Hydroxyl aryl uracil compound and application thereof

Abstract

The invention provides a hydroxyl aryl uracil compound and application thereof, the structure of the hydroxyl aryl uracil compound is as shown in formula (I), in the formula (I), R1 and R2 are respectively and independently selected from C1-C4 alkyl, C1-C4 halogenated alkyl and the like; x and Y are respectively and independently selected from hydrogen atoms, halogen atoms and the like; z is selected from oxygen atoms or sulfur atoms; a is selected from-CH or a nitrogen atom; l is selected from a substituted or unsubstituted first group, and the first group is selected from C3-C8 cycloalkyl,-Ra-Rb-,-Rb-Rc-,-Ra-Rb-Rc-or a C2-C20 carbon chain containing 1 to 6 ether oxygen atoms. The hydroxyl aryl uracil compound has the advantages of being high in selectivity, wide in weeding spectrum, low in production cost and the like, weeds are not prone to generating resistance, and particularly has a good control effect on gramineous worst weeds such as goosegrass, barnyard grass and moleplant seeds.

Description

Technical Field

[0001] This invention relates to the field of organic compound technology, specifically to a hydroxyaryluracil compound and its applications. Background Technology

[0002] Because weeds compete with crops for light and fertilizer, they cause significant economic losses to agricultural production every year. Currently, the main method for weed control is still spraying chemical herbicides. However, with the widespread overuse of herbicides (such as glyphosate and glufosinate), many weeds have developed resistance, especially species like goosegrass, barnyard grass, and fleabane, which have become highly adaptable, prolific, and competitive dominant and noxious weeds. Existing herbicides on the market generally suffer from poor control efficacy, narrow weed removal range, and high dosage requirements, particularly against noxious grasses such as goosegrass, barnyard grass, and fleabane. Furthermore, these herbicides are expensive to produce and require large dosages, resulting in high prices and high weed control costs. Therefore, it is necessary to provide new herbicidal compounds with a broad spectrum of weed control, low resistance to weeds, and particularly good control efficacy against noxious grasses. Summary of the Invention

[0003] In view of this, this application provides a hydroxyaryluracil compound and its application. The hydroxyaryluracil compound has the advantages of high selectivity, broad spectrum of weed control, low resistance of weeds, and low production cost. In particular, it has a good control effect on noxious weeds such as goosegrass. Moreover, the compound has low toxicity to mammals and little impact on crops.

[0004] The first aspect of this application provides a hydroxyaryluracil compound, characterized in that the structure of the hydroxyaryluracil compound is shown in formula (I):

[0005]

[0006] In formula (Ⅰ), R1 and R2 are independently selected from hydrogen atoms, amino groups, C1-C4 alkyl groups, or C1-C4 haloalkyl groups, respectively;

[0007] X and Y are each independently selected from hydrogen atoms, halogen atoms, or cyano groups;

[0008] Z is selected from oxygen or sulfur atoms;

[0009] A is selected from -CH or a nitrogen atom;

[0010] L is selected from a substituted or unsubstituted first group, wherein the first group is selected from C3-C8 cycloalkyl, -R a -R b -、-R b -Rc -、-R a -R b -R c - or a C2-C20 carbon chain containing 1-6 ether oxygen atoms; wherein, R a R c Each is independently selected from C1-C10 alkylene, C2-C10 alkenylene, or C2-C10 ynylene, R b It is a C3-C8 cycloalkyl group; when L is the first substituted group, the substituted group is selected from hydroxyl, halogen atom, nitro, amino, cyano or C1-C6 alkyl.

[0011] In some embodiments of this application, L is selected from C3-C6 cycloalkyl groups, -R a -R b -、-R b -R c -、-R a -R b -R c - or a C2-C16 carbon chain containing 1-5 ether oxygen atoms; wherein, R a R c Each is independently selected from C1-C6 alkylene, C2-C6 alkenylene, or C2-C6 ynylene, R b It is a C3-C6 cycloalkyl group.

[0012] In some embodiments of this application, L is selected from C3-C5 cycloalkyl groups, -R a -R b -、-R b -R c -、-R a -R b -R c - or a C2-C14 carbon chain containing 1-4 ether oxygen atoms; wherein, R a R c Each is independently selected from C1-C4 alkylene, C2-C4 alkenylene, or C2-C4 ynylene, R b It is a C3-C4 cycloalkyl group.

[0013] In some embodiments of this application, L is selected from any one of the structures shown in formulas (L-1) to (L-9):

[0014]

[0015] In some embodiments of this application, R1 and R2 are each independently selected from C1-C4 alkyl or C1-C4 haloalkyl;

[0016] X and Y are halogen atoms;

[0017] Z represents an oxygen atom;

[0018] A is -CH.

[0019] In some embodiments of this application, R1 is trifluoromethyl, R2 is methyl or ethyl, X and Y are fluorine or chlorine atoms, and Z is oxygen atom.

[0020] The second aspect of this application provides a tautomer, enantiomer, diastereomer, or pesticide-acceptable salt thereof of the hydroxyaryluracil compound provided in the first aspect.

[0021] The third aspect of this application provides the use of tautomers, enantiomers, diastereomers, or pesticide-acceptable salts of the hydroxyaryluracil compounds provided in the first aspect or the second aspect in the preparation of herbicides or defoliants in the agricultural, forestry, or health fields.

[0022] The fourth aspect of this application provides a pesticide composition comprising an active ingredient and excipients, wherein the active ingredient comprises a tautomer, enantiomer, diastereomer, or pesticide-acceptable salt thereof of a hydroxyaryluracil compound provided in the first aspect or a hydroxyaryluracil compound provided in the second aspect.

[0023] In some embodiments of this application, the active ingredient in the pesticide composition has a mass percentage content of 1%-99%. Detailed Implementation

[0024] The technical solutions in the embodiments of this application are described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of the embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0025] Because weeds compete with crops for light and fertilizer, they cause significant economic losses to agricultural production every year. Currently, the main method for weed control is still spraying chemical herbicides. However, with the widespread overuse of herbicides (such as glyphosate and glufosinate), many weeds have developed resistance, especially species like goosegrass, barnyard grass, and fleabane, which have become highly adaptable, prolific, and competitive dominant and noxious weeds. Existing herbicides on the market generally suffer from poor control efficacy, narrow weed removal range, and high dosage requirements, particularly against noxious grasses such as goosegrass, barnyard grass, and barnyard grass. Furthermore, these herbicides are expensive to produce and require large dosages, resulting in high prices and high weed control costs. Therefore, it is necessary to provide new herbicidal compounds with a broad spectrum of weed control, low resistance to weeds, and particularly good control efficacy against noxious grasses.

[0026] In view of this, this application provides a hydroxyaryluracil compound and its application. This hydroxyaryluracil compound has advantages such as high selectivity, broad weed control spectrum, low resistance in weeds, and low production cost. In particular, it has a good control effect on noxious weeds such as goosegrass, barnyard grass, and Echinochloa crus-galli. Moreover, this hydroxyaryluracil compound can effectively control weeds while having minimal impact on crops.

[0027] This application provides a hydroxyaryluracil compound, the structure of which is shown in formula (I):

[0028]

[0029] In formula (Ⅰ), R1 and R2 are independently selected from hydrogen atoms, amino groups, C1-C4 alkyl groups, or C1-C4 haloalkyl groups, respectively;

[0030] X and Y are each independently selected from hydrogen atoms, halogen atoms, or cyano groups;

[0031] Z is selected from oxygen or sulfur atoms;

[0032] A is selected from -CH or a nitrogen atom;

[0033] L is selected from a substituted or unsubstituted first group, wherein the first group is selected from C3-C8 cycloalkyl, -R a -R b -、-R b -R c -、-R a -R b -R c - or a C2-C20 carbon chain containing 1-6 ether oxygen atoms; wherein, R a R cEach is independently selected from C1-C10 alkylene, C2-C10 alkenylene, or C2-C10 ynylene, R b It is a C3-C8 cycloalkyl group; when L is the first substituted group, the substituted group is selected from hydroxyl, halogen atom, nitro, amino, cyano, and C1-C6 alkyl.

[0034] This application provides the structure of a novel hydroxyaryluracil compound with excellent herbicidal effect. By selectively targeting specific sites, this hydroxyaryluracil compound enhances herbicidal selectivity and expands the range of weeds it can control. It is particularly effective against noxious weeds such as goosegrass, barnyard grass, and sedge, effectively eliminating these weeds while minimizing impact on the plants or crops that require protection. Furthermore, the selective targeting of certain sites reduces the amount of some high-cost raw materials (such as phenyluracil) used in the preparation process, thereby lowering production costs and facilitating large-scale industrial production.

[0035] In this application, R1 and R2 are independently selected from hydrogen atoms, amino groups, C1-C4 alkyl groups, or C1-C4 haloalkyl groups. In this application, the number of carbon atoms in the C1-C4 alkyl group can be, for example, 1, 2, 3, or 4. In some specific embodiments, the C1-C4 alkyl group can be, for example, methyl, ethyl, propyl, isopropyl, or butyl. In this application, the number of carbon atoms in the C1-C4 haloalkyl group can be, for example, 1, 2, 3, or 4. In this application, the halogen atom in the C1-C4 haloalkyl group can be, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. In this application, the C1-C4 haloalkyl group can have one or more halogen atoms. When the C1-C4 haloalkyl group contains multiple halogen atoms, the halogen atoms can be the same or different.

[0036] In some embodiments of this application, R1 and R2 are independently selected from C1-C2 alkyl or C1-C2 haloalkyl groups. In some specific embodiments of this application, R1 and R2 may be, for example, methyl, ethyl, monochloromethyl, dichloromethyl, trichloromethyl, monofluoromethyl, difluoromethyl, or trifluoromethyl. In embodiments of this application, R1 and R2 may be the same group or different groups. In some specific embodiments of this application, R1 is trifluoromethyl and R2 is methyl.

[0037] In this application, X and Y are independently selected from hydrogen atoms, halogen atoms, or cyano groups. In some embodiments of this application, X and Y are independently selected from hydrogen atoms, fluorine atoms, or chlorine atoms. In some embodiments of this application, Z is selected from oxygen atoms or sulfur atoms. In some specific embodiments, Z is an oxygen atom.

[0038] In the embodiments of this application, A is selected from -CH or a nitrogen atom. In some embodiments of this application, A is -CH, in which case the six-membered ring containing A is a benzene ring. In other embodiments of this application, A is a nitrogen atom, in which case the six-membered ring containing A is a nitrogen-containing heterocycle.

[0039] In this embodiment, L is selected from a substituted or unsubstituted first group, and the first group is selected from C3-C8 cycloalkyl groups, -R a -R b -、-R b -R c -、-R a -R b -R c - or a C2-C20 carbon chain containing 1-6 ether oxygen atoms; wherein, R a R c Each is independently selected from C1-C10 alkylene, C2-C10 alkenylene, or C2-C10 ynylene, R b It is a C3-C8 cycloalkyl group.

[0040] In some embodiments of this application, L is a divalent group containing a C3-C8 cycloalkyl group. In these embodiments, the C3-C8 cycloalkyl group may have, for example, 3, 4, 5, 6, 7, or 8 carbon atoms. In some specific embodiments, the C3-C8 cycloalkyl group may be, for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, or cyclooctane. In some embodiments of this application, the C3-C8 cycloalkyl group may be, for example, cyclopropane or cyclobutane. By selecting L containing a C3-C8 cycloalkyl group, the spatial volume of the molecule can be increased, thereby better utilizing the pocket space of the binding site and improving the herbicidal effect of the compound.

[0041] In some embodiments of this application, L is a C3-C8 cycloalkyl group. In some embodiments of this application, the Z atom and the hydroxyl group (-OH) adjacent to L can be grafted onto the same carbon atom in the C3-C8 cycloalkyl group. Taking cyclopropane as an example, L can be as follows: As shown; in some embodiments of this application, the Z and hydroxyl (-OH) atoms adjacent to L can also be grafted onto different carbon atoms in C3-C8 cycloalkyl groups. Taking cyclopropane as an example, L can be grafted onto different carbon atoms in C3-C8 cycloalkyl groups. As shown.

[0042] In some embodiments of this application, L is -R a -R b -、-R b -R c -or-R a -R b -R c -, where R a R cEach is independently selected from C1-C10 alkylene, C2-C10 alkenylene, or C2-C10 ynylene, R b It is a C3-C8 cycloalkyl group. In some embodiments of this application, it is related to R. b The groups attached to the left and right sides can be grafted onto the same carbon atom in a C3-C8 cycloalkyl group, or onto different carbon atoms in a C3-C8 cycloalkyl group.

[0043] In this application, alkylene refers to a divalent saturated hydrocarbon group formed by removing two hydrogen atoms from an alkane. It can be a branched hydrocarbon group or a branched hydrocarbon group. In this application, the number of carbon atoms in the C1-C10 alkylene group can be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. In some specific embodiments, the C1-C10 alkylene group can be, for example, methylene (-CH2-), ethylene (-CH2-CH2-), propylene (-CH2-CH2-CH2- or -CH(CH3)CH2-).

[0044] In this application, an alkenyl group refers to a divalent unsaturated hydrocarbon group formed by removing two hydrogen atoms from an olefin and containing at least one carbon-carbon double bond. It can be a branched hydrocarbon group or a branched hydrocarbon group. In this application, the number of carbon atoms in the C1-C10 alkenyl group can be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. In some specific embodiments, the C1-C10 alkenyl group can be, for example, vinylidene (-CH=CH-) or propenylidene (-CH=CH-CH2- or -CH2-CH=CH-).

[0045] In this application, the ynylene group refers to a divalent unsaturated hydrocarbon group formed by removing two hydrogen atoms from an alkyne and containing at least one carbon-carbon triple bond. It can be a branched hydrocarbon group or a branched hydrocarbon group. In this application, the number of carbon atoms in the C1-C10 ynylene group can be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. In some specific embodiments, the C1-C10 ynylene group can be, for example, an ethynylene group (-CH≡CH-) or a propynylene group (-CH≡CH-CH2- or -CH2-CH≡CH-).

[0046] In some embodiments of this application, L represents the first substituted group, which is selected from hydroxyl, halogen, nitro, amino, cyano, or C1-C6 alkyl groups. In these embodiments, the first group can be substituted by one or more substituted groups. When the first group is substituted by multiple substituted groups, the substituted groups can be the same or different. In some embodiments of this application, the substituted group can be a halogen atom, specifically, halogen atoms include, but are not limited to, fluorine, chlorine, bromine, or iodine atoms. In some embodiments of this application, the substituted group can be a C1-C6 alkyl group, and the number of carbon atoms in the C1-C6 alkyl group can be, for example, 1, 2, 3, 4, 5, or 6. Specifically, the C1-C6 alkyl group can be, for example, methyl, ethyl, propyl, isopropyl, or butyl.

[0047] In some embodiments of this application, L can be any of the structures shown in equations (L-1) to (L-9):

[0048]

[0049] By selecting the L structure containing cyclopropane and cyclobutane, the water solubility and systemic properties of the molecule can be further improved, thereby further enhancing the herbicidal effect of the compound.

[0050] In some embodiments of this application, L contains a C2-C20 carbon chain with 1-6 ether oxygen atoms. In these embodiments, L can contain 1, 2, 3, 4, 5, or 6 ether oxygen atoms, and the number of carbon atoms in L can be, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. In some specific embodiments, L is a divalent group composed of an ether oxygen atom and an alkylene group. In some embodiments, L contains a C2-C14 carbon chain with 1-4 ether oxygen atoms. In some specific embodiments, L can be, for example, -CH2OCH2-, -CH2CH2OCH2-, etc.

[0051] -CH2OCH2CH2-, -CH2CH2OCH2CH2-, -CH2CH2OCH2CH2OCH2CH2-, -CH2CH2OCH2CH2OCH2CH2OCH2CH2-. By selecting the aforementioned special structures containing ether oxygen atoms, the L-structures can, on the one hand, interact with other groups in the compound to enhance the water solubility and systemic properties of hydroxyaryluracil compounds, thereby improving their herbicidal effect. On the other hand, these L-structures have a large relative molecular mass, resulting in a large relative molecular mass for the structure on the right side of the compound that does not contain benzene rings or heterocycles. Therefore, in the preparation of hydroxyaryluracil compounds, the amount of high-cost raw materials such as phenyluracil can be reduced, thus lowering the production cost of the compound.

[0052] This application provides the structure of a novel hydroxyaryluracil compound with excellent weed-control effect. By selectively targeting specific sites, this hydroxyaryluracil compound enhances the herbicidal selectivity and expands the range of weeds it can control. It is particularly effective against noxious weeds such as goosegrass, barnyard grass, and sedge, effectively eliminating these weeds while minimizing impact on the plants or crops that require protection. Furthermore, the selective targeting of certain sites reduces the amount of some high-cost raw materials (such as phenyluracil) used in the preparation process, thereby lowering production costs and facilitating large-scale industrial production. Moreover, most weeds have developed resistance to commonly used herbicides after long-term use. The hydroxyaryluracil compound provided in this application is a novel compound not yet used in weed control, therefore it does not induce resistance in most weeds and exhibits excellent weed-control effects. Furthermore, this hydroxyaryluracil compound can specifically and effectively bind to chlorophyll protoporphyrinogen oxidase (PPO) in plants, and due to the difference in target structure in mammals, this compound exhibits extremely high safety for mammals.

[0053] This application also provides a tautomer, enantiomer, diastereomer, or pesticide-acceptable salt thereof of the hydroxyaryluracil compound described above.

[0054] This application also provides the use of the hydroxyaryluracil compounds described above, their tautomers, enantiomers, diastereomers, or pesticide-acceptable salts thereof, in the preparation of herbicides or defoliants in the agricultural, forestry, or health fields.

[0055] This application also provides a pesticide composition comprising an active ingredient and excipients. The active ingredient includes the aforementioned hydroxyaryluracil compounds and their tautomers, enantiomers, diastereomers, or pesticide-acceptable salts thereof. This pesticide composition offers advantages such as high selectivity, low dosage, broad-spectrum weed control, low risk of weed resistance, and low cost. It is particularly effective against noxious weeds such as goosegrass, barnyard grass, and Echinochloa crus-galli. Furthermore, this pesticide composition exhibits low toxicity to mammals and minimal impact on crops.

[0056] In this application, the mass percentage of the active ingredient in the pesticide composition is 1%-99%. In some specific embodiments, the mass percentage of the active ingredient in the pesticide composition can be, for example, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 99%. In some embodiments of this application, the mass percentage of the active ingredient in the pesticide composition can be 5%-50%. By further limiting the content of the active ingredient in the pesticide composition, the cost of the pesticide composition can be effectively controlled while ensuring good efficacy.

[0057] In this application, the pesticide composition may be used by means including but not limited to spraying.

[0058] In the embodiments of this application, excipients include, but are not limited to, fillers, carriers, emulsifiers, dispersants, wetting agents, and synergists. These excipients can help the pesticide composition exert its effects in different ways, including but not limited to improving efficacy, delaying the development of resistance, and enhancing the spreading and penetrability of the pesticide solution.

[0059] In some embodiments of this application, the pesticide composition may be a herbicide, and the weeds controlled by the herbicide include, but are not limited to, goosegrass, barnyard grass, Echinochloa crus-galli, crabgrass, foxtail grass, amaranth, purslane, lambsquarters, Erigeron tiglium, Lespedeza bicolor, alfalfa, geranium, tribulus terrestris, Elsholtzia ciliata, sesame, shepherd's purse, Veronica persica, cricket grass, sedge, euphorbia pekinensis, willowherb, Japanese golden grass, duckweed, jointed greens, chickweed, plantain, and oxalis.

[0060] In some embodiments of this application, the pesticide composition may be a defoliant, and the defoliant is used on plants that have lost their leaves, including but not limited to cotton, soybeans, sugarcane, grapes, fruit trees, etc.

[0061] The embodiments of the present invention will be further described below with reference to several examples.

[0062] Specifically, some of the hydroxyaryluracil compounds are listed in Table 1, but the hydroxyaryluracil compounds described in this invention are not limited to all the compounds in Table 1.

[0063] The structure of (L-1)-(L-9) in Table 1 is as follows:

[0064]

[0065] Table 1: Hydroxyaryluracil compounds with the chemical structure shown in formula (Ⅰ):

[0066]

[0067]

[0068] Example 1

[0069] The structural formulas of the hydroxyaryluracil compound numbered 20 in Table 1 are shown below:

[0070] The preparation method of this compound is as follows:

[0071] Weigh 0.22 g (0.00060 mol) of 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoic acid into a 50 mL round-bottom flask. Then weigh 5 mL of thionyl chloride and add it to the benzoic acid. Heat the mixture to 80 °C and reflux for 4 h. After the reaction is complete, evaporate the thionyl chloride to dryness at 40 °C to obtain a pale yellow solid. Weigh 0.064 g (0.00072 mL) of 1-(hydroxymethyl)cyclopropanol, 0.0014 g (0.000006 mol) of dimethyl tin dichloride, and 0.17 g (0.0012 mol) of potassium carbonate into 10 mL of anhydrous dichloromethane under nitrogen protection. The 2-chloro-4-fluoro-5-(1,2,3,6-tetrahydro-2,6-dioxo-4-trifluoromethylpyrimidin-1-yl)benzoyl chloride prepared above was added to 10 mL of dichloromethane and then slowly added dropwise to a mixed solution of 1-(hydroxymethyl)cyclopropanol. The reaction was allowed to proceed for 10 h. The complete reaction of the 2-chloro-4-fluoro-5-(1,2,3,6-tetrahydro-2,6-dioxo-4-trifluoromethylpyrimidin-1-yl)benzoyl chloride was monitored by TLC (Thin-Layer Chromatography). The above reaction solution was washed twice with dilute hydrochloric acid, twice with sodium bicarbonate, and twice with saturated sodium chloride. It was dried over anhydrous magnesium sulfate and evaporated to remove dichloromethane to obtain a white solid, 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoic acid (1-hydroxycyclopropyl) methyl ester (0.188 g, yield 71.2%), which was dried in an oven at 40 °C.

[0072] The 1H NMR spectrum (500MHz, DMSO-d6) of this compound is as follows (δ[ppm]): δ 8.11 (d, J=7.7Hz, 1H, Ph-H), 7.91 (d, J=9.5Hz, 1H, Ph-H), 6.63 (s, 1H, Ph-H), 5.65 (s, 1H, -OH), 4.32 (s, 2H, -CH2), 3.43 (s, 3H, -CH3), 0.73-0.63 (m, 4H, -CH2).

[0073] ESI-MS (m / z): [M+Na] + Theoretical value: 459.0341, measured value: 459.03412.

[0074] Example 2

[0075] The structural formula of the hydroxyaryluracil compound numbered 28 in Table 1 is shown below:

[0076]

[0077] The preparation method of this compound is as follows:

[0078] Weigh 0.25 g (0.00068 mol) of 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoic acid, 0.0012 g (0.000012 mol), N-methylimidazolium (NMI, 0.162 mL, 0.00204 mol), 1,1-cyclopropanediethanol (0.14 g, 0.00136 mol), and 20 mL of acetonitrile into a 50 mL round-bottom flask. Stir at room temperature for 5 min. Monitor by TLC. The benzoic acid is completely converted into the active intermediate. Weigh N,N,N',N'-tetramethylchloroformamidine hexafluorophosphate (TCFH, 0.286 g, 0.00102 mol) and add it to the above reaction solution. Stir the reaction for 20 min. Monitor by TLC. The active intermediate is completely converted into the product. After the reaction was completed, a large amount of ethyl acetate was added to dilute the reaction solution, and then it was washed twice with water and twice with saturated saline solution. The solution was dried with anhydrous magnesium sulfate and the solution was evaporated to dryness to obtain a white solid powder (0.282 g, yield 92.3%).

[0079] The 1H NMR spectrum (600MHz, DMSO-d6) of this compound is as follows (δ[ppm]): δ 8.06 (dd, J = 7.8, 3.0Hz, 1H, Ph-H), 7.89 (dd, J = 9.5, 2.6Hz, 1H, Ph-H), 6.61 (d, J = 2.6Hz, 1H, Ph-H), 4.60 (t, J = 5.4Hz, 1H, -OH), 4.42 (q, J = 4.1Hz, 2H, -CH2), 3.73 (q, J = 4.3Hz, 2H, -CH2), 3.49 (dq, J = 13.2, 4.8Hz, 4H, -CH2), 3.42 (s, 3H, -CH3).

[0080] ESI-MS (m / z): [M+Na] + Theoretical value: 473.0498, measured value: 473.05005.

[0081] Example 3

[0082] The structural formula of the hydroxyaryluracil compound numbered 40 in Table 1 is shown below:

[0083]

[0084] The preparation method of this compound is as follows:

[0085] Weigh out 0.12 g (0.00033 mol) of 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoic acid, 0.00033 g (0.0007 g (0.0000033 mol)), N-methylimidazolium (NMI, 0.084 mL (0.00099 mol)), excess diethylene glycol, and 15 mL of acetonitrile, and add them to a 50 mL round-bottom flask. After stirring at a warm temperature for 5 min, TLC monitoring showed that 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoic acid was completely converted to the active intermediate. N,N,N',N'-tetramethylchloroformamidine hexafluorophosphate (TCFH, 0.123 g, 0.00050 mol) was weighed and added to the above reaction solution. The mixture was stirred for 20 min, and TLC monitoring showed that the active intermediate was completely converted to the product. After the reaction was complete, the reaction solution was diluted with a large amount of ethyl acetate, then washed twice with water and twice with saturated brine. The solution was dried over anhydrous magnesium sulfate and evaporated to dryness to obtain a pale yellow viscous solid (0.125 g, yield 83.4%).

[0086] The 1H NMR spectrum (500MHz, DMSO-d6) of this compound is as follows (δ[ppm]): δ 8.10-8.00 (m, 1H, Ph-H), 7.90 (d, J=9.5Hz, 1H, Ph-H), 6.63 (s, 1H, Ph-H), 4.70 (t, J=5.7Hz, 1H, -OH), 4.26 (s, 2H, -CH2), 3.44 (s, 3H, -CH3), 3.39 (d, J=5.7Hz, 2H, -CH2), 0.57 (d, J=3.9Hz, 2H, -CH2), 0.53 (t, J=2.6Hz, 2H, CH2).

[0087] ESI-MS (m / z): [M+Na] + Theoretical value: 477.0447, measured value: 477.04489.

[0088] Example 4

[0089] The structural formula of the hydroxyaryluracil compound numbered 48 in Table 1 is shown below:

[0090]

[0091] The preparation method of this compound is as follows:

[0092] Weigh out 0.25 g (0.00068 mol) of 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoic acid, 0.0012 g (0.000012 mol) of dimethylstannous chloride, 0.162 mL (0.00204 mol) of N-methylimidazolium chloride (NMI), and 0.264 g (0.00136 mol) of 2,2'-[(oxobis(ethane-2,1-diyl))bis(oxy)]bis(ethanol). 20 mL of acetonitrile was added to a 50 mL round-bottom flask and stirred at room temperature for 5 min. TLC monitoring showed that 2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoic acid was completely converted to the active intermediate. N,N,N',N'-tetramethylchloroformamidine hexafluorophosphate (TCFH, 0.286 g, 0.00102 mol) was weighed and added to the above reaction solution. The mixture was stirred for 20 min, and TLC monitoring showed that the active intermediate was completely converted to the product. After the reaction was complete, the reaction solution was diluted with a large amount of ethyl acetate, then washed twice with water and twice with saturated brine. The solution was dried over anhydrous magnesium sulfate and evaporated to dryness to obtain a white viscous solid (0.173 g, yield 47.2%).

[0093] The 1H NMR spectrum (500MHz, DMSO-d6) of the compound is as follows (δ[ppm]): δ 8.06 (d, J = 7.7Hz, 1H), 7.91 (d, J = 9.5Hz, 1H), 6.62 (s, 1H), 4.57 (t, J = 5.5Hz, 1H), 4.49–4.41 (m, 2H), 3.81–3.73 (m, 2H), 3.58 (dd, J = 6.2, 3.6Hz, 2H), 3.55–3.48 (m, 8H), 3.41 (t, J = 5.3Hz, 2H).

[0094] ESI-MS (m / z): [M+Na] + Theoretical value: 565.0971, measured value: 565.09686.

[0095] In this embodiment of the invention, the hydroxyaryluracil compounds listed in Table 1 can be prepared by adjusting the preparation method described in the above embodiments; this will not be discussed further in this embodiment. Equivalent variations made in the claims are still within the scope of the invention.

[0096] Example 1

[0097] Herbicidal activity of some compounds listed in Table 1 of this application was determined using a post-emergence foliar treatment method. The experimental steps included:

[0098] (1) Fill the soil that has not been treated with the pesticide into flower pots, then sow the seeds and let them germinate and grow. When the dicotyledons grow to the two-leaf-one-heart stage and the monocotyledons grow to the 2-3-leaf stage, perform foliar spray treatment (when applying the compound, the compound is first dissolved in a small amount of organic solvent, then a small amount of emulsifier is added, and then diluted with water to obtain a solution containing the compound). The control group is the commercial compound KC1 (benzylsulfuron-methyl).

[0099]

[0100] (2) The plants were naturally grown under laboratory conditions and the potted plants were watered every day. The results of the investigation after 15 days of herbicide treatment are shown in Table 3. The herbicide scoring criteria are shown in Table 2. In this experiment, the target plants were common grass weeds: goosegrass, barnyard grass, and purslane, as well as broadleaf weeds: amaranth and purslane.

[0101] Table 2: Herbicide Scoring Criteria

[0102]

[0103] Table 3: Comparison of herbicidal activity scores of some hydroxyaryluracil compounds and control compounds in Table 1

[0104]

[0105] Note: The compound numbers correspond to those in Table 1.

[0106] Example 2

[0107] The herbicidal activity and crop safety of the target compound were determined using a pre-emergence soil treatment experiment.

[0108] Fill flowerpots with untreated soil, add water until the soil is completely moist, and then sow 10-15 seeds of each type of weed into the pots. Cover with 1 cm of soil. One day after sowing, treat with pesticides. After the pesticide solution has dried naturally in the shade, store the pots indoors and manage them using standard methods. The results of the survey 15 days after pesticide treatment are shown in Table 4.

[0109] Table 4: Comparison of herbicidal activity and crop damage scores of some hydroxyaryluracil compounds in Table 1

[0110]

[0111]

[0112] The results in Tables 3 and 4 show that the hydroxyaryluracil compounds provided by this invention exhibit high herbicidal activity against both grasses and broadleaf weeds; while the existing KC1 sulfadiazine has herbicidal activity against broadleaf weeds but poor efficacy against grasses. Therefore, the hydroxyaryluracil compounds provided by this invention have a wide weed control range and highly efficient herbicidal activity. The hydroxyaryluracil compounds provided by this invention have particularly outstanding herbicidal activity against difficult-to-control weeds such as goosegrass, barnyard grass, and sedge. When used in soil treatment, these hydroxyaryluracil compounds show almost no phytotoxicity to corn and excellent herbicidal activity against grasses and broadleaf weeds, making them suitable as selective herbicides for crop cultivation.

[0113] The preferred embodiments have been described in detail above, but the present invention is not limited to the specific implementation methods described above. Those skilled in the art can make various specific modifications under the guidance of this application without departing from the scope of protection of this application, and these modifications all fall within the scope of protection of the present invention.

Claims

1. A hydroxyaryluracil compound, characterized in that, The structure of the hydroxyaryluracil compound is shown in formula (Ⅰ): In formula (Ⅰ), R1 and R2 are independently selected from hydrogen atoms, amino groups, C1-C4 alkyl groups, or C1-C4 haloalkyl groups, respectively; X and Y are each independently selected from hydrogen atoms, halogen atoms, or cyano groups; Z is selected from oxygen or sulfur atoms; A is selected from -CH or a nitrogen atom; L is selected from a substituted or unsubstituted first group, wherein the first group is selected from C3-C8 cycloalkyl, -R a -R b -、-R b -R c -、-R a -R b -R c - or a C2-C20 carbon chain containing 1-6 ether oxygen atoms; wherein, R a R c Each is independently selected from C1-C10 alkylene, C2-C10 alkenylene, or C2-C10 ynylene, R b It is a C3-C8 cycloalkyl group; when L is the first substituted group, the substituted group is selected from hydroxyl, halogen atom, nitro, amino, cyano or C1-C6 alkyl.

2. The hydroxyaryluracil compound as described in claim 1, characterized in that, L is selected from C3-C6 cycloalkyl groups, -R a -R b -、-R b -R c -、-R a -R b -R c - or a C2-C16 carbon chain containing 1-5 ether oxygen atoms; wherein, R a R c Each is independently selected from C1-C6 alkylene, C2-C6 alkenylene, or C2-C6 ynylene, R b It is a C3-C6 cycloalkyl group.

3. The hydroxyaryluracil compound as described in claim 1, characterized in that, L is selected from C3-C5 cycloalkyl groups, -R a -R b -、-R b -R c -、-R a -R b -R c - or a C2-C14 carbon chain containing 1-4 ether oxygen atoms; wherein, R a R c Each is independently selected from C1-C4 alkylene, C2-C4 alkenylene, or C2-C4 ynylene, R b It is a C3-C4 cycloalkyl group.

4. The hydroxyaryluracil compound as described in claim 1, characterized in that, L is selected from any one of the structures shown in equations (L-1) to (L-9):

5. The hydroxyaryluracil compound as described in claim 1, characterized in that, R1 and R2 are each independently selected from C1-C4 alkyl or C1-C4 haloalkyl; X and Y are halogen atoms; Z represents an oxygen atom; A is -CH.

6. The hydroxyaryluracil compound as described in claim 1, characterized in that, R1 is trifluoromethyl, R2 is methyl or ethyl, X and Y are fluorine or chlorine atoms respectively, and Z is oxygen atom.

7. A tautomer, enantiomer, diastereomer, or pesticide-acceptable salt thereof of a hydroxyaryluracil compound as described in any one of claims 1-6.

8. The use of a tautomer, enantiomer, diastereomer, or pesticide-acceptable salt thereof of a hydroxyaryluracil compound as described in any one of claims 1-6 or as described in claim 7 in the preparation of a herbicide or defoliant in the agricultural, forestry, or sanitary fields.

9. A pesticide composition, characterized in that, The pesticide composition comprises an active ingredient and excipients, wherein the active ingredient comprises a tautomer, enantiomer, diastereomer, or pesticide-acceptable salt thereof of a hydroxyaryluracil compound as described in any one of claims 1-6 or as described in claim 7.

10. The pesticide composition according to claim 9, characterized in that, In the pesticide composition, the mass percentage of the active ingredient is 1%-99%.

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