Triazine ring substituted phenylsulfonylurea compound, preparation method thereof, weeding composition and application of triazine ring substituted phenylsulfonylurea compound

Abstract

The invention belongs to the technical field of pesticides, and particularly relates to a triazine ring substituted phenylsulfonylurea compound, a preparation method thereof, a weeding composition and application. The compound is shown as a general formula I: # imgabs0 #, wherein Z is hydrogen or alkyl; r is alkyl, halogenated alkyl or alkoxy. The compound has excellent herbicidal activity on gramineous weeds, broadleaf weeds and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of pesticides, and specifically relates to a triazine ring-substituted phenylsulfonylurea compound, a preparation method thereof, a herbicidal composition and application thereof. Background Art

[0002] Weed control is a crucial link in achieving efficient agriculture. Although there are various types of herbicides on the market, such as patent WO2012059050A1, which discloses the use of substituted biarylbenzenesulfonamide compounds as herbicides. However, the herbicidal performance of these known compounds against harmful plants and the selectivity for crops are not completely satisfactory. In addition, due to the continuous expansion of the market, weed resistance, service life of drugs, economic efficiency of drugs, and people's increasing attention to the environment, scientists need to continue to study and develop new varieties of herbicides that are efficient, safe, economical, and have different modes of action. Summary of the invention

[0003] The invention provides a triazine ring substituted phenylsulfonylurea compound and a preparation method thereof, a herbicidal composition and application thereof. The compound has excellent herbicidal activity against gramineous weeds, broadleaf weeds and the like even at a low application rate and has high selectivity for crops.

[0004] The technical solution adopted by the present invention is as follows:

[0005] A triazine ring substituted phenylsulfonylurea compound, as shown in general formula I:

[0006]

[0007] Wherein, Z is hydrogen or alkyl;

[0008] R is an alkyl group, a haloalkyl group or an alkoxy group.

[0009] In one embodiment, Z is hydrogen or C1-C8 alkyl;

[0010] R is a C1-C8 alkyl group, a halogenated C1-C8 alkyl group or a C1-C8 alkoxy group.

[0011] In another embodiment, Z is hydrogen or C1-C6 alkyl;

[0012] R is a C1-C6 alkyl group, a halogenated C1-C6 alkyl group or a C1-C6 alkoxy group.

[0013] In another embodiment, Z is hydrogen or methyl;

[0014] R is methyl, trifluoromethyl or methoxy.

[0015] In the definition of the compounds represented by the above general formula and in all the following structural formulae, the technical terms used, whether used alone or in compound words, represent the following substituents: Alkyl groups with more than two carbon atoms can be straight-chain or branched. Alkyl groups are, for example, C1 alkyl-methyl; C2 alkyl-ethyl; C3 alkyl-propyl such as n-propyl or isopropyl; C4 alkyl-butyl such as n-butyl, isobutyl, tert-butyl or 2-butyl; C5 alkyl-pentyl such as n-pentyl; C6 alkyl-hexyl such as n-hexyl, isohexyl and 1,3-dimethylbutyl. Halogen is fluorine, chlorine, bromine or iodine.

[0016] The preparation method of the triazine ring substituted phenylsulfonylurea compound comprises the following steps:

[0017] The compound represented by the general formula II is reacted with the compound represented by the general formula III to obtain the compound represented by the general formula I, and the chemical reaction equation is as follows:

[0018]

[0019] Wherein, Q represents an alkyl group or an aryl group, preferably a C1-C6 alkyl group or a phenyl group, and the substituents R and Z are as defined above.

[0020] In one embodiment, the reaction is carried out in the presence of a base and a solvent.

[0021] In another specific embodiment, the base is selected from at least one of an inorganic base (such as K2CO3, Na2CO3, Cs2CO3, NaHCO3, KF, CsF, K3PO4, NaOH, KOH, etc.) or an organic base [KOAc, AcONa, t-BuONa, EtONa, NaOMe, DBU, C1-C6 alkylamine (preferably tri-(C1-C6)-alkylamine, such as triethylamine, trimethylamine, N-ethyldiisopropylamine)].

[0022] In another specific embodiment, the solvent is selected from at least one of aromatic hydrocarbons (such as benzene, chlorobenzene, toluene, cresol or o-, m- and p-xylene), THF, DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, Dioxane, dichloromethane, toluene or ethyl acetate.

[0023] The compounds of the present invention can also be prepared by referring to the methods described in WO2012059050A1, WO2006114220A1, US06 / 396959 or US06 / 458799.

[0024] A herbicide composition comprises a herbicidally effective amount of at least one of the triazine ring-substituted phenylsulfonylurea compounds, and preferably further comprises a formulation adjuvant.

[0025] A method for controlling weeds comprises applying a herbicidally effective amount of at least one of the triazine ring substituted phenylsulfonylurea compounds or the herbicide composition on plants or weedy areas.

[0026] The use of at least one of the triazine ring-substituted phenylsulfonylurea compounds or the herbicide composition in controlling weeds. Preferably, the triazine ring-substituted phenylsulfonylurea compounds are used to control weeds in useful crops, and the useful crops are transgenic crops or crops treated with genome editing technology.

[0027] The compounds of formula I of the present invention have outstanding herbicidal activity against many economically important monocotyledonous and dicotyledonous harmful plants. The active substances of the present invention are also effective against perennial weeds, which grow from rhizomes, rootstocks, or other perennial organs and are difficult to control. In this regard, it is generally unimportant whether the substance is used before sowing, before germination, or after germination. Representative examples of monocotyledonous and dicotyledonous weed groups that can be controlled by the compounds of the present invention are particularly mentioned, without limiting to certain species. Examples of weed species on which the active substances are effective include monocotyledonous plants: annual oats, rye, grass, alopecuroides, phalaris, barnyardgrass, crabgrass, Setaria and sedge, and perennial wheatgrass, bermudagrass, Imperata and sorghum, and perennial sedge.

[0028] With regard to dicotyledonous weed species, its effect can be extended to species such as annual Galium, Viola, Veronica, Sesame, Chickweed, Amaranth, Sinapis, Ipomoea, Rhizoma Coptidis, Matricaria and Abutilon, and perennial weeds Convolvulus, Thistle, Rumex and Artemisia. The active substance of the present invention effectively controls harmful plants such as Echinochloa, Sagittaria, Alisma, Eriobotrya, Sugarcane and Cyperus under such undetermined conditions of rice sowing. If the compound of the present invention is applied to the soil surface before germination, the seedlings of the weeds can be completely prevented before the weeds grow, or the weeds stop growing when the cotyledons grow, and finally die completely after three to four weeks. The compound of the present invention is particularly good in activity against the following plants, Apila, Sesame, Polygonum, Chickweed, Veronica hedera, Veronica arabica, Pansy and Amaranth, Galium and Kochia.

[0029] Although the compounds of the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, they do not damage economically important crop plants, such as wheat, barley, rye, rice, corn, sugar beet, cotton and soybeans, or the damage is negligible. In particular, they are very compatible with cereal crops, such as wheat, barley and corn, especially wheat. Therefore, the compounds of the invention are very suitable for selectively controlling unwanted plants in agricultural crops or ornamental plants.

[0030] Due to their herbicidal properties, these active substances can be used to control harmful plants in known or upcoming genetically engineered plant cultivation. Transgenic plants usually have superior properties, such as resistance to specific pesticides, especially specific herbicides, resistance to plant diseases or pathogenic microorganisms of plant diseases, such as specific insects or fungal, bacterial or viral microorganisms. Other special properties are related to the following conditions of the product, for example, quantity, quality, storage stability, composition and special ingredients. In this way, it is known to obtain transgenic plant products with increased starch content or improved starch quality or different fatty acid compositions.

[0031] The compounds of formula I of the present invention or their salts are preferably used in economically important genetically modified crops and ornamental plants, for example cereals, for example wheat, barley, rye, oats, millet, rice, cassava and corn, or in the cultivation of beets, cotton, soybeans, rapeseed, potatoes, tomatoes, peas and other vegetable plants. The compounds of formula I are preferably used as herbicides for the cultivation of useful plants, which are resistant or genetically engineered to the toxic effects of herbicides.

[0032] Conventional methods for breeding plants with improved shapes compared to known plants include, for example, conventional mating methods and mutant breeding. In other words, new plants with improved traits can be obtained by means of genetic engineering methods (see, for example, EP-0221044A, EP-0131624A). For example, several methods have been described:

[0033] - genetic engineering of crop plants to improve starch synthesis in plants (e.g. WO 92 / 11376, WO 92 / 14827, WO 91 / 19806);

[0034] - transgenic crop plants resistant to specific herbicides, such as glufosinate herbicides (e.g. EP-0242236A, EP-0242246A) or glyphosate herbicides (WO 92 / 00377), or sulfonylurea herbicides (EP-0257993A, US-5013659A);

[0035] - genetically modified crop plants such as cotton, which produce Bacillus thuringiensis toxins (Bt toxins) that protect plants from attack by certain pests (EP-0142924A, EP-0193259A);

[0036] - Transgenic crop plants with improved fatty acid composition (WO 91 / 13972).

[0037] A number of molecular biotechniques are known which allow the production of transgenic plants with improved traits (see, for example, Sambrook et al., 1989, Molecular Amplification, A Laboratory Manual, 2nd edition, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, New York; or Winnacker "Gene und Klone" [Genes and Clones], VCH Weinheim, 2nd edition 1996 or Christou, "Trends in Plant Science" 1 (1996) 423-431)). In order to carry out genetic engineering operations, it is possible to introduce nucleic acid molecules into plasmids, to cause mutations or sequence changes by recombination of DNA sequences. Using the above-mentioned standard methods, for example, substrates can be exchanged, parts of sequences can be removed or natural or synthetic sequences can be added. In order to connect DNA fragments to each other, it is possible to attach binding bodies or linkers to the fragments.

[0038] Plant cells in which the activity of a gene product is reduced can be prepared by, for example, expressing at least one appropriate antisense RNA, sense RNA to achieve a co-suppression effect, or by expressing at least one appropriately constructed ribozyme which specifically cleaves the transcript of the above gene product.

[0039] For this purpose, it is possible to use a DNA molecule comprising the entire coding sequence of the gene product, including any flanking sequences that may be present, and to use a DNA molecule comprising only a portion of the coding sequence, which portion must be long enough to achieve an antisense effect in the cell. It is also possible to use sequences that have a high degree of homology to the gene product coding sequence, but are not identical.

[0040] When expressing nucleic acid molecules in plants, the synthesized protein can be localized in any desired plant cell compartment. However, for localization in a specific compartment, it is possible, for example, to link the coding region and the DNA sequence to ensure localization at a specific position. These sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992) 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al. Plant J. 1 (1991), 95-106).

[0041] Transgenic plant cells can be recombined into whole plants using known techniques. Transgenic plants can be any desired plant species, i.e. monocots and dicots. In this way, it is possible to obtain transgenic plants with improved traits by overexpression, inhibition or suppression of homologous (=natural) genes or gene sequences, or by expression of heterologous (=foreign) genes or gene sequences.

[0042] When the active substance of the present invention is used on genetically modified crops, in addition to the effect of inhibiting harmful plants observed on other crops, there are often special effects on the corresponding genetically modified crops, such as improving or expanding the scope of weed control, improving the application rate during application, preferably combining the resistance of genetically modified crops with the performance of herbicides well, and affecting the growth and yield of genetically modified crop plants. Therefore, the present invention also provides the use of the compound as a herbicide to control harmful plants in genetically modified crop plants.

[0043] In addition, the compounds according to the invention can significantly regulate the growth of crop plants. By regulating the plant metabolism, these compounds can be used to control the composition of the plant and promote the harvest, for example to dry out the plant and dwarf the growth. They are also suitable for regulating and inhibiting undesirable plant growth without destroying the growth of the crop. Inhibiting plant growth plays a very important role in many monocotyledonous and dicotyledonous crops, because this can reduce or completely prevent lodging.

[0044] The compounds of the present invention can be applied using general formulations, and wettable powders, emulsion concentrates, sprayable solutions, powders or granules can be used. Thus, the present invention also provides herbicidal compositions comprising compounds of formula I. According to the usual biological and / or chemical physical parameters, compounds of formula I can be formulated in a variety of ways. Suitable formulation selection examples are: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, concentrated emulsions (EC), such as oil-in-water dispersions and water-in-oil dispersions (EW), sprayable solutions, suspension concentrates (SC), dispersible oil suspensions (OD), suspensions with oil or water as diluents, solutions of miscible oils, powders (DP), capsule suspensions (CS), seeddressing compositions, granules for broadcasting and soil application, spray granules, coated granules and absorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV (ultra-low volume) formulations, microcapsules and wax products. These individual formulation types are known and are described, for example, in Winnacker-Küchler, "Chemische Techonologie" [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th edition 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, NY, 1973; K. Martens, "Spray Drying" Handbook, 3rd edition 1979, G. Goodwin Ltd. London.

[0045] Necessary formulation auxiliaries, such as inert substances, surfactants, solvents and other additives are likewise known and described in documents such as Watkins, "Handbook of Powder Diluents, Pesticides and Carriers", 2nd edition, Darland Books, Caldwell NJ; Hv01phen, "Introduction to Clay Colloid Chemistry", 2nd edition, J. Wiley and Sons, NY; C. Marsden, "Solvent Guide", 2nd edition, Interscience, NY 1963; McCutcheon, "Detergents and Emulsifiers Annual", MC Publishing Company, Ridgewood NJ; Sisley and Wood, "Encyclopedia of Surfactants", Chemical Publishing Company, NY 1964; of" "[Ethylene oxide adduct surfactants], Wiss. Verlagagesell. Stuttgart 1976; Winnacker-Küchler "Chemische Technologie" [Chemical Technology], Volume 7, C. Hauser Verlag Munich, 4th edition 1986.

[0046] Wettable powders are homogeneously dispersible in water and contain, in addition to the active substance, diluents or inert substances, ionic and nonionic surfactants (wetting agents, dispersants), for example polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkylsulfonates, alkylphenylsulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthomethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate or sodium oleoylmethyltaurate. To prepare wettable powders, the active substance of the herbicide is finely ground, for example using conventional apparatus such as hammer mills, fan mills and jet mills, and adjuvants are mixed in simultaneously or sequentially.

[0047] The concentrated emulsion is prepared by dissolving the active substance in an organic solvent, such as butanol, cyclohexanone, dimethylformamide, xylene or a mixture of aromatic compounds or hydrocarbons with a higher boiling point or solvents, and adding one or more ionic and / or nonionic surfactants (emulsifiers). Examples of emulsifiers that can be used are calcium alkylaryl sulfonates such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkyl aromatic polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as sorbitan fatty acid esters, or polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan fatty esters.

[0048] Powders are obtained by grinding the active substance with finely divided solid materials, such as talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth. Suspensions based on water or oil can be prepared, for example, by wet grinding using a commercially available bead mill, with or without the addition of a surfactant of another formulation type as described above.

[0049] Emulsions such as oil-in-water emulsions (EW) can be prepared using aqueous organic solvents using stirrers, colloid mills and / or static mixers and, if necessary, adding surfactants of another formulation type as described above.

[0050] Granules are prepared by spraying the active substance onto an adsorbent, granulating with an inert material, or concentrating the active substance on the surface of a carrier such as sand or kaolinite and granulating the inert material with a binder such as polyvinyl alcohol, sodium polyacrylate or mineral oil. Suitable active substances can be granulated by the same method as for preparing fertilizer granules, and fertilizers can be mixed if necessary. Water suspension granules are prepared by the usual methods, such as spray-drying, fluidized bed granulation, disc granulation, mixing with a high-speed mixer, and extrusion in the absence of solid inert material.

[0051] For the preparation of granules using a grinding disc, a fluidized bed, an extruder and spraying, see the following processes, for example, "Spray Drying Handbook", third edition 1979, G. Goodwin Co., Ltd., London; JE Brawning, "Agglomeration", Chemistry and Engineering 1967, 147ff pages; "Perry's Chemical Engineer's Handbook", fifth edition, McGraw-Hill, New York 1973, 8-57 pages. If you want to know about the formulation of crop protection products, see, for example, GCKlingman, "Weed Control as a Science", John Wiley and Sons, New York, 1961, pp. 81-96 and JD Freyer, SAE vans "Weed Control Handbook", fifth edition, Blackwell Scientific Rublications, Oxford University 1968, pp. 101-103.

[0052] Agrochemical formulations usually contain 0.1 to 99% by weight, especially 0.1 to 95% of active substance formula I. The concentration of active substance in wettable powders is, for example, from about 10 to 99% by weight, and the usual formulation components constitute the remainder to 100% by weight. The concentration of active substance in concentrated emulsions can be about 1 to 90% by weight, preferably 5 to 80%. Powder formulations contain 1 to 30% by weight of active substance, usually preferably 5 to 20% by weight of active substance, while sprayable solutions contain about 0.05 to 80% by weight, preferably 2 to 50% of active substance. Regarding the content of active substance in water-suspended granules, it mainly depends on whether the active substance is liquid or solid, and the adjuvants, fillers, etc. used during granulation. The content of active substance in water-suspended granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

[0053] The formulations of the active substances may additionally contain tackifiers, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, carriers, colorants, antifoams, evaporation inhibitors and, generally, the pH and viscosity regulators customary in each case.

[0054] Based on these preparations, it is also possible to mix with other pesticide active substances such as insecticides, acaricides, herbicides and fungicides, and also with safeners, fertilizers and / or plant growth regulators, and the mixing method can be pre-mixed or canned mixed.

[0055] In mixed formulations or tank-mixed formulations, suitable active substances that can be mixed with the active substances of the present invention are, for example, known substances in "World New Pesticide Variety Technology Encyclopedia", China Agricultural Science and Technology Press, 2010.9 and the literature cited therein. For example, the following herbicide active substances can be mixed with the mixture of formula I (Note: the name of the compound is either the common name according to the International Organization for Standardization (ISO) or the chemical name, with a code number when appropriate): acetochlor, butachlor, alachlor, isopropylamine, isopropylamine, s-isopropylamine, pretilachlor, cypermethrin, cypermethrin, naphthiachlor, R-(-)-naphthiachlor, propanil, mefenacet, bisbencarb, fluazifop, flufenac, cyfluthrin, flumethalin, bromobutyric acid, dimethoate, high-efficiency dimethoate, ethoxybencarb, flumethoate, methoxyfenacet, metazachlor, isopropylamine, high-efficiency methyl fumarate, high-efficiency propyl fumarate, Dipropylene chloramine, pethochlor, butyrac, cyprothamide, flusulfuronamide, heptyl chloramine, isobutachlor, propargyl chloramine, terbutachlor, dimethyl chloramine, dimethoate, chlorfenapyr, trimethylcyclohexane, chlorfenapyr, propyzamide, valeryl chloramine, carbam, new Yanling, tricyclic chlorfenapyr, butyrac, chlorfenapyr, benzyl chloramine, quinone chloramine, benzyl chloramine, naphthamide, acetoacetamide, naphthamide, cyproconazole, cyproconazole, benzaclostrobin, chlorpyrifos, chlorpyrifos, chlorpyrifos, atrazine, simazine, promethazine, cyanamide, cyproconazole, amethoxazole, fluazifop, terbutaline, terbutaline, triazine fluazifop, cyprodinil, ganpoxetine, grass dazine , Promethazine, Simatoton, Azide, Diquat, Isoamyl, Cyprodinil, Metazine, Another Butyl, Zhongdingtong, Terbutalone, Methoxypropyl, Cyanamide, Izodone, Colazine, Ataton, Metazine, Licorice, Cyanuric Acid, Indaziflam, Chlorsulfuron, Metsulfuron-methyl, Benzsulfuron-methyl, Chlorsulfuron-methyl, Bensulfuron-methyl, Thisulfuron-methyl, Pyrazosulfuron-methyl, Methyl Disulfuron-methyl, Methyl Iodosulfuron Sodium, Formamidosulfuron-methyl, Ethersulfuron-methyl, Etherbensulfuron-methyl, Methsulfuron-methyl, Nicosulfuron, Ethamidosulfuron-methyl, Amidosulfuron-methyl, Ethoxysulfuron-methyl, Cyprosulfuron-methyl, Sulfonsulfuron-methyl, Tetrazosulfuron-methyl, Furasulfuron-methyl, Monosulfuron-methyl, Monosulfuron, Fluazsulfuron-methyl, Fluazsulfuron-methyl, Cyclosulfuron-methyl, Cyclosulfuron Sulfuron, pyrazosulfuron-methyl, sulfamethoxazole, propasulfuron-methyl, trifloxysulfuron-methyl, sulfamethoxazole-methyl, trifloxysulfuron, trifloxysulfuron-methyl, metsulfuron-methyl sodium salt, flucetosulfuron, methylthiosulfuron, pyrimidinesulfuron, Propyrisulfuron (promazine sulfuron), pyrazosulfuron-methyl, acifluorfen, fomesulfuron, lactofen, fluazifop-butyl, ethoxyfluorfen, oxazolidinone, chlorfenapyr, ethyl chlorpyrifos, methylcarboxyhexidine, trifluoroacetic acid butyl, methoxy-nitropropane, trifluoroacetic acid butyl, fluorinated herbicide, flusulfuron-methyl, nitropropane, acetosulfuron, dimethoate, fluazifop-butyl, fluazifop-butyl, halosafen, chlorotoluron, isoproturon, linuron, diuron,Saproron, Fluorouron, Benthiocarb, Methyl Benthiocarb, Benthiocarb, Sulfathiocarb, Isoxaluron, Terbuthiuron, Clomiduron, Chlorbromocarb, Methylthiocarb, Acylamuron, Methoxythiocarb, Bromothiocarb, Methoxythiocarb, Chlorthiocarb, Methiocarb, Cyclothiocarb, Fenthiocarb, Fluorouron, Cyclothiocarb ... le, Chlorprocarb, Fenasulam, BCPC, CPPC, Carbasulam, Butyl, Cyclocarb, Cyclocarb, Cyclocarb, Wild Wheat, Piperidin, Cyclocarb ... 2-Methyl-4-chlorobutyric acid, 2,4,5-T, 2,4,5-T propionic acid, 2,4,5-T butyric acid, 2-Methyl-4-chloroamine salt, dicamba, cypermethrin, fumarate, cypermethrin, trichlorobenzoic acid, ammonia dichlorobenzoic acid, methoxy trichlorobenzoic acid, diclofenac, fluazifop-butyl, fluazifop-butyl, fluazifop-butyl, high-efficiency fluazifop-butyl, quizalofop-butyl, quinazolin-butyl, oxadiazol-butyl, oxadiazol-butyl, cyhalofop-butyl, oxadiazol-butyl, cyhalofop-butyl, oxadiazol-butyl, cyhalofop-butyl, oxadiazol-butyl, cyhalofop-butyl, oxadiazol-butyl, cyhalofop-butyl, oxadiazol-butyl, cyhalofop-butyl, oxadiazol-butyl, cyhalofop-butyl, oxadiazol-butyl, cyhalofop-butyl, oxadiazol-butyl, chlorfenapyr ... in, propanediol, glyphosate, safflower, glufosinate, methylamine glufosinate, glufosinate sulfide, piperphosinate, bialaphos, dimethoate, oxazolidinone, chlorpyrifos, vinegrass, falcon, dimethylaminophosphine, oxazolidinone, imazapic acid, imazapic acid, imazapic acid, methoxyimazapic acid ammonium salt, imazapic acid, imazapic acid, clofopyralid, clofopyralid isooctyl, diclopyralid, aminopyralid, triclopyralid, fluthiopyr, halofopyr, triclopyralid, thiopyralid, fluazifop, clofopyralid, fluazifop, fluazifop, triclopyralid butoxyethyl, Cliodinate, sethoxydim, clethodim, cypermethrin, chlorpyrifos, cyclohexanone, butyroxenone, oxathiophene, pyraclostrobin, Buthidazole, methicillin,Hexazinone, Metamitron, Ethylmetazoxone, Ametridione, Amibuzin, Bromoxynil, Octanoyl Bromoxynil, Octanoyl Iodobenzonil, Iodobenzonil, Dichlobenil, Diphenylacetonitrile, Dipyridoxil, Hydroxychlorpyrifos, Iodobonil, Sulfonamide, Dipyridoxal, Penoxsulam, Sulfonamide, Sulfonamide, Sulfonamide, Dipyridoxal, Dipyridoxal, Dipyridoxal, Fluorosulfuron, Bispyribac-butyl, Cyclopyralid, Pyrimidinesulfuron, Pyrimidinesulfuron, Bispyribac-butyl, Pyrimidinesulfuron, Bispyribac-butyl, Mesotrione, Sulcotrione, Tembotrione, Tefuryltrione, Bicyclopyrone, Ketodpiradox, Isoxaflutole, Isoxachlorpyrifos, Fenoxasulfone, M ethiozolin, isopropylpyraclostrobin, pyrasulfobutyl, pyrazoline, wild yanquat, benzylpyrachlor, pyrazoline, pyrasulfotole, benzylpyrazone, pyroxasulfone, pyrazoline, fluazifop, chlorfenapyr, amine chlorpyrifos, chlorpyrifos, fluazifop, sulfentrazone, bencarbazone, fluazifop, chlorpyrifos, chlorpyrifos, chlorpyrifos, flupropacil, flumethoxam, flumethoxam, chlorpyrifos, phthalic acid, flumezin, pentachlorophenol (sodium), dinoseb, teloseb, teloseb, pentachlorophenol, dinitrophenol, chlorpyrifos, dinoseb, teloseb, oxadiazine, oxadiazine, cyclopentane Oxychloride, fluazifop-butyl, flupyridazine-butyl, chlorpyrifos ... , dalapon, trichloroacetic acid, monochloroacetic acid, hexachloroacetone, tetrafluoropropionic acid, grass fast, bromophenol oxime, triazole sulfone, chloranil, furochlor, furochlor, ethyl furochlor, chloranil, chloranil, fluchloralone, barnyard grass, acrolein, benzylpyridinium, benzylpyridinium, avena sativa, thiamethoxam, cotton amine, hydroxythiocarb, methoxybenzone, benzylpyridinium, chloranil, trichloropropionic acid, Al orac, Diethamquat, Etnipromid, Iprymidam, Ipfencarbazone, Thiencarbazone-methyl, Pyrimisulfan, Chlorflurazole, Tripropindan, Sulglycapin, Methylsulfuron, Cambendichlor, Cyprodinil, Thiencarbazone-methyl, Fenpyrimidin ...D489,LS 82-556, KPP-300, NC-324, NC-330, KH-218, DPX-N8189, SC-0744, DOWCO535, D K-8910, V-53482, PP-600, MBH-001, KIH-9201, ET-751, KIH-6127 and KIH-2023. ,

[0056] When used, if necessary, commercially available preparations are diluted in a common manner, for example, in the case of wettable powders, concentrated emulsions, suspensions and particles suspended in water, with water dilution. Powders, granules used for soil application or solutions for broadcasting and spraying generally do not require further dilution with inert substances before use. The required use amount of the compound of formula I varies with the changes in external conditions, such as temperature, humidity, the nature of the herbicide used, etc. It can have a large range of variation, for example between 0.001 and 1.0 kg ai / ha, or more active substances, but preferably between 0.005 and 750 g ai / ha, particularly between 0.005 and 250 g ai / ha. DETAILED DESCRIPTION

[0057] The following examples are used to illustrate the present invention and should not be considered to limit the present invention in any way. The scope of the rights required to be protected by the present invention is described by the claims.

[0058] In view of the economic efficiency and diversity of the compounds, we preferably synthesized some compounds, and among the many synthesized compounds, some are selected and listed in the following Table 1. The specific compound structures and corresponding compound information are shown in Table 1. The compounds in Table 1 are only for better illustrating the present invention, but not for limiting the present invention. For those skilled in the art, this should not be understood as the scope of the above subject matter of the present invention is limited to the following compounds.

[0059] Table 1 Compound structures and 1 H NMR

[0060]

[0061] Several methods for preparing the compounds of the present invention are described in detail in the following schemes and examples. The raw materials can be purchased from the market or can be prepared by methods known in the literature or as shown in the detailed description. It will be appreciated by those skilled in the art that other synthetic routes can also be used to synthesize the compounds of the present invention. Although the specific raw materials and conditions in the synthetic route have been described below, it can be easily replaced with other similar raw materials and conditions, and these modifications or variations of the preparation method of the present invention such as various isomers of the compound are included within the scope of the present invention. In addition, the preparation method described below can be further modified according to the disclosure of the present invention using conventional chemical methods well known to those skilled in the art. For example, appropriate groups are protected during the reaction, etc.

[0062] The method examples provided below are used to promote further understanding of the preparation method of the present invention. The specific substances, types and conditions used are determined to further illustrate the present invention and are not intended to limit its reasonable scope. The reagents used in the synthetic compounds shown in the following table can be purchased commercially or can be easily prepared by a person of ordinary skill in the art.

[0063] Examples of representative compounds are as follows. The synthesis methods of other compounds are similar and will not be described in detail here.

[0064] 1. Synthesis of Compound 1

[0065] 500 mg 1-1 (1.0 eq) and 1-2 (1.2 eq) were added to a single-mouth bottle, dissolved in 10 mL acetonitrile, and DBU (1.5 eq) was slowly added dropwise. The reaction was allowed to react at room temperature for 10-30 min. The liquid mass spectrometry reaction was basically completed. After the acetonitrile was dried, the residue was dissolved in DCM and washed three times with 1 M hydrochloric acid water. The organic phase was dried with anhydrous sodium sulfate and then dried by spin drying. A trace amount of ethyl acetate was used to beat the pulp to obtain 510 mg of pure solid product compound 1, with a yield of 62%.

[0066]

[0067] Biological activity evaluation:

[0068] The activity level standards for plant damage (i.e., growth control rate) are as follows:

[0069] Level 10: Complete death;

[0070] Level 9: Growth control rate is greater than or equal to 90% and less than 100%;

[0071] Level 8: Growth control rate is greater than or equal to 80% and less than 90%;

[0072] Level 7: Growth control rate is greater than or equal to 70% and less than 80%;

[0073] Level 6: Growth control rate is greater than or equal to 60% and less than 70%;

[0074] Level 5: Growth control rate is greater than or equal to 50% and less than 60%;

[0075] Level 4: Growth control rate is greater than or equal to 40% and less than 50%;

[0076] Level 3: Growth control rate is greater than or equal to 30% and less than 40%;

[0077] Level 2: Growth control rate is greater than or equal to 20% and less than 30%;

[0078] Level 1: Growth control rate is less than 20%;

[0079] Level 0: No effect.

[0080] The above growth control rates are fresh weight control rates.

[0081] Post-emergence test experiment:

[0082] Monocotyledonous and dicotyledonous weed seeds (artemisia selengensis, shepherd's purse, ramie, cleaver, chickweed, wheat family, shepherd's purse, alopecuroides, Japanese alopecuroides, goosegrass, weed grass, hard grass, small fleabane, candle grass, Veronica, brome, knotweed, phalaenopsis, amaranth, quinoa, dayflower, sonchus, field bindweed, prickly lettuce, nightshade, amaranth, crabgrass, barnyard grass, foxtail grass, chinensis, duckweed, wild arrowhead, firefly rush, cyperus, broken rice sedge, sedge, floating grass, purslane, Xanthium, morning glory, white wine grass, etc.) and major crops Seeds (wheat, corn, rice, soybean, cotton, rapeseed, millet, sorghum, potato, sesame, castor, etc.) were placed in a plastic pot filled with soil, and then covered with 0.5-2 cm of soil to grow in a good greenhouse environment. Two weeks after sowing, the test plants were treated at the 2-3 leaf stage. The tested compounds of the present invention were dissolved in acetone, and then Tween 80 was added. 1.5 liters / hectare of methyl oleate emulsifiable concentrate was used as a synergist, diluted with a certain amount of water to a certain concentration of solution, and sprayed on the plants with a spray tower. After culturing in a greenhouse for 3 weeks after application, the experimental effects of weeds were counted. The compound dosages used were 60, 15, and 7.5 g.i. / ha, repeated three times, and the average value was taken. Representative data are listed in Table 2.

[0083] Table 2 Post-emergence weed test results

[0084]

[0085] Note: N stands for no data; Reference compound A: Control compound B:

[0086]

[0087] It can be seen from this that compound 1 of the present application is more active than the control compound, is safe for wheat, and has higher selectivity.

[0088] Pre-emergence test experiment:

[0089] Monocotyledonous and dicotyledonous weed seeds and main crop seeds (corn, wheat, rice, soybean, rape, pepper, eggplant, potato, tobacco, cotton, flax, millet, sorghum, etc.) are placed in a plastic pot filled with soil, and then covered with 0.5-2 cm of soil, and the tested compounds of the present invention are respectively dissolved with acetone, and then Tween 80 is added, and diluted with a certain amount of water to a solution of a certain concentration, and sprayed immediately after sowing. After culturing in a greenhouse for 4 weeks after application, the experimental results are observed, and it is found that most of the agents of the present invention have outstanding effects at a dosage of 60g ai / ha, especially for weeds such as Amaranthus retroflexus, Ramie, and Caulis, and many compounds have good selectivity for corn, wheat, rice, soybean, rape, pepper, eggplant, potato, tobacco, cotton, flax, sorghum, etc.

[0090] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the spirit and scope of the technical solution of the present invention.

Claims

1. A triazine ring substituted phenylsulfonylurea compound, as shown in the general formula I: in, Z is hydrogen or alkyl; R is an alkyl group, a haloalkyl group or an alkoxy group.

2. A triazine ring substituted phenylsulfonylurea compound according to claim 1, characterized in that: Z is hydrogen or C1-C8 alkyl; R is a C1-C8 alkyl group, a halogenated C1-C8 alkyl group or a C1-C8 alkoxy group.

3. A triazine ring substituted phenylsulfonylurea compound according to claim 1 or 2, characterized in that: Z is hydrogen or C1-C6 alkyl; R is a C1-C6 alkyl group, a halogenated C1-C6 alkyl group or a C1-C6 alkoxy group.

4. A triazine ring substituted phenylsulfonylurea compound according to any one of claims 1 to 3, characterized in that: Z is hydrogen or methyl; R is methyl, trifluoromethyl or methoxy; Preferably, the compound is selected from any one of Table 1 in the specification.

5. A method for preparing a triazine ring substituted phenylsulfonylurea compound as claimed in any one of claims 1 to 4, characterized in that: The following steps are involved: The compound represented by the general formula II is reacted with the compound represented by the general formula III to obtain the compound represented by the general formula I, and the reaction equation is as follows: Wherein, Q represents an alkyl group or an aryl group, preferably a C1-C6 alkyl group or a phenyl group, and the substituents R and Z are defined as described in any one of claims 1 to 4; Preferably, the reaction is carried out in the presence of a base and a solvent; more preferably, the base is selected from at least one of an inorganic base (such as K2CO3, Na2CO3, Cs2CO3, NaHCO3, KF, CsF, K3PO4, NaOH, KOH, etc.) or an organic base [KOAc, AcONa, t-BuONa, EtONa, NaOMe, DBU, C1-C6 alkylamine (preferably tri-(C1-C6)-alkylamine, such as triethylamine, trimethylamine, N-ethyldiisopropylamine)]; the solvent is selected from at least one of aromatic hydrocarbons (such as benzene, chlorobenzene, toluene, cresol or o-, m- and p-xylene), THF, DMF, DMA, methanol, ethanol, acetonitrile, dichloroethane, DMSO, Dioxane, dichloromethane, toluene or ethyl acetate.

6. A herbicide composition, characterized in that: The method comprises a herbicidally effective amount of at least one of the triazine ring-substituted phenylsulfonylurea compounds according to any one of claims 1 to 4, and preferably further comprises a formulation adjuvant.

7. A method for controlling weeds, characterized in that: The method comprises applying a herbicidally effective amount of at least one of the triazine ring substituted phenylsulfonylurea compounds according to any one of claims 1 to 4 or the herbicide composition according to claim 6 on plants or weedy areas.

8. Use of at least one of the triazine ring-substituted phenylsulfonylurea compounds according to any one of claims 1 to 4 or the herbicide composition according to claim 6 for controlling weeds, preferably, the triazine ring-substituted phenylsulfonylurea compounds are used to control weeds in useful crops, and the useful crops are transgenic crops or crops treated with genome editing technology.

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