Trifluorouracil compound containing semicarbazide structure as well as preparation method and application of trifluorouracil compound

Abstract

The invention relates to a trifluoro-uracil compound containing a semicarbazide structure and a preparation method and application thereof, and provides the trifluoro-uracil compound containing the semicarbazide structure, and the structure is shown as a formula I; the compound has excellent herbicidal toxicological properties, can be used as a pesticide, and particularly can be used as an active ingredient of a herbicide; when being applied to pesticides, the compound has a wider weed control spectrum, can generate a better killing or preventing and treating effect on various weeds, and shows excellent herbicidal activity; the compound is simple in structure, raw materials are easy to obtain and low in cost, and the compound has higher industrial value.

Description

Technical Field

[0001] This invention belongs to the field of pesticide technology, and in particular relates to a trifluorouracil compound containing an aminourea structure, its preparation method and application. Background Technology

[0002] Harmful weeds in farmland are a major enemy of agricultural production. Statistics show that crops worldwide lose an average of 12% of their yield annually due to weed infestations. Therefore, weed control is a crucial aspect of achieving efficient agriculture. Although there are various herbicides on the market, the continuous expansion of the market, the increasing severity of herbicide resistance in weeds in recent years, and people's growing emphasis on environmental protection mean that there is still a need to continuously develop new, efficient, and safe herbicides.

[0003] In the prior art, various uracil compounds used as herbicides have been disclosed. For example, WO9100278A1 discloses the herbicidal use of trifluorouracil phenyl ester compound, whose commercial product is flupropargyl. This compound has a simple structure and a broad spectrum of weed control, but it is extremely toxic to aquatic organisms. CN114431236A discloses a chiral oxime ether compound containing a trifluorouracil structure, which can be used as a herbicide. Its commercial name is flupropargyl, and it has a relatively broad spectrum of weed control activity. However, its effect on some resistant weeds is not ideal, and it needs to be compounded with active ingredients with other mechanisms of action to improve the weed control spectrum and efficacy. CN105753853B discloses an isoxazole carboxylic acid ester compound containing a trifluorouracil structure and its weed control use. Its representative compound is commercially known as pyrimethanil. This product has a broad spectrum of weed control and good killing activity against a variety of weeds, but its structure is complex, and its industrial manufacturing and commercialization costs are high. WO0183459 discloses the use of ureapridine-substituted phenylsulfonyl carboxamide compounds as herbicides. Its representative product, bensulfuron-methyl, is considered the most successful herbicide of the past 20 years and remains BASF's most influential herbicide product. Bensulfuron-methyl is currently the most widely used herbicide, but with its extensive and prolonged application, resistance has been found in various weeds. This herbicide exhibits poor activity against grassy weeds, and its main formulation, 70% WG, requires the addition of large amounts of oils as adjuvants to achieve its effect. There is an urgent need to develop herbicide compounds that offer superior weed control performance, toxicity, and manufacturing costs. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a trifluorouracil compound containing an aminourea structure, its preparation method, and its applications.

[0005] The technical solution adopted in this invention is: a trifluorouracil compound containing an aminourea structure, the structure of which is shown in Formula 1;

[0006] Formula I;

[0007] Wherein, W is the functional group W1 or W2;

[0008] W1; W2;

[0009] Wherein, Z is O or S; R1 is H, CH3 or C2H5; R2 is H, CH3 or C2H5; R3 is H, C1-C5 alkyl or haloalkyl, C1-C5 alkyl or haloalkyl substituted with alkoxy, alkylthio or alkylamino, benzene ring, pyridine ring, thiazole ring containing one or more substituents, or five-membered heterocycle or six-membered heterocycle containing O, S, N heteroatoms and containing one or more substituents.

[0010] Preferably, R3 is H, a C1-C5 alkyl group, a substituted C1-C5 alkyl group, or a monosubstituted or polysubstituted benzene ring;

[0011] The substituted C1-C5 alkyl groups are haloalkyl, alkoxy-substituted C1-C5 alkyl, alkylthio-substituted C1-C5 alkyl, alkoxy-substituted C1-C5 alkyl, or alkylthio-substituted C1-C5 haloalkyl; the monosubstituted or polysubstituted benzene rings are ortho / meta / para-position mono / dialkyl, alkoxy, halogen, trifluoromethyl, or trifluoromethoxy-substituted benzene.

[0012] Preferably, R3 is further preferably H, methyl, ethyl, n-propyl, isopropyl, 2-methoxyisopropyl, 2-methylthioisopropyl, 2-methylaminoisopropyl, heptafluoroisopropyl, 2-difluoroisopropyl, 2-trifluoroisopropyl, o-trifluoromethylbenzene, p-trifluoromethylbenzene, p-trifluoromethoxybenzene, 2,6-dimethyl, 2,6-dimethoxybenzene, 2,4-dimethyl, 2,4-dimethoxybenzene.

[0013] Preferably, the structure is as shown in formula Ia or formula Ib;

[0014] Formula Ia; Formula Ib.

[0015] Preferably, the structure is such as Ia-1, Ia-144, Ib-144, Ia-189, Ia-169, Ib-157, Ia-2, Ia-3, Ia-4, Ia-5, Ia-6, Ia-7, Ia-8, Ia-9, Ia-10, Ia-11, Ia-12, Ia-13, Ia -14, Ia-15, Ia-16, Ia-17, Ia-18, Ia-19, Ia-20, Ia-131, Ia-163, Ia-164, Ia-156, Ia-162, Ia-174, Ib-163, Ia-148, Ia-178, Ib-152, Ib-132, Ia-132, Ib-155, Ia-167, Ia-181, Ia-135 and Ib-135.

[0016] A method for preparing trifluorouracil compounds containing an aminourea structure, wherein the compound shown in Formula II or the compound shown in Formula III is synthesized with the compound shown in Formula IV through a condensation reaction to obtain the compound shown in Formula I;

[0017] Formula II; Formula III;

[0018] Formula IV;

[0019] Wherein, X is OH or a halogen; Z is O or S; R1 is H, CH3 or C2H5; R2 is H, CH3 or C2H5; R3 is H, C1-C5 alkyl or haloalkyl, C1-C5 alkyl or haloalkyl substituted with alkoxy, alkylthio or alkylamino, benzene ring, pyridine ring, thiazole ring containing one or more substituents, or five-membered heterocycle or six-membered heterocycle containing O, S, N heteroatoms and containing one or more substituents.

[0020] Application of trifluorouracil compounds containing an aminourea structure in pesticides.

[0021] A pesticide composition comprising a trifluorouracil compound containing an aminourea structure as the active ingredient.

[0022] Preferably, it includes one, two, or a combination of more of the following: a compound of Formula I, a stereoisomer of the compound of Formula I, a racemate, a tautomer, an isotope label, a nitrogen oxide, a pharmaceutically acceptable salt or ester, a solvate, or a solvate of a pharmaceutically acceptable salt;

[0023] Preferably, it is formulated as a liquid or solid dosage form;

[0024] Preferably, the weight percentage of the active ingredient in the composition is 0.1-99.9%, more preferably 0.5-99%;

[0025] Preferably, it also includes an agriculturally, forestry, or sanitarily acceptable carrier.

[0026] Application of pesticide compositions in herbicides.

[0027] The advantages and positive effects of this invention are: it provides a trifluorouracil compound containing an aminourea structure, which has excellent herbicidal toxicological properties; it not only has a broader spectrum of weed control and can produce better killing or control effects on a variety of weeds, exhibiting excellent herbicidal activity; but also the compound has a simple structure, readily available raw materials, and low cost, thus having higher industrial value. Detailed Implementation

[0028] The embodiments of the present invention will be described below.

[0029] This invention relates to a trifluorouracil compound containing an aminourea structure, the structure of which is shown in Formula I;

[0030] Formula I;

[0031] Wherein, W is the functional group W1 or W2;

[0032] W1; W2;

[0033] Where Z is O or S; R1 is H, CH3 or C2H5; R2 is H, CH3 or C2H5;

[0034] R3 is H, a C1-C5 alkyl or haloalkyl, a C1-C5 alkyl or haloalkyl substituted with alkoxy, alkylthio, or alkylamino, a benzene ring containing one or more substituents, a pyridine ring, a thiazole ring, or other five-membered or six-membered heterocycles containing O, S, or N heteroatoms and containing one or more substituents.

[0035] R3 is preferably H, a C1-C5 alkyl group, a substituted C1-C5 alkyl group, or a monosubstituted or polysubstituted benzene ring, wherein the substituted C1-C5 alkyl group is a haloalkyl group, a C1-C5 alkyl group substituted with an alkoxy group, or a C1-C5 alkyl group substituted with an alkylthio group; the monosubstituted or polysubstituted benzene ring is an ortho / meta / para mono / dialkyl group, an alkoxy group, a halogen, a trifluoromethyl group, or a trifluoromethoxy substituted benzene ring;

[0036] R3 is further preferably H, methyl, ethyl, n-propyl, isopropyl, 2-methoxyisopropyl, 2-methylthioisopropyl, 2-methylaminoisopropyl, heptafluoroisopropyl, 2-difluoroisopropyl, 2-trifluoroisopropyl, o-trifluoromethylbenzene, p-trifluoromethylbenzene, p-trifluoromethoxybenzene, 2,6-dimethyl, 2,6-dimethoxybenzene, 2,4-dimethyl, 2,4-dimethoxybenzene.

[0037] In some embodiments of the present invention, the trifluorouracil compound containing the aminourea structure has the structure shown in Formula Ia;

[0038] Formula Ia;

[0039] Specifically, it can be one of compounds Ia-1 to Ia-192. The selection of Z, R1, R2 and R3 in compounds Ia-1 to Ia-192 is shown in Table 1.

[0040] Table 1

[0041]

[0042] In some embodiments of the present invention, the trifluorouracil compound containing the aminourea structure has the structure shown in Formula Ib;

[0043] Formula Ib;

[0044] Specifically, it can be one of compounds Ib-1 to Ib-170. The selection of Z, R2 and R3 in compounds Ib-1 to Ib-170 is shown in Table 2.

[0045] Table 2

[0046]

[0047] When preparing a compound with the structure shown in Formula I, the compound shown in Formula II or Formula III is synthesized by condensation reaction with the compound shown in Formula IV to obtain the compound shown in Formula I.

[0048] Formula II; Formula III;

[0049] Formula IV;

[0050] Wherein, X is OH or a halogen; Z is O or S; R1 is H, CH3 or C2H5; R2 is H, CH3 or C2H5; R3 is H, a C1-C5 alkyl or haloalkyl group, a C1-C5 alkyl or haloalkyl group substituted with alkoxy, alkylthio, or alkylamino groups, a benzene ring containing one or more substituents, a pyridine ring, a thiazole ring, or other five-membered or six-membered heterocycles containing O, S, or N heteroatoms and containing one or more substituents.

[0051] The trifluoromethyluracil-substituted benzaldehyde or ketone of Formula II, the trifluoromethyluracil-substituted benzoic acid or acyl halide of Formula III, and the aminourea and aminothiourea compounds shown in Formula IV can be carried out in inert solvents, dipolar solvents, and proton solvents, such as C1-C4 alcohols, benzene and substituted benzenes, C1-C4 chloroalkanes, C4-C6 cyclic ethers, C1-C4 nitriles, C1-C4 carboxylic acids, and C1-C3 amides.

[0052] Specifically, when the trifluoromethyluracil-substituted benzaldehyde or ketone of Formula II reacts with the aminourea or aminothiourea compound of Formula IV, the solvent is preferably DMF, DMAC, acetonitrile, THF, or an alcohol solvent, and more preferably methanol, ethanol, propanol, or isopropanol. When the trifluoromethyluracil-substituted benzoic acid or acyl halide of Formula III reacts with the aminourea or aminothiourea compound of Formula IV, the solvent is preferably an aromatic amide, aromatic hydrocarbon, or haloalkane solvent, such as DMF, DMAC, toluene, xylene, chlorobenzene, dichloromethane, trichloromethane, or dichloroethane.

[0053] When the benzaldehyde or ketone substituted with trifluoromethyluracil of Formula II reacts with the aminourea or aminothiourea compound of Formula IV, the trifluoromethyluracil will decompose to a certain extent in an alkaline aqueous environment, and the degree of decomposition increases with the increase of water content, temperature and alkalinity. The addition of a certain amount of Lewis acid helps to improve the selectivity and conversion efficiency of the reaction. Such as inorganic Lewis acids such as hydrohalic acid, sulfuric acid, and phosphoric acid, or organic acids such as acetic acid, trifluoroacetic acid, propionic acid, and p-toluenesulfonic acid, acetic acid and trifluoroacetic acid are preferred.

[0054] When the benzaldehyde or ketone substituted with trifluoromethyluracil of Formula II reacts with the aminourea or aminothiourea compound of Formula IV, the reaction conditions are mild, the temperature range is generally selected as 0-80℃, preferably 20-50℃, and the reaction time is 2-10h.

[0055] When a trifluoromethyluracil-substituted benzoic acid or acyl halide of Formula III reacts with an aminourea or aminothiourea compound of Formula IV, and X is chlorine or bromine, an organic or inorganic base is required as an acid-binding agent. The organic base can be a tertiary amine, an unsubstituted or pyridine heterocycle with one or more substituents, a guanidine, or an imine, preferably triethylamine, diisopropylethylamine, N-methylmorpholine, tetramethylethylenediamine, DMAP, DBU, DBN, etc.; more preferably pyridine, 3-methylpyridine, DMAP, triethylamine, diisopropylethylamine, etc. The inorganic base is preferably sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, calcium hydroxide, or lithium hydroxide, etc.

[0056] When the trifluoromethyluracil-substituted benzoic acid or acyl halide of Formula III reacts with the aminourea or aminothiourea compound of Formula IV, a condensing agent is required when X is -OH. The preferred condensing agent is PyBOP, HATU, HOBT, HBTU, TBTU, DCC, DIC, EDCI, CDI, etc. Correspondingly, an organic base is also added to promote the reaction conversion. Commonly used organic bases are tertiary amines, unsubstituted or pyridine heterocycles with one or more substituents, guanidines, imines, preferably triethylamine, diisopropylethylamine, N-methylmorpholine, tetramethylethylenediamine, DMAP, etc.

[0057] When the trifluoromethyluracil-substituted benzoic acid or acyl halide of Formula III reacts with the aminourea or aminothiourea compound of Formula IV, the reaction conditions are mild, the temperature range is generally selected as 0-60℃, preferably 0-30℃, and the reaction time is 2-5h.

[0058] The compound shown in Formula I has a simpler structure, milder reaction conditions, and more readily available and lower-cost raw materials compared to the compound pyrimethanil, making it more valuable for industrialization.

[0059] The compound represented by Formula I can be used as an active ingredient in pesticides or pesticide compositions. One of the stereoisomers, racemates, tautomers, nitrogen oxides, or pharmaceutically acceptable salts of the compound represented by Formula I can also be used directly as a pesticide or as an active ingredient in a pesticide composition. The pesticide composition may include one or more combinations of the compound represented by Formula I, its stereoisomers, racemates, tautomers, isotope-labeled compounds, nitrogen oxides, pharmaceutically acceptable salts or esters, solvates, or solvates of pharmaceutically acceptable salts. The weight percentage of the active ingredient in the pesticide composition is 0.1-99.9%, preferably 0.5-99%. The pesticide composition can be applied in formulation form, such as by dissolving or dispersing the compound represented by Formula I as an active ingredient in a carrier or formulating it into a formulation for easy dispersion during herbicidal use. Formulation forms include, but are not limited to, granules, oil suspensions, water suspensions, water-in-oil emulsions, aqueous solutions, emulsifiable concentrates, or microcapsules. Solid carriers and liquid carriers may also be added to the pesticide composition, and surfactants may also be added. The surfactants can be selected according to conventional pesticide preparation methods.

[0060] The above-mentioned pesticides or pesticide compositions can be prepared into liquid or solid formulations. Liquid formulations can be solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and / or suspensions), etc.; solid formulations can be powders, granules, tablets, pellets, films, etc., and can be water-dispersible or water-soluble. The active ingredient of the pesticide or pesticide composition can be microencapsulated and then formulated into a suspension or solid formulation. The active ingredient of the pesticide or pesticide composition can be encapsulated, which can control or delay the release of the active ingredient. The active ingredient of the pesticide or pesticide composition can be formulated into a spray formulation, diluted in a suitable medium, with a spray volume of approximately one hundred to several hundred liters per hectare. The selection of other components in the formulation or other components of the composition should be consistent with the physical properties of the active ingredient, the application method, and environmental factors (e.g., soil type, humidity, and temperature).

[0061] The above-mentioned pesticides or pesticide compositions can be used as herbicides, exhibiting excellent weed control efficacy against a wide range of economically important monocot and dicot annual pests. The active ingredients effectively target perennial weeds that germinate from rhizomes, rootstocks, and other perennial organs and are difficult to control. The effective application rate of the active ingredients is 10 to 1000 grams per hectare, preferably 20 to 500 grams per hectare.

[0062] The above-mentioned pesticide or pesticide composition can be used to control unwanted plants by applying an effective amount of the compound of formula (I), its stereoisomers, racemates, tautomers, isotopic markers, nitrogen oxides, pharmaceutically acceptable salts or esters, solvates or solvates of pharmaceutically acceptable salts, or the composition to the neck, leaves, seeds or other reproductive parts of the target plant.

[0063] The above-mentioned pesticides or pesticide combinations can be used to control monocotyledonous and dicotyledonous weeds. Some representative examples are shown below, but this is not intended to limit the list to specific species. For example, among monocotyledonous harmful plant species, the method can control Aegilops genus (…). Aegilops ), ice grass ( Agropyron ), genus *Pterocarya* Agrostis ), genus *Alopecurus* ( Alopecurus ), Oat genus ( Avena ), Arm-shaped Grass ( Brachiaria ), Brome ( Bromus Tribulus genus ( Cenchrus ), Commelina genus ( Commelina ), Cynodon genus ( Cynodon ), Cyperus ( Cyperus ), genus *Dracaena* ( Dactyloctenium ), Crataegus pinnatifida ( Digitaria ), Barnyardgrass ( Echinochloa ), genus *Cypripedium* ( Eleocharis ), Gryllus ( ) Eleusine ), genus *Lysimachia* ( Eragrostis ), Wild millet ( Eriochloa ), Festuca ( Festuca ), genus *Pteris* ( Fimbristylis ), Imperata genus ( Imperata ), genus *Chamaedorea* ( Ischaemum ), Heterostachys ( Heteranthera ), genus Echinopsis ( Leptochloa ), Ryegrass ( Lolium ), genus *Pyrrosia* Monochoria ), millet ( Panicum ), Paspalum ( Paspalum ), Grasses ( Phalaris ), Tigrass genus ( Phleum ), Poa ( Poa ), Cylindrica genus ( Rottboellia ), Arrowhead ( Sagittaria ), genus *Strombyx* Scirpus ), genus *Setaria* ( Setaria ), Sorghum ( Sorghum ) and the genus *Acer pentaphyllum* ( Sphenoclea For dicotyledonous weeds, the method can control species such as Abutilon (*vellum*). Abutilon ), Amaranth ( Amaranthus ), Ragweed ( Ambrosia ), Chamomile ( Anthemis Artemisia genus Artemisia ), genus Acerola Atriplex ), Daisy ( Bellis ), genus Bidens ( Bidens ), Capsella genus (Capsella ), genus *Pteris* ( Carduus ), Cassia tora ( Cassia ), Cornflower genus ( Centaurea ), genus Chenopodiaceae Chenopodium ), Thistle genus ( Cirsium ), Convolvulaceae ( Convolvulus ), Datura genus ( Datura ), genus Locust ( Desmodium ), Sorrel ( Emex Geraniaceae ( ) Erodium ), Sugar Mustard ( Erysimum Euphorbia ( ) Euphorbia ), genus *Ichthyophthirius* ( Galeopsis ), Achyranthes genus ( Galinsoga ), genus *Lysimachia* Galium ), Geranium ( Geranium ), Hibiscus genus ( Hibiscus ), Ipomoea genus ( Ipomoea ), Kochia genus ( Kochia ), Sesamum genus ( Lamium ), genus *Lysimachia* Lepidium Motherwort () Lindernia ), Matricaria ( Matricaria ), Mentha genus ( Mentha ), Indigofera genus ( Mercurialis ), Poppy genus ( Papaver ), genus Ipomoea ( Pharbitis Plantago asiatica () Plantago ), Polygonum genus ( Polygonum ), purslane genus ( Portulaca ), Ranunculaceae ( Ranunculus Radix ( ) Raphanus ), genus *Gynostemma* Rorippa ), genus *Gnaphalium* Rotala ), Sorrel ( Rumex ), Pigweed genus ( Salsola ), Senecio genus ( Senecio ), Sesbania ( Sesbania ), genus *Rhododendron* ( Sida ), white mustard ( Sinapis Solanaceae () Solanum ), Sow thistle genus ( Sonchus ), genus *Acer pentaphyllum* ( Sphenoclea ), Stellaria genus ( Stellaria ), Dandelion ( Taraxacum ), genus *Iris* ( Thlaspi ), Clover ( Trifolium ), genus *Urtica* Urtica ), Veronica genus ( Veronica ), Violets ( Viola ), Xanthium genus ( Xanthium ).

[0064] The above-mentioned pesticides or pesticide compositions exhibit excellent herbicidal activity against both monocot and dicot weeds. These pesticides or pesticide compositions are suitable for a variety of target plants, such as cash crops, agricultural crops, ornamental plants, or genetically modified crops. For example, dicot crops of the following genera: peanut (…). Arachis ), Beet ( Beta ), Brassica ( Brassica Cucumber ( ) Cucumis ), Cucurbita ( Cucurbita ), Sunflower genus ( Helianthus Carrot genus ( Daucus ), Glycine ( Glycine ), Gossypium ( Gossypium ), Ipomoea genus ( Ipomoea ), Lettuce ( Lactuca ), Linum ( Linum ), Tomato genus ( Lycopersicon ), stigmata ( Miscanthus ), Tobacco ( Nicotiana ), genus *Vaccinium* Phaseolus ), Pea ( Pisum Solanaceae () Solanum ), broad bean genus ( Vicia ); or the following monocotyledonous crops: Allium ( Allium ), bromeliad ( Ananas ), Asparagus genus ( Asparagus ), Oat genus ( Avena ), Barley ( Hordeum ), Rice ( Oryza ), millet ( Panicum ), Sugarcane ( Saccharum ), Rye ( Secale ), Sorghum ( Sorghum ), Triticum ( Triticale ), wheat ( Wheat ) and the genus *Cephalotaxus* ( Zea It can also be used for grains such as wheat, barley, rye, oats, millet, rice, cassava, and corn, or other crops such as sugar beets, cotton, soybeans, rapeseed, potatoes, tomatoes, peas, and many other vegetables.

[0065] When applying the above-mentioned pesticides or pesticide combinations, they can be applied to the green parts of the plants after emergence. After treatment, growth stops, and harmful plants remain in the growth stage at the time of application or die completely after a certain period of time. This allows for the long-term elimination of harmful competition from weeds to the target crop plants at a very early stage.

[0066] The present invention will now be described. Experimental methods that do not specify the operation steps are performed in accordance with the corresponding product manuals. Unless otherwise specified, the instruments, reagents and consumables used in the embodiments can be purchased from commercial companies.

[0067] Example 1

[0068] (E)-2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)phenylmethylene)-N-(3,5-difluorophenyl)hydrazyl-1-carboxamide

[0069] Ia-1;

[0070] 0.94 g of N-methyl-N-(3,5-difluorophenyl)aminourea, 35 g of methanol, and 0.2 g of acetic acid were added to a 100 ml reaction flask and dissolved by stirring at 30-35 °C. 1.75 g of 2-chloro-4-fluoro-5-(3-methyl-1-2,6-dihexadioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzaldehyde was added to the above solution. The mixture was then stirred at 30-35 °C for 8 h, filtered, and the filter cake was washed twice with an appropriate amount of methanol. The filter cake was then dried under vacuum at 50-60 °C to obtain 1.46 g of white granular crystals, with a yield of 56.0%.

[0071] Melting point 255-256℃, LC-MS: [M+H] + =520.0611

[0072] 1 H NMR (400 MHz, DMSO-d6) δ 11.26 (s, 1H, Ar-CH=N-), 9.27 (s, 1H, -(CO)-NH-Ar), 8.38 (d, J = 8.0 Hz, 1H , Ar-H), 8.36 (s, 1H, =N-NH-(CO)-), 7.83(d, J = 9.4 Hz, 1H, Ar-H), 7.47–7.39 (m, 2H, Ar-H), 6.84 (tt, J = 9.3, 2.4Hz, 1H, Ar-H), 6.68 (s, 1H, CF3-C=CH-), 3.45 (s, 3H, -NCH3)

[0073] Example 2

[0074] (E)-2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)phenylmethylene)-N-isopropyl-N-methylhydrazyl-1-carboxamide

[0075] Ia-144;

[0076] 0.66 g of N-methyl-N-isopropylaminourea and 25 g of methanol were added to a 100 ml reaction flask and dissolved by stirring at 25-30 °C. 1.75 g of 2-chloro-4-fluoro-5-(3-methyl-1-2,6-dihexadioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzaldehyde was added to the above solution. The mixture was then stirred at 20-25 °C for 6 h, filtered, and the filter cake was washed twice with an appropriate amount of methanol and dried under vacuum at 50-60 °C to obtain 1.04 g of white granular crystals, with a yield of 45.0%.

[0077] Melting point 210-211℃, LC-MS: [M+H] + =464.1113

[0078] 1 H NMR (400 MHz, Chloroform-d) δ 9.55 (s, 1H, Ar-CH=N-), 8.12 (s, 1H,=N-NH-(CO)-), 7.81 (d, J = 6.3 Hz, 1H, Ar-H), 7.13 (d, J = 8.0 Hz, 1H, Ar-H), 6.30 (s, 1H, CF3-C=CH-), 4.49 (s, 1H, -NCH-), 3.51 (s, 3H, -NCH3), 2.70 (s,3H, -(CO)-NCH3), 1.06 (d, J = 6.0 Hz, 6H, -CH3)

[0079] Example 3

[0080] 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoyl)-N-isopropyl-N-methylhydrazine-1-carboxamide

[0081] Ib-144;

[0082] 1.93 g of 2-chloro-4-fluoro-5-(3-methyl-1-2,6-dihexadioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoyl chloride and 70 g of chloroform were added to a 100 ml reaction flask and stirred to dissolve at 15-20 °C. The mixture was then cooled to 5-10 °C, and 0.66 g of N-methyl-N-isopropylaminourea was added, followed by dropwise addition of 0.56 g of triethylamine over 30 min. The mixture was then incubated at 5-10 °C with stirring for 3 h. After incubation, 30 ml of water was added, and the mixture was separated. The chloroform phase was dried over anhydrous MgSO4 and concentrated under reduced pressure to obtain 2.3 g of a gel-like crude product. This crude product was separated by silica gel column chromatography to obtain 0.74 g of a white solid, with a yield of 31.0%.

[0083] Melting point 174-175℃, LC-MS: [M+H] + =480.1062

[0084] 1 H NMR (400 MHz, Chloroform-d) δ 9.32 (s, 1H, Ar-CO-NH-), 7.66 (d, J= 7.5 Hz, 1H, Ar-H), 7.23 (d, J = 9.4 Hz, 1H, Ar-H), 7.22 (s, 1H, Ar-CO-NH-NH-), 6.18 (s, 1H, CF3-C=CH-), 4.30 (p, J = 6.6 Hz, 1H, -NCH-), 3.36 (s, 3H,-NCH3), 2.67 (s, 3H, -(CO)-NCH3), 1.00 (d, J = 6.7 Hz, 6H, -CH3)

[0085] Example 4

[0086] (E)-2-(1-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)phenyl)ethylmethylene)-N-isopropyl-N-methylhydrazine-1-thiocarboxamide

[0087] Ia-189;

[0088] 0.74 g of N-methyl-N-isopropylaminothiourea, 25 g of methanol, and 0.2 g of acetic acid were added to a 100 ml reaction flask and stirred at 20-25 °C to dissolve. 1.82 g of 3-(5-acetyl-4-chloro-2-fluorophenyl)-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione was added to the above solution, and the mixture was then stirred at 40-45 °C for 6 h. After the reaction was complete, methanol was removed under reduced pressure to obtain 2.1 g of crude product, which was separated by silica gel column chromatography to give 1.47 g of a pale yellow solid, with a yield of 59.1%.

[0089] Melting point 115-116℃, LC-MS: [M+H] + =494.1041

[0090] 1 H NMR (400 MHz, Chloroform-d6) δ 7.32–7.24 (m, 3H,-NH-, Ar-H), 6.34(s, 1H, CF3-C=CH-), 3.91 (p, J = 6.9 Hz, 1H, -NCH-), 3.52 (s, 3H, -NCH3), 2.82(s, 3H, -(CS)-NCH3), 2.42 (s, 3H,-N=C-CH3), 1.16 (d, J = 6.6 Hz, 6H, -CH3)

[0091] Example 5

[0092] (E)-2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)phenylmethylene)-N-(1-methoxypropane-2-yl)hydrazyl-1-thiocarboxamide

[0093] Ia-169;

[0094] 0.41 g of N-(1-methoxypropane-2-yl)aminourea, 30 g of methanol, and 0.2 g of acetic acid were added to a 100 ml reaction flask and dissolved by stirring at 25-30 °C. 0.88 g of 2-chloro-4-fluoro-5-(3-methyl-1-2,6-dihexadioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzaldehyde was added to the above solution, and the mixture was then stirred at 30-35 °C for 10 h. After the reaction was complete, the mixture was concentrated under reduced pressure to remove methanol and a small amount of acetic acid. The residue was recrystallized from anhydrous ethanol, filtered, and the filter cake was washed twice with ethanol and dried to obtain 0.95 g of a white powdery solid, with a yield of 76.6%.

[0095] Melting point 173-174℃, LC-MS: [M+H]+ =496.0833

[0096] 1 H NMR (400 MHz, Chloroform-d) δ 10.09 (s, 1H, Ar-CH=N-), 8.11 (d, J= 3.0 Hz, 1H, =N-NH-(CS)-), 7.78 (d, J = 7.7 Hz, 1H, Ar-H), 7.44 (t, J = 8.7Hz, 1H, Ar-H), 7.33 (d, J = 8.9 Hz, 1H, -(CS)-NH-), 6.45 (d, J = 3.1 Hz, 1H,CF3-C=CH-), 4.73 (td, J = 6.8, 4.2 Hz, 1H,-NCH-), 3.62 (d, J = 4.7 Hz, 3H, -NCH3), 3.53 (dt, J = 11.2, 6.5 Hz, 2H, -OCH2-), 3.38 (d, J = 3.4 Hz, 3H, -OCH3), 1.38–1.29 (m, 3H, -CH3)

[0097] Example 6

[0098] 2-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoyl)-N-(1-methoxypropane-2-yl)hydrazyl-1-thiocarboxamide

[0099] Ib-157;

[0100] In a 100 ml reaction flask, 0.41 g of N-(1-methoxypropane-2-yl)aminourea, 40 g of chloroform, and 0.26 g of triethylamine were added, and the temperature was lowered to 5-10 °C. A 20 g chloroform solution containing 0.97 g of 2-chloro-4-fluoro-5-(3-methyl-1-2,6-dihexadioxo-4-(trifluoromethyl)-3,6-dihydropyrimidin-1(2H)-yl)benzoyl chloride was added dropwise to the mixture, and the mixture was stirred at 5-10 °C for 3 h. After the reaction was complete, 30 ml of water was added, and the mixture was separated. The organic phase was desolvated under reduced pressure to obtain 1.2 g of crude product, which was dissolved in 10 ml of ethanol. Hexane was gradually added dropwise at 35 °C, and crystals gradually precipitated. The mixture was filtered, and the filter cake was washed twice with hexane / ethanol at a ratio of 3:1. After drying, 0.40 g of white granular crystals were obtained, with a yield of 31.4%.

[0101] Melting point 169-170℃, LC-MS: [M+H] + =512.0782

[0102] 1 H NMR (400 MHz, DMSO-d6) δ 10.57 (s, 1H, Ar-CO-NH-NH-), 9.60 (s, 1H,Ar-CO-NH-NH-), 7.84 (d, J = 9.5 Hz, 1H, Ar-H), 7.76 (d, J = 7.7 Hz, 1H, Ar-H), 7.36 (s, 1H, Ar-CO-NH-), 6.60 (s, 1H, CF3-C=CH-), 4.52 (s, 1H, -NCH-), 3.43 (d, J = 6.8 Hz, 6H, -NCH3 & -OCH3), 3.35 (dd, J = 9.5, 5.0 Hz, 2H, -OCH2-), 1.16 (d, J = 6.7 Hz, 3H, -CH3)

[0103] Example 7:

[0104] Compounds with the structures shown in Table 3 were synthesized using the methods described in Examples 1-6 above.

[0105] Table 3

[0106]

[0107] Example 8: Preparation of pesticide formulations

[0108] The compounds obtained in Examples 1-7 were prepared into granules or aqueous suspensions. All percentages are by weight, and all dosage forms were prepared using conventional methods.

[0109] The granules are prepared using the following raw material composition: compound Ia-169 20.0%, sodium dodecyl sulfate 2.0%, calcium lignosulfonate 6.0%, potassium chloride 10.0%, polydimethylsiloxane 1.0%, and soluble starch to make up to 100%.

[0110] The aqueous suspension is prepared using the following raw material composition: compound Ib-157 30.0%, POE polystyrene phenyl ether sulfate 5.0%, xanthan gum 0.5%, polyethylene glycol 5%, triethanolamine 1%, sorbitol 0.5%, and water to 100.0%.

[0111] Example 9: Herbicidal Activity Assay

[0112] The experiment was conducted in accordance with NY / T 1155.4-2006 "Guidelines for Indoor Bioassay Tests of Pesticides - Herbicides Part 4: Activity Assay Test - Foliar Spray Method". Quantitative amounts of grass weeds (barnyard grass, foxtail grass) and broadleaf weeds (velvetleaf, cocklebur) were sown separately in paper cups with a diameter of 7 cm filled with nutrient soil. After sowing, the seeds were covered with 1 cm of soil, compacted, and watered before being cultivated in a greenhouse using conventional methods. The test results for barnyard grass (4-6 leaves), foxtail grass (3-5 leaves), velvetleaf (2-3 leaves), and cocklebur (4-6 leaves) are shown in Table 4.

[0113] Table 4

[0114]

[0115] Comparative data in the table show that, under indoor foliar treatment conditions, the immediate efficacy results 3 days after application indicate that multiple compounds, including Ia-167, Ia-169, Ia-174, Ia-189, Ib-155, Ib-157, and Ib-163, showed superior immediate efficacy against broadleaf weeds compared to the control herbicide benzoyl permethrin, and significantly superior immediate efficacy against gramineous weeds compared to benzoyl permethrin. The efficacy results 7 days after application show that, at a dosage of 60 g ai / Ha, multiple compounds achieved visual control efficacy of over 95% against velvetleaf and cocklebur, superior to the control herbicides benzoyl permethrin and benzoyl permethrin, and achieved control efficacy of over 90% against barnyardgrass and foxtail millet, significantly superior to the control herbicide benzoyl permethrin, demonstrating a broader spectrum of weed control. Meanwhile, compounds such as Ia-174, Ib-155, and Ib-163 still exhibited excellent herbicidal activity at a low dosage of 15 g ai / Ha.

[0116] The embodiments of the present invention have been described in detail above, but the content described is only a preferred embodiment of the present invention and should not be considered as limiting the scope of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the patent coverage of the present invention.

Claims

1. A trifluorouracil compound containing an aminourea structure, characterized in that: The structure is shown in Equation 1; Formula I; Wherein, W is the functional group W1 or W2; W1; W2; Wherein, Z is O or S; R1 is H, CH3 or C2H5; R2 is H, CH3 or C2H5; R3 is H, C1-C5 alkyl or haloalkyl, C1-C5 alkyl or haloalkyl substituted with alkoxy, alkylthio or alkylamino, benzene ring, pyridine ring, thiazole ring containing one or more substituents, or five-membered heterocycle or six-membered heterocycle containing O, S, N heteroatoms and containing one or more substituents.

2. The trifluorouracil compound containing an aminourea structure according to claim 1, characterized in that: R3 is preferably H, a C1-C5 alkyl group, a substituted C1-C5 alkyl group, or a monosubstituted or polysubstituted benzene ring; The substituted C1-C5 alkyl groups are haloalkyl, alkoxy-substituted C1-C5 alkyl, alkylthio-substituted C1-C5 alkyl, alkoxy-substituted C1-C5 alkyl, or alkylthio-substituted C1-C5 haloalkyl; the monosubstituted or polysubstituted benzene rings are ortho / meta / para-position mono / dialkyl, alkoxy, halogen, trifluoromethyl, or trifluoromethoxy-substituted benzene.

3. The trifluorouracil compound containing an aminourea structure according to claim 2, characterized in that: R3 is further preferably H, methyl, ethyl, n-propyl, isopropyl, 2-methoxyisopropyl, 2-methylthioisopropyl, 2-methylaminoisopropyl, heptafluoroisopropyl, 2-difluoroisopropyl, 2-trifluoroisopropyl, o-trifluoromethylbenzene, p-trifluoromethylbenzene, p-trifluoromethoxybenzene, 2,6-dimethyl, 2,6-dimethoxybenzene, 2,4-dimethyl, 2,4-dimethoxybenzene.

4. The trifluorouracil compound containing an aminourea structure according to any one of claims 1-3, characterized in that: The structure is shown in equation Ia or equation Ib; Formula Ia; Formula Ib.

5. The trifluorouracil compound containing an aminourea structure according to claim 1, characterized in that: Structures such as Ia-1, Ia-144, Ib-144, Ia-189, Ia-169, Ib-157, Ia-2, Ia-3, Ia-4, Ia-5, Ia-6, Ia-7, Ia-8, Ia-9, Ia-10, Ia-11, Ia-12, Ia-13, Ia -14, Ia-15, Ia-16, Ia-17, Ia-18, Ia-19, Ia-20, Ia-131, Ia-163, Ia-164, Ia-156, Ia-162, Ia-174, It is represented by one of Ib-163, Ia-148, Ia-178, Ib-152, Ib-132, Ia-132, Ib-155, Ia-167, Ia-181, Ia-135 and Ib-135; It-1; It-144; Ib-144; It-181; It-169; Ib-157; It-2; It-3; It-4; It-5; It-6; It-7; It-8; It-9; It-10; It-11; It-12; It-13; It is -14; It-15; It-16; It-17; It-18; It-19; It-20; It-131; It-163; It-164; It-156; It-162; It-174; Ib-163; It-148; It-178; Ib-152; Ib-132; It-132; Ib-155; It-167; It-189; It-135; Ib-135.

6. A method for preparing the trifluorouracil compound containing an aminourea structure as described in any one of claims 1-5, characterized in that: The compound shown in Formula I is synthesized by condensation reaction of the compound shown in Formula II or the compound shown in Formula III with the compound shown in Formula IV. Formula II; Formula III; Formula IV; Wherein, X is OH or a halogen; Z is O or S; R1 is H, CH3 or C2H5; R2 is H, CH3 or C2H5; R3 is H, C1-C5 alkyl or haloalkyl, C1-C5 alkyl or haloalkyl substituted with alkoxy, alkylthio or alkylamino, benzene ring, pyridine ring, thiazole ring containing one or more substituents, or five-membered heterocycle or six-membered heterocycle containing O, S, N heteroatoms and containing one or more substituents.

7. The use of the trifluorouracil compound containing an aminourea structure as described in any one of claims 1-5 in pesticides.

8. A pesticide composition, characterized in that: The active ingredient is a trifluorouracil compound containing an aminourea structure as described in any one of claims 1-5.

9. The pesticide composition according to claim 8, characterized in that: Includes one, two or more of the following: compounds represented by Formula I, stereoisomers, racemates, tautomers, isotope labels, nitrogen oxides, pharmaceutically acceptable salts or esters, solvates, or solvates of pharmaceutically acceptable salts; Preferably, it is formulated as a liquid or solid dosage form; Preferably, the weight percentage of the active ingredient in the composition is 0.1-99.9%, more preferably 0.5-99%; Preferably, it also includes an agriculturally, forestry, or sanitarily acceptable carrier.

10. The use of the pesticide composition according to claim 8 or 9 in a herbicide.

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