-143, 4-151, 4-152, 4-176, 4-226, 4-227, 4-230, 4-231, 4-233, 4-243, 4-251, 4-252, 4-253, 4-255, 4-256 , 4-258, 4-268, 5-1, 5-8, 5-13, 5-18, 5-26, 5-30, 5-31, 5-76, 5-77, 5-78, 5-80, 5-81, 5-83, 5-88, 5-89, 5-93, 5-101, 5-102, 5-103, 5-113, 5-115 and 5-118.

[0322] The results of the soil treatment herbicidal activity test showed that the compounds of formula I generally had good control effects on sedge weeds. Some of the tested compounds had good control effects on sedge weeds at an application dose of 75 g ai / hm 2Under the condition of high temperature, the compounds have good control effect on Cyperus rotundus, with a control effect of not less than 80%. They are: compounds 3-1, 3-2, 3-3, 3-4, 3-6, 3-7, 3-8, 3-14, 3-15, 3-18, 3-26, 3-52, 3-151, 3-152, 3-153, 3-154, 3-155, 3-156, 3-157, 3-158, 3-163, 3- 164, 3-165, 3-168, 3-176, 3-177, 3-188, 3-189, 3-190, 3-193, 3-201, 3-202, 3-226, 3-303, 3-306, 4-1, 4-2, 4-4, 4-26, 4-27, 4-101, 4-102, 4-103, 4-104, 4-105, 4-106, 4 -107, 4-108, 4-113, 4-114, 4-116, 4-118, 4-126, 4-127, 4-138, 4-139, 4-140, 4-143, 4-151, 4-152, 4-176, 4-226, 4-227, 4-230, 4-231, 4-233, 4-243, 4-251, 4-252, 4-2 53, 4-255, 4-256, 4-258, 4-268, 5-1, 5-8, 5-13, 5-18, 5-26, 5-30, 5-31, 5-76, 5-77, 5-78, 5-80, 5-81, 5-83, 5-88, 5-89, 5-93, 5-101, 5-102, 5-103, 5-113, 5-115 and 5-118.

[0323] Example 9: Testing of Crop Safety

[0324] Stem and leaf activity test: Sow wheat, rice, corn, cotton and soybean seeds in plastic cups with a diameter of 5 cm filled with nutrient soil. Cover with 1 cm of soil after sowing and flatten. Absorb enough water from the bottom of the plastic cup and keep the soil moist. Place in a greenhouse and cultivate according to the conventional method. After each test crop grows to the 2-3 leaf stage, spray the stems and leaves.

[0325] Soil activity test: The sowing method is the same as the stem and leaf activity determination, and the soil is sprayed 24 hours after sowing.

[0326] Test and phytotoxicity evaluation method: After the original drug is dissolved in N,N-dimethylformamide solvent, 0.1% Tween 80 water is used to prepare the required concentration of the test solution according to the test requirements. According to the designed test dosage, spray treatment is carried out in a 3WP-2000 walking spray tower (manufactured by Nanjing Agricultural Machinery Research Institute) (spray pressure 0.3MPa, spray volume 45mL / m 2, nozzle model TP6501E, spray height 300mm, nozzle travel speed 320mm / s), the test was repeated 3 times. After the test materials were treated with the pesticide, the liquid was naturally dried in the shade, and then transferred to the greenhouse for cultivation according to the conventional method. The crop reaction symptoms were regularly observed and recorded. The damage of the test pesticide to the crops was investigated 14 days after the pesticide was applied, and the damage grade was used to indicate the damage:

[0327] The pesticide damage level is "0", which means that the growth inhibition rate or mortality rate of crops is 0, and there is no pesticide damage;

[0328] The pesticide damage level is "1", which means that the growth inhibition rate or mortality rate of crops is 1-20%, which is a slight pesticide damage;

[0329] The pesticide damage level is "2", which means that the growth inhibition rate or mortality rate of crops is 21-30%, which is moderate pesticide damage;

[0330] The pesticide damage level is "3", which means that the growth inhibition rate or mortality rate of crops is 31-40%, which is a serious pesticide damage;

[0331] The pesticide damage level is "4", which means that the growth inhibition rate or mortality rate of crops is 41-50%, which is severe pesticide damage;

[0332] A pesticide damage grade of "5" indicates that the growth inhibition rate or mortality rate of crops is greater than 50%, which is severe pesticide damage.

[0333] The Chinese, English and Latin names of the crops used in the experiment are as follows:

[0334] Wheat (Triticum aestivum);

[0335] Rice (Oryza sativa);

[0336] Corn (corn, Zea mays);

[0337] Cotton (Gossypium herbaceum);

[0338] Soybean (soybean, Glycine max);

[0339] The results of the crop safety test on stem and leaf treatment showed that the compounds of formula I generally have good safety for wheat. Some of the tested compounds were 2 The phytotoxicity level to wheat is no more than 1, indicating no phytotoxicity or slight phytotoxicity. For example, compound 3-152.

[0340] The results of the crop safety test on stem and leaf treatment showed that the compounds of formula I generally have good safety to rice. Some of the tested compounds were 2 The phytotoxicity level to rice is not greater than 1, no phytotoxicity or slight phytotoxicity, such as compounds 3-151, 3-152, 4-101, 4-102 and 4-127.

[0341] The results of the safety test on stem and leaf treatment of crops showed that the compounds of formula I generally have good safety for corn. Some of the tested compounds were effective at a dosage of 75 g ai / hm2. 2 The phytotoxicity level to corn is not greater than 1, indicating no phytotoxicity or slight phytotoxicity, such as compounds 3-151 and 3-152.

[0342] The results of the soil treatment crop safety test showed that the compounds of formula I generally have good safety for wheat. Some of the tested compounds were applied at a dose of 75 g ai / hm 2 The phytotoxicity level to wheat is not greater than 1, no phytotoxicity or slight phytotoxicity. Such as compounds 3-151, 3-152, 4-101, 4-102, 4-127, 5-76 and 5-77.

[0343] The results of soil treatment crop safety tests showed that the compounds of formula I generally have good safety for rice. Some of the tested compounds were 2 The phytotoxicity level to rice is not greater than 1, indicating no phytotoxicity or slight phytotoxicity, such as compounds 3-151 and 3-152.

[0344] The results of the soil treatment crop safety test showed that the compounds of formula I generally have good safety for corn. Some of the tested compounds were applied at a dose of 75 g ai / hm 2 The phytotoxicity level to corn is not greater than 1, no phytotoxicity or slight phytotoxicity, such as compounds 3-151, 3-152, 4-101, 4-102, 4-127, 5-76 and 5-77.

[0345] The results of the soil treatment crop safety test showed that the compounds of formula I generally have good safety for soybeans. Some of the tested compounds were 2 The phytotoxicity level to soybean is not greater than 1, no phytotoxicity or slight phytotoxicity, such as compounds 3-151, 3-152, 4-101, 4-102, 5-76 and 5-77.

[0346] Example 10: Parallel testing of indoor herbicidal activity

[0347] According to the above test method, some compounds of formula I and patent reference compound KC1 (compound No. 57 in Table 1 of patent EP83055A2 specification) were selected for parallel test of herbicidal activity in greenhouse. The herbicidal activity test application dose was 18.75 g ai / hm 2 , the test results are shown in Table 6 and Table 7.

[0348] Table 6: Parallel test results of herbicidal activity of some compounds of formula I (stem and leaf treatment, control effect 14 days after drug application)

[0349]

[0350]

[0351] Table 7: Parallel test results of herbicidal activity of some compounds of formula I (soil treatment, control effect 14 days after application)

[0352] Compound Amaranth Shepherd's Purse Solanum nigrum Crataegus Qianjinzi Cyperus rotundus 4-126 100 100 100 60 60 90 4-152 100 100 100 60 70 70 4-226 100 100 100 90 100 100 4-227 100 100 100 70 90 90 5-1 100 100 100 90 80 100 5-26 100 100 100 90 90 100 5-76 90 100 100 80 90 80 5-80 100 100 100 80 70 90 5-93 100 100 100 70 90 100 <![CDATA[KC1]]> 30 0 50 0 0 0

[0353] Example 11: Parallel testing of indoor herbicidal activity and crop safety

[0354] According to the above test method, some compounds of formula I and patent reference compound KC2 (the compound of Example 1 in the specification of patent WO2016120116A1) were selected for parallel tests of herbicidal activity and crop safety in the greenhouse. The herbicidal activity is expressed by 0-100%, and the crop damage is graded by the damage grade. The test results are shown in Table 8.

[0355] Table 8: Parallel test results of herbicidal activity and crop safety of some compounds of formula I (stem and leaf treatment, 14 days after drug application. " / " indicates not tested)

[0356]

[0357]

Claims

1. A tetrasubstituted phenyl ether (thioether) compound containing an alkoxyacetate substituent, characterized in that The tetrasubstituted phenyl ether (thioether) compound containing an alkoxyacetate substituent has a structure shown in the following formula I: in: X is selected from hydrogen, halogen, C1-C6 alkyl or C1-C6 alkoxy; Y is selected from halogen, cyano, nitro, C1-C6 alkyl, C1-C6 alkoxy, CONH2 or CSNH2; Z is selected from oxygen or sulfur; R and Ak are each independently selected from C1-C6 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkylthio C1-C6 alkyl, C1-C6 alkylamino C1-C6 alkyl, C3-C8 cycloalkyl C1-C6 alkyl, C2-C8 oxacycloalkyl C1-C6 alkyl, C1-C6 alkoxycarbonyl C1-C6 alkyl, phenyl or benzyl, and the above groups may be further substituted by any combination of one or more halogens, cyano, nitro, C1-C6 alkoxy, C1-C6 haloalkyl or C1-C6 haloalkoxy, or R and Ak together with the atoms to which they are attached form a 5- to 7-membered heterocyclic ring; Het is selected from in, W1, W2 and W3 are each independently oxygen or sulfur; R1 and R2 are each independently selected from hydrogen, cyano, amino, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 haloalkoxy, C3-C7 cycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, benzyl, C1-C6 cyanoalkyl, OR7, or R1 and R2 together with the atoms to which they are attached form a 3-membered to 7-membered ring system, and the ring system may be further substituted by any combination of one to more halogens, nitro, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino or C1-C4 alkylthio; R3 and R4 are each independently selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 haloalkoxy, C3-C7 cycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, OR7, S(O) n R7, OSO2R7, NR7R8, or R3 and R4 together with the atoms to which they are attached form a 3- to 7-membered ring system, and the ring system may be further substituted by any combination of one to more halogen, nitro, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino or C1-C4 alkylthio, wherein n is 0, 1 or 2; R5 is selected from hydrogen, halogen or C1-C6 alkyl; R6 is selected from hydrogen, halogen, C1-C6 alkyl, OR7, SR7, S(O) n R7, OSO2R7 or NR7R8; R7 and R8 are each independently selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C3-C7 cycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, phenyl or benzyl, and the above groups may be further substituted by any combination of one to more halogen, nitro, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino or C1-C4 alkylthio.

2. The tetrasubstituted phenyl ether (thioether) compound containing an alkoxyacetate substituent according to claim 1, characterized in that: In Formula I: X is selected from hydrogen or halogen; Y is selected from halogen or cyano; Z is selected from oxygen or sulfur; R and Ak are each independently selected from C1-C6 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkylthio C1-C6 alkyl, C1-C6 alkylamino C1-C6 alkyl, C3-C8 cycloalkyl C1-C6 alkyl, C2-C8 oxacycloalkyl C1-C6 alkyl, C1-C6 alkoxycarbonyl C1-C6 alkyl, phenyl or benzyl, and the above groups may be further substituted by any combination of one or more halogens, cyano, nitro, C1-C6 alkoxy, C1-C6 haloalkyl or C1-C6 haloalkoxy; Het is selected from Het1, Het2, Het3, Het4, Het6, Het7, Het8 or Het 10 .

3. The tetrasubstituted phenyl ether (thioether) compound containing an alkoxyacetate substituent according to claim 1-2, characterized in that: In Formula I: X is selected from hydrogen, fluorine or chlorine; Y is selected from fluorine, chlorine, bromine or cyano; Z is selected from oxygen or sulfur; R and Ak are each independently selected from C1-C6 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, C3-C8 cycloalkyl, C1-C6 haloalkyl, C1-C6 alkoxy C1-C6 alkyl, C1-C6 alkylthio C1-C6 alkyl, C1-C6 alkylamino C1-C6 alkyl, C3-C8 cycloalkyl C1-C6 alkyl, C2-C8 oxacycloalkyl C1-C6 alkyl, C1-C6 alkoxycarbonyl C1-C6 alkyl, phenyl or benzyl, and the above groups may be further substituted by any combination of one or more halogens, cyano, nitro, C1-C6 alkoxy, C1-C6 haloalkyl or C1-C6 haloalkoxy; Het is selected from Het1, Het3, Het6, Het8 or Het 10 .

4. The tetrasubstituted phenyl ether (thioether) compound containing an alkoxyacetate substituent according to claim 1-3, characterized in that: In Formula I: X is selected from hydrogen, fluorine or chlorine; Y is selected from fluorine or chlorine; Z is selected from oxygen or sulfur; Ak is selected from methyl, ethyl, n-propyl, isopropyl, phenyl or 2,4-dichlorophenyl; R is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, allyl, 2-buten-1-yl, propargyl, 2-butyn-1-yl, cyclopropyl, cyclopentyl, trifluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2-chloroethyl, 3-chloro-n-propyl, 4-chloro-n-butyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, methylthiomethyl, 2-methylthioethyl, cyclopropylmethyl, 2-cyclopropylethyl, cyclo Butyl methyl, cyclopentyl methyl, cyclohexyl methyl, oxirane methyl, tetrahydrofuran-2-methyl, tetrahydrofuran-3-methyl, 2,2-dimethyl-1,3-dioxolane-4-methyl, methoxycarbonyl methyl, ethoxycarbonyl methyl, 1-ethoxycarbonyl ethyl, 2-ethoxycarbonyl ethyl, cyanomethyl, 2-nitroethyl, 2-(2-methoxyethoxy)ethyl, 2-(trifluoroethoxy)ethyl, 2-(2-chloroethoxy)ethyl, 2-(cyanomethoxy)ethyl, etc.; When Het is selected from Het1 or Het3, wherein R1 and R2 together with the atoms to which they are attached form a 6-membered ring system, W1 and W2 are selected from oxygen; when Het is selected from Het6, wherein R1 and R2 are selected from methyl, W1 and W2 are selected from oxygen, and W3 is selected from sulfur; when Het is selected from Het8, wherein R1 is selected from methyl, R3 is selected from trifluoromethyl, R4 is selected from hydrogen, and W1 and W2 are selected from oxygen; when Het is selected from Het 10 When R3 is selected from trifluoromethyl, R4 and R6 are selected from hydrogen or methyl, and W1 is selected from oxygen.

5. The tetrasubstituted phenyl ether (thioether) compound containing an alkoxyacetate substituent according to claims 1-4, characterized in that: The tetrasubstituted phenyl ether (thioether) compound containing an alkoxyacetate substituent is selected from any one of the following compounds: 2-methoxy-2-(2-chloro-4-fluoro-5-(1,3-dioxohexahydroimidazo[1,5-a]pyridin-2(3H)-yl)phenoxy)acetic acid n-pentyl ester (Compound 1-31); 2-ethoxy-2-(2-chloro-4-fluoro-5-(1,3-dioxotetrahydro-1H-[1,2,4]triazolo[1,2-a]pyridazin-2(3H)-yl)phenoxy)acetic acid methyl ester (Compound 2-51); 2-methoxy-(2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazin-1-yl)phenoxy)acetic acid ethyl ester (Compound 3-152); 2-methoxy-(2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazin-1-yl)phenoxy)acetate (Compound 3-153); 2-methoxy-(2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazin-1-yl)phenoxy)acetate isopentyl ester (Compound 3-157); 2-methoxy-(2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazin-1-yl)phenoxy)acetate (Compound 3-158); 2-isopropoxy-(2-chloro-4-fluoro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazin-1-yl)phenoxy)acetic acid ethyl ester (Compound 3-202); 2-methoxy-(2,4-dichloro-5-(3,5-dimethyl-2,6-dioxo-4-thioxo-1,3,5-triazin-1-yl)phenoxy)acetic acid ethyl ester (Compound 3-301); 2-methoxy-2-(2-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenoxy)acetic acid ethyl ester (Compound 4-2); 2-methoxy-2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenoxy)acetate (Compound 4-101); 2-methoxy-2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenoxy)acetic acid n-butyl ester (Compound 4-105); 2-methoxy-2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenoxy)acetate (Compound 4-106); 2-methoxy-2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenoxy)acetate (Compound 4-108); 2-methoxy-2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenoxy)acetate (2-methoxyethanol) (Compound 4-116); 2-ethoxy-2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenoxy)acetic acid ethyl ester (Compound 4-127); Ethyl 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenoxy)-2-phenoxyacetate (Compound 4-176); 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenoxy)-ethyl 2-(2,4-dichlorophenoxy)acetate (Compound 4-205); 2-methoxy-2-(2-fluoro-4-chloro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)-yl)phenylthio)acetate (Compound 4-276); 2-methoxy-2-(2-chloro-4-fluoro-5-(5-methyl-6-oxo-4-trifluoromethylpyridazin-1(6H)-yl)phenoxy)acetic acid methyl ester (Compound 5-76); 2-Methoxy-2-(2-chloro-4-fluoro-5-(5-methyl-6-oxo-4-trifluoromethylpyridazin-1(6H)-yl)phenoxy)acetate (2-chloroethanol) (Compound 5-88); 2-methoxy-2-(2-chloro-4-fluoro-5-(5-methyl-6-oxo-4-trifluoromethylpyridazin-1(6H)-yl)phenoxy)acetic acid cyclopropylmethyl ester (Compound 5-93); Methyl 2-ethoxy-2-(2-chloro-4-fluoro-5-(5-methyl-6-oxo-4-trifluoromethylpyridazin-1(6H)-yl)phenoxy)acetate (Compound 5-101).

6. Use of the tetrasubstituted phenyl ether (thioether) compound containing an alkoxyacetate substituent according to any one of claims 1 to 5 in controlling weeds.

7. A herbicidal composition, characterized in that: The herbicidal composition comprises an active substance and an agriculturally acceptable carrier, wherein the active component is a tetrasubstituted phenyl ether (thioether) compound containing an alkoxyacetate substituent as described in claims 1-5, and the weight percentage of the active component in the composition is 1% to 99%.

8. A method for controlling weeds, characterized in that: Apply a herbicidally effective amount of the tetrasubstituted phenyl ether (thioether) compound containing an alkoxyacetate substituent as claimed in any one of claims 1 to 5 or the herbicidal composition as claimed in claim 7 to weeds or a growth medium or site of weeds.

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